EP2268848A1 - Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit - Google Patents

Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit

Info

Publication number
EP2268848A1
EP2268848A1 EP09727119A EP09727119A EP2268848A1 EP 2268848 A1 EP2268848 A1 EP 2268848A1 EP 09727119 A EP09727119 A EP 09727119A EP 09727119 A EP09727119 A EP 09727119A EP 2268848 A1 EP2268848 A1 EP 2268848A1
Authority
EP
European Patent Office
Prior art keywords
group
formula
thin film
saturated
different
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Withdrawn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
EP09727119A
Other languages
German (de)
French (fr)
Inventor
Stéphane DANIELE
Mohamad Eleter
Catherine Dubourdieu
Virginie Brize
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.)
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Institut Polytechnique de Grenoble
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Institut Polytechnique de Grenoble
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 Centre National de la Recherche Scientifique CNRS, Universite Claude Bernard Lyon 1 UCBL, Institut Polytechnique de Grenoble filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2268848A1 publication Critical patent/EP2268848A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • 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
    • C23C16/308—Oxynitrides
    • 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 invention provides a process for producing a thin film of nitrided hafnium oxide or nitrided hafnium silicate from asymmetric ligand guanidinate-type coordination compounds. It also relates to a method of producing an integrated electronic circuit which comprises a step of producing a thin film of silicate oxide or nitrided hafnium silicate by the method of the invention.
  • hafnium oxide or hafnium silicate films are being studied with a view to replacing SiO 2 films, in particular for producing oxide of grids. of CMOS transistors and oxide MIM and DRAM capabilities for example.
  • hafnium oxide of stoichiometric formula HfO 2 , or of a hafnium silicate of formula HfSi x Oy in the manufacture of integrated electronic circuits is known, in particular for producing portions of high value of dielectric permittivity.
  • this high value of the dielectric permittivity depends on the crystallographic structure of the hafnium oxide. In its monoclinic phase, hafnium oxide has a relative dielectric permittivity ⁇ r of the order of 16 to less than 20, whereas this value is between 25 and 80 when the hafnium oxide has a cubic structure , tetragonal or orthorhombic.
  • the films formed are generally nitrided, after deposition, to improve their thermal stability and their barrier properties to the diffusion of oxygen and dopants.
  • HfO 2 has a permittivity of the order of 22 to about 26. But when the material is amorphous, it subsequently crystallizes in monoclinic form when the circuit is heated during its manufacture, after the formation of the hafnium oxide portion. The relative dielectric permittivity of the hafnium oxide portion then becomes less than about 20.
  • MOCVD organometallic or coordination compound
  • ALD atomic layers
  • each source compound is vaporized and introduced separately from each of the other compounds, and alternately into the deposition chamber.
  • An inert gas purge step or evacuation precedes and follows each introduction of the vapor of each source compound.
  • a monatomic layer of the compound is formed, by a chemical reaction, at the exposed surface of the substrate.
  • the vapor form compounds are introduced together or separately into the deposition chamber where one or more chemical reactions occur to form a film on the exposed surface of the substrate.
  • hafnium alkoxides and amides such as compounds of formula Hf (NRiRa) 4 in which R 1 and R 2 may be identical or different and are usually alkyl groups.
  • the aim of the invention is to overcome the disadvantages of the precursors used in the processes for the chemical production of hafnium oxide or hafnium silicate films of the prior art by proposing the use of particular hafnium precursors for these deposits.
  • of guanidinate structure with asymmetric ligands which make it possible to obtain thin films, of the order of a few nanometers in thickness, nitrided hafnium oxide or silicate without a nitriding step after the deposition of the film, which make it possible to obtain to obtain films in which the HfO 2 phase is of predominantly non-monoclinic crystalline structure, which make it possible to obtain films in which the nitrided hafnium silicate phase is amorphous, which make it possible to obtain films in which the HfO 2 phase at a crystallization temperature above 475 ° C.
  • the invention will be better understood and other advantages and characteristics thereof will appear more clearly on reading the explanatory description which follows.
  • non-monoclinic phase or “non-monoclinic” mean an HfO 2 phase of crystalline structure of symmetry greater than the monoclinic phase, that is to say a phase of cubic structure , orthorhombic or quadratic.
  • the terms "predominantly non-monoclinic crystalline structure film” or “predominantly non-monoclinic structure film” are understood to mean in the invention that the crystalline structure film in question contains at least 50% by volume relative to the total volume of crystalline structures present, non-monoclinic crystalline structure.
  • the term "layer or thin film” means a layer of material which has two substantially parallel faces separated by a layer thickness of less than 100 nm.
  • the obtaining of the hafnium oxide material in the form of such a thin layer is particularly suitable for the manufacture of an integrated electronic circuit which has a layered structure superimposed on a substrate.
  • the invention proposes a process for the chemical vapor phase preparation of a thin film of amorphous nitride hafnium oxide or in which the hafnium oxide phase has a predominantly non-monoclinic crystalline structure or a thin film.
  • amorphous nitrided hafnium silicate which consists in generating a gaseous phase by evaporation of at least one coordination compound, dissolved in a solvent, of the following formula I:
  • R 1 and R 2 are identical or different and are selected from an alkyl group, linear or branched, saturated or unsaturated C 1 to C 2, a cyclic group, saturated or unsaturated C 3 -C 12,
  • R 3 and R 4 are different and are selected from an alkyl group, linear or branched, saturated or unsaturated Cl-C 12, a cyclic group, saturated or unsaturated, C 3 to C 2, or a group of formula Si (R 5 ) 3 in which R 5 is a linear C 1 -C 6 alkyl group, and x is an integer between 1 and 4 inclusive, and then decomposing this gaseous phase on a heated substrate.
  • the groups R 1 and R 2 are identical or different and are chosen from a methyl group or an ethyl group
  • the groups R 3 and R 4 are chosen from an ethyl group and an isopropyl group, tert-butyl group
  • SiMe 3 group and x is 1 or 2.
  • the gas phase is generated by heating at a temperature between 180 ° C. and 220 ° C. of at least one coordination compound of formula I dissolved in octane as a solvent, and this The gaseous phase is decomposed on a substrate heated to a temperature of between 300 ° C. and 600 ° C. inclusive.
