EP2171751A2 - Substrate for the epitaxial growth of gallium nitride - Google Patents

Substrate for the epitaxial growth of gallium nitride

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Publication number
EP2171751A2
EP2171751A2 EP08826629A EP08826629A EP2171751A2 EP 2171751 A2 EP2171751 A2 EP 2171751A2 EP 08826629 A EP08826629 A EP 08826629A EP 08826629 A EP08826629 A EP 08826629A EP 2171751 A2 EP2171751 A2 EP 2171751A2
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EP
European Patent Office
Prior art keywords
layer
substrate according
zinc oxide
substrate
support material
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.)
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Application number
EP08826629A
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German (de)
French (fr)
Inventor
Eric Mattmann
Pascal Reutler
Fabien Lienhart
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.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Publication of EP2171751A2 publication Critical patent/EP2171751A2/en
Withdrawn legal-status Critical Current

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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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • 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
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • 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
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02483—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02488—Insulating materials
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02494—Structure
    • H01L21/02496—Layer structure
    • H01L21/02502—Layer structure consisting of two layers
    • 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
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • 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
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation

Definitions

  • the present invention relates to the field of semiconductors of the Nl-N or N-Vl type, in particular based on gallium nitride (GaN) and in particular used in electronic components such as light emitting diodes (LEDs) or transistors. It relates more particularly to a new type of substrate on which it is possible to grow layers based in particular gallium nitride.
  • GaN gallium nitride
  • LEDs light emitting diodes
  • transistors transistors. It relates more particularly to a new type of substrate on which it is possible to grow layers based in particular gallium nitride.
  • Gallium nitride is a semiconductor whose gap is of the order of 3.45 eV. It is commonly used for the production of light-emitting diodes emitting in the wavelength range from blue to violet.
  • the essential element of these diodes in their simplest expression, consists of a pn junction comprising doped GaN-based layers deposited on a substrate.
  • the GaN-based layers generally comprise layers comprising materials of the general formula In x Ga y Al x- y N, where x and y vary from 0 to 1. They are most often obtained by hetero-epitaxy.
  • MOCVD Metal Organic Chemical Vapor Deposition, chemical vapor deposition using organometallic precursors such as triethylgallium or trimethylgallium and ammonia
  • MOCVD Metal Organic Chemical Vapor Deposition, chemical vapor deposition using organometallic precursors such as triethylgallium or trimethylgallium and ammonia
  • the substrates that can be used are sapphire (Ct-Al 2 O 3 , also called corundum) or silicon carbide (SiC).
  • SiC silicon carbide
  • No. 6,362,496 B1 discloses a substrate for the growth of GaN at low temperature, comprising a borosilicate glass substrate coated with a layer of zinc oxide (ZnO).
  • Zinc oxide has the advantage of having a wurtzite hexagonal structure whose axis "a” has a size of about 0.32 nm, which is almost identical to the dimension of the "a" axis of GaN . Because of this similarity in terms of crystallographic structure and mesh parameters (of the order of 2% in relative terms), the epitaxial growth of GaN is very clearly favored.
  • the aim of the invention is to further improve the crystallinity of GaN, or more generally of type Nl-N (such as GaN) or N-Vl (as ZnO) type semiconductors, in particular to increase the intensity of emission and the lifetime of the light emitting diodes comprising this material.
  • the invention therefore also aims to provide a substrate capable of improving these properties when semiconductor structures are deposited on it.
  • the invention also aims to provide a substrate that can be made economically and in large dimensions.
  • the subject of the invention is a substrate which can be used as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material coated on at least one of its faces by at least one stack of layers comprising at least one at least one layer based on zinc oxide, said substrate being coated with a Nl-N or N-Vl type semiconductor structure.
  • the substrate is characterized in that between the support material and said at least one layer based on zinc oxide is disposed at least one intermediate layer comprising oxides of at least two elements chosen from tin (Sn), zinc (Zn), indium (In), gallium (Ga), antimony (Sb).
  • the subject of the invention is also a substrate that can be used as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material coated on at least one of its faces by at least one stack of layers comprising at least one layer. based on zinc oxide.
  • the substrate according to the invention is characterized in that between the support material and the at least one layer based on zinc oxide is disposed at least one intermediate layer comprising oxides of at least two elements chosen from tin. (Sn), zinc (Zn), gallium (Ga), antimony (Sb).
  • the first object of the invention is therefore a substrate coated with a semiconductor structure. It will be called "substrate coated" in the rest of the text.
  • the second subject of the invention is a particular substrate specially adapted for producing the first object, that is to say for the epitaxial growth of Nl-N or N-Vl type semiconductor structures.
  • the inventors have in fact demonstrated that the crystallinity of the GaN layer, or more generally of Nl-N or N-Vl type semiconductor layers, could be further improved thanks to the interposition between the support material and the ZnO layer of such an intermediate layer.
  • This intermediate layer makes it possible to improve the crystallization properties of the semiconductor layers by increasing in particular the quantity of crystallized material and / or by promoting a growth of gallium nitride or zinc oxide along its "c" axis, this axis being further perfectly perpendicular to the surface of the support material. It has also appeared to the inventors that the presence of this sub-layer makes it possible to improve the electronic conductivity of the ZnO / GaN or ZnO / ZnO stack. This results in a more homogeneous current distribution within these layers, an increase in the quantum efficiency, therefore a higher emission intensity, and a decrease in the heating of the component, thus an increase in its lifetime.
  • the support material is preferably coated on only one of its faces.
  • the stack deposited on this support material preferably comprises a single layer based on ZnO and / or a single intermediate layer.
  • the support material may be any type of material used as a support in the field of electronics, such as sapphire, silicon carbide, silicon, a metal such as copper, quartz, zinc oxide ( ZnO), spinels such as MgAl 2 O 4 , LiGaO 2 .
  • the support material is preferably a glassy or amorphous material, such as silica glass, or silica-based glasses. It may also be glass-ceramic, therefore a material consisting of at least one vitreous phase and at least one crystallized phase.
  • Silica-based glasses means glasses comprising silica in a weight content greater than or equal to about 40%, generally 50%.
  • Glasses resistant to high temperatures and thermal shocks such as borosilicate glasses are preferred for reasons of cost.
  • LCD liquid crystal displays
  • PDP plasma screens
  • These glass substrates used in the field of electronics have the advantage of being available in large dimensions for a moderate cost. Their coefficient of thermal expansion is also closer to that of GaN than the coefficient of thermal expansion of sapphire.
  • the glasses used for the manufacture of liquid crystal screens are generally borosilicate and alumina glasses without alkaline oxides.
  • the glasses used for the manufacture of plasma screens are generally glasses of alkaline earth silicates and alkalis.
  • the lower annealing temperature of said glass is preferably greater than or equal to 550 ° C., or even 600 ° C. or even 650 ° C. or 700 ° C., so as to be compatible with all GaN deposition processes at "low temperature”.
  • the lower annealing temperature of a glass (also called "Strain Point”) corresponds to the temperature at which the glass viscosity is 10 14 5 Poises (10 135 Pa-S).
  • the intermediate layer may be deposited in direct contact with the support material.
  • at least one underlayer is preferably disposed between the support material and the intermediate layer. This sub-layer is part of the stack. It may especially be, when the support material comprises alkaline ions, an underlayer acting as a barrier to the migration of alkaline ions.
  • barrier it is meant that the layer prevents the migration of a significant amount of alkali ions from the support material to the surface of the substrate.
  • the support material comprises alkaline ions (lithium, sodium, potassium), which is the case for example glass substrates used for the manufacture of plasma screens, these ions are likely to migrate within the layer-based of GaN and disrupt its semiconductor properties.
  • the sub-layer serving as a barrier to the migration of alkaline ions may consist of the following materials, or be based on one of the following materials, or any of their mixtures: SiOC, Si 3 N 4 , SiO 2 , TiN, Al 2 O 3 .
  • the intermediate layer is preferably arranged in direct contact under the zinc oxide layer, so as to directly influence the crystallization of zinc oxide, and subsequently the crystallization of gallium nitride.
  • a preferred substrate consists of a support material coated on one of its faces by a stack consisting of an intermediate layer and deposited directly on this intermediate layer, a layer based on zinc oxide.
  • the intermediate layer is preferably amorphous before deposition of the zinc oxide layer.
  • amorphous it is meant that the X-ray diffraction methods do not make it possible to detect crystalline phases in a significant amount.
  • the proportion of amorphous phase is greater than or equal to 90% by weight, in particular 95% and even 99%, relative to the total weight of the material.
  • the simple oxides (SnO 2 , ZnO, In 2 O 3 , Ga 2 O 3 , Sb 2 O 3 , optionally doped with other elements) are excluded because they are generally obtained when they are deposited in at least predominantly crystallized form, which does not make it possible to obtain the effect of improving the crystallization of gallium nitride.
  • the intermediate layer may, however, be able to crystallize at least in part after the deposition of the zinc oxide layer, for example under the effect of heat treatment or ion bombardment, which does not affect not its effect on subsequent crystallization of GaN-based layers. It seems indeed that the final technical effect of the intermediate layer is due to its influence on the zinc oxide-based layer during the deposition of the latter. Therefore, once the deposition of the ZnO-based layer is carried out, any changes in the structure of the intermediate layer do not seem to have any effect on the deposition of the subsequent layers.
  • the intermediate layer preferably contains oxides of metals selected from Sn / Zn, Sn / In, Sn / Ga, Sn / Sb, Zn / In, Zn / Ga, Zn / Sb, In / Ga, In / Sb, Ga / Sb.
  • the intermediate layer may also comprise three metal oxides, for example Sn / Zn / In, Sn / Zn / Sb, Sn / Zn / Ga, Zn / In / Sb, Zn / In / Ga, Sn / In / Sb, Sn / ln / Ga ...
  • the mass ratio of one of these elements relative to the other preferably varies between 10/90 and 50/50, especially between 20/80 and 45/55. Levels too low in one element with respect to the other (for example doping) are not preferred because they generate more easily a crystallization, which we saw that it was not generally desired.
  • the intermediate layer is preferably a layer based on zinc oxides and tin, in particular a layer of SnZnO type.
  • SnZnO type layer is meant any layer formed of any solid solution between ZnO on the one hand and SnO or SnO 2 on the other hand. This layer may be stoichiometric or not, and in particular be substoichiometric. Solid solutions having the composition of defined compounds, for example Zn 2 SnO 4 , are not preferred, however, because they tend to crystallize spontaneously when they are deposited. However, as indicated above, it is preferred that the intermediate layer be amorphous during the deposition of the ZnO-based layer.
  • the layers based on zinc oxides and tin have good thermal and chemical stability. This stability can, however, be improved by doping with at least one atom chosen from Al, Ga, In, B, Y, La, Ge, Si, P, As, Sb, Bi, Ce and Ti Zr. Nb and Ta. This doping also makes it possible to facilitate the deposition of the intermediate layer when it is produced by sputtering, in particular assisted by a magnetic field (a process commonly known as a "magnetron").
  • the atoms of Al and Sb, in particular Sb are preferred because the ionic radius of the associated ions is close to that of the ions associated with the Sn and Zn atoms.
  • the content of doping atoms is preferably between 0.5 and 5% by weight relative to the total amount of metal ion in the layer, in particular between 0.5 and 2%.
  • the layer based on ZnO is preferably a layer consisting of ZnO, in particular polycrystalline and crystallized in its hexagonal form (Wurtzite type structure). It is indeed advisable to promote as much as possible the crystallization of ZnO in this form in order to improve the crystallization of the overlying gallium nitride layers.
  • a material is said to be "polycrystalline" within the meaning of the invention if it is composed of a plurality of crystals, so if it is not a single crystal, regardless of the orientation of said crystals (which may be identical for each of them).
