EP4065742A1 - Method for producing non-contiguous metal oxide nanostructures of uniform and controlled size and density - Google Patents
Method for producing non-contiguous metal oxide nanostructures of uniform and controlled size and densityInfo
- Publication number
- EP4065742A1 EP4065742A1 EP20811003.1A EP20811003A EP4065742A1 EP 4065742 A1 EP4065742 A1 EP 4065742A1 EP 20811003 A EP20811003 A EP 20811003A EP 4065742 A1 EP4065742 A1 EP 4065742A1
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- EP
- European Patent Office
- Prior art keywords
- metal
- nanostructures
- deposition
- growth
- organometallic precursor
- 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.)
- Pending
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- 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
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
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- 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
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
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- 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
- C23C16/56—After-treatment
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/16—Controlling or regulating
- C30B25/165—Controlling or regulating the flow of the reactive gases
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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- 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
Definitions
- the present invention relates to the field of manufacturing metal oxide nanostructures on a microelectronic substrate by chemical vapor deposition with organometallic precursors (MOCVD). It finds a particularly advantageous application in the field of emerging memories of the RRAM (Resistive Random Access Memory) type or in chemical sensors. More specifically, the nanostructures obtained by the invention can be used in RRAMs integrated in CMOS (from the English Complementary Metal Oxide Semiconductor or Complementary Metal Oxide Semiconductor in French) Back End Off Line (end of the integration process) .
- Ion implantation is also a nanostructure deposition technique that is already well known to the industry. It consists of the bombardment of an oxide by metal ions which form aggregates at depth.
- the disadvantage of the technique is a difficulty in controlling the size, density, position and nature of the nanoparticles.
- CVD chemical vapor deposition
- MOCVD organometallic precursors
- Document EP 1426328A2 describes a stepwise deposition technique for nanoparticles consisting of a first nucleation step and a second particle growth step allowing deposition of semiconductor nanostructure, in particular germanium, on a dielectric substrate in two steps. This method has the drawback of having little control over the size and density of the particles on the substrate, in particular of large size.
- An object of the present invention is therefore to propose to resolve all or part of the drawbacks of the known techniques.
- a method for producing nanostructures, having a metal oxide envelope, carried by an upper face of a substrate, the largest dimension of which is greater than or equal to 100 mm by chemical vapor deposition. with MOCVD organometallic precursors.
- the method comprises the following successive steps carried out in a reactor configured for deposition by MOCVD: a.
- a nucleation step comprising: i. a step of forming non-contiguous metallic nuclei by depositing a metal by MOCVD by means of an organometallic precursor on said upper face of the substrate, then ii. a step of oxidizing the metal of the metallic nuclei, configured to form oxidized nuclei and intended to ensure the stabilization of the nuclei, b.
- At least one growth step comprising: i. a step of depositing a metal, preferably at least one metal, by MOCVD using the organometallic precursor, preferably at least one organometallic precursor, intended for the formation of non-contiguous nanostructures by growth of oxidized nuclei, then ii. a step of oxidizing the deposited metal of the nanostructures formed in the previous step configured to form oxidized nanostructures.
- the method comprises an oxidation step after each deposition step so as to stabilize the deposition by allowing time for the deposited metal, preferably the at least one metal, to diffuse in order to arrange itself into a nanostructure and allow it. to be oxidized.
- the metal oxide formed is thus more stable than the metal, in particular advantageously exhibiting stability up to a higher melting temperature than that of metal.
- the temperature of the oxidation step is chosen so that the metal is in the liquid state, but its oxide in the solid state. This is in particular possible for all the metals mentioned below, with a more or less extended temperature range depending on the metal / oxide pair.
- the stability of the oxidized particles also ensures a selectivity of the deposit during the growth step.
- the metallic species obtained by decomposing the organometallic precursor will diffuse and deposit preferably on the nucleus or the nanostructure already formed rather than on the substrate.
- the method according to the invention ensures the formation of non-contiguous nanostructures of homogeneous and controlled size and density.
- the method may further exhibit at least any one of the following characteristics:
- the substrate can be of various types, whether it is dielectric or not.
- the growth step comprising the deposition of organometallic precursor, preferably at least one organometallic precursor, and the oxidation step, is repeated at least once.
- the invention allows a non-touching layer of nanostructures, for example indium oxide, to be deposited on large surfaces, for example 300mm in diameter, with control of the size of the particles as well as of their density with excellent homogeneity.