  • Substrate heating temperatures above 600 ° C could be used but without additional benefits.
  • the pressure used in the deposition process is about 1 to 10 Torr (ie.0.13 to 1.3 kPa).
  • the coordination compound in order to obtain a nitrided hafnium oxide thin film, the coordination compound must be a compound of formula I in which neither R 3 nor R 4 have the formula Si (R 5 ) 3 and to obtain a thin film of nitrided hafnium silicate, the coordinating compound should be a compound of formula I wherein one of R 3 and R 4 has the formula Si (R 5 ) 3 .
  • the temperature of the substrate is between 300 ° C. and 475 ° C. inclusive.
  • the films obtained with the hafnium precursors of the prior art crystallize at a temperature greater than 475 ° C., which enables them to maintain a protective structure. amorphous during subsequent heat treatments which would take place at a temperature of less than or equal to 475 ° C., in particular devices in which they are integrated.
  • the temperature of the substrate is greater than 475 ° C. and less than or equal to 600 ° C.
  • the gaseous phase is generated by heating the compound of formula I at a temperature between 160 0 C and 220 0 C inclusive.
  • the process for producing a nitrided hafnium nitride oxide or nitrided hafnium silicate thin film of the invention makes it possible to eliminate an additional nitriding step since it allows the nitriding in situ of these films, which allows a saving of time and reagents.
  • the obtaining of a non-monoclinic HfO 2 phase with a higher permittivity than the monoclinic HfO 2 phase usually obtained has advantages for the production of MOS transistors or capacitive MIM structures, if we consider the thickness of the silica which is electronically equivalent to the actual thickness of the nitrided hafnium oxide or nitrided hafnium silicate layer.
  • ⁇ r and e respectively denote the relative dielectric permittivity and the actual thickness of the thin layer of nitrided hafnium oxide or nitrided hafnium silicate and ⁇ r (Si0 2 ) denotes the relative dielectric permittivity of the silica.
  • ⁇ r (Si0 2 ) is equal to approximately 3.9.
  • the increase in permittivity makes it possible to achieve a lower EOT while maintaining a sufficient film thickness so that the leakage currents remain within acceptable limits for the application.
  • the films obtained, when amorphous, have an increased thermal stability up to a temperature of about 475 ° C.
  • the deposition of the nitrided hafnium oxide or nitrided hafnium silicate from the at least one coordination compound of the invention may be, as will be clear to those skilled in the art, carried out both by a MOCVD injection process pulsed or not, only by an ALD method.
  • the films obtained in the invention have a thickness of between 0.9 and 30 nm.
  • the invention also relates to coordination compounds for obtaining thin films of nitrided hafnium silicate by the process of the invention.
  • R 1 , R 2 , R 3 , R 4 and x are as defined for compounds of formula I but wherein one of R 3 or R 4 has the formula Si (Rs) 3 , preferably one of R 3 or R 4 is SiMe 3 .
  • the invention also proposes a method for producing an electronic circuit which comprises a thin film layer portion based on hafnium oxide or nitrided hafnium silicate.
  • this process comprises a step of producing a nitrided hafnium oxide or nitrided hafnium silicate film by the method of the invention described above.
  • the invention also provides an electronic circuit which comprises a nitrided hafnium oxide layer or nitrided oxide film or nitrided hafnium silicate layer produced by the process of the invention.
  • the nitrided hafnium oxide thin film was formed by the pulsed injection MOCVD method. A volume of 0.60 ml of solution of the above coordination compound, diluted in octane, was injected.
  • the frequency of the injection is 1 Hz with an opening time of 1ms.
  • the injector is pressurized at a pressure of 1 bar of argon.
  • the coordination compound is vaporized at a temperature of 160 ° C. and then decomposed on a Si / SiO 2 substrate having a thickness of 0.8 nm heated to 350 ° C. using a flow of 100 sccm of nitrogen and 200 sccm of oxygen and a total pressure of 0.13 kPa.
  • the nitrided hafnium oxide film obtained is amorphous and has a thickness of 12.6 nm.
  • the same results are obtained when the vaporization temperature of the coordination compound is increased at 180 ° C. and 205 ° C., respectively.
  • Example 2 The procedure was as in Example 1, except that the substrate was heated to a temperature of 375 ° C, and a volume of 0.58 ml of the solution of the coordination compound, diluted in octane, was injected.
  • the resulting film is amorphous and has a thickness of 4.9 nm.
  • Example 2 The procedure was as in Example 1 except that the substrate was heated to a temperature of 400 ° C. In this example, a volume of 0.60 ml of the coordination compound diluted in octane was injected.
  • the resulting film is amorphous and has a thickness of 2.9 nm.
  • Example 2 The procedure was as in Example 1, except that the substrate was heated to a temperature of 450 ° C.
  • the injected volume of coordination compound diluted in octane is 0.60 ml.
  • the resulting film is amorphous and has a thickness of 4.1 nm.
  • Example 2 The procedure was as in Example 1 except that the substrate was heated to a temperature of 475 ° C.
  • the injected volume of coordination compound diluted in the octane is 0.53 ml.
  • the resulting film is amorphous and has a thickness of 1.3 nm.
  • Example 2 The procedure was as in Example 1, except that the substrate was heated to a temperature of 530 ° C. and that the volume of coordination compound diluted in the injected octane was 0.80 ml.
  • the film obtained consists of nitrided HfO 2 in which the HfO 2 phase has a predominantly non-monoclinic structure.
  • the resulting film has a thickness of 12.3 nm.
  • Example 2 The procedure was as in Example 1 except that the substrate was heated to a temperature of 580 ° C. and a volume of 0.86 ml of the coordination compound diluted in octane was injected.
  • the film obtained is a nitrided hafnium oxide film having a thickness of 14.7 nm.
  • the HfO 2 phase has a crystalline structure that is predominantly non-monoclinic.
  • the resulting film consisted of nitrided hafnium oxide in which the hafnium oxide phase has a monoclinic / orthorhombic or monoclinic / quadratic or monoclinic / cubic mixed crystalline structure.
  • the film has a thickness of 4.1 nm.
  • Example 8 The procedure was as in Example 8 except that the substrate was heated at 580 c C and a volume of 0.70 ml coordination compound diluted in octane was injected.
  • the film obtained is a nitrided hafnium oxide film in which the hafnium oxide phase is predominantly of non-monoclinic structure.
  • the film obtained has a thickness of 24.9 nm.
  • Example 2 The procedure was as in Example 1 except that the substrate was heated to a temperature of 475 ° C and the injected volume of the octane-diluted coordination compound was 0.45 ml.
  • the resulting film is amorphous and has a thickness of 4.45 nm.