  • the ZnO crystals have a single orientation, in particular along an axis c perpendicular to the main surface of the substrate.
  • the ZnO-based layer can be used as a transparent electrode within the layer stack when its electronic conductivity is sufficient.
  • the ZnO-based layer is preferably a ZnO layer or a doped ZnO layer, in particular with aluminum (Al), indium (In) or gallium (Ga) atoms, in order to increase its electronic conductivity.
  • Gallium doping is preferred to doping with aluminum or indium because the latter is likely to migrate within the GaN-based semiconductor structure, creating a risk of short-circuiting.
  • a stack deposited on a support material as defined above comprising a layer based on ZnO (in particular doped ZnO or ZnO, for example Al, Ga or In) as a heteroepitaxial growth layer for gallium nitride-based layers.
  • ZnO in particular doped ZnO or ZnO, for example Al, Ga or In
  • the ZnO-based layer may be deposited directly on the support material or on one or more sub-layers, for example the intermediate layer according to the invention.
  • this substrate can be used in a so-called "flip-chip” diode structure (flip-chip) in which light emission is on the side of the substrate.
  • the ZnO-based layer then has three distinct functions: to facilitate heteroepitaxy, to bring current (via an ohmic contact) and to allow the extraction of light.
  • the ZnO-based layer is advantageously the last layer of the stack, and therefore the layer in contact with the atmosphere, insofar as it is preferable that the gallium nitride be subsequently deposited directly on this layer.
  • the substrate according to the invention preferably does not comprise a metal layer such as a silver layer or a layer comprising nickel and / or chromium.
  • a preferred substrate consists of a glass support material coated on one of its faces by a stack comprising a layer based on zinc oxides and tin and, deposited directly on this layer, an oxide-based layer. zinc (in particular a ZnO layer), a sub- layer acting as a barrier to the migration of alkaline ions being optionally disposed between the support material and the layer based on zinc oxides and tin and their direct contact.
  • the thickness of the layer based on ZnO is preferably between 10 and 500 nm. It has been observed that a relatively high thickness favors a better subsequent growth of
  • the thickness of the ZnO-based layer is therefore preferably between 100 and 300 nm.
  • the thickness of the intermediate layer is preferably between 2 and 100 nm, especially between 10 and 50 nm, or even between 20 and 30 nm. Such thicknesses promote crystal growth of zinc oxide.
  • the invention is partly concerned with the "coated substrate”.
  • This coated substrate is a substrate according to the invention, coated with a semiconductor structure of the Nl-N or N-Vl type.
  • the Nl-N type semiconductor structure preferably comprises at least one layer based on In x Ga y Ah- x - y N, where "x" and “y” vary from 0 to 1, and in particular a layer with gallium nitride (GaN) base.
  • GaN-based layer is generally meant any layer comprising doped (n or p) gallium nitride, or not, therefore a layer of general formula InxGayAh-x-yN described above, in which "Y" is non-zero, and more generally greater than 0.5.
  • the GaN-based layers may be undoped, n-doped (for example by Si, Ge, Se, Te, etc.) or p (for example doped with Mg, Zn, Ca, Sr, Ba ).
  • the Nl-N type semiconductor structure preferably comprises at least one n-doped GaN layer (for example doped with Si, Ge, Se, Te atoms, etc.) and at least one p-doped GaN layer (for example doped with atoms of Mg, Zn, Ca, Sr, Ba ).
  • the ZnO-based layer is then preferably in direct contact with the at least one n-doped GaN layer.
  • a buffer layer based on gallium nitride and / or amorphous aluminum may be arranged between the ZnO-based layer and the semiconductor structure. Such a buffer layer is intended to further promote the crystallization of the GaN-based layer.
  • the N-Vl type semiconductor structure preferably comprises at least one ZnO-based layer.
  • ZnO-based layer is meant any layer containing zinc oxide, for example doped n (using Al, In, etc.) or p.
  • the ZnO-based layer of the substrate according to the invention can indeed constitute an epitaxial layer ideal for semiconductor structures themselves based on ZnO.
  • the semiconductor structure may comprise or consist of at least one non-continuous layer formed of nanostructures, such as nanowires, or structures commonly known by their English expressions “nano-rods", “nano-pillars”, “Nano-wires”.
  • nanostructures such as nanowires, or structures commonly known by their English expressions "nano-rods", “nano-pillars", “Nano-wires”.
  • These structures are generally in the form of son or columns oriented along an axis substantially perpendicular to the surface of the substrate. These son or columns preferably have a diameter of between 50 and 500 nm, and a height of between 500 nm and 5 micrometers.
  • These structures make it possible to improve the guiding of the light, limiting as much as possible the losses of light on the sides of the diode.
  • These structures also make it possible to create cavity effects, allowing amplification of the light.
  • the ZnO layer of the substrate is preferably in direct contact with the at least one GaN-based or ZnO-based layer of this semiconductor structure.
  • the substrate according to the invention in particular the coated substrate according to the invention can be used for the manufacture of light-emitting diodes.
  • These light-emitting diodes may for example be integrated in laser systems and / or be used in the field of lighting (road signs, road lighting, urban or interior, automobile), display screens, data storage.
  • the semiconductor structure is preferably a heterostructure in the sense that it comprises heterojunctions, that is to say assemblies of semiconductors of different chemical compositions having different energy gaps, and preferably selected from pure compounds or alloys of the InxGayAh-x-yN type, where x and y vary from 0 to 1.
  • the variation of the parameters x and y makes it possible to directly influence the gap of the driver.
  • the structures obtained are generally of the single quantum well (SQW) or multiple quantum well type.
  • the diodes thus produced can emit in a wide range of the electromagnetic spectrum covering the field of ultraviolet and visible, and in particular the field of blue or green. Coupled with phosphorescent materials, the diodes can also allow the emission of white light.
  • the substrate according to the invention can also serve as a substrate for other types of semiconductor structures than diodes, for example transistor structures, such as bipolar transistors, field effect transistors (FETs) in particular of the MESFET type. (Metal Semiconductor Field Effect Transistor) or HFET (Heterostructure Field Effect Transistor). Transistors employing GaN-based semiconductor structures are of particular interest in microwave (typically 5-50 GHz) and / or power (typically 50 W) applications. The transparent nature of these semiconductor structures also makes it possible to envisage transparent electronic devices.
  • transistor structures such as bipolar transistors, field effect transistors (FETs) in particular of the MESFET type. (Metal Semiconductor Field Effect Transistor) or HFET (Heterostructure Field Effect Transistor).
  • Transistors employing GaN-based semiconductor structures are of particular interest in microwave (typically 5-50 GHz) and / or power (typically 50 W) applications.
  • the transparent nature of these semiconductor structures also makes it possible to envisage transparent electronic devices.
  • the subject of the invention is also a process for obtaining the substrate according to the invention, in which said at least one layer based on zinc oxide and said at least one intermediate layer are deposited by cathodic sputtering.
  • the magnetic field assisted sputtering method (“magnetron” method) is advantageously employed. In a preferred manner, all the layers of the stack are deposited by this technique, including consequently the possible sub-layer disposed between the support material and the intermediate layer.
  • the cathode sputtering method in particular assisted by a magnetic field, has the advantage of growing the layer based on zinc oxide along the axis c, thus allowing a subsequent epitaxial growth of GaN along this same axis.
  • the magnetron method may be of the reactive type or not.
  • the step of deposition by sputtering of the intermediate layer makes it possible to obtain a layer that is preferably amorphous, for the reasons mentioned above.
  • a preferred method consists in depositing, by magnetron method on a glass support material, an intermediate layer based on oxides of zinc and tin as described above and then a layer of zinc oxide.
  • the glass used contains alkaline ions
  • This deposit is preferably followed by a heat treatment intended to promote the crystallization of the zinc oxide-based layer, since it has been found that a better crystallization of the zinc oxide-based layer improves the crystallization of the layers. overlying layers.
  • This heat treatment is generally carried out at temperatures of between 200 and 1100 ° C., in particular between 200 and 700 ° C.
  • an improvement in the crystallization of ZnO can be obtained by depositing the layer on a hot substrate, the temperature of which is in particular between 150 and 400 ° C., in particular between 200 and 300 ° C.
  • the layers of the stack in particular the ZnO-based layer
  • an ion beam in particular an argon ion beam.
  • the ion beam is preferably generated by an ion gun or an ion source, which may advantageously be positioned within the cathode sputtering chamber itself.
  • an ion gun or an ion source which may advantageously be positioned within the cathode sputtering chamber itself.
  • it is possible to smooth the ZnO layer to increase its chemical resistance, especially to the ammonia that can be used during the growth of GaN) or on the contrary to texture the ZnO surface to promote lateral epitaxy and thus reduce or eliminate dislocations.
  • Figures 1 and 2 are a schematic representation of substrates according to the invention.
  • Figures 3 and 4 are scanning electron micrographs taken on the sample wafer described hereinafter.
  • Figure 1 shows a schematic section of a preferred substrate according to the invention.
  • the substrate is composed of a support material 11, coated with a stack consisting of an intermediate layer 12 coated with a layer 13 based on ZnO.
  • Figure 2 shows a schematic section of another preferred substrate according to the invention.
  • the substrate is composed of a support material 21, coated by a stack comprising a layer 22 acting as a barrier to the migration of alkaline ions deposited directly on the support material 21, coated by an intermediate layer 23, itself coated. a layer 23 based on ZnO.
  • the support material and the various layers of the stack are as described in the general part of the description.
  • the support material is made of glass, in particular of the type intended for the manufacture of plasma screens.
  • the intermediate layer is advantageously based on zinc and tin oxides, in particular doped with Al or Sb.
  • the ZnO layer is preferably a ZnO layer.
  • the optional layer serving as a barrier to the migration of alkaline ions is advantageously a layer of Si 3 N 4 .
  • the substrate according to the comparative example consists of a glass support material coated with a sub-layer of Si 3 N 4 acting as a barrier to the migration of alkaline ions and a zinc oxide layer.
  • the stack is as follows, the geometric thicknesses being indicated in parentheses:
  • the glass used is a glass intended for the manufacture of plasma screens as described in the patent application WO 98/40320.
  • This stack is deposited by magnetron method.
  • the Si 3 N 4 layer is deposited using a silicon target powered by a power of
  • the pressure is 2.5 microbars and the plasma gas is a mixture of argon (flow rate of 40 sccm, standard cubic centimeters per minute) and nitrogen (flow rate of 58 sccm).
  • the deposition of the ZnO layer implements a Zinc target raised to a voltage of 290 V at 50 kHz, under a pressure of 2 microbars and a mixture of argon (40 sccm) and oxygen (18 sccm).
  • the magnetron deposition of each of these layers is, moreover, well known to those skilled in the art, and the details of the deposition (target used, pressure, gas, etc.) do not significantly influence the results.
  • This substrate is then coated in a known manner with a layer of GaN 80 nm thick (example noted C1) or 200 nm thick (example noted C2), by the method RPCVD (Remote Plasma Chemical Vapor Deposition, chemical deposition vapor phase assisted by a remote plasma).
  • RPCVD Remote Plasma Chemical Vapor Deposition, chemical deposition vapor phase assisted by a remote plasma. Any other type of deposition process compatible in terms of deposition temperature with the nature of the substrate used is of course possible, without significantly affecting the results.
  • the examples according to the invention are distinguished from the comparative example in that a layer of mixed zinc oxide and antimony-doped tin (Sb) is deposited between the Si 3 N 4 underlayer and the zinc oxide layer, still by magnetron process.
  • the deposition of the SnZnO layer uses a target formed of an alloy of tin and zinc doped with antimony, a power of 2kW and a frequency of 50 kHz, a pressure of 2 microbars and a mixture of argon (12 sccm) and oxygen (45 sccm).
  • the mixed oxide layer comprises approximately by weight of metals 65% Sn, 34% Zn and 1% Sb.