- the present invention proposes to use only a single precursor, for example trimethylindium TMIn, and preferably no oxidizing species, unlike the deposits described in the literature.
- Germanium is deposited directly after the Si nucleus formation step without proceeding to a long growth arrest or oxidation step.
- a substrate comprising on its upper face non-contiguous nanostructures obtained by the preceding method.
- the non-contiguous nanostructures are at least partially oxidized, preferably totally oxidized.
- the non-contiguous nanostructures are of a size between 1 and 200 nm, of which 95% of the nanostructures have a size of within plus or minus 20% around the mean value.
- the non-contiguous nanostructures have a maximum size variation of 2nm between the center and the edge of the substrate.
- the density of non-contiguous nanostructures is between 10 8 and 10 1 ° NCs.cm 2 .
- the maximum size of the nanoparticles is a function of the density, if the density is low, the maximum size that the nanoparticles can reach without being contiguous will be greater than for a greater density of nanoparticles.
- Another aspect relates to a microelectronic device comprising at least one nanostructure obtained by said method.
- FIG. 1 represents the step of forming nuclei on a substrate during the nucleation step.
- FIG. 2 represents the step of oxidation of the nuclei during the nucleation step.
- FIG. 3 represents the step of enlarging the nuclei on a substrate during the growth step.
- FIG. 4 represents the step of oxidation of the nanostructures during the growth step.
- the method comprises c. at least one further subsequent growth step comprising: i. a step of depositing a metal, preferably at least one metal, by MOCVD by means of the organometallic precursor, more preferably of the at least one organometallic precursor of the step of depositing the growth step b) i) intended the growth of non-contiguous nanostructures by growth of oxidized nanostructures, then ii. a step of oxidation of the metal deposited from the nanostructures in the previous step configured to form oxidized nanostructures.
- the metal of the metal oxide is chosen from indium, gallium, aluminum, tin, antimony, selenium, bismuth, tellurium, zinc and cadmium.
- indium in addition to its interest in microelectronics, indium oxide is the subject of much research in optics, optoelectronics and photovoltaics for its properties both as an electrical conductor and its transparency in the visible.
- the process according to the invention is particularly suitable for indium. Indeed, the oxidation step ensures stabilization of indium, an excessively reactive species.
- the organometallic precursor is a gas.
- the organometallic precursor / metal pair being chosen so that the decomposition temperature of the precursor is lower than the evaporation temperature of the metal.
- the method comprises several growth steps then the at least one organometallic precursor is identical at each growth step, more precisely the at least one organometallic precursor of a subsequent growth step is identical to the at least one organometallic precursor. from the deposit step of the growth step b) i).
- the organometallic precursor chosen for the nucleation step is trimethylindium or trimethylgallium.
- the deposition step is a deposition of two metals by means of a mixture of two organometallic precursors.
- the at least one organometallic precursor chosen for the deposition step is trimethylindium and / or trimethylgallium.
- the organometallic precursor is the same during all the steps of the process.
- the step of depositing metal by means of the organometallic precursor has a duration of less than 30 seconds, preferably 15 seconds.
- the deposition step during the nucleation step is advantageously a pulse of metallic precursor.
- a pulse is a supply for a short time of metallic precursor. This step must be controlled, because it makes it possible to define the density of the nanostructures on the substrate.
- the defined time of the oxidation step has a duration greater than the duration of the step of depositing the metal precursor, preferably at least 45 seconds, or even preferably at least 60 seconds.
- the oxidation step can be considered as a rest or stabilization step. The time is advantageously sufficient to ensure total oxidation of the metal deposit produced in the preceding deposition step.
- the oxidation step is carried out without injection of an oxidizing precursor into the reactor.
- the oxidation occurs by capturing the oxygen present in the environment of the deposited metal, such as for example in the ambient oxygen or else the oxygen of the substrate.
- the quantity of organometallic precursor injected into the reactor during the deposition step of the nucleation step is less than 50 pmol / min.
- the amount of organometallic precursor injected into the reactor during the deposition step of the growth step is less than 50 pmol / min.
- the oxidation step is carried out at a temperature identical to a temperature of the nucleation step.
- the temperature of the oxidation step is chosen so that the metal is in the liquid state, but its oxide in the solid state.