Abstract

The invention provides a method for developing a thin film from oxide or silicate of hafnium nitride, and also provides asymmetric guanidinate coordinate compounds. The invention furthermore provides a method for producing an electronic circuit that includes a step for developing a thin film from oxide or silicate of hafnium nitride through the method of the invention. The method for developing a thin film from hafnium nitride oxide or hafnium nitride silicate according to the invention involves generating the gas phase by heating at least one coordinate compound from the following formula (I): Hf(NR1R2)4-x [R3-N=C(NR1R2)-NR4]x wherein R1 and R2 are the same or different and selected from a straight or branched, saturated or unsaturated alkyl group in C1 through C12 and from a saturated or unsaturated cyclic group in C3 through C12; R3 and R4 are different and selected from a straight or branched, saturated or unsaturated alkyl group in C1 through C12 and from a saturated or unsaturated cyclic group in C3 through C12 or a group from the Si(R5)3 formula wherein R5 is a straight alkyl group in C1 through C6; and x is an integer between 1 and 4 inclusive; then decomposing this gas phase on a heated substrate. The invention is used particularly in the field of microelectronics.

Description

PROCEDE D'ELABORATION D'UN FILM MINCE D'OXYDE OU DE SILICATE D1HAFNIUM NITRURE, COMPOSE DE COORDINATION UTILISE DANS CE PROCEDE ET PROCEDE DE REALISATION D'UN CIRCUIT ELECTRONIQUE INTEGREMETHOD OF MAKING THIN FILM OXIDE OR SILICATE D 1 HAFNIUM NITRIDE, COORDINATION COMPOUND USED IN THIS METHOD AND METHOD FOR PRODUCING AN INTEGRATED CIRCUIT ELECTRONIC
L'invention propose un procédé d'élaboration d'un film mince d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré à partir de composés de coordination de type guanidinate à ligands asymétriques. Elle concerne aussi un procédé de réalisation d'un circuit électronique intégré qui comprend une étape d'élaboration d'un film mince d'oxyde de silicate ou de silicate d'hafnium nitruré par le procédé de l'invention.The invention provides a process for producing a thin film of nitrided hafnium oxide or nitrided hafnium silicate from asymmetric ligand guanidinate-type coordination compounds. It also relates to a method of producing an integrated electronic circuit which comprises a step of producing a thin film of silicate oxide or nitrided hafnium silicate by the method of the invention.
Dans la course actuelle vers la miniaturisation des dispositifs électroniques, les films d'oxyde d'hafnium ou de silicate d'hafnium sont très étudiés en vue de remplacer les films de SiO2, en particulier pour l'élaboration de l'oxyde de grilles de transistors CMOS et de l'oxyde des capacités MIM et DRAM par exemple.In the current race towards the miniaturization of electronic devices, hafnium oxide or hafnium silicate films are being studied with a view to replacing SiO 2 films, in particular for producing oxide of grids. of CMOS transistors and oxide MIM and DRAM capabilities for example.
L'utilisation de couches minces d'oxyde d'hafnium, de formule stœchiométrique HfO2, ou d'un silicate d'hafnium de formule HfSixOy dans la fabrication de circuits électroniques intégrés est connue, notamment pour réaliser des portions de matériau à haute valeur de permittivité diélectrique. Mais cette valeur élevée de la permittivité diélectrique dépend de la structure cristallographique de l'oxyde d'hafnium. Dans sa phase monoclinique, l'oxyde d'hafnium présente une permittivité diélectrique relative εr de l'ordre de 16 à moins de 20, alors que cette valeur est comprise entre 25 et 80 lorsque l'oxyde d'hafnium possède une structure cubique, tétragonale ou orthorhombique. Pour stabiliser ces phases de plus hautes symétries, l'ajout d'additifs a été proposé (par exemple lanthanides, Y, Sc...). Les films formés sont généralement nitrurés, après dépôt, pour améliorer leur stabilité thermique et leurs propriétés de barrière à la diffusion de l'oxygène et des dopants.The use of thin layers of hafnium oxide, of stoichiometric formula HfO 2 , or of a hafnium silicate of formula HfSi x Oy in the manufacture of integrated electronic circuits is known, in particular for producing portions of high value of dielectric permittivity. But this high value of the dielectric permittivity depends on the crystallographic structure of the hafnium oxide. In its monoclinic phase, hafnium oxide has a relative dielectric permittivity ε r of the order of 16 to less than 20, whereas this value is between 25 and 80 when the hafnium oxide has a cubic structure , tetragonal or orthorhombic. To stabilize these phases of higher symmetries, the addition of additives has been proposed (for example lanthanides, Y, Sc ...). The films formed are generally nitrided, after deposition, to improve their thermal stability and their barrier properties to the diffusion of oxygen and dopants.
Pour certaines applications de la microélectronique, on peut souhaiter garder une structure amorphe de la couche d'oxyde. Sous forme amorphe, HfO2 présente une permittivité de l'ordre de 22 à 26 environ. Mais quand le matériau est amorphe, il cristallise ultérieurement sous forme monoclinique lorsque le circuit est chauffé pendant sa fabrication, après la formation de la portion d'oxyde d'hafnium. La permittivité diélectrique relative de la portion d'oxyde d'hafnium redevient alors inférieure à 20 environ. II existe de nombreux procédés pour déposer des films sur un substrat. Parmi tous ces procédés, le dépôt chimique en phase vapeur d'un composé organométallique ou de coordination (MOCVD) et le dépôt de couches atomiques (ALD) sont particulièrement appropriés pour Ie dépôt de films minces pour des applications microélectroniques.For some applications of microelectronics, it may be desirable to keep an amorphous structure of the oxide layer. In amorphous form, HfO 2 has a permittivity of the order of 22 to about 26. But when the material is amorphous, it subsequently crystallizes in monoclinic form when the circuit is heated during its manufacture, after the formation of the hafnium oxide portion. The relative dielectric permittivity of the hafnium oxide portion then becomes less than about 20. There are many methods for depositing films on a substrate. Of all these methods, the chemical vapor deposition of an organometallic or coordination compound (MOCVD) and the deposition of atomic layers (ALD) are particularly suitable for deposition of thin films for microelectronic applications.
Dans le procédé ALD, chaque composé source est vaporisé et introduit séparément de chacun des autres composés, et en alternance, dans la chambre de dépôt.In the ALD process, each source compound is vaporized and introduced separately from each of the other compounds, and alternately into the deposition chamber.
Une étape de purge par gaz inerte ou une mise sous vide précède et suit chaque introduction de la vapeur de chaque composé source.An inert gas purge step or evacuation precedes and follows each introduction of the vapor of each source compound.
A chaque injection du composé particulier sous forme gazeuse, une couche monoatomique du composé se forme, par une réaction chimique, à la surface exposée du substrat.At each injection of the particular compound in gaseous form, a monatomic layer of the compound is formed, by a chemical reaction, at the exposed surface of the substrate.
Dans le procédé MOCVD, les composés sous forme vapeur sont introduits ensemble ou séparément dans la chambre de dépôt où a lieu une ou plusieurs réactions chimiques pour former un film sur la surface exposée du substrat.In the MOCVD process, the vapor form compounds are introduced together or separately into the deposition chamber where one or more chemical reactions occur to form a film on the exposed surface of the substrate.
Les composés couramment utilisés jusqu'à présent pour obtenir des films d'oxyde ou de silicate d'hafnium sont les alcoxydes et amidures d'hafnium, tels que les composés de formule Hf(NRiRa)4 dans laquelle Ri et R2 peuvent être identiques ou différents et sont généralement des groupements alkyles.The compounds commonly used until now to obtain oxide or hafnium silicate films are hafnium alkoxides and amides, such as compounds of formula Hf (NRiRa) 4 in which R 1 and R 2 may be identical or different and are usually alkyl groups.