  • the different examples according to the invention are distinguished by the thicknesses of the ZnO layer and the zinc oxide and tin oxide layer.
  • Table 1 reproduces the thicknesses of these layers for each of Examples 1 to 4 according to the invention.
  • the effect of the invention on the crystallization of the GaN-based layer has been studied by various methods.
  • the orientation of the GaN crystals was compared by measuring the area of diffraction peaks associated with GaN in an X-ray diffraction pattern.
  • X-ray diffraction is performed in ⁇ / 2 ⁇ configuration. Given the small difference in mesh parameters between ZnO and GaN, their peaks overlap in part, requiring a mathematical treatment to separate them. This mathematical treatment is in particular based on the diffraction characteristics of the ZnO layer alone, measured before GaN deposition.
  • Table 2 indicates in arbitrary units the area of the diffraction peak associated with the crystallographic plane (0002), which corresponds to an orientation of the crystals along the axis c.
  • FIGS. 3 and 4 are clichés, respectively examples C2 and 1, taken by scanning electron microscopy at a magnification of 100,000. The images are taken on the wafer, thus making it possible to visualize the ZnO / GaN stack.
  • the direction of growth of the GaN crystals is perfectly perpendicular to the substrate, and therefore less free of defects.
  • the overall electrical resistivity of the stack has been evaluated in a known manner by means of the 4-point method or Van der Pauw method.
  • Table 3 gives the values obtained for examples C1, 3 and 4.
  • the resistivity drop due to the addition of the intermediate layer corresponds to a very large increase in the electronic conductivity, reflecting a smaller amount of structural defects.
  • the interposition in the substrate according to the invention of the intermediate layer between the support material and the zinc oxide layer therefore makes it possible to improve the crystalline characteristics of the gallium nitride layer and to increase its conductivity. electronic. This results in an increase in the emission intensity and the lifetime of the light-emitting diodes using these substrates.

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Abstract

The invention relates to a substrate which may be used for as a substrate for the epitaxial growth of layers made from gallium nitride and comprising a support material (11, 21) coated on at least one side by at least one series of layers having at least one layer made from zinc oxide (13, 24). The substrate is coated with a semiconductor structure of the Nl-N or N-Vl type and characterised in that between the support material (11, 21 ) and said at least one layer made from zinc oxide (13, 24) at least one intermediate layer (12, 23) is provided which comprises oxides of at least two elements selected from tin (Sn), zinc (Zn), indium (In), gallium (Ga), or antimony (Sb).

Description

SUBSTRAT POUR LA CROISSANCE EPITAXIALE DE NITRURE DE SUBSTRATE FOR THE EPITAXIAL GROWTH OF NITRIDE
GALLIUMGALLIUM
La présente invention concerne le domaine des semi-conducteurs du type Nl-N ou N-Vl, en particulier à base de nitrure de gallium (GaN) et notamment utilisés dans des composants électroniques tels que des diodes électroluminescentes (DEL) ou des transistors. Elle concerne plus particulièrement un nouveau type de substrat sur lequel il est possible de faire croître des couches à base notamment de nitrure de gallium.The present invention relates to the field of semiconductors of the Nl-N or N-Vl type, in particular based on gallium nitride (GaN) and in particular used in electronic components such as light emitting diodes (LEDs) or transistors. It relates more particularly to a new type of substrate on which it is possible to grow layers based in particular gallium nitride.
Le nitrure de gallium est un semi-conducteur dont le gap est de l'ordre de 3,45 eV. Il est couramment employé pour la réalisation de diodes électroluminescentes émettant dans le domaine de longueurs d'ondes allant du bleu au violet. L'élément essentiel de ces diodes, dans leur expression la plus simple, est constitué par une jonction p-n comprenant des couches à base de GaN dopé déposées sur un substrat. Les couches à base de GaN comprennent d'une manière générale les couches comprenant des matériaux de formule générale lnxGayAli-x-yN, où x et y varient de 0 à 1. Elles sont le plus souvent obtenues par hétéro-épitaxie à l'aide d'une technique appelée MOCVD (Métal Organic Chemical Vapor Déposition, dépôt chimique en phase vapeur à l'aide de précurseurs organométalliques comme le triéthylgallium ou le triméthylgallium et d'ammoniac) à très haute température (entre 10000C et 12000C). Du fait de ces températures élevées, les substrats utilisables sont le saphir (Ct-AI2O3, également appelé corindon) ou le carbure de silicium (SiC). Compte tenu toutefois du désaccord de maille important entre le GaN et le saphir (environ 14%), et de la forte différence entre leurs coefficients de dilatation thermique respectifs, le GaN ainsi obtenu présente une cristallinité de mauvaise qualité et un grand nombre de défauts cristallins (à raison d'une densité de défauts, notamment dislocations, allant jusqu'à 1010 /cm2), ce qui limite à la fois l'intensité d'émission (efficacité lumineuse et énergétique) et la durée de vie des diodes.Gallium nitride is a semiconductor whose gap is of the order of 3.45 eV. It is commonly used for the production of light-emitting diodes emitting in the wavelength range from blue to violet. The essential element of these diodes, in their simplest expression, consists of a pn junction comprising doped GaN-based layers deposited on a substrate. The GaN-based layers generally comprise layers comprising materials of the general formula In x Ga y Al x- y N, where x and y vary from 0 to 1. They are most often obtained by hetero-epitaxy. using a technique called MOCVD (Metal Organic Chemical Vapor Deposition, chemical vapor deposition using organometallic precursors such as triethylgallium or trimethylgallium and ammonia) at very high temperature (between 1000 ° C. and 1200 0 C). Because of these high temperatures, the substrates that can be used are sapphire (Ct-Al 2 O 3 , also called corundum) or silicon carbide (SiC). However, given the significant gap cleavage between GaN and sapphire (about 14%), and the large difference between their respective thermal expansion coefficients, the GaN thus obtained has poor quality crystallinity and a large number of crystalline defects. (due to a density of defects, in particular dislocations, up to 10 10 / cm 2 ), which limits both the intensity of emission (light and energy efficiency) and the lifetime of the diodes.
Des procédés alternatifs de dépôt ont été proposés plus récemment, qui grâce à une température de dépôt plus faible autorisent l'emploi de substrats mieux adaptés du point de vue cristallographique et moins coûteux. On peut citer à titre d'exemples les procédés PLD (Pulsed Laser Déposition, dépôt par laser puisé), PAMBE (Plasma Assisted Molecular Beam Epitaxy, épitaxie par jet moléculaire assistée par plasma), RPCVD (Remote Plasma Chemical Vapor Déposition, dépôt chimique en phase vapeur assisté par un plasma déporté) ou encore ENABLE (Energetic Neutral Atom Beam Lithography/Epitaxy, épitaxie ou lithographie par jet énergétique d'atomes neutres). Ces procédés permettent de réaliser le dépôt de GaN à des températures inférieures à 8000C, voire inférieures à 1000C pour certains d'entre eux. Il devient ainsi possible d'employer d'autres types de substrats, notamment plus adaptés en termes de paramètres de maille.Alternative deposition methods have been proposed more recently, which, thanks to a lower deposition temperature, allow the use of substrates that are better crystallographically and less costly. Examples that may be mentioned include PLD (Pulsed Laser Deposition, Pulsed Laser Deposition), PAMBE (Plasma Assisted Molecular Beam Epitaxy, Plasma Assisted Molecular Spiking), RPCVD (Remote Plasma Chemical Vapor Deposition, Chemical Deposition). vapor phase assisted by a remote plasma) or ENABLE (Energetic Neutral Atom Beam Lithography / Epitaxy, epitaxy or energy jet lithography of neutral atoms). These methods make it possible to deposit GaN at temperatures below 800 ° C., or even below 100 ° C. for some of them. It thus becomes possible to use other types of substrates, especially more suited in terms of mesh parameters.
Il est connu du document de brevet US 6,362,496 B1 un substrat pour la croissance de GaN à basse température, comprenant un substrat de verre borosilicate revêtu par une couche d'oxyde de zinc (ZnO).No. 6,362,496 B1 discloses a substrate for the growth of GaN at low temperature, comprising a borosilicate glass substrate coated with a layer of zinc oxide (ZnO).
L'oxyde de zinc a l'avantage de posséder une structure hexagonale du type wurtzite dont l'axe « a » présente une dimension d'environ 0,32 nm, soit presque identique à la dimension de l'axe « a » de GaN. Du fait de cette similitude en termes de structure cristallographique et de paramètres de maille (de l'ordre de 2% en relatif), la croissance épitaxiale de GaN est très nettement favorisée. L'invention a pour but d'améliorer encore la cristallinité de GaN, ou plus généralement de semi-conducteurs du type Nl-N (comme GaN) ou N-Vl (comme ZnO), afin notamment d'augmenter l'intensité d'émission et la durée de vie des diodes électroluminescentes comprenant ce matériau.Zinc oxide has the advantage of having a wurtzite hexagonal structure whose axis "a" has a size of about 0.32 nm, which is almost identical to the dimension of the "a" axis of GaN . Because of this similarity in terms of crystallographic structure and mesh parameters (of the order of 2% in relative terms), the epitaxial growth of GaN is very clearly favored. The aim of the invention is to further improve the crystallinity of GaN, or more generally of type Nl-N (such as GaN) or N-Vl (as ZnO) type semiconductors, in particular to increase the intensity of emission and the lifetime of the light emitting diodes comprising this material.
L'invention a donc aussi pour but de proposer un substrat capable d'améliorer ces propriétés lorsque des structures semi-conductrices sont déposées sur lui.The invention therefore also aims to provide a substrate capable of improving these properties when semiconductor structures are deposited on it.
L'invention a également pour but de proposer un substrat pouvant être réalisé de manière économique et en grandes dimensions. A cet effet, l'invention a pour objet un substrat utilisable comme substrat pour la croissance épitaxiale de couches à base de nitrure de gallium et comprenant un matériau de support revêtu sur au moins une des ses faces par au moins un empilement de couches comprenant au moins une couche à base d'oxyde de zinc, ledit substrat étant revêtu par une structure semi-conductrice du type Nl-N ou N-Vl. Le substrat est caractérisé en ce qu'entre le matériau support et ladite au moins une couche à base d'oxyde de zinc est disposée au moins une couche intermédiaire comprenant des oxydes d'au moins deux éléments choisis parmi l'étain (Sn), le zinc (Zn), l'indium (In), le gallium (Ga), l'antimoine (Sb).The invention also aims to provide a substrate that can be made economically and in large dimensions. For this purpose, the subject of the invention is a substrate which can be used as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material coated on at least one of its faces by at least one stack of layers comprising at least one at least one layer based on zinc oxide, said substrate being coated with a Nl-N or N-Vl type semiconductor structure. The substrate is characterized in that between the support material and said at least one layer based on zinc oxide is disposed at least one intermediate layer comprising oxides of at least two elements chosen from tin (Sn), zinc (Zn), indium (In), gallium (Ga), antimony (Sb).