- the oxidized nanostructures are partially oxidized.
- the oxidized nanostructures are totally oxidized.
- the nanostructures consist of the metal oxide envelope.
- the nanostructure consists entirely of metal oxide.
- the upper face of the substrate is a layer of an electrically conductive material.
- the substrate is advantageously of a diameter of 300mm.
- the invention also relates to a microelectronic device comprising at least one nanostructure obtained by the method as described above.
- the integration of nanoparticles, for example indium oxide, within the oxide of resistive memories by MOCVD allows a reduction in the variability of resistive switching thanks to this single technological step.
- the term “on”, “overcomes”, “covers” or “underlying” or their equivalents do not mean “in contact with”.
- the deposition of a first layer on a second layer does not necessarily mean that the two layers are directly in contact with one of the the other, but this means that the first layer at least partially covers the second layer by being either directly in contact with it or by being separated from it by at least one other layer or at least one other element.
- the thickness is taken in a direction perpendicular to the main faces of the substrate on which the different layers rest. If the substrate has faces forming discs, then its thickness is taken perpendicular to these faces. In the figures, the thickness is taken from the vertical.
- the width is taken in a direction parallel to the main faces of the substrate on which the different layers rest. In the figures, the width is taken in the horizontal direction.
- the method of the invention is intended for the formation of nanostructures.
- the nanostructures obtained by the present process are not joined.
- the nanostructures 6 are formed on the surface of a substrate 1. They are supported by a face 7 of the substrate 1.
- the nanostructures 6 are not joined, that is to say they do not touch each other.
- the nanostructures are separated from each other.
- the minimum space between the nanostructures is 50 nm.
- all the nanostructures 6 formed are supported by a face 7 of the substrate 1.
- the nanostructures form a non-contiguous layer.
- the nanostructures obtained by the method according to the invention comprise a metal oxide envelope.
- the nanostructure comprises either an at least partially metallic core encapsulated in an oxide envelope, or the nanostructure consists of the metallic oxide envelope, that is to say that the nanostructure 6 is entirely made of metal oxide.
- the nanostructures are of homogeneous size and advantageously of homogeneous density on the surface of the substrate.
- the size of the nanostructures is homogeneous with a size variation of 2 nm maximum between the edge of the substrate and the center.
- the nanostructures formed have a size of between 1 and more than 100 nm in height.
- the nanostructures are nanoparticles.
- the nanoparticles have a hemispherical shape.
- the density of the nanostructures at the surface of the substrate is between 10 8 NCs.cm 2 and 10 1 ° NCs.cm 2 (nanoparticles per cm 2 ).
- the process is carried out on a substrate advantageously suited to the microelectronics process.
- the substrate is commonly referred to as a wafer.
- the method according to the invention is particularly suitable for industrial-size substrates.
- the largest dimension of the substrate is greater than or equal to 100 mm.
- the industrial substrates are circular in shape, the largest dimension of which is the diameter.
- a large-dimension substrate is understood to be a substrate with a diameter greater than or equal to 100 mm and preferably at least 300 mm.
- the substrate according to the invention can be of all kinds.
- the substrate has an affinity with the organometallic precursor used in said process making it possible to ensure its deposition on the surface of the substrate.
- Affinity is advantageously defined in the present invention as the wettability of the organometallic precursor on the substrate. Wettability being the ability of one material to spread over another.
- the substrate is configured to accept the formation of the nanostructures.
- the substrate can be a dielectric or non-dielectric, monocrystalline or not.
- the substrate is chosen from silicon dioxide (Si0 2 ), silicon nitride (Si 3 N 4 ), or silicon (Si) or aluminum oxide or d oxide. 'hafnium.
- MOCVD MetalOrganic Chemical Vapor Deposition in English or chemical vapor deposition of organometallic in French.
- MOCVD is a crystal growth technique in which the elements to be deposited, in organometallic form, are brought to the substrate by a carrier gas 3.
- the substrate 1 is heated and scanned by a carrier gas 3.
- the carrier gas 3 allows to cause the metal to be deposited on the substrate 1.
- the metal is in the form of an organometallic precursor. If the conditions are well chosen, the precursor pyrolysis in contact with the heated substrate 1, the desired metal is deposited on the substrate 1, and the residues of the precursors are evacuated by the carrier gas 3.
- the process is carried out within a reactor, more precisely a chamber of a reactor.