L'invention vise à résoudre les inconvénients des précurseurs utilisés dans les procédés d'élaboration par voie chimique de films d'oxyde ou de silicate d'hafnium de l'art antérieur en proposant d'utiliser pour ces dépôts des précurseurs d'hafnium particuliers de structure guanidinate à ligands asymétriques: qui permettent d'obtenir des films minces, de l'ordre de quelques nanomètres d'épaisseur, d'oxyde ou de silicate d'hafnium nitruré sans étape de nitruration après le dépôt du film, qui permettent d'obtenir des films dans lesquels la phase HfO2 est de structure cristalline majoritairement non monoclinique, qui permettent d'obtenir des films dans lesquels la phase silicate d'hafnium nitruré est amorphe, qui permettent d'obtenir des films dans lesquels la phase HfO2 a une température de cristallisation supérieure à 475°C. L'invention sera mieux comprise et d'autres avantages et caractéristiques de celle-ci apparaîtront plus clairement à la lecture de la description explicative qui suit.The aim of the invention is to overcome the disadvantages of the precursors used in the processes for the chemical production of hafnium oxide or hafnium silicate films of the prior art by proposing the use of particular hafnium precursors for these deposits. of guanidinate structure with asymmetric ligands: which make it possible to obtain thin films, of the order of a few nanometers in thickness, nitrided hafnium oxide or silicate without a nitriding step after the deposition of the film, which make it possible to obtain to obtain films in which the HfO 2 phase is of predominantly non-monoclinic crystalline structure, which make it possible to obtain films in which the nitrided hafnium silicate phase is amorphous, which make it possible to obtain films in which the HfO 2 phase at a crystallization temperature above 475 ° C. The invention will be better understood and other advantages and characteristics thereof will appear more clearly on reading the explanatory description which follows.
Dans ce qui suit et qui précède, les termes "phase non monoclinique" ou "non monoclinique" signifient une phase d'HfO2 de structure cristalline de symétrie supérieure à la phase monoclinique, c'est-à-dire une phase de structure cubique, orthorhombique ou quadratique.In what follows and above, the terms "non-monoclinic phase" or "non-monoclinic" mean an HfO 2 phase of crystalline structure of symmetry greater than the monoclinic phase, that is to say a phase of cubic structure , orthorhombic or quadratic.
Au sens de l'invention, par les termes "film à structure cristalline majoritairement non monoclinique" ou "film à structure majoritairement non monoclinique", on entend dans l'invention, que le film à structure cristalline concerné contient au moins 50 % en volume, par rapport au volume total de structures cristallines présentes, de structure cristalline non monoclinique.For the purposes of the invention, the terms "predominantly non-monoclinic crystalline structure film" or "predominantly non-monoclinic structure film" are understood to mean in the invention that the crystalline structure film in question contains at least 50% by volume relative to the total volume of crystalline structures present, non-monoclinic crystalline structure.
Au sens de l'invention, on entend par "couche ou film mince" une couche de matériau qui a deux faces sensiblement parallèles séparées par une épaisseur de couche inférieure à 100 nm. L'obtention du matériau d'oxyde à base d'hafnium sous la forme d'une telle couche mince est particulièrement adaptée à la fabrication d'un circuit électronique intégré qui présente une structure en couches superposées sur un substrat.For the purposes of the invention, the term "layer or thin film" means a layer of material which has two substantially parallel faces separated by a layer thickness of less than 100 nm. The obtaining of the hafnium oxide material in the form of such a thin layer is particularly suitable for the manufacture of an integrated electronic circuit which has a layered structure superimposed on a substrate.
L'invention propose un procédé d'élaboration par voie chimique en phase vapeur d'un film mince d'oxyde d'hafnium nitruré amorphe ou dans lequel la phase oxyde d'hafnium a une structure cristalline majoritairement non monoclinique ou d'un film mince de silicate d'hafnium nitruré amorphe, qui consiste à générer une phase gazeuse par évaporation d'au moins un composé de coordination, dissout dans un solvant, de formule I suivante :The invention proposes a process for the chemical vapor phase preparation of a thin film of amorphous nitride hafnium oxide or in which the hafnium oxide phase has a predominantly non-monoclinic crystalline structure or a thin film. amorphous nitrided hafnium silicate, which consists in generating a gaseous phase by evaporation of at least one coordination compound, dissolved in a solvent, of the following formula I:
Hf(NR1 R2)4-χ [R3-N=C(NR1 R2)-NR4]X Hf (NR 1 R 2 ) 4- χ [R 3 -N = C (NR 1 R 2 ) -NR 4 ] X
dans laquelle :in which :
R1 et R2 sont identiques ou différents et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en C1 à Ci2, un groupe cyclique, saturé ou insaturé, en C3 à C12,R 1 and R 2 are identical or different and are selected from an alkyl group, linear or branched, saturated or unsaturated C 1 to C 2, a cyclic group, saturated or unsaturated C 3 -C 12,
R3 et R4 sont différents et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en Ci à C12, un groupe cyclique, saturé ou insaturé, en C3 à Ci2, ou un groupe de formule Si(R5)3 dans laquelle R5 est un groupe alkyle linéaire en Ci à C6, et x est un entier compris entre 1 et 4 inclus, puis à décomposer cette phase gazeuse sur un substrat chauffé.R 3 and R 4 are different and are selected from an alkyl group, linear or branched, saturated or unsaturated Cl-C 12, a cyclic group, saturated or unsaturated, C 3 to C 2, or a group of formula Si (R 5 ) 3 in which R 5 is a linear C 1 -C 6 alkyl group, and x is an integer between 1 and 4 inclusive, and then decomposing this gaseous phase on a heated substrate.
De préférence, dans les composés de formule I, les groupements Ri et R2 sont identiques ou différents et sont choisis parmi un groupe méthyle ou un groupe éthyle, les groupes R3 et R4 sont choisis parmi un groupe éthyle, un groupe isopropyle, un groupe tertiobutyle, et un groupe SiMe3 et x est égal à 1 ou 2.Preferably, in the compounds of formula I, the groups R 1 and R 2 are identical or different and are chosen from a methyl group or an ethyl group, the groups R 3 and R 4 are chosen from an ethyl group and an isopropyl group, tert-butyl group, and SiMe 3 group and x is 1 or 2.
De préférence, dans ce procédé, la phase gazeuse est générée par chauffage à une température comprise entre 16O0C et 220°C d'au moins un composé de coordination de formule I dissout dans de l'octane en tant que solvant, et cette phase gazeuse est décomposée sur un substrat chauffé à une température comprise entre 3000C et 6000C inclus.Preferably, in this process, the gas phase is generated by heating at a temperature between 180 ° C. and 220 ° C. of at least one coordination compound of formula I dissolved in octane as a solvent, and this The gaseous phase is decomposed on a substrate heated to a temperature of between 300 ° C. and 600 ° C. inclusive.
Il apparaîtra clairement à l'homme de l'art que tout autre solvant de type hydrocarbure pourra également être utilisé.It will be clear to those skilled in the art that any other hydrocarbon solvent may also be used.
Des températures de chauffage de substrat supérieures à 600°C pourraient être utilisées mais sans obtenir d'avantages supplémentaires.Substrate heating temperatures above 600 ° C could be used but without additional benefits.
De préférence, la pression utilisée dans le procédé de dépôt est d'environ 1 à 10 Torr (soit.0.13 à 1.3 kPa).Preferably, the pressure used in the deposition process is about 1 to 10 Torr (ie.0.13 to 1.3 kPa).
Bien sûr, pour obtenir un film mince d'oxyde d'hafnium nitruré, le composé de coordination doit être un composé de formule I dans laquelle ni R3 ni R4 n'ont la formule Si(R5)3 et pour obtenir un film mince de silicate d'hafnium nitruré, le composé de coordination doit être un composé de formule I dans laquelle l'un de R3 et R4 a la formule Si(R5)3.Of course, in order to obtain a nitrided hafnium oxide thin film, the coordination compound must be a compound of formula I in which neither R 3 nor R 4 have the formula Si (R 5 ) 3 and to obtain a thin film of nitrided hafnium silicate, the coordinating compound should be a compound of formula I wherein one of R 3 and R 4 has the formula Si (R 5 ) 3 .
Par ailleurs, pour obtenir un film mince, amorphe, nitruré de HfO2, de préférence la température du substrat est comprise entre 3000C et 475°C inclus.Furthermore, to obtain a thin, amorphous, nitrided film of HfO 2 , preferably the temperature of the substrate is between 300 ° C. and 475 ° C. inclusive.