L'invention a également pour objet un substrat utilisable comme substrat pour la croissance épitaxiale de couches à base de nitrure de gallium et comprenant un matériau de support revêtu sur au moins une des ses faces par au moins un empilement de couches comprenant au moins une couche à base d'oxyde de zinc. Le substrat selon l'invention est caractérisé en ce qu'entre le matériau support et la au moins une couche à base d'oxyde de zinc est disposée au moins une couche intermédiaire comprenant des oxydes d'au moins deux éléments choisis parmi l'étain (Sn), le zinc (Zn), le gallium (Ga), l'antimoine (Sb). Le premier objet de l'invention est donc un substrat revêtu d'une structure semi-conductrice. On l'appellera « substrat revêtu » dans la suite du texte. Le second objet de l'invention est un substrat particulier spécialement adapté à la réalisation du premier objet, c'est-à-dire à la croissance épitaxiale de structures semi-conductrices du type Nl-N ou N-Vl. Les inventeurs ont en effet mis en évidence que la cristallinité de la couche de GaN, ou plus généralement de couches de semi-conducteurs du type Nl-N ou N-Vl, pouvait encore être améliorée grâce à l'interposition entre le matériau support et la couche de ZnO d'une telle couche intermédiaire.The subject of the invention is also a substrate that can be used as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material coated on at least one of its faces by at least one stack of layers comprising at least one layer. based on zinc oxide. The substrate according to the invention is characterized in that between the support material and the at least one layer based on zinc oxide is disposed at least one intermediate layer comprising oxides of at least two elements chosen from tin. (Sn), zinc (Zn), gallium (Ga), antimony (Sb). The first object of the invention is therefore a substrate coated with a semiconductor structure. It will be called "substrate coated" in the rest of the text. The second subject of the invention is a particular substrate specially adapted for producing the first object, that is to say for the epitaxial growth of Nl-N or N-Vl type semiconductor structures. The inventors have in fact demonstrated that the crystallinity of the GaN layer, or more generally of Nl-N or N-Vl type semiconductor layers, could be further improved thanks to the interposition between the support material and the ZnO layer of such an intermediate layer.
Cette couche intermédiaire permet d'améliorer les propriétés de cristallisation des couches semi-conductrices en augmentant en particulier la quantité de matière cristallisée et/ou en favorisant une croissance du nitrure de gallium ou de l'oxyde de zinc selon son axe « c », cet axe étant en outre parfaitement perpendiculaire à la surface du matériau support. II est également apparu aux inventeurs que la présence de cette sous- couche permettait d'améliorer la conductivité électronique de l'empilement ZnO/GaN ou ZnO/ZnO. Il en résulte une distribution de courant plus homogène au sein de ces couches, une augmentation du rendement quantique, donc une intensité d'émission plus forte, et une diminution de réchauffement du composant, donc une augmentation de sa durée de vie.This intermediate layer makes it possible to improve the crystallization properties of the semiconductor layers by increasing in particular the quantity of crystallized material and / or by promoting a growth of gallium nitride or zinc oxide along its "c" axis, this axis being further perfectly perpendicular to the surface of the support material. It has also appeared to the inventors that the presence of this sub-layer makes it possible to improve the electronic conductivity of the ZnO / GaN or ZnO / ZnO stack. This results in a more homogeneous current distribution within these layers, an increase in the quantum efficiency, therefore a higher emission intensity, and a decrease in the heating of the component, thus an increase in its lifetime.
Le matériau de support est de préférence revêtu sur une seule de ses faces. L'empilement déposé sur ce matériau de support comprend de préférence une seule couche à base de ZnO et/ou une seule couche intermédiaire.The support material is preferably coated on only one of its faces. The stack deposited on this support material preferably comprises a single layer based on ZnO and / or a single intermediate layer.
Le matériau de support peut être tout type de matériau utilisé comme support dans le domaine de l'électronique, comme du saphir, du carbure de silicium, du silicium, un métal tel que le cuivre, du quartz, de l'oxyde de zinc (ZnO), des spinelles telles que MgAI2O4, LiGaO2. Les effets de l'invention se révélant plus importants pour les matériaux vitreux ou amorphes, le matériau de support est de préférence un matériau vitreux ou amorphe, tel que le verre de silice, ou les verres à base de silice. Il peut également être en vitrocéramique, donc en un matériau constitué d'au moins une phase vitreuse et d'au moins une phase cristallisée. Par « verres à base de silice », on entend des verres comprenant de la silice en une teneur pondérale supérieure ou égale à environ 40%, généralement 50%. Des verres résistants aux températures élevées et aux chocs thermiques comme les verres de borosilicate sont préférés, pour des raisons de coût. Parmi les verres préférés figurent en particulier les verres employés en tant que substrats pour la fabrication d'écrans plats, écrans à cristaux liquides (LCD) ou écrans à plasma (PDP). Ces substrats de verre utilisés dans le domaine de l'électronique présentent en effet l'avantage d'être disponibles en grandes dimensions pour un coût modéré. Leur coefficient de dilatation thermique est en outre plus proche de celui de GaN que le coefficient de dilatation thermique du saphir. Les verres employés pour la fabrication d'écrans à cristaux liquides sont généralement des verres de borosilicate et d'alumine dépourvus d'oxydes alcalins. Les verres employés pour la fabrication d'écrans à plasma sont généralement des verres de silicates d'alcalino-terreux et d'alcalins. Lorsque le matériau de support est en verre à base de silice, la température inférieure de recuit dudit verre est de préférence supérieure ou égale à 5500C, voire 6000C ou même 6500C ou 7000C, de manière à être compatible avec tous les procédés de dépôt de GaN à « basse température ». La température inférieure de recuit d'un verre (également appelée « Strain Point ») correspond à la température à laquelle la viscosité du verre est égale à 1014'5 Poises (10135 Pa-S).The support material may be any type of material used as a support in the field of electronics, such as sapphire, silicon carbide, silicon, a metal such as copper, quartz, zinc oxide ( ZnO), spinels such as MgAl 2 O 4 , LiGaO 2 . As the effects of the invention are more important for vitreous or amorphous materials, the support material is preferably a glassy or amorphous material, such as silica glass, or silica-based glasses. It may also be glass-ceramic, therefore a material consisting of at least one vitreous phase and at least one crystallized phase. "Silica-based glasses" means glasses comprising silica in a weight content greater than or equal to about 40%, generally 50%. Glasses resistant to high temperatures and thermal shocks such as borosilicate glasses are preferred for reasons of cost. Among the preferred glasses are in particular glasses used as substrates for the manufacture of flat screens, liquid crystal displays (LCD) or plasma screens (PDP). These glass substrates used in the field of electronics have the advantage of being available in large dimensions for a moderate cost. Their coefficient of thermal expansion is also closer to that of GaN than the coefficient of thermal expansion of sapphire. The glasses used for the manufacture of liquid crystal screens are generally borosilicate and alumina glasses without alkaline oxides. The glasses used for the manufacture of plasma screens are generally glasses of alkaline earth silicates and alkalis. When the support material is made of silica-based glass, the lower annealing temperature of said glass is preferably greater than or equal to 550 ° C., or even 600 ° C. or even 650 ° C. or 700 ° C., so as to be compatible with all GaN deposition processes at "low temperature". The lower annealing temperature of a glass (also called "Strain Point") corresponds to the temperature at which the glass viscosity is 10 14 5 Poises (10 135 Pa-S).
La couche intermédiaire peut être déposée en contact direct sur le matériau de support. De manière alternative, au moins une sous-couche est de préférence disposée entre le matériau de support et la couche intermédiaire. Cette sous- couche fait partie de l'empilement. Il peut notamment s'agir, lorsque le matériau de support comprend des ions alcalins, d'une sous-couche faisant office de barrière à la migration des ions alcalins. Par « faisant office de barrière », on entend que la couche empêche la migration d'une quantité significative d'ions alcalins du matériau de support vers la surface du substrat. Lorsque le matériau de support comprend des ions alcalins (lithium, sodium, potassium), ce qui est le cas par exemple des substrats de verre employés pour la fabrication d'écrans plasma, ces ions sont susceptibles de migrer au sein de la couche à base de GaN et de perturber ses propriétés semi-conductrices. Cette migration peut notamment se produire lorsque le substrat est soumis à des températures élevées, donc en particulier lors du dépôt des couches à base de GaN. Elle peut également se produire lors du fonctionnement du composant électronique (diode ou transistor), les températures atteintes étant moins élevées, mais les temps étant beaucoup plus longs. La sous-couche faisant office de barrière à la migration des ions alcalins peut être constituée des matériaux suivants, ou être à base d'une des matériaux suivants, ou de l'un quelconque de leurs mélanges : SiOC, Si3N4, SiO2, TiN, AI2O3.The intermediate layer may be deposited in direct contact with the support material. Alternatively, at least one underlayer is preferably disposed between the support material and the intermediate layer. This sub-layer is part of the stack. It may especially be, when the support material comprises alkaline ions, an underlayer acting as a barrier to the migration of alkaline ions. By "barrier" it is meant that the layer prevents the migration of a significant amount of alkali ions from the support material to the surface of the substrate. When the support material comprises alkaline ions (lithium, sodium, potassium), which is the case for example glass substrates used for the manufacture of plasma screens, these ions are likely to migrate within the layer-based of GaN and disrupt its semiconductor properties. This migration can occur especially when the substrate is subjected to high temperatures, so in particular during the deposition of GaN-based layers. It can also occur during the operation of the electronic component (diode or transistor), the temperatures reached being lower, but the times being much longer. The sub-layer serving as a barrier to the migration of alkaline ions may consist of the following materials, or be based on one of the following materials, or any of their mixtures: SiOC, Si 3 N 4 , SiO 2 , TiN, Al 2 O 3 .
La couche intermédiaire est de préférence disposée en contact direct sous la couche à base d'oxyde de zinc, de manière à influencer directement la cristallisation de l'oxyde de zinc, et, ultérieurement, la cristallisation du nitrure de gallium. Un substrat préféré consiste en un matériau de support revêtu sur une seule de ses faces par un empilement constitué d'une couche intermédiaire et, déposée directement sur cette couche intermédiaire, d'une couche à base d'oxyde de zinc. La couche intermédiaire est de préférence amorphe avant le dépôt de la couche à base d'oxyde de zinc. Par « amorphe », on entend que les méthodes de diffraction des rayons X ne permettent pas de détecter de phases cristallines en quantité significative. De préférence, la proportion de phase amorphe est supérieure ou égale à 90% en poids, notamment 95% et même 99%, relativement au poids total du matériau. Les oxydes simples (SnO2, ZnO, In2O3, Ga2O3, Sb2O3, éventuellement dopés par d'autres éléments) sont exclus car généralement obtenus lors de leur dépôt sous forme au moins majoritairement cristallisée, ce qui ne permet pas d'obtenir l'effet d'amélioration de la cristallisation du nitrure de gallium. La couche intermédiaire peut toutefois être susceptible de cristalliser au moins en partie après le dépôt de la couche à base d'oxyde de zinc, par exemple sous l'effet d'un traitement thermique ou d'un bombardement ionique, ce qui n'affecte pas son effet sur la cristallisation ultérieure de couches à base de GaN. Il semble en effet que l'effet technique final de la couche intermédiaire soit dû à son influence sur la couche à base d'oxyde de zinc lors du dépôt de cette dernière. Dès lors, une fois le dépôt de la couche à base de ZnO réalisé, les éventuelles modifications de la structure de la couche intermédiaire ne semblent pas avoir d'effet sur le dépôt des couches ultérieures.The intermediate layer is preferably arranged in direct contact under the zinc oxide layer, so as to directly influence the crystallization of zinc oxide, and subsequently the crystallization of gallium nitride. A preferred substrate consists of a support material coated on one of its faces by a stack consisting of an intermediate layer and deposited directly on this intermediate layer, a layer based on zinc oxide. The intermediate layer is preferably amorphous before deposition of the zinc oxide layer. By "amorphous" it is meant that the X-ray diffraction methods do not make it possible to detect crystalline phases in a significant amount. Preferably, the proportion of amorphous phase is greater than or equal to 90% by weight, in particular 95% and even 99%, relative to the total weight of the material. The simple oxides (SnO 2 , ZnO, In 2 O 3 , Ga 2 O 3 , Sb 2 O 3 , optionally doped with other elements) are excluded because they are generally obtained when they are deposited in at least predominantly crystallized form, which does not make it possible to obtain the effect of improving the crystallization of gallium nitride. The intermediate layer may, however, be able to crystallize at least in part after the deposition of the zinc oxide layer, for example under the effect of heat treatment or ion bombardment, which does not affect not its effect on subsequent crystallization of GaN-based layers. It seems indeed that the final technical effect of the intermediate layer is due to its influence on the zinc oxide-based layer during the deposition of the latter. Therefore, once the deposition of the ZnO-based layer is carried out, any changes in the structure of the intermediate layer do not seem to have any effect on the deposition of the subsequent layers.