- the reactor is laminar flow.
- the method comprises at least two steps.
- a first step called the nucleation step and then at least one growth step.
- the nucleation step is intended for the formation of nuclei on the surface of the substrate.
- the nucleation step is configured to control the density of nanostructures on the substrate.
- the nucleation step comprises two steps.
- the nucleation step preferably begins with a step of depositing (A1) an organometallic precursor on the substrate, also called a formation step. More specifically on an upper face 7 of the substrate 1.
- the deposition step comprises the deposition of a small quantity of metal, advantageously by drawing off the metal precursor. By pulses is meant that the duration of supply of the organometallic precursor to the surface of the substrate by the carrier gas 3 is short.
- the deposition of a small quantity of metal is controlled in particular by the duration of the deposition and the flow of organometallic precursor.
- the quantity of metal to be deposited in order to obtain non-contiguous nuclei 2 is advantageously less than the quantity of metal for a monolayer.
- the rate of growth of the material in his reactor the rate of decomposition of the precursor and the size of the substrate will thus adapt the volume of precursor introduced.
- the amount of precursor injected is between 2 and 40 pmol / min.
- the duration of the deposition step during the nucleation step is less than 1 minute, preferably less than 30 seconds and even more preferably of the order of 15 seconds.
- the amount of organometallic precursor decomposed during this deposition step controls the density of deposited nuclei.
- the flow of carrier gas is preferably a constant flow, at least during the deposition step of the nucleation step.
- the flux varies between 10 sim and 40slm.
- the gas can be dihydrogen, dinitrogen, argon or helium.
- the carrier gas is hydrogen, for example at 10slm (for Standard Liter per Minute).
- This deposition step of the nucleation step can be carried out over a wide temperature range going from the decomposition temperature of the precursor to the desorption temperature of the species from the surface of the substrate.
- the maximum temperature is chosen so that the competition between the deposition of the organometallic precursor and desorption of the metallic species from the surface is in favor of the deposition.
- the organometallic precursor is advantageously provided by a carrier gas.
- the organometallic precursor is chosen as a function of the metal that is to be deposited on the substrate.
- the organometallic precursor is chosen from trimethylindium (TMIn) or trimethylgallium (TMGa).
- the deposited metal is chosen from indium, gallium, zinc, cadmium, aluminum, tin, antimony, bismuth, tellurium, selenium.
- the metal and the deposition temperature are chosen so that the metal is in the liquid state and its oxide is in the solid state at the deposition temperature.
- the nucleation step comprises an oxidation step (A2).
- the deposition step and the oxidation step are advantageously successive, that is to say sequential and distinct.
- the oxidation step (A2) can take place.
- the oxidation step (A2) ensures the stabilization of the nuclei 2 formed during the previous deposition step (1). Stabilization allows the deposited metal to be arranged in nanostructures. This step makes it possible to oxidize the metal, giving it the possibility of pumping oxygen into its environment.
- the oxidized nuclei 4 exhibit greater stability. In fact, the oxidized nuclei 4 behave as traps for the metallic species injected subsequently.
- the oxidation step (A2) is defined as a time during which the supply of organometallic precursor is stopped. It is a stabilization stage.
- the oxidation step (A2) of the nucleation step is advantageously carried out at a temperature below the evaporation temperature of the metal, preferably, the temperature of the oxidation step of the nucleation step is identical to that of the deposition step of the nucleation step.
- the oxidation step (A2) is carried out without supplying an oxidizing precursor, in particular in the reactor. That is to say that the process does not include the injection of an oxidizing precursor into the reactor.
- the oxidation is carried out by the oxygen present in the environment of the deposited metal, the oxygen comes either from the substrate which can be oxidized, or from the residual oxygen present in the atmosphere of the reactor and this even when the step is carried out. under an inert atmosphere.
- the oxidation step (A2) is a resting step.
- the oxidation step is preferably longer than the deposition step of the nucleation step. By way of example, the oxidation step lasts more than 45 seconds, preferably more than 60 seconds.
- an oxidizing precursor can be added to the reactor during this oxidation step.
- the oxidizing precursor can be chosen from dioxygen (0 2 ), or dihydrogen oxide (H 2 0).
- the oxidizing precursor is introduced into the reactor in the form of gas.
- the advantage is not to intentionally introduce oxygen into the reactor and to avoid oxidation. other materials present on the substrate.