En effet, en contraste avec les films obtenus avec les précurseurs d'hafnium de l'art antérieur, les films obtenus avec les composés de coordination de formule I cristallisent à une température supérieure à 4750C, ce qui leur permet de conserver une structure amorphe lors de traitements thermiques postérieurs qui auraient lieu à une température inférieure ou égale à 4750C, en particulier des dispositifs dans lesquels ils sont intégrés.In fact, in contrast with the films obtained with the hafnium precursors of the prior art, the films obtained with the coordination compounds of formula I crystallize at a temperature greater than 475 ° C., which enables them to maintain a protective structure. amorphous during subsequent heat treatments which would take place at a temperature of less than or equal to 475 ° C., in particular devices in which they are integrated.
En revanche, pour obtenir un film mince, nitruré, d'oxyde d'hafnium ayant une structure majoritairement non monoclinique, de préférence, la température du substrat est supérieure à 475°C et inférieure ou égale à 600°C.On the other hand, in order to obtain a thin nitrided film of hafnium oxide having a predominantly non-monoclinic structure, preferably the temperature of the substrate is greater than 475 ° C. and less than or equal to 600 ° C.
Là encore, des températures supérieures à 6000C peuvent être utilisées mais n'amènent aucun avantage. Dans tous les cas, la phase gazeuse est générée par chauffage du composé de formule I à une température comprise entre 1600C et 2200C inclus.Again, temperatures above 600 0 C can be used but bring no benefit. In all cases, the gaseous phase is generated by heating the compound of formula I at a temperature between 160 0 C and 220 0 C inclusive.
L'obtention d'un film mince d'une structure amorphe ou d'une structure majoritairement non monoclinique, nitruré, en une simple étape de dépôt, c'est-à-dire n'impliquant pas d'étape de nitruration postérieure, et le maintien d'une structure amorphe, lorsque voulue, jusqu'à une température de 475°C est donc particulièrement avantageux.Obtaining a thin film of an amorphous structure or a predominantly non-monoclinic, nitrided structure, in a simple deposition step, that is to say not involving a subsequent nitriding step, and the maintenance of an amorphous structure, when desired, up to a temperature of 475 ° C. is therefore particularly advantageous.
Le procédé d'élaboration d'un film mince d'oxyde nitruré d'hafnium ou de silicate d'hafnium nitruré de l'invention permet de supprimer une étape supplémentaire de nitruration car il permet la nitruration in situ de ces films, ce qui permet un gain de temps et de réactifs. Par ailleurs, l'obtention d'une phase HfO2 non monoclinique de permittivité plus élevée que la phase HfO2 monoclinique habituellement obtenue, présente des avantages pour la réalisation de transistors MOS ou de structures capacitives MIM si l'on considère l'épaisseur de silice qui est équivalente électroniquement à l'épaisseur réelle de Ia couche d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré.The process for producing a nitrided hafnium nitride oxide or nitrided hafnium silicate thin film of the invention makes it possible to eliminate an additional nitriding step since it allows the nitriding in situ of these films, which allows a saving of time and reagents. Moreover, the obtaining of a non-monoclinic HfO 2 phase with a higher permittivity than the monoclinic HfO 2 phase usually obtained has advantages for the production of MOS transistors or capacitive MIM structures, if we consider the thickness of the silica which is electronically equivalent to the actual thickness of the nitrided hafnium oxide or nitrided hafnium silicate layer.
Cette épaisseur équivalente, qui est désignée par EOT pour «Equivalent electric Oxide Thickness» en anglais, est égale à :This equivalent thickness, which is designated by EOT for Equivalent electric Oxide Thickness in English, is equal to:
où εr et e désignent respectivement la permittivité diélectrique relative et l'épaisseur réelle de la couche mince d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré et εr(Si02) désigne la permittivité diélectrique relative de la silice. De façon usuelle, εr(Si02) est égale à 3,9 environ.where ε r and e respectively denote the relative dielectric permittivity and the actual thickness of the thin layer of nitrided hafnium oxide or nitrided hafnium silicate and ε r (Si0 2 ) denotes the relative dielectric permittivity of the silica. In the usual way, ε r (Si0 2 ) is equal to approximately 3.9.
Ainsi, l'augmentation de la permittivité permet d'atteindre une EOT plus faible tout en conservant une épaisseur de film suffisante pour que les courants de fuite restent dans les limites acceptables pour l'application.Thus, the increase in permittivity makes it possible to achieve a lower EOT while maintaining a sufficient film thickness so that the leakage currents remain within acceptable limits for the application.
Par ailleurs, les films obtenus, lorsque amorphes, ont une stabilité thermique augmentée jusqu'à une température d'environ 475°C.Moreover, the films obtained, when amorphous, have an increased thermal stability up to a temperature of about 475 ° C.
Le dépôt de l'oxyde d'hafnium nitruré ou du silicate d'hafnium nitruré à partir du au moins un composé de coordination de l'invention peut être, comme cela apparaîtra clairement à l'homme de l'art, effectué aussi bien par un procédé MOCVD à injection puisée ou non, que par un procédé ALD.The deposition of the nitrided hafnium oxide or nitrided hafnium silicate from the at least one coordination compound of the invention may be, as will be clear to those skilled in the art, carried out both by a MOCVD injection process pulsed or not, only by an ALD method.
Les films obtenus dans l'invention ont une épaisseur comprise entre 0,9 et 30nm. L'invention concerne également des composés de coordination permettant d'obtenir des films minces de silicate d'hafnium nitruré, par le procédé de l'invention.The films obtained in the invention have a thickness of between 0.9 and 30 nm. The invention also relates to coordination compounds for obtaining thin films of nitrided hafnium silicate by the process of the invention.
Ces composés ont la formule la suivante :These compounds have the following formula:
Hf(NR1Ra)4-X [R3-N=C(NR1 R2)-NR4]X Hf (NR 1 Ra) 4- X [R 3 -N = C (NR 1 R 2 ) -NR 4 ] X
dans laquelle R1, R2, R3, R4 et x sont tels que définis pour les composés de formule I mais dans laquelle l'un de R3 ou R4 a la formule Si(Rs)3, de préférence l'un de R3 ou R4 est SiMe3.wherein R 1 , R 2 , R 3 , R 4 and x are as defined for compounds of formula I but wherein one of R 3 or R 4 has the formula Si (Rs) 3 , preferably one of R 3 or R 4 is SiMe 3 .
L'invention propose également un procédé de réalisation d'un circuit électronique qui comprend une portion de couche de film mince à base d'oxyde d'hafnium ou de silicate d'hafnium nitruré.The invention also proposes a method for producing an electronic circuit which comprises a thin film layer portion based on hafnium oxide or nitrided hafnium silicate.
Selon l'invention, ce procédé comprend une étape d'élaboration d'un film d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré par le procédé de l'invention précédemment décrit.According to the invention, this process comprises a step of producing a nitrided hafnium oxide or nitrided hafnium silicate film by the method of the invention described above.
L'invention propose encore un circuit électronique qui comprend une portion de couche ou film d'oxyde à base d'hafnium nitruré ou de silicate d'hafnium nitruré élaboré par le procédé de l'invention.The invention also provides an electronic circuit which comprises a nitrided hafnium oxide layer or nitrided oxide film or nitrided hafnium silicate layer produced by the process of the invention.
Afin de mieux faire comprendre l'invention, on va maintenant en décrire, à titre d'exemples purement illustratifs et non limitatifs, plusieurs modes de mise en œuvre.In order to better understand the invention, we will now describe, as purely illustrative and non-limiting examples, several modes of implementation.
Exemple 1Example 1
Le composé de coordination, de formuleThe coordinating compound, of formula
Hf[N(CH2CH3)2]3{(CH3)2CH-N=C[N(CH2CH3)2]-NC(CH3)3}Hf [N (CH 2 CH 3) 2] 3 {(CH 3) 2 CH-N = C [N (CH 2 CH 3) 2] -NC (CH 3) 3}
est dilué dans de l'octane à une concentration de 0,05M.is diluted in octane at a concentration of 0.05M.