La couche intermédiaire contient de préférence des oxydes de métaux choisis parmi les couples Sn/Zn, Sn/ln, Sn/Ga, Sn/Sb, Zn/ln, Zn/Ga, Zn/Sb, In/Ga, In/Sb, Ga/Sb. La couche intermédiaire peut également comprendre trois oxydes de métaux, par exemple des oxydes de Sn/Zn/ln, Sn/Zn/Sb, Sn/Zn/Ga, Zn/ln/Sb, Zn/ln/Ga, Sn/ln/Sb, Sn/ln/Ga...The intermediate layer preferably contains oxides of metals selected from Sn / Zn, Sn / In, Sn / Ga, Sn / Sb, Zn / In, Zn / Ga, Zn / Sb, In / Ga, In / Sb, Ga / Sb. The intermediate layer may also comprise three metal oxides, for example Sn / Zn / In, Sn / Zn / Sb, Sn / Zn / Ga, Zn / In / Sb, Zn / In / Ga, Sn / In / Sb, Sn / ln / Ga ...
Lorsque la couche intermédiaire contient des oxydes de deux éléments choisis parmi Sn, Zn, In, Ga, Sb, le rapport massique de l'un des ces éléments par rapport à l'autre varie de préférence entre 10/90 et 50/50, notamment entre 20/80 et 45/55. Des teneurs trop faibles en un élément par rapport à l'autre (cas par exemple du dopage) ne sont pas préférées car elles engendrent plus aisément une cristallisation, dont nous avons vu qu'elle n'était généralement pas souhaitée.When the intermediate layer contains oxides of two elements chosen from Sn, Zn, In, Ga, Sb, the mass ratio of one of these elements relative to the other preferably varies between 10/90 and 50/50, especially between 20/80 and 45/55. Levels too low in one element with respect to the other (for example doping) are not preferred because they generate more easily a crystallization, which we saw that it was not generally desired.
La couche intermédiaire est de préférence une couche à base d'oxydes de zinc et d'étain, notamment une couche du type SnZnO. Par « couche du type SnZnO », on entend toute couche formée d'une solution solide quelconque entre ZnO d'une part et SnO ou SnO2 d'autre part. Cette couche peut être stœchiométrique ou non, et en particulier être sous-stœchiométrique. Les solutions solides présentant la composition de composés définis, par exemple Zn2SnO4, ne sont toutefois pas préférées, car elles ont tendance à cristalliser de manière spontanée lors de leur dépôt. Or, tel qu'indiqué précédemment, il est préféré que la couche intermédiaire soit amorphe lors du dépôt de la couche à base de ZnO.The intermediate layer is preferably a layer based on zinc oxides and tin, in particular a layer of SnZnO type. By "SnZnO type layer" is meant any layer formed of any solid solution between ZnO on the one hand and SnO or SnO 2 on the other hand. This layer may be stoichiometric or not, and in particular be substoichiometric. Solid solutions having the composition of defined compounds, for example Zn 2 SnO 4 , are not preferred, however, because they tend to crystallize spontaneously when they are deposited. However, as indicated above, it is preferred that the intermediate layer be amorphous during the deposition of the ZnO-based layer.
Les couches à base d'oxydes de zinc et d'étain présentent une bonne stabilité thermique et chimique. Cette stabilité peut toutefois être améliorée à l'aide d'un dopage par au moins un atome choisi parmi Al, Ga, In, B, Y, La, Ge, Si, P, As, Sb, Bi, Ce, Ti Zr, Nb et Ta. Ce dopage permet également de faciliter le dépôt de la couche intermédiaire lorsqu'il est réalisé par pulvérisation cathodique, notamment assistée par champ magnétique (procédé communément appelé « magnétron »). Les atomes de Al et Sb, en particulier Sb sont préférés car le rayon ionique des ions associés est proche de celui des ions associés aux atomes de Sn et Zn. La teneur en atomes dopants est de préférence comprise entre 0,5 et 5% en poids relativement à la quantité totale d'ion métallique dans la couche, notamment entre 0,5 et 2%.The layers based on zinc oxides and tin have good thermal and chemical stability. This stability can, however, be improved by doping with at least one atom chosen from Al, Ga, In, B, Y, La, Ge, Si, P, As, Sb, Bi, Ce and Ti Zr. Nb and Ta. This doping also makes it possible to facilitate the deposition of the intermediate layer when it is produced by sputtering, in particular assisted by a magnetic field (a process commonly known as a "magnetron"). The atoms of Al and Sb, in particular Sb are preferred because the ionic radius of the associated ions is close to that of the ions associated with the Sn and Zn atoms. The content of doping atoms is preferably between 0.5 and 5% by weight relative to the total amount of metal ion in the layer, in particular between 0.5 and 2%.
La couche à base de ZnO est de préférence une couche constituée de ZnO, notamment polycristallin et cristallisé sous sa forme hexagonale (structure de type Wurtzite). Il convient en effet de favoriser au maximum la cristallisation de ZnO sous cette forme pour améliorer la cristallisation des couches à base de nitrure de gallium sus-jacentes.The layer based on ZnO is preferably a layer consisting of ZnO, in particular polycrystalline and crystallized in its hexagonal form (Wurtzite type structure). It is indeed advisable to promote as much as possible the crystallization of ZnO in this form in order to improve the crystallization of the overlying gallium nitride layers.
Un matériau est dit « polycristallin » au sens de l'invention s'il est composé d'une pluralité de cristaux, donc s'il n'est pas un monocristal, indépendamment de l'orientation desdits cristaux (qui peut être identique pour chacun d'entre eux). De préférence, les cristaux de ZnO présentent une seule orientation, en particulier selon un axe c perpendiculaire à la surface principale du substrat.A material is said to be "polycrystalline" within the meaning of the invention if it is composed of a plurality of crystals, so if it is not a single crystal, regardless of the orientation of said crystals (which may be identical for each of them). Preferably, the ZnO crystals have a single orientation, in particular along an axis c perpendicular to the main surface of the substrate.
La couche à base de ZnO peut être employée comme électrode transparente au sein de l'empilement de couches lorsque sa conductivité électronique est suffisante. A cet effet la couche à base de ZnO est de préférence une couche de ZnO ou une couche de ZnO dopée, notamment avec des atomes d'aluminium (Al), d'indium (In) ou de gallium (Ga), ce afin d'augmenter sa conductivité électronique. Le dopage par du gallium est préféré au dopage par l'aluminium ou l'indium car ce dernier est susceptible de migrer au sein de la structure semi-conductrice à base de GaN, créant un risque de court-circuit. On peut ainsi créer un empilement déposé sur un matériau de support tel que défini précédemment (en particulier en verre à base de silice), ledit empilement comprenant une couche à base de ZnO (notamment de ZnO ou de ZnO dopé, par exemple Al, Ga ou In) servant de couche de croissance hétéroépitaxiale pour des couches à base de nitrure de gallium. La couche à base de ZnO peut être déposée directement sur le matériau de support ou sur une ou plusieurs sous-couches, par exemple la couche intermédiaire selon l'invention. Compte tenu de la transparence de la couche à base de ZnO, ce substrat est utilisable dans une structure de diode dite « flip-chip » (puce retournée) dans laquelle l'émission de lumière se fait du côté du substrat. La couche à base de ZnO présente alors trois fonctions distinctes : faciliter l'hétéroépitaxie, apporter le courant (via un contact ohmique) et permettre l'extraction de la lumière.The ZnO-based layer can be used as a transparent electrode within the layer stack when its electronic conductivity is sufficient. For this purpose, the ZnO-based layer is preferably a ZnO layer or a doped ZnO layer, in particular with aluminum (Al), indium (In) or gallium (Ga) atoms, in order to increase its electronic conductivity. Gallium doping is preferred to doping with aluminum or indium because the latter is likely to migrate within the GaN-based semiconductor structure, creating a risk of short-circuiting. It is thus possible to create a stack deposited on a support material as defined above (in particular silica-based glass), said stack comprising a layer based on ZnO (in particular doped ZnO or ZnO, for example Al, Ga or In) as a heteroepitaxial growth layer for gallium nitride-based layers. The ZnO-based layer may be deposited directly on the support material or on one or more sub-layers, for example the intermediate layer according to the invention. Given the transparency of the ZnO-based layer, this substrate can be used in a so-called "flip-chip" diode structure (flip-chip) in which light emission is on the side of the substrate. The ZnO-based layer then has three distinct functions: to facilitate heteroepitaxy, to bring current (via an ohmic contact) and to allow the extraction of light.
La couche à base de ZnO est avantageusement la dernière couche de l'empilement, donc la couche en contact avec l'atmosphère, dans la mesure où il est préférable que le nitrure de gallium soit ultérieurement déposé directement sur cette couche. Le substrat selon l'invention ne comprend de préférence pas de couche métallique telle qu'une couche d'argent ou une couche comprenant du nickel et/ou du chrome. Un substrat préféré consiste en un matériau de support en verre revêtu sur une seule de ses faces par un empilement comprenant une couche à base d'oxydes de zinc et d'étain et, déposée directement sur cette couche, une couche à base d'oxyde de zinc (notamment un couche en ZnO), une sous- couche faisant office de barrière à la migration des ions alcalins étant éventuellement disposée entre le matériau de support et la couche à base d'oxydes de zinc et d'étain et à leur contact direct.The ZnO-based layer is advantageously the last layer of the stack, and therefore the layer in contact with the atmosphere, insofar as it is preferable that the gallium nitride be subsequently deposited directly on this layer. The substrate according to the invention preferably does not comprise a metal layer such as a silver layer or a layer comprising nickel and / or chromium. A preferred substrate consists of a glass support material coated on one of its faces by a stack comprising a layer based on zinc oxides and tin and, deposited directly on this layer, an oxide-based layer. zinc (in particular a ZnO layer), a sub- layer acting as a barrier to the migration of alkaline ions being optionally disposed between the support material and the layer based on zinc oxides and tin and their direct contact.
L'épaisseur de la couche à base de ZnO (notamment constituée de ZnO) est de préférence comprise entre 10 et 500 nm. Il a été observé qu'une épaisseur relativement élevée favorisait une meilleure croissance ultérieure deThe thickness of the layer based on ZnO (in particular consisting of ZnO) is preferably between 10 and 500 nm. It has been observed that a relatively high thickness favors a better subsequent growth of
GaN, en augmentant notamment la taille des cristallites. L'épaisseur de la couche à base de ZnO est donc de préférence comprise entre 100 et 300 nm.GaN, notably by increasing the size of the crystallites. The thickness of the ZnO-based layer is therefore preferably between 100 and 300 nm.
L'épaisseur de la couche intermédiaire est de préférence comprise entre 2 et 100 nm, notamment entre 10 et 50 nm, voire entre 20 et 30 nm. De telles épaisseurs favorisent la croissance cristalline de l'oxyde de zinc.The thickness of the intermediate layer is preferably between 2 and 100 nm, especially between 10 and 50 nm, or even between 20 and 30 nm. Such thicknesses promote crystal growth of zinc oxide.