- the intentional introduction of an oxidizing precursor could make it possible to increase the rate of oxidation and therefore to reduce the time of the oxidation step and also to completely oxidize the metal particles.
- the oxidized nuclei 4 obtained at the end of the nucleation step (A1 and A2) are of very small sizes compared to the size of the nanostructures obtained at the end of the process.
- nuclei are made up of at most a few tens of atoms, for example, an indium nucleus 5nm in diameter contains 20 indium atoms.
- the method comprises a second step following the nucleation step.
- the second step of the process is the nucleus growth step.
- the growth step follows the oxidation step (A2) of the nucleation step.
- the nucleation step and the growth step are advantageously successive, that is to say sequential and distinct. When the nucleation step is completed then the growth step can take place. More precisely, when the oxidation step (A2) of the nucleation step is completed, then the growth step can begin.
- the nuclei growth step is intended to make the nuclei grow to reach the desired size of nanostructures.
- the growth step advantageously comprises two steps.
- the first step of the growth step is a step of depositing (B1) the metal obtained by decomposition of at least one organometallic precursor intended for the growth of the nuclei 4 formed during the nucleation step.
- this deposition step (B1) is carried out with an organometallic precursor advantageously identical to the organometallic precursor of the nucleation step.
- the process according to the invention is carried out with a single type of organometallic precursor.
- this deposition step (B1) of the growth step is carried out with an organometallic precursor different from the organometallic precursor used in the formation step of the nucleation step.
- this deposition step (B1) of the growth step is carried out with a mixture of organometallic precursors.
- the mixture of organometallic precursors comprising at least two, preferably two, organometallic precursors.
- the mixture of organometallic precursors can comprise the organometallic precursor used in the deposition step of the nucleation step or comprise organometallic precursors different from the organometallic precursor used in the formation step of the nucleation step.
- the use of a mixing of organometallic precursors at the deposition step of the growth step leads to the formation of an alloy.
- an alloy is formed.
- an indium-gallium alloy is formed by the use of two different organometallic precursors at the deposition stage of the growth stage: trimethylindium (TMIn) and trimethylgallium (TMGa).
- the organometallic precursor (s) is (are) advantageously provided by a carrier gas.
- the organometallic precursor (s) is (are) chosen as a function of the metal that is to be deposited on the substrate.
- the at least one organometallic precursor is chosen from trimethylindium (TMIn) and / or trimethylgallium (TMGa).
- the deposition step comprises the deposition of a small quantity of metal, advantageously by drawing off the organometallic precursor.
- This arrangement helps to promote the deposition of metal on the nuclei rather than on the surface of the substrate.
- the growth of nuclei is favored over nuclei germination.
- the homogeneity of the size and density of the nuclei at the substrate surface is maintained and controlled.
- pulses is meant that the duration of supply of the organometallic precursor to the surface of the substrate by the carrier gas is short.
- the deposition of a small amount of metal is controlled by the duration of the deposition and the flow of precursor.
- the quantity of metal to be deposited in order to obtain non-contiguous nanostructures is advantageously less than the quantity of metal for a monolayer. To determine this, those skilled in the art knowing the rate of growth of the material in his reactor, the rate of decomposition of the precursor and the size of the substrate will thus adapt the volume of precursor introduced.
- the duration of the deposition step during the growth step is less than 1 minute, preferably less than 30 seconds and even more preferably of the order of 15 seconds.
- the amount of organometallic precursor decomposed during this deposition step controls the size of the nanostructure being formed.
- the flow of carrier gas is preferably a constant flow at least during the deposition stage of the growth stage.
- the flux varies between 10 sim and 40slm.
- the gas can be dihydrogen, dinitrogen, argon or helium.
- the carrier gas is hydrogen, for example at 10slm (for Standard Liter per Minute).
- This deposition step (B1) of the growth step can be carried out over a wide temperature range going from the decomposition temperature of the precursor organometallic up to the desorption temperature of the metal species from the surface of the substrate.
- the maximum temperature is chosen so that the competition between the deposition of precursor and desorption of species from the surface is in favor of the deposition.
- the temperature is identical to that chosen for the nucleation step and more precisely of the deposition step (A1) of the nucleation step which limits the modifications of parameters and facilitates the process without requiring energy d increase and decrease in temperature.