Le film mince d'oxyde d'hafnium nitruré a été formé par le procédé MOCVD à injection puisée. Un volume de 0,60 ml de solution du composé de coordination ci-dessus, dilué dans l'octane, a été injecté.The nitrided hafnium oxide thin film was formed by the pulsed injection MOCVD method. A volume of 0.60 ml of solution of the above coordination compound, diluted in octane, was injected.
La fréquence de l'injection est de 1 Hz avec un temps d'ouverture de 1ms. L'injecteur est pressurisé à une pression de 1 bar d'argon. Le composé de coordination est vaporisé à une température de 1600C puis décomposé sur un substrat en Si/SiO2 d'une épaisseur de 0,8 nm chauffé à 350°C en utilisant un flux de 100sccm d'azote et de 200sccm d'oxygène et une pression totale de 0.13 kPa.The frequency of the injection is 1 Hz with an opening time of 1ms. The injector is pressurized at a pressure of 1 bar of argon. The coordination compound is vaporized at a temperature of 160 ° C. and then decomposed on a Si / SiO 2 substrate having a thickness of 0.8 nm heated to 350 ° C. using a flow of 100 sccm of nitrogen and 200 sccm of oxygen and a total pressure of 0.13 kPa.
Le film d'oxyde d'hafnium nitruré obtenu est amorphe et a une épaisseur de 12,6nm. Les mêmes résultats sont obtenus lorsque la température de vaporisation du composé de coordination est augmentée à 1800C et à 2050C, respectivement.The nitrided hafnium oxide film obtained is amorphous and has a thickness of 12.6 nm. The same results are obtained when the vaporization temperature of the coordination compound is increased at 180 ° C. and 205 ° C., respectively.
Exemple 2Example 2
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 375°C, et qu'un volume de 0,58 ml de solution du composé de coordination, dilué dans l'octane, a été injecté.The procedure was as in Example 1, except that the substrate was heated to a temperature of 375 ° C, and a volume of 0.58 ml of the solution of the coordination compound, diluted in octane, was injected.
Le film obtenu est amorphe et a une épaisseur de 4,9 nm.The resulting film is amorphous and has a thickness of 4.9 nm.
Exemple 3Example 3
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 4000C. Dans cet exemple, un volume de 0,60 ml du composé de coordination dilué dans l'octane a été injecté.The procedure was as in Example 1 except that the substrate was heated to a temperature of 400 ° C. In this example, a volume of 0.60 ml of the coordination compound diluted in octane was injected.
Le film obtenu est amorphe et a une épaisseur de 2,9 nm.The resulting film is amorphous and has a thickness of 2.9 nm.
Exemple 4Example 4
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 4500C. Le volume injecté de composé de coordination dilué dans l'octane est de 0,60 ml.The procedure was as in Example 1, except that the substrate was heated to a temperature of 450 ° C. The injected volume of coordination compound diluted in octane is 0.60 ml.
Le film obtenu est amorphe et a une épaisseur de 4,1 nm.The resulting film is amorphous and has a thickness of 4.1 nm.
Exemple 5Example 5
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 475°C. Le volume injecté de composé de coordination dilué dans l'octane est de 0,53 ml.The procedure was as in Example 1 except that the substrate was heated to a temperature of 475 ° C. The injected volume of coordination compound diluted in the octane is 0.53 ml.
Le film obtenu est amorphe et a une épaisseur de 1,3 nm.The resulting film is amorphous and has a thickness of 1.3 nm.
Exemple 6Example 6
On a procédé comme à l'exemple 1, sauf que le substrat a été chauffé à une température de 5300C et que le volume de composé de coordination dilué dans l'octane injecté était de 0,80 ml.The procedure was as in Example 1, except that the substrate was heated to a temperature of 530 ° C. and that the volume of coordination compound diluted in the injected octane was 0.80 ml.
Le film obtenu est constitué de HfO2 nitruré dans lequel la phase Hfθ2 a une structure majoritairement non monoclinique. Le film obtenu a une épaisseur de 12,3 nm.The film obtained consists of nitrided HfO 2 in which the HfO 2 phase has a predominantly non-monoclinic structure. The resulting film has a thickness of 12.3 nm.
Exemple 7Example 7
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 5800C et qu'on a injecté un volume de 0,86 ml du composé de coordination dilué dans l'octane.The procedure was as in Example 1 except that the substrate was heated to a temperature of 580 ° C. and a volume of 0.86 ml of the coordination compound diluted in octane was injected.
Le film obtenu est un film d'oxyde d'hafnium nitruré d'une épaisseur de 14,7nm. La phase HfO2 a une structure cristalline majoritairement non monoclinique. Exemple 8The film obtained is a nitrided hafnium oxide film having a thickness of 14.7 nm. The HfO 2 phase has a crystalline structure that is predominantly non-monoclinic. Example 8
On a procédé comme à l'exemple 6, mais en utilisant un composé de coordination de formule :The procedure was as in Example 6, but using a coordination compound of formula:
Hf[N(CH3)2]2{CH3CH2-N=C[N(CH3)2]-NC(CH3)3}2.Hf [N (CH 3) 2] 2 {CH3CH2-N = C [N (CH 3) 2] -NC (CH3) 3} 2.
Le volume injecté de ce composé de coordination dilué dans l'octane était de 0,40 ml.The injected volume of this coordination compound diluted in octane was 0.40 ml.
Le film obtenu était constitué d'oxyde d'hafnium nitruré dans lequel la phase oxyde d'hafnium a une structure cristalline mixte monoclinique/orthorhombique ou monoclinique/quadratique ou monoclinique/cubique. Le film a une épaisseur de 4,1 nm.The resulting film consisted of nitrided hafnium oxide in which the hafnium oxide phase has a monoclinic / orthorhombic or monoclinic / quadratic or monoclinic / cubic mixed crystalline structure. The film has a thickness of 4.1 nm.
Exemple 9Example 9
On a procédé comme à l'exemple 8, sauf que le substrat a été chauffé à une température de 580cC et qu'un volume de 0,70 ml du composé de coordination dilué dans l'octane a été injecté.The procedure was as in Example 8 except that the substrate was heated at 580 c C and a volume of 0.70 ml coordination compound diluted in octane was injected.
Le film obtenu est un film d'oxyde d'hafnium nitruré dans lequel la phase oxyde d'hafnium est majoritairement de structure non monoclinique. Le film obtenu a une épaisseur de 24,9 nm.The film obtained is a nitrided hafnium oxide film in which the hafnium oxide phase is predominantly of non-monoclinic structure. The film obtained has a thickness of 24.9 nm.
Exemple 10Example 10
On a procédé comme à l'exemple 1 , sauf que le substrat a été chauffé à une température de 475°C et que le volume injecté du composé de coordination dilué dans l'octane était de 0,45 ml.The procedure was as in Example 1 except that the substrate was heated to a temperature of 475 ° C and the injected volume of the octane-diluted coordination compound was 0.45 ml.
Le film obtenu est amorphe et a une épaisseur de 4,45 nm.The resulting film is amorphous and has a thickness of 4.45 nm.
Exemple 11Example 11
Cet exemple décrit la synthèse d'un composé de coordination utilisé dans l'invention :This example describes the synthesis of a coordination compound used in the invention:
Hf[N(CH2CH3)2]3{(CH3)2CH-N=C[N(CH2CH3)2]-NC(CH3)3}.Hf [N (CH 2 CH 3 ) 2] 3 {(CH 3 ) 2 CH-N = C [N (CH 2 CH 3) 2] -NC (CH 3) 3}.
Un équivalent de N.N'éthyl-terbutylcarbodiimide (280mg ; 2,22mmol) dans 5ml de toluène est ajouté à une solution de Hf[N(CH2CH3)2]4 (1 ,05g ; 2,24mmol) dans 15ml de toluène. Après agitation à température ambiante pendant 18 heures, le solvant est évaporé sous vide. Après extraction avec du pentane, on obtient Hf[N(CH2CH3)2]3{(CH3)2CH-N=C[N(CH2CH3)2]-NC(CH3)3} sous forme d'une huile jaune (masse = 1 ,25g ; rendement = 95%)One equivalent of N, N-tert-butylcarbodiimide (280 mg, 2.22 mmol) in 5 ml of toluene is added to a solution of Hf [N (CH 2 CH 3 ) 2 ] 4 (1.05 g, 2.24 mmol) in 15 ml. toluene. After stirring at room temperature for 18 hours, the solvent is evaporated under vacuum. After extraction with pentane, Hf [N (CH 2 CH 3) 2] 3 {(CH 3) 2 CH-N = C [N (CH 2 CH 3) 2 ] -NC (CH 3) 3} is obtained in the form of an oil. yellow (mass = 1.25 g, yield = 95%)
RMN 1H (25°C, C6D6, ppm) : 0,96 (6H, doublet, 3J = 7,16Hz) ; 1 ,11(3H1 triplet, 3J = 7,00Hz) ; 1 ,16(18H1 triplet, 3J = 7,00Hz) ; 1 ,32(9H, singulet) ; 2,93(4H1 quadruplet, 3J = 7,16Hz) ; 3,21 (2H1 quadruplet, 3J = 7,00Hz) ; 3,44(12H, quadruplet, 3J = 7,00Hz). 1 H NMR (25 ° C, C 6 D 6 , ppm): 0.96 (6H, doublet, 3 J = 7.16 Hz); 1, 11 (3H 1 triplet, 3 J = 7.00Hz); 1, 16 (18H 1 triplet, 3 J = 7.00Hz); 1, 32 (9H, singlet); 2.93 (4H 1 quadruplet, 3 J = 7.16Hz); 3.21 (2H 1 quadruplet, 3 J = 7.00Hz); 3.44 (12H, quartet, 3 J = 7.00Hz).