Comme indiqué précédemment, l'invention a en partie pour objet le « substrat revêtu ». Ce substrat revêtu est un substrat selon l'invention, revêtu par une structure semi-conductrice du type Nl-N ou N-Vl. La structure semi-conductrice du type Nl-N comprend de préférence au moins une couche à base de InxGayAh-x-yN, où « x » et « y » varient de 0 à 1 , et notamment une couche à base de nitrure de gallium (GaN). Par « couche à base de GaN », on entend d'une manière générale toute couche comprenant du nitrure de gallium dopé (n ou p) ou non, donc une couche de formule générale InxGayAh-x-yN décrite ci-dessus, dans laquelle « y » est non-nul, et plus généralement supérieur à 0,5. Les couches à base de GaN peuvent être non-dopées, dopées n (par exemple par des atomes de Si, Ge, Se, Te...) ou p (par exemple dopé par des atomes de Mg, Zn, Ca, Sr, Ba...).As indicated above, the invention is partly concerned with the "coated substrate". This coated substrate is a substrate according to the invention, coated with a semiconductor structure of the Nl-N or N-Vl type. The Nl-N type semiconductor structure preferably comprises at least one layer based on In x Ga y Ah- x - y N, where "x" and "y" vary from 0 to 1, and in particular a layer with gallium nitride (GaN) base. By "GaN-based layer" is generally meant any layer comprising doped (n or p) gallium nitride, or not, therefore a layer of general formula InxGayAh-x-yN described above, in which "Y" is non-zero, and more generally greater than 0.5. The GaN-based layers may be undoped, n-doped (for example by Si, Ge, Se, Te, etc.) or p (for example doped with Mg, Zn, Ca, Sr, Ba ...).
La structure semi-conductrice du type Nl-N comprend de préférence au moins une couche de GaN dopé n (par exemple dopé par des atomes de Si, Ge, Se, Te...) et au moins une couche de GaN dopé p (par exemple dopé par des atomes de Mg, Zn, Ca, Sr, Ba...). La couche à base de ZnO est alors de préférence en contact direct avec la au moins une couche de GaN dopé n. Alternativement, une couche tampon à base de nitrure de gallium et/ou aluminium amorphe peut être disposée entre la couche à base de ZnO et la structure semi-conductrice. Une telle couche tampon est destinée à favoriser encore la cristallisation de la couche à base de GaN. La structure semi-conductrice du type N-Vl comprend de préférence au moins une couche à base de ZnO. Par « couche à base de ZnO », on entend toute couche contenant de l'oxyde de zinc, par exemple dopé n (à l'aide de Al, In...) ou p. La couche à base de ZnO du substrat selon l'invention peut en effet constituer une couche d'épitaxie idéale pour des structures semi-conductrices elles-mêmes à base de ZnO.The Nl-N type semiconductor structure preferably comprises at least one n-doped GaN layer (for example doped with Si, Ge, Se, Te atoms, etc.) and at least one p-doped GaN layer ( for example doped with atoms of Mg, Zn, Ca, Sr, Ba ...). The ZnO-based layer is then preferably in direct contact with the at least one n-doped GaN layer. Alternatively, a buffer layer based on gallium nitride and / or amorphous aluminum may be arranged between the ZnO-based layer and the semiconductor structure. Such a buffer layer is intended to further promote the crystallization of the GaN-based layer. The N-Vl type semiconductor structure preferably comprises at least one ZnO-based layer. By "ZnO-based layer" is meant any layer containing zinc oxide, for example doped n (using Al, In, etc.) or p. The ZnO-based layer of the substrate according to the invention can indeed constitute an epitaxial layer ideal for semiconductor structures themselves based on ZnO.
La structure semi-conductrice peut comprendre ou être constituée d'au moins une couche non-continue formée de nano-structures, comme des nanofils, ou des structures communément appelées sous leurs expressions anglaises « nano-rods », « nano-pillars », « nano-wires ». Ces structures se présentent généralement sous forme de fils ou de colonnes orientés selon un axe sensiblement perpendiculaire à la surface du substrat. Ces fils ou colonnes présentent de préférence un diamètre compris entre 50 et 500 nm, et une hauteur comprise entre 500 nm et 5 micromètres. Ces structures permettent d'améliorer le guidage de la lumière, en limitant au maximum les pertes de lumière sur les côtés de la diode. Ces structures permettent en outre de créer des effets de cavité, permettant l'amplification de la lumière.The semiconductor structure may comprise or consist of at least one non-continuous layer formed of nanostructures, such as nanowires, or structures commonly known by their English expressions "nano-rods", "nano-pillars", "Nano-wires". These structures are generally in the form of son or columns oriented along an axis substantially perpendicular to the surface of the substrate. These son or columns preferably have a diameter of between 50 and 500 nm, and a height of between 500 nm and 5 micrometers. These structures make it possible to improve the guiding of the light, limiting as much as possible the losses of light on the sides of the diode. These structures also make it possible to create cavity effects, allowing amplification of the light.
La couche à base de ZnO du substrat est de préférence en contact direct avec la au moins une couche à base de GaN ou à base de ZnO de cette structure semi-conductrice.The ZnO layer of the substrate is preferably in direct contact with the at least one GaN-based or ZnO-based layer of this semiconductor structure.
Le substrat selon l'invention, en particulier le substrat revêtu selon l'invention peut être employé pour la fabrication de diodes électroluminescentes. Ces diodes électroluminescentes peuvent par exemple être intégrées dans des systèmes laser et/ou être employées dans le domaine de l'éclairage (signalisation routière, éclairage routier, urbain ou intérieur, automobile), des écrans de visualisation, du stockage de données.The substrate according to the invention, in particular the coated substrate according to the invention can be used for the manufacture of light-emitting diodes. These light-emitting diodes may for example be integrated in laser systems and / or be used in the field of lighting (road signs, road lighting, urban or interior, automobile), display screens, data storage.
Lorsque le substrat revêtu est employé pour la fabrication de diodes électroluminescentes, la structure semi-conductrice est de préférence une hétérostructure au sens où elle comprend des hétérojonctions, c'est-à-dire des assemblages de semi-conducteurs de différentes compositions chimiques présentant des gaps énergétiques différents, et de préférence choisis parmi les composés purs ou alliages du type InxGayAh-x-yN, où x et y varient de O à 1. La variation des paramètres x et y permet d'influer directement sur le gap du semi- conducteur. Les structures obtenues sont généralement du type à simple puits quantique (SQW) ou à puits quantiques multiples. Les diodes ainsi produites peuvent émettre dans une large gamme du spectre électromagnétique couvrant le domaine de l'ultraviolet et du visible, et en particulier le domaine du bleu ou du vert. Couplées à des matières phosphorescentes, les diodes peuvent également permettre l'émission d'une lumière blanche.When the coated substrate is used for the manufacture of light-emitting diodes, the semiconductor structure is preferably a heterostructure in the sense that it comprises heterojunctions, that is to say assemblies of semiconductors of different chemical compositions having different energy gaps, and preferably selected from pure compounds or alloys of the InxGayAh-x-yN type, where x and y vary from 0 to 1. The variation of the parameters x and y makes it possible to directly influence the gap of the driver. The structures obtained are generally of the single quantum well (SQW) or multiple quantum well type. The diodes thus produced can emit in a wide range of the electromagnetic spectrum covering the field of ultraviolet and visible, and in particular the field of blue or green. Coupled with phosphorescent materials, the diodes can also allow the emission of white light.
Le substrat selon l'invention peut également servir de substrat à d'autres types de structures semi-conductrices que des diodes, par exemples à des structures de transistors, tels que transistors bipolaires, transistors à effet de champ (FET) notamment du type MESFET (Metal-Semiconductor Field Effect Transistor) ou HFET (Heterostructure Field Effect Transistor). Les transistors employant des structures semi-conductrices à base de GaN sont particulièrement intéressants dans des applications hyperfréquences (typiquement 5-50 GHz) et/ou de puissance (typiquement 50 W). Le caractère transparent de ces structures semi-conductrices permet également d'envisager des dispositifs électroniques transparents.The substrate according to the invention can also serve as a substrate for other types of semiconductor structures than diodes, for example transistor structures, such as bipolar transistors, field effect transistors (FETs) in particular of the MESFET type. (Metal Semiconductor Field Effect Transistor) or HFET (Heterostructure Field Effect Transistor). Transistors employing GaN-based semiconductor structures are of particular interest in microwave (typically 5-50 GHz) and / or power (typically 50 W) applications. The transparent nature of these semiconductor structures also makes it possible to envisage transparent electronic devices.
L'invention a aussi pour objet un procédé d'obtention du substrat selon l'invention, dans lequel on dépose par pulvérisation cathodique ladite au moins une couche à base d'oxyde de zinc et ladite au moins une couche intermédiaire. Le procédé de pulvérisation cathodique assisté par champ magnétique (procédé « magnétron ») est avantageusement employé. D'une manière préférée, l'ensemble des couches de l'empilement est déposé par cette technique, y compris par conséquent l'éventuelle sous-couche disposée entre le matériau de support et la couche intermédiaire. Le procédé de pulvérisation cathodique, notamment assisté par champ magnétique présente l'avantage de faire croître la couche à base d'oxyde de zinc selon l'axe c, permettant ainsi une croissance épitaxiale ultérieure de GaN selon ce même axe. Le procédé magnétron peut être du type réactif ou non.The subject of the invention is also a process for obtaining the substrate according to the invention, in which said at least one layer based on zinc oxide and said at least one intermediate layer are deposited by cathodic sputtering. The magnetic field assisted sputtering method ("magnetron" method) is advantageously employed. In a preferred manner, all the layers of the stack are deposited by this technique, including consequently the possible sub-layer disposed between the support material and the intermediate layer. The cathode sputtering method, in particular assisted by a magnetic field, has the advantage of growing the layer based on zinc oxide along the axis c, thus allowing a subsequent epitaxial growth of GaN along this same axis. The magnetron method may be of the reactive type or not.
L'étape de dépôt par pulvérisation cathodique de la couche intermédiaire permet d'obtenir une couche de préférence amorphe, pour les raisons évoquées précédemment.The step of deposition by sputtering of the intermediate layer makes it possible to obtain a layer that is preferably amorphous, for the reasons mentioned above.
Un procédé préféré consiste à déposer par procédé magnétron sur un matériau de support en verre une couche intermédiaire à base d'oxydes de zinc et d'étain telle que décrite précédemment puis une couche en oxyde de zinc. Lorsque le verre utilisé contient des ions alcalins, il est préférable de déposer, également par procédé magnétron, une sous-couche faisant office de barrière à la migration des ions alcalins telle que décrite précédemment, notamment une couche en SJsN4.A preferred method consists in depositing, by magnetron method on a glass support material, an intermediate layer based on oxides of zinc and tin as described above and then a layer of zinc oxide. When the glass used contains alkaline ions, it is preferable to deposit, also by magnetron method, an undercoating acting as a barrier to the migration of alkaline ions as described above, in particular a layer of SJsN 4 .
Ce dépôt est de préférence suivi d'un traitement thermique destiné à favoriser la cristallisation de la couche à base d'oxyde de zinc, car il est apparu qu'une meilleure cristallisation de la couche à base d'oxyde de zinc améliorait la cristallisation des couches sus-jacentes. Ce traitement thermique est généralement opéré à des températures comprises entre 200 et 11000C, notamment entre 200 et 7000C.This deposit is preferably followed by a heat treatment intended to promote the crystallization of the zinc oxide-based layer, since it has been found that a better crystallization of the zinc oxide-based layer improves the crystallization of the layers. overlying layers. This heat treatment is generally carried out at temperatures of between 200 and 1100 ° C., in particular between 200 and 700 ° C.
Alternativement ou cumulativement, une amélioration de la cristallisation de ZnO peut être obtenue en déposant la couche sur un substrat chaud, dont la température est notamment comprise entre 150 et 400°C, en particulier entre 200 et 3000C.Alternatively or cumulatively, an improvement in the crystallization of ZnO can be obtained by depositing the layer on a hot substrate, the temperature of which is in particular between 150 and 400 ° C., in particular between 200 and 300 ° C.