- the deposition step (B1) of the growth step is advantageously identical to the deposition step (A1) of the nucleation step, in particular in the selection of parameters.
- the difference lies in the selectivity of the deposition on the nuclei already formed 4 rather than on the surface 7 of the substrate 1.
- the deposition temperature is between the melting point of the metal and that of the oxide, thus contributing to the melting point. deposit selectivity.
- the growth step comprises an oxidation step (B2).
- the deposition step (B1) and the oxidation step (B2) are advantageously successive, that is to say sequential and distinct. When the deposition step (B1) is completed then the oxidation step (B2) can take place.
- the oxidation step (B2) ensures the stabilization of the metal deposit produced during the previous deposition step (B1). Stabilization allows the deposited metal to be arranged in solid nanostructures. This step makes it possible to oxidize the metal, giving it the possibility of pumping oxygen into its environment. Oxidized metal exhibits greater stability. Indeed, the metal is stable as long as the melting temperature of the metal is not reached while the oxidized metal is stable as long as the melting temperature of the metal oxide is not reached, or the melting temperature of the metal oxide is greater than that of the metal ensuring greater stability.
- the oxidation step (B2) is defined as a time during which the supply of organometallic precursor is stopped. It is a stabilization stage.
- the oxidation step of the growth step is advantageously carried out at a temperature below the evaporation temperature of the metal, and at a temperature below the melting temperature of the oxide, preferably the temperature of the metal.
- oxidation step of the growth step is the same as that of the deposit step of the growth step
- the oxidation step (B2) is carried out without the addition of an oxidizing precursor, in particular in the reactor.
- the oxidation is carried out by the oxygen present in the environment of the deposited metal, it seems that the oxygen comes either from the substrate which can be oxidized, or from the residual oxygen present in the atmosphere of the reactor and this even when the step is carried out under an inert atmosphere.
- the oxidation step is a resting step.
- the oxidation step is preferably longer than the deposition step of the growth step. By way of example, the oxidation step lasts more than 45 seconds, preferably more than 60 seconds.
- an oxidizing precursor can be added to the reactor during this oxidation step.
- the oxidizing precursor can be chosen from dioxygen (0 2 ), or dihydrogen oxide (H 2 0).
- the oxidizing precursor is introduced into the reactor in the form of gas.
- the growth step (B1 and B2) can be repeated.
- the deposition step cycle (B1) followed by oxidation step (B2), of the growth step can be repeated several times.
- the growth step is repeated at least once, ie the method comprises two successive growth steps. The number of repetitions of the growth step influences the quantity of metal deposited and therefore the desired size of nanostructures.
- the nanostructure comprises a shell of oxidized metal and an at least partially metallic core.
- a step of depositing the growth step of a longer duration and / or with a large supply of precursor can be provided. This allows rapid growth of the nucleus.
- the deposition of deposited metal being important, the oxidation step of the growth step may be insufficient to oxidize all of the deposited metal.
- the nanostructure is composed of the shell of oxidized metal 6.
- the nanostructure is fully oxidized 6.
- the method according to the invention is particularly useful, the successive growth steps ensuring complete oxidation of the nanostructure.
- FIG. 1 illustrates the deposition step of the nucleation step, called A1.
- the organometallic precursor is injected into the chamber with the carrier gas 3 so as to sweep the surface of the face 7 of the substrate 1.
- Non-contiguous metallic nuclei 2 are formed on the surface of the face 7 of the substrate 1.
- the nanostructures are of homogeneous and controlled size and density.
- FIG. 2 illustrates the oxidation step of the nucleation step, called A2.
- the flow of carrier gas and organometallic precursor is advantageously stopped.
- the metal of nuclei 2 oxidizes forming metal oxide nuclei 4.
- FIG. 3 illustrates the deposit step of the growth step, called B1.
- the organometallic precursor is injected into the chamber with the carrier gas 3 so as to sweep the surface of the face 7 of the substrate 1.
- the metal is advantageously selectively deposited on the oxidized metal nuclei 4 rather than on the surface of the face 7. of the substrate 1.
- the nanostructures 5 have an oxidized metal core covered with metal.
- FIG. 4 illustrates the oxidation step of the growth step, called B2.
- the flow of carrier gas and organometallic precursor is advantageously stopped.
- the metal of the nanostructures 5 oxidizes forming metal oxide nanostructures 6.
- the nanostructures are of homogeneous and controlled size and density.