Claims

REVENDICATIONS
1. Procédé d'élaboration d'un film mince d'oxyde d'hafnium nitruré amorphe ou dans lequel l'oxyde d'hafnium a une structure cristalline majoritairement non monoclinique ou d'un film mince de silicate d'hafnium nitruré amorphe caractérisé en ce qu'il consiste à générer une phase gazeuse par l'évaporation d'au moins un composé de coordination, dissout dans un solvant, de formule I suivante : A process for preparing a thin film of amorphous nitride hafnium oxide or in which the hafnium oxide has a predominantly non-monoclinic crystalline structure or a thin film of amorphous nitrided hafnium silicate characterized by it consists in generating a gaseous phase by the evaporation of at least one coordination compound, dissolved in a solvent, of formula I below:
dans laquelle :in which :
R1 et R2 sont identiques ou différents et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en Ci à C12, un groupe cyclique, saturé ou insaturé, en C3 à C12,R 1 and R 2 are identical or different and are chosen from a linear or branched, saturated or unsaturated C 1 -C 12 alkyl group, a saturated or unsaturated C 3 -C 12 cyclic group,
R3 et R4 sont différents et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en C1 à C12, un groupe cyclique, saturé ou insaturé, en C3 à C12, et un groupe Si(R5)3 dans laquelle R5 est un groupe alkyle linéaire en Ci à C6, et x est un entier compris entre 1 et 4 inclus, puis à décomposer cette phase gazeuse sur un substrat chauffé.R 3 and R 4 are different and are selected from a linear or branched, saturated or unsaturated C 1 to C 12 alkyl group, a C 3 to C 12 saturated or unsaturated cyclic group, and an Si group ( R 5) 3 wherein R 5 is a linear alkyl to C 6, and x is an integer between 1 and 4 inclusive, and then decomposing the gas phase over a heated substrate.
2. Procédé selon la revendication 1 caractérisé en ce que le dit au moins un composé de coordination a la formule I dans laquelle R1 et R2 sont identiques ou différents l'un de l'autre et sont choisis parmi un groupe méthyle ou un groupe éthyle, R3 et R4 sont différents et sont choisis parmi un groupe éthyle, un groupe isopropyle, un groupe tertiobutyle ou un groupe SiMe3, et x = 1 ou 2.2. Process according to claim 1, characterized in that the said at least one coordination compound has formula I in which R 1 and R 2 are identical to or different from one another and are chosen from a methyl group or a ethyl group, R 3 and R 4 are different and are selected from an ethyl group, an isopropyl group, a tert-butyl group or an SiMe 3 group, and x = 1 or 2.
3. Procédé d'élaboration d'un film mince d'oxyde d'hafnium nitruré selon l'une quelconque des revendications précédentes caractérisé en ce que la phase gazeuse est générée par chauffage à une température comprise entre 1600C et 22O0C inclus d'au moins un composé de coordination de formule I dans laquelle R3 et R4 sont différents de Si(Rs)3 dissout dans de l'octane, puis est décomposée sur un substrat chauffé à une température comprise entre 3000C et 600°C inclus.3. Process for producing a nitrided hafnium oxide thin film according to any one of the preceding claims, characterized in that the gaseous phase is generated by heating at a temperature of between 160 ° C. and 220 ° C. inclusive. at least one coordinating compound of formula I in which R 3 and R 4 are different from Si (Rs) 3 dissolved in octane, and then is decomposed on a heated substrate at a temperature of between 300 ° C. and 600 ° C. ° C included.
4. Procédé d'élaboration d'un film mince d'oxyde d'hafnium nitruré amorphe selon l'une quelconque des revendications précédentes caractérisé en ce que la phase gazeuse est générée par chauffage à une température comprise entre 1600C et 22O0C inclus d'au moins un composé de coordination de formule I dans laquelle R3 et R4 sont différents de Si(R5)3ι puis est décomposée sur un substrat chauffé à une température comprise entre 350°C et 475°C inclus.4. Process for preparing a thin film of amorphous nitrided hafnium oxide according to any one of the preceding claims, characterized in that the gaseous phase is generated by heating at a temperature of temperature between 160 0 C and 22O 0 C inclusive of at least one coordination compound of formula I in which R 3 and R 4 are different from Si (R 5 ) 3ι and is then decomposed on a substrate heated to a temperature between 350 ° C and 475 ° C inclusive.
5. Procédé d'élaboration d'un film mince d'oxyde d'hafnium nitruré dans lequel la phase oxyde d'hafnium a une structure cristalline majoritairement non monoclinique, selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la phase gazeuse est générée par chauffage à une température comprise entre 1600C et 22O0C d'au moins un composé de coordination ayant la formule I dans laquelle R3 et R4 sont différents de Si(Rs)3 et décomposée sur un substrat chauffé à une température supérieure à 475°C et inférieure ou égale à 6000C.5. A process for preparing a nitrided hafnium oxide thin film in which the hafnium oxide phase has a predominantly non-monoclinic crystalline structure, according to any one of claims 1 to 3, characterized in that the gas phase is generated by heating at a temperature between 160 0 C and 22O 0 C of at least one coordination compound having the formula I wherein R 3 and R 4 are different from Si (Rs) 3 and decomposed on a substrate heated to a temperature greater than 475 ° C and less than or equal to 600 ° C.
6. Procédé d'élaboration d'un film mince de silicate d'hafnium nitruré selon la revendication 1 ou 2 caractérisé en ce que la phase gazeuse est générée par chauffage à une température comprise entre 160°C et 2200C d'au moins un composé de formule I dans laquelle l'un de R3 et R4 est un groupe de formule Si(R5)3 et décomposée sur un substrat chauffé à une température comprise entre 350°C et 600°C inclus.6. Process for producing a nitrided hafnium silicate thin film according to claim 1 or 2, characterized in that the gaseous phase is generated by heating at a temperature of between 160 ° C. and 220 ° C. a compound of formula I wherein one of R 3 and R 4 is a group of formula Si (R 5 ) 3 and decomposed on a heated substrate at a temperature of between 350 ° C and 600 ° C inclusive.
7. Composé de coordination de formule la suivante : 7. The following formula coordination compound:
dans laquelle :in which :
Ri et R2 sont identiques ou différents et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en Ci à Ci2, un groupe cyclique, saturé ou insaturé, en C3 à C12,Ri and R 2 are identical or different and are selected from an alkyl group, linear or branched, saturated or unsaturated Ci to Ci 2, a cyclic group, saturated or unsaturated C 3 -C 12,
R3 et R4 sont différents l'un de l'autre et sont choisis parmi un groupe alkyle, linéaire ou ramifié, saturé ou insaturé, en Ci à Ci2, un groupe cyclique, saturé ou insaturé, en C3 à Ci2, et un groupe de formule Si(R5)3 dans laquelle R5 peut être un groupe alkyle linéaire en Ci à C6, l'un de R3 et R4 étant un groupe de Si(R5)3, et x est un entier valant entre 1 et 4 compris.R 3 and R 4 are different from each other and are selected from a linear or branched, saturated or unsaturated C 1 to C 2 alkyl group, a saturated or unsaturated C 3 to C 2 ring group and a group of formula Si (R 5 ) 3 in which R 5 may be a linear C 1 -C 6 alkyl group, one of R 3 and R 4 being a group of Si (R 5 ) 3 , and x is an integer between 1 and 4 inclusive.
8. Composé de coordination selon la revendication 7 caractérisé en ce qu'il a la formule la dans laquelle Ri et R2 sont identiques ou différents et sont choisis parmi un groupe méthyle et un groupe éthyle, R3 et R4 sont différents l'un de l'autre et sont choisis parmi un groupe éthyle, un groupe isopropyle, un groupe tertiobutyie ou un groupe SiMe3, l'un de R3 et R4 étant un groupe SiMe3, et x = 1 ou 2.8. Coordination compound according to claim 7, characterized in that it has the formula la in which R 1 and R 2 are identical or different and are chosen from a methyl group and an ethyl group, R 3 and R 4 are different from one another and are chosen from an ethyl group, an isopropyl group, a tert-butyl group or an SiMe 3 group, one of R 3 and R 4 being a SiMe 3 group, and x = 1 or 2.
9. Procédé de réalisation d'un circuit électronique caractérisé en ce qu'il comprend une étape d'élaboration d'un film mince d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré par le procédé selon l'une quelconque des revendications 1 à 6.9. A method for producing an electronic circuit characterized in that it comprises a step of producing a thin film of nitrided hafnium oxide or nitrided hafnium silicate by the method according to any one of Claims 1 to 6.
10. Circuit électronique caractérisé en ce qu'il comprend une portion de couche ou film mince à base d'oxyde d'hafnium nitruré ou de silicate d'hafnium nitruré obtenu par le procédé selon l'une quelconque des revendications 1 à 6. 10. An electronic circuit characterized in that it comprises a portion of thin layer or film based on nitrided hafnium oxide or nitrided hafnium silicate obtained by the method according to any one of claims 1 to 6.
EP09727119A 2008-03-17 2009-03-16 Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit Withdrawn EP2268848A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0801445A FR2928663A1 (en) 2008-03-17 2008-03-17 PROCESS FOR PRODUCING A THIN FILM OF OXIDE OR HAFNIUM SILICATE NITRIDE, COORDINATION COMPOUND USED IN THIS METHOD AND METHOD FOR PRODUCING AN INTEGRATED ELECTRONIC CIRCUIT
PCT/FR2009/000272 WO2009122036A1 (en) 2008-03-17 2009-03-16 Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit

Publications (1)

Publication Number Publication Date
EP2268848A1 true EP2268848A1 (en) 2011-01-05

Family

ID=39495959

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09727119A Withdrawn EP2268848A1 (en) 2008-03-17 2009-03-16 Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit

Country Status (7)

Country Link
US (1) US20110049512A1 (en)
EP (1) EP2268848A1 (en)
JP (1) JP2011521440A (en)
KR (1) KR20100134035A (en)
CN (1) CN102007228A (en)
FR (1) FR2928663A1 (en)
WO (1) WO2009122036A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014139861A1 (en) * 2013-03-11 2014-09-18 Universität Bayreuth Complexes for the catalytic oligomerization of olefins
EP2857423B1 (en) * 2013-10-07 2020-09-16 Arlanxeo Netherlands B.V. Catalyst system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1860609A (en) * 2004-07-22 2006-11-08 日本电信电话株式会社 Bistable resistance value acquisition device, manufacturing method thereof, metal oxide thin film, and manufacturing method thereof
US7300873B2 (en) * 2004-08-13 2007-11-27 Micron Technology, Inc. Systems and methods for forming metal-containing layers using vapor deposition processes
US7498247B2 (en) * 2005-02-23 2009-03-03 Micron Technology, Inc. Atomic layer deposition of Hf3N4/HfO2 films as gate dielectrics
WO2007005088A2 (en) * 2005-07-01 2007-01-11 Honeywell International Inc. Vaporizable metalorganic compounds for deposition of metals and metal-containing thin films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009122036A1 *

Also Published As

Publication number Publication date
FR2928663A1 (en) 2009-09-18
JP2011521440A (en) 2011-07-21
CN102007228A (en) 2011-04-06
WO2009122036A1 (en) 2009-10-08
KR20100134035A (en) 2010-12-22
US20110049512A1 (en) 2011-03-03

Similar Documents

Publication Publication Date Title
TWI464291B (en) Methods of preparing thin films by atomic layer deposition using titanium-based precursors
JP6596737B2 (en) Metal complexes containing amidoimine ligands
KR101273024B1 (en) Unsymmetrical ligand sources, reduced symmetry metal-containing compounds, and systems and methods including same
US9045509B2 (en) Hafnium- and zirconium-containing precursors and methods of using the same
JP5128289B2 (en) Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method
KR20090068179A (en) Process for producing a thin film comprising silicon dioxide
US9828402B2 (en) Film-forming composition and method for fabricating film by using the same
TWI693229B (en) Zirconium-containing film forming compositions for vapor deposition of zirconium-containing films
CN111655899A (en) Method for the vapor deposition of ruthenium using oxygen-free coreactants
KR101337690B1 (en) Methods of forming a tellurium alkoxide and methods of forming a mixed halide-alkoxide of tellurium
US20220144861A1 (en) Rare earth precursor, method of manufacturing same and method of forming thin film using same
EP2268848A1 (en) Method for developing thin film from oxide or silicate of hafnium nitride, coordination compound used in said method, and method for producing integrated electronic circuit
JP2023512623A (en) Ruthenium-containing films deposited on ruthenium-titanium nitride films and methods of forming the same
TWI794671B (en) Compounds and methods for selectively forming metal-containing films
CN114746573B (en) Compounds and methods for selectively forming metal-containing films
JP7232307B2 (en) Rare earth precursor, method for producing same, and method for forming thin film using same
US20230227966A1 (en) Methods Of Forming Ruthenium-Containing Films Without A Co-Reactant
KR20160007187A (en) boron-containing precursors, boron-containing compositions containing them and boron-containing thin film using the same
KR20210153114A (en) Raw material for chemical vapor deposition containing organic manganese compound and chemical vapor deposition method using the raw material for chemical vapor deposition
JP2006063065A (en) Alkyltetrazole derivative and method for producing nitrogen-containing film by using the same derivative and method for refining alkyltetrazole derivative
TW202128720A (en) Precursor compound for atomic layer deposition (ald) and chemical vapor deposition (cvd) and ald/cvd process using same
KR20050015441A (en) Method for Deposition of Hafnium Oxide Thin Films

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: 20101012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INSTITUT POLYTECHNIQUE DE GRENOBLE

Owner name: UNIVERSITY CLAUDE BERNARD LYON I

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BRIZE, VIRGINIE

Inventor name: DUBOURDIEU, CATHERINE

Inventor name: ELETER, MOHAMAD

Inventor name: DANIELE, STEPHANE

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INSTITUT POLYTECHNIQUE DE GRENOBLE

Owner name: UNIVERSITE CLAUDE BERNARD LYON

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INSTITUT POLYTECHNIQUE DE GRENOBLE

Owner name: UNIVERSITE CLAUDE BERNARD LYON I

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

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: 20131001