Il est également possible de soumettre une ou plusieurs des couches de l'empilement, en particulier la couche à base de ZnO, à l'action d'un faisceau d'ions, notamment un faisceau d'ions argon. Le faisceau d'ions est de préférence généré par un canon ionique ou une source ionique, qui peut avantageusement être positionné au sein même de l'enceinte de dépôt par pulvérisation cathodique. En fonction de la puissance, de l'angle d'incidence, de la divergence, il est possible de lisser la couche de ZnO (pour augmenter sa résistance chimique, notamment à l'ammoniac qui peut être employé lors de la croissance de GaN) ou au contraire de texturer la surface de ZnO pour favoriser une épitaxie latérale et ainsi réduire voire éliminer les dislocations.It is also possible to subject one or more of the layers of the stack, in particular the ZnO-based layer, to the action of an ion beam, in particular an argon ion beam. The ion beam is preferably generated by an ion gun or an ion source, which may advantageously be positioned within the cathode sputtering chamber itself. Depending on the power, the angle of incidence, the divergence, it is possible to smooth the ZnO layer (to increase its chemical resistance, especially to the ammonia that can be used during the growth of GaN) or on the contrary to texture the ZnO surface to promote lateral epitaxy and thus reduce or eliminate dislocations.
L'invention sera mieux comprise à l'aide des exemples de réalisation non-limitatifs qui suivent, illustrés par les Figures 1 à 4.The invention will be better understood with the aid of the nonlimiting exemplary embodiments which follow, illustrated by FIGS. 1 to 4.
Les Figures 1 et 2 sont une représentation schématique de substrats selon l'invention. Les Figures 3 et 4 sont des clichés de microscopie électronique à balayage pris sur la tranche d'échantillons décrits ci-après.Figures 1 and 2 are a schematic representation of substrates according to the invention. Figures 3 and 4 are scanning electron micrographs taken on the sample wafer described hereinafter.
La Figure 1 présente une coupe schématique d'un substrat préféré selon l'invention. Le substrat est composé d'un matériau de support 11 , revêtu par un empilement constitué d'une couche intermédiaire 12 revêtue d'une couche 13 à base de ZnO.Figure 1 shows a schematic section of a preferred substrate according to the invention. The substrate is composed of a support material 11, coated with a stack consisting of an intermediate layer 12 coated with a layer 13 based on ZnO.
La Figure 2 présente une coupe schématique d'un autre substrat préféré selon l'invention. Le substrat est composé d'un matériau de support 21 , revêtu par un empilement comprenant une couche 22 faisant office de barrière à la migration des ions alcalins déposée directement sur le matériau de support 21 , revêtue par une couche intermédiaire 23, elle-même revêtue d'une couche 23 à base de ZnO.Figure 2 shows a schematic section of another preferred substrate according to the invention. The substrate is composed of a support material 21, coated by a stack comprising a layer 22 acting as a barrier to the migration of alkaline ions deposited directly on the support material 21, coated by an intermediate layer 23, itself coated. a layer 23 based on ZnO.
Pour les substrats des figures 1 et 2, le matériau de support et les diverses couches de l'empilement sont tels que décrits dans la partie générale de la description. De préférence, le matériau de support est en verre, notamment du type destiné à la fabrication d'écrans plasma. La couche intermédiaire est avantageusement à base d'oxydes de zinc et d'étain, en particulier dopé Al ou Sb. La couche à base de ZnO est de préférence une couche en ZnO. La couche optionnelle faisant office de barrière à la migration des ions alcalins est avantageusement une couche en Si3N4.For the substrates of FIGS. 1 and 2, the support material and the various layers of the stack are as described in the general part of the description. Preferably, the support material is made of glass, in particular of the type intended for the manufacture of plasma screens. The intermediate layer is advantageously based on zinc and tin oxides, in particular doped with Al or Sb. The ZnO layer is preferably a ZnO layer. The optional layer serving as a barrier to the migration of alkaline ions is advantageously a layer of Si 3 N 4 .
EXEMPLES COMPARATIFSCOMPARATIVE EXAMPLES
Le substrat selon l'exemple comparatif est constitué par un matériau de support en verre revêtu d'une sous-couche en Si3N4 faisant office de barrière à la migration des ions alcalins et d'une couche d'oxyde de zinc.The substrate according to the comparative example consists of a glass support material coated with a sub-layer of Si 3 N 4 acting as a barrier to the migration of alkaline ions and a zinc oxide layer.
L'empilement est le suivant, les épaisseurs géométriques étant indiquées entre parenthèses :The stack is as follows, the geometric thicknesses being indicated in parentheses:
Verre / Si3N4 (20 nm) / ZnO (200 nm)Glass / Si 3 N 4 (20 nm) / ZnO (200 nm)
Le verre employé est un verre destiné à la fabrication d'écrans plasma tel que décrit dans la demande de brevet WO 98/40320.The glass used is a glass intended for the manufacture of plasma screens as described in the patent application WO 98/40320.
Cet empilement est déposé par procédé magnétron. La couche de Si3N4 est déposée à l'aide d'une cible de silicium alimentée par une puissance deThis stack is deposited by magnetron method. The Si 3 N 4 layer is deposited using a silicon target powered by a power of
5kW à 100 kHz. La pression est de 2,5 microbars et le gaz plasmagène est un mélange d'argon (débit de 40 sccm, centimètres-cube standard par minute) et d'azote (débit de 58 sccm). Le dépôt de la couche de ZnO met en œuvre une cible de zinc portée à une tension de 290 V à 50 kHz, sous une pression de 2 microbars et un mélange d'argon (40 sccm) et d'oxygène (18 sccm).5kW at 100 kHz. The pressure is 2.5 microbars and the plasma gas is a mixture of argon (flow rate of 40 sccm, standard cubic centimeters per minute) and nitrogen (flow rate of 58 sccm). The deposition of the ZnO layer implements a Zinc target raised to a voltage of 290 V at 50 kHz, under a pressure of 2 microbars and a mixture of argon (40 sccm) and oxygen (18 sccm).
Le dépôt par procédé magnétron de chacune de ces couches est par ailleurs bien connu de l'homme du métier, et les détails du dépôt (cible utilisée, pression, gaz etc ..) n'influent pas de manière significative sur les résultats.The magnetron deposition of each of these layers is, moreover, well known to those skilled in the art, and the details of the deposition (target used, pressure, gas, etc.) do not significantly influence the results.
Ce substrat est ensuite revêtu de manière connue d'une couche de GaN de 80 nm d'épaisseur (exemple noté C1 ) ou 200 nm d'épaisseur (exemple noté C2), par le procédé RPCVD (Remote Plasma Chemical Vapor Déposition, dépôt chimique en phase vapeur assisté par un plasma déporté). Tout autre type de procédé de dépôt compatible en termes de température de dépôt avec la nature du substrat utilisé est bien entendu possible, sans influer de manière significative sur les résultats.This substrate is then coated in a known manner with a layer of GaN 80 nm thick (example noted C1) or 200 nm thick (example noted C2), by the method RPCVD (Remote Plasma Chemical Vapor Deposition, chemical deposition vapor phase assisted by a remote plasma). Any other type of deposition process compatible in terms of deposition temperature with the nature of the substrate used is of course possible, without significantly affecting the results.
EXEMPLES SELON L'INVENTIONEXAMPLES ACCORDING TO THE INVENTION
Les exemples selon l'invention se distinguent de l'exemple comparatif en ce qu'une couche d'oxyde mixte de zinc et d'étain dopée à l'antimoine (Sb) est déposée entre la sous-couche en Si3N4 et la couche d'oxyde de zinc, toujours par procédé magnétron. Le dépôt de la couche de SnZnO met en œuvre une cible formée d'un alliage d'étain et de zinc dopé à l'antimoine, une puissance de 2kW et une fréquence de 50 kHz, une pression de 2 microbars et un mélange d'argon (12 sccm) et d'oxygène (45 sccm).The examples according to the invention are distinguished from the comparative example in that a layer of mixed zinc oxide and antimony-doped tin (Sb) is deposited between the Si 3 N 4 underlayer and the zinc oxide layer, still by magnetron process. The deposition of the SnZnO layer uses a target formed of an alloy of tin and zinc doped with antimony, a power of 2kW and a frequency of 50 kHz, a pressure of 2 microbars and a mixture of argon (12 sccm) and oxygen (45 sccm).
La couche d'oxyde mixte comprend approximativement en poids de métaux 65% de Sn, 34% de Zn et 1 % de Sb.The mixed oxide layer comprises approximately by weight of metals 65% Sn, 34% Zn and 1% Sb.
Les différents exemples selon l'invention se différencient par les épaisseurs de la couche de ZnO et de la couche d'oxydes de zinc et d'étain.The different examples according to the invention are distinguished by the thicknesses of the ZnO layer and the zinc oxide and tin oxide layer.
Le tableau 1 reproduit les épaisseurs de ces couches pour chacun des exemples 1 à 4 selon l'invention. Tableau 1Table 1 reproduces the thicknesses of these layers for each of Examples 1 to 4 according to the invention. Table 1
EFFETS SUR LA CRISTALLISATIONEFFECTS ON CRYSTALLIZATION
L'effet de l'invention sur la cristallisation de la couche à base de GaN a été étudié par différentes méthodes.The effect of the invention on the crystallization of the GaN-based layer has been studied by various methods.
Selon une première méthode, l'orientation des cristaux de GaN a été comparée en mesurant l'aire de pics de diffraction associés au GaN dans un diagramme de diffraction des rayons X.According to a first method, the orientation of the GaN crystals was compared by measuring the area of diffraction peaks associated with GaN in an X-ray diffraction pattern.
La diffraction des rayons X est réalisée en configuration Θ/2Θ. Compte tenu de la faible différence de paramètres de maille entre ZnO et GaN, leurs pics se recouvrent en partie, nécessitant un traitement mathématique pour les séparer. Ce traitement mathématique est en particulier basé sur les caractéristiques de diffraction de la couche de ZnO seule, mesurées avant le dépôt de GaN.X-ray diffraction is performed in Θ / 2Θ configuration. Given the small difference in mesh parameters between ZnO and GaN, their peaks overlap in part, requiring a mathematical treatment to separate them. This mathematical treatment is in particular based on the diffraction characteristics of the ZnO layer alone, measured before GaN deposition.
Le tableau 2 indique en unités arbitraires l'aire du pic de diffraction associé au plan cristallographique (0002), qui correspond à une orientation des cristaux selon l'axe c.Table 2 indicates in arbitrary units the area of the diffraction peak associated with the crystallographic plane (0002), which corresponds to an orientation of the crystals along the axis c.
Tableau 2Table 2
Ces résultats traduisent une très forte amélioration de l'orientation de GaN selon l'axe c grâce à l'ajout de la couche intermédiaire. Selon une deuxième méthode, l'orientation des cristaux de GaN a été comparée par observation directe en microscopie électronique à balayage.These results show a very strong improvement in the orientation of GaN along the axis c by adding the intermediate layer. In a second method, the orientation of the GaN crystals was compared by direct observation by scanning electron microscopy.
Les figures 3 et 4 sont des clichés, respectivement des exemples C2 et 1 , pris en microscopie électronique à balayage à grossissement 100000. Les clichés sont pris sur la tranche, permettant ainsi de visualiser l'empilement ZnO/GaN.FIGS. 3 and 4 are clichés, respectively examples C2 and 1, taken by scanning electron microscopy at a magnification of 100,000. The images are taken on the wafer, thus making it possible to visualize the ZnO / GaN stack.
En figure 3, les cristaux hexagonaux de GaN on tendance à croître selon leur axe c, mais la direction de l'axe n'est pas parfaitement perpendiculaire au substrat.In Figure 3, the hexagonal crystals of GaN tend to grow along their axis c, but the direction of the axis is not perfectly perpendicular to the substrate.