- the nanostructures are non-contiguous and hemispherical in shape.
- steps B1 and B2 can be repeated in cycles after steps A1 and A2 so as to control the size of the nanostructures produced.
- the process for producing nanostructures is carried out by depositing indium oxide nanoparticles chemically in the vapor phase with organometallic precursors (MOCVD) on a monocrystalline silicon wafer 300mm in diameter thermally oxidized to obtain an oxide layer. thermal of 5nm.
- MOCVD organometallic precursors
- the process begins with the nucleation step. Pure indium is deposited by decomposing the organometallic precursor, trimethyl indium (TMIn), at 420 ° C and under a pressure inside the reactor of 80 Torr or 10.7KPa. This deposition is carried out under an inert atmosphere with a constant flow of dihydrogen of 10 sim. This temperature and the gas flow are maintained throughout the process, that is, from the insertion of the wafer into the reactor until it exits.
- TMIn trimethyl indium
- the first deposition step of the nucleation step aims first of all to control the nucleation of the first indium oxide seeds by adjusting the quantity of indium inserted into the reactor.
- the step consists of a 5s pulse of TMIn precursor with a flow of 40 pmol / min.
- the partial pressure of the precursor is 401.2 Pa and the quantity of organometallic precursor injected into the reactor chamber is 3.3pmol.
- the pulse time, the temperature in the reactor, the flow of precursor as well as that of carrier gas are parameters to be taken into account, because they determine the quantity of organometallic precursor going to decompose. By extension, they are directly linked to the quantity of indium going to react to form the seeds.
- these parameters control the density of nuclei which will form during this step, which is equal to the final particle density. It should also be noted that these parameters can play an important role on the decomposition profile of the precursor in the chamber. If this profile is poorly controlled, it would impact the homogeneity of the deposit. They should be adapted as a function in particular of the geometry of each CVD deposition reactor.
- the second step consists of a step d 'oxidation.
- This step is a stabilization of 60s at the temperature of 420 ° C. This step ensures the oxidation of all the nuclei to indium oxide. This stabilization makes it possible to prevent the surplus of precursors from forming new nuclei, which would generate a gradient in the size of the nanoparticles and a loss of homogeneity.
- AFM atomic force microscope
- the second step of the process corresponds to at least one growth step.
- the growth step comprising a deposition step and an oxidation step can be repeated. It is then possible to carry out deposition-oxidation cycles.
- the growth stage can therefore be cycles of pulses and stabilization of the deposited indium. In the case of the example, a single deposition / oxidation (stabilization) cycle is sufficient to achieve the desired nanoparticle size.
- This growth step takes place in the same way as the first nucleation step: a deposition step by a pulse of 5 s of TMIn with a flow of 40 pmol / min followed by stabilization by an oxidation step of 60 s to 420 ° C. This growth step makes it possible to grow the nanoparticles to reach sizes of 11 nm on average without germinating new particles.
- the characterization of the wafer shows a deposit of nanoparticles of average size 11 nm with a density of 2.10 10 cm 2 over the entire surface.
- the nanoparticle dispersion is low with 95% of the particles between 8 and 14nm and an average of 11.5nm and a standard deviation of 1.7nm.
- the homogeneity is also very good with a variation in the average particle size of 2 nm between the edge of the wafer and its center (ie 15 cm apart).
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1913421A FR3103806B1 (en) | 2019-11-28 | 2019-11-28 | process for producing nanostructure by MOCVD |
PCT/EP2020/083488 WO2021105273A1 (en) | 2019-11-28 | 2020-11-26 | Method for producing non-contiguous metal oxide nanostructures of uniform and controlled size and density |
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US (1) | US20230360912A1 (en) |
EP (1) | EP4065742A1 (en) |
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WO (1) | WO2021105273A1 (en) |
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FR2847567B1 (en) | 2002-11-22 | 2005-07-01 | Commissariat Energie Atomique | METHOD FOR PRODUCING A CVD OF NANO-STRUCTURES OF SEMI-CONDUCTOR MATERIAL ON DIELECTRIC, HOMOGENEOUS SIZES AND CONTROLLED |
US7192802B2 (en) * | 2004-10-29 | 2007-03-20 | Sharp Laboratories Of America, Inc. | ALD ZnO seed layer for deposition of ZnO nanostructures on a silicon substrate |
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