En figure 4 en revanche, la direction de croissance des cristaux de GaN est parfaitement perpendiculaire au substrat, donc moins exempte de défauts.In FIG. 4, on the other hand, the direction of growth of the GaN crystals is perfectly perpendicular to the substrate, and therefore less free of defects.
Selon une troisième méthode, la résistivité électrique globale de l'empilement a été évaluée de manière connue à l'aide de la méthode 4-pointes ou méthode de Van der Pauw.According to a third method, the overall electrical resistivity of the stack has been evaluated in a known manner by means of the 4-point method or Van der Pauw method.
Le tableau 3 indique les valeurs obtenues pour les exemples C1 , 3 et 4.Table 3 gives the values obtained for examples C1, 3 and 4.
Tableau 3Table 3
La chute de résistivité due à l'ajout de la couche intermédiaire correspond à une augmentation très importante de la conductivité électronique, traduisant une quantité moins grande de défauts de structure.The resistivity drop due to the addition of the intermediate layer corresponds to a very large increase in the electronic conductivity, reflecting a smaller amount of structural defects.
L'interposition dans le substrat selon l'invention de la couche intermédiaire entre le matériau de support et la couche d'oxyde de zinc permet par conséquent d'améliorer les caractéristiques cristallines de la couche de nitrure de gallium ainsi que d'augmenter sa conductivité électronique. Il en résulte une augmentation de l'intensité d'émission et de la durée de vie des diodes électroluminescentes utilisant ces substrats. The interposition in the substrate according to the invention of the intermediate layer between the support material and the zinc oxide layer therefore makes it possible to improve the crystalline characteristics of the gallium nitride layer and to increase its conductivity. electronic. This results in an increase in the emission intensity and the lifetime of the light-emitting diodes using these substrates.

Claims

REVENDICATIONS
1. Substrat utilisable comme substrat pour la croissance épitaxiale de couches à base de nitrure de gallium et comprenant un matériau de support (11 , 21 ) revêtu sur au moins une des ses faces par au moins un empilement de couches comprenant au moins une couche à base d'oxyde de zinc (13, 24), ledit substrat étant revêtu par une structure semi-conductrice du type Nl-N ou N-Vl, caractérisé en ce qu'entre le matériau support (11 , 21 ) et ladite au moins une couche à base d'oxyde de zinc (13, 24) est disposée au moins une couche intermédiaire (12, 23) comprenant des oxydes d'au moins deux éléments choisis parmi l'étain (Sn), le zinc (Zn), l'indium (In), le gallium (Ga), l'antimoine (Sb).1. Substrate usable as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material (11, 21) coated on at least one of its faces by at least one stack of layers comprising at least one layer with zinc oxide base (13, 24), said substrate being coated with a Nl-N or N-VI type semiconductor structure, characterized in that between the support material (11, 21) and said at least one a layer based on zinc oxide (13, 24) is disposed at least one intermediate layer (12, 23) comprising oxides of at least two elements selected from tin (Sn), zinc (Zn), indium (In), gallium (Ga), antimony (Sb).
2. Substrat utilisable comme substrat pour la croissance épitaxiale de couches à base de nitrure de gallium et comprenant un matériau de support (11 , 21 ) revêtu sur au moins une des ses faces par au moins un empilement de couches comprenant au moins une couche à base d'oxyde de zinc (13, 24), caractérisé en ce qu'entre le matériau support (11 , 21 ) et ladite au moins une couche à base d'oxyde de zinc (13, 24) est disposée au moins une couche intermédiaire (12, 23) comprenant des oxydes d'au moins deux éléments choisis parmi l'étain (Sn), le zinc (Zn), le gallium (Ga), l'antimoine (Sb).2. Substrate usable as a substrate for the epitaxial growth of gallium nitride-based layers and comprising a support material (11, 21) coated on at least one of its faces by at least one stack of layers comprising at least one layer with zinc oxide base (13, 24), characterized in that between the support material (11, 21) and said at least one layer of zinc oxide (13, 24) is arranged at least one layer intermediate (12, 23) comprising oxides of at least two elements selected from tin (Sn), zinc (Zn), gallium (Ga), antimony (Sb).
3. Substrat selon l'une des revendications précédentes, tel que le matériau de support (11 , 21 ) est revêtu sur une seule de ses faces et l'empilement comprend une seule couche (13, 24) à base d'oxyde de zinc et/ou une seule couche intermédiaire (12, 23).3. Substrate according to one of the preceding claims, such that the support material (11, 21) is coated on one of its faces and the stack comprises a single layer (13, 24) based on zinc oxide. and / or a single intermediate layer (12, 23).
4. Substrat selon l'une des revendications précédentes, tel que le matériau de support (11 , 21 ) est un matériau choisi parmi le saphir, le carbure de silicium, le silicium, un métal tel que le cuivre, le quartz, l'oxyde de zinc (ZnO), les spinelles telles que MgAI2O4, LiGaO2, ou encore un matériau vitreux ou amorphe, tel que le verre de silice ou un verre à base de silice. 4. Substrate according to one of the preceding claims, such that the support material (11, 21) is a material chosen from sapphire, silicon carbide, silicon, a metal such as copper, quartz, zinc oxide (ZnO), spinels such as MgAl 2 O 4 , LiGaO 2 , or a vitreous or amorphous material, such as silica glass or a silica-based glass.
5. Substrat selon la revendication précédente, tel que le matériau de support (11 , 21 ) est en verre à base de silice dont la température inférieure de recuit est supérieure ou égale à 5500C, voire 6000C ou même 650°C ou 7000C.5. Substrate according to the preceding claim, such that the support material (11, 21) is silica-based glass whose lower annealing temperature is greater than or equal to 550 0 C, or 600 0 C or even 650 ° C or 700 ° C.
6. Substrat selon l'une des revendications précédentes, tel qu'au moins une sous-couche (22) est disposée entre le matériau de support (21 ) et la couche intermédiaire (23).6. Substrate according to one of the preceding claims, such that at least one underlayer (22) is disposed between the support material (21) and the intermediate layer (23).
7. Substrat selon la revendication précédente, tel que la sous-couche (22) est une sous-couche faisant office de barrière à la migration des ions alcalins, notamment constituée des matériaux suivants, ou à base d'une des matériaux suivants, ou de l'un quelconque de leurs mélanges : SiOC, Si3N4, SiO2, TiN, AI2O3.7. Substrate according to the preceding claim, such that the underlayer (22) is an underlayer acting as a barrier to the migration of alkaline ions, in particular consisting of the following materials, or based on one of the following materials, or of any of their mixtures: SiOC, Si 3 N 4 , SiO 2 , TiN, Al 2 O 3 .
8. Substrat selon l'une des revendications précédentes, tel que la couche intermédiaire (12, 23) est disposée en contact direct sous la couche à base d'oxyde de zinc (13, 24). 8. Substrate according to one of the preceding claims, such that the intermediate layer (12, 23) is disposed in direct contact under the zinc oxide-based layer (13, 24).
9. Substrat selon l'une des revendications précédentes, tel que la couche intermédiaire (12, 23) est amorphe avant le dépôt de la couche à base d'oxyde de zinc (13, 24).9. Substrate according to one of the preceding claims, such that the intermediate layer (12, 23) is amorphous before the deposition of the zinc oxide layer (13, 24).
10. Substrat selon l'une des revendications précédentes, tel que la couche intermédiaire (12, 23) est une couche à base d'oxydes de zinc et d'étain. 10. Substrate according to one of the preceding claims, such that the intermediate layer (12, 23) is a layer based on zinc oxides and tin.
11. Substrat selon la revendication précédente, tel que la couche (12, 23) à base d'oxydes de zinc et d'étain est dopée par au moins un atome choisi parmi Al, Ga, In, B, Y, La, Ge, Si, P, As, Sb, Bi, Ce, Ti Zr, Nb et Ta.11. Substrate according to the preceding claim, such that the layer (12, 23) based on zinc oxides and tin is doped with at least one atom selected from Al, Ga, In, B, Y, La, Ge , Si, P, As, Sb, Bi, Ce, Ti Zr, Nb and Ta.
12. Substrat selon l'une des revendications précédentes, tel que la couche à base d'oxyde de zinc (13, 24) est une couche constituée d'oxyde de zinc, notamment polycristallin et cristallisé sous sa forme hexagonale, dans une structure de type Wurtzite.12. Substrate according to one of the preceding claims, such that the layer based on zinc oxide (13, 24) is a layer consisting of zinc oxide, in particular polycrystalline and crystallized in its hexagonal form, in a structure of Wurtzite type.
13. Substrat selon l'une des revendications 2 à 12, tel que la couche à base d'oxyde de zinc (13, 24) est la dernière couche de l'empilement.13. Substrate according to one of claims 2 to 12, such that the layer based on zinc oxide (13, 24) is the last layer of the stack.
14. Substrat selon l'une des revendications précédentes, tel que l'épaisseur de la couche à base d'oxyde de zinc (13, 24) est comprise entre 10 et 500 nm, notamment entre 100 et 300 nm. 14. Substrate according to one of the preceding claims, such that the thickness of the layer based on zinc oxide (13, 24) is between 10 and 500 nm, especially between 100 and 300 nm.
15. Substrat selon l'une des revendications précédentes, tel que l'épaisseur de la couche intermédiaire (12, 23) est comprise entre 2 et 100 nm, notamment entre 10 et 50 nm, voire entre 20 et 30 nm.15. Substrate according to one of the preceding claims, such that the thickness of the intermediate layer (12, 23) is between 2 and 100 nm, especially between 10 and 50 nm, or even between 20 and 30 nm.
16. Substrat selon l'une des revendications 2 à 15, revêtu par une structure semi-conductrice du type Nl-N ou N-Vl.16. Substrate according to one of claims 2 to 15, coated with a semiconductor structure of the type Nl-N or N-Vl.
17. Substrat selon la revendication précédente ou selon la revendication 1 , tel que la structure semi-conductrice du type Nl-N comprend au moins une couche à base de nitrure de gallium (GaN).17. Substrate according to the preceding claim or according to claim 1, such that the Nl-N type semiconductor structure comprises at least one layer based on gallium nitride (GaN).
18. Substrat selon la revendication 16 ou selon la revendication 1 , tel que la structure semi-conductrice du type N-Vl comprend au moins une couche à base d'oxyde de zinc (ZnO).18. Substrate according to claim 16 or claim 1, such that the N-VI type semiconductor structure comprises at least one layer based on zinc oxide (ZnO).
19. Substrat selon les revendications 1 ou 16 à 18, tel que la structure semi-conductrice comprend ou est constituée d'au moins une couche non- continue formée de nano-structures. Substrate according to claims 1 or 16 to 18, such that the semiconductor structure comprises or consists of at least one noncontinuous layer formed of nano-structures.
20. Procédé d'obtention d'un substrat selon l'une des revendications précédentes, dans lequel on dépose par pulvérisation cathodique ladite au moins une couche à base d'oxyde de zinc (13, 24) et ladite au moins une couche intermédiaire (12, 23). Method for obtaining a substrate according to one of the preceding claims, in which said at least one zinc oxide-based layer (13, 24) and said at least one intermediate layer are deposited by cathodic sputtering ( 12, 23).
21. Procédé selon la revendication précédente, tel que l'étape de dépôt de la couche intermédiaire (12, 23) permet d'obtenir une couche amorphe. 21. Method according to the preceding claim, such that the deposition step of the intermediate layer (12, 23) makes it possible to obtain an amorphous layer.
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JP5102357B2 (en) 2012-12-19
JP2010533371A (en) 2010-10-21
FR2918791A1 (en) 2009-01-16
FR2918791B1 (en) 2009-12-04
US20100207116A1 (en) 2010-08-19
WO2009013425A3 (en) 2009-03-12
US8278656B2 (en) 2012-10-02
WO2009013425A2 (en) 2009-01-29
KR20100048995A (en) 2010-05-11

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