WO2000068981A1 - Procede de croissance d'une couche d'oxyde de silicium de faible epaisseur sur une surface de substrat de silicium et machine a deux reacteurs - Google Patents
Procede de croissance d'une couche d'oxyde de silicium de faible epaisseur sur une surface de substrat de silicium et machine a deux reacteurs Download PDFInfo
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- WO2000068981A1 WO2000068981A1 PCT/FR2000/001181 FR0001181W WO0068981A1 WO 2000068981 A1 WO2000068981 A1 WO 2000068981A1 FR 0001181 W FR0001181 W FR 0001181W WO 0068981 A1 WO0068981 A1 WO 0068981A1
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- ions
- silicon substrate
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- silicon
- oxide
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- 239000000758 substrate Substances 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 64
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 99
- -1 oxygen ions Chemical class 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 229910008045 Si-Si Inorganic materials 0.000 claims abstract description 4
- 229910006411 Si—Si Inorganic materials 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 14
- 230000003993 interaction Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 21
- 238000000605 extraction Methods 0.000 description 10
- 238000010884 ion-beam technique Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007737 ion beam deposition Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/002—Controlling or regulating
-
- 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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02046—Dry cleaning only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
- H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/511—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures
- H01L29/513—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures the variation being perpendicular to the channel plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02301—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment in-situ cleaning
Definitions
- the invention relates to a method for growing a thin layer of silicon oxide on a surface of a silicon substrate, such a layer being in particular capable of forming a diffusion barrier of refractory oxides for integrated electronic components.
- the invention applies to the field of microelectronics on silicon substrate for the manufacture of integrated circuits and memories with very high integration density, and more specifically to electronic components integrated into such circuits or memories, such as diodes or transistors, which involve active interfaces between a silicon substrate and insulating oxides.
- a MOS type transistor is, as illustrated in section in FIG. 1, in the form of a monocrystalline silicon substrate 10, conventionally cut along the crystallographic plane 100.
- This substrate comprises two strongly doped zones n + , constituting two electrodes, the source 11 and the drain 12, limited by two terminals 15 and 16 formed by thick layers of Si0 2 , with a thickness of the order of 1 to 3 ⁇ m, and called “field oxides "
- the substrate 10 is surmounted by a grid 20 which has a surface 14 in contact with the substrate.
- the lower part of the grid consists of an oxide layer forming the grid oxide 30.
- the source, the drain and the grid form three poles.
- the source and the drain are coated with metallic contact blades 40, generally made of aluminum, completing the Metal - Semiconductor Oxide structure (or in short MOS) of the transistor.
- a current flows in an active portion 13 of the substrate, called “Channel”, located between the source and the drain and facing the surface 14 of the gate 20.
- This current is controlled by the polarity of the gate which, with the channel 13, constitutes the faces of a capacitor.
- the capacity of this capacitor is proportional to the relative dielectric constant of the insulator formed between them by the gate oxide (relative dielectric constant " ⁇ r " equal to 4.4 for Si0 2 ).
- the gate oxide and the field oxide are conventionally produced by thermal oxidation at high temperature, of the order of 900 to 1000 ° C. Since the accuracy of the measurements must be better than a tenth of the thickness of the layers, the thickness of the grid oxide is more difficult to control: with a grid oxide of thickness approximately equal to 25 ⁇ , the control of thickness should be more precise than ⁇ 1.25 ⁇ , which in fact constitutes the limit of what it is possible to achieve industrially with current processes.
- IBD ion bombardment deposition under oxidizing conditions
- an object of the invention is to form a thin layer of silica of constant thickness and less than 10 ⁇ on the surface of the silicon, without this layer having any structural defects of the “pinhole” type. .
- Such a thin layer can then serve as an effective diffusion barrier of refractory oxides to look at the active surface of the silicon substrate by prohibiting any interactive contact with the silicon substrate.
- a process for the treatment of silicon surface by remote ion interaction has been described in French patent application FR 2 757 881.
- the purpose of this process is to treat said surface to clean it and form a layer of a compound therein. insulating. However, it implements the interaction between highly charged ions (for example Argon Ar 17+ or Ar 18+ ions) and a silicon surface along the crystallographic plane 111.
- highly charged ions for example Argon Ar 17+ or Ar 18+ ions
- an orientation silicon substrate 100 has connections which are substantially more difficult to oxidize than a section of orientation 111 silicon.
- the highly charged ions create electrostatic charges in the Si0 2 and weaken the Si-0 bonds: agglomerates of Si0 2 will burst by a "Coulomb explosion" effect.
- the formation of craters created by the Coulomb explosion effect is not very compatible with the deposition of a refractory oxide on such a surface.
- the invention provides a method of growing a layer of thin silicon oxide less than 10 ⁇ on the surface of a silicon substrate oriented along the plane 100, said layer being in particular suitable for form a diffusion barrier of refractory oxides for integrated electronic components, the method consisting in cleaning said silicon surface, in producing vacuum weakly charged oxidizing ions, in directing these ions towards said surface while controlling their kinetic energy so that their speed is substantially zero when approaching said surface, so as to causing an opening of Si-Si bonds on said surface and filling these bonds with oxygen ions, the silicon substrate being maintained at a temperature below 500 ° C.
- the process performs an oxidation in two phases, a first rapid phase of formation of a monolayer of Si0 2 , by saturation of the pendant bonds with oxygen ions, then a phase of slow oxidation of silicon by the oxidizing ions through the monolayer forming a screen, with a low oxidation speed, which tends asymptotically towards zero, but homogeneous over the entire surface.
- a homogeneous and slow oxidation makes it possible to control the thickness of the layer with precision.
- the silicon substrate is cleaned beforehand by vacuum etching of the native oxide formed on the substrate.
- This cleaning can be carried out by a process of reactive ion etching type, known to those skilled in the art (abbreviated RIE, initials of Reactive Ionic Etching in English terminology). Then, the process is checked under vacuum using the following parameters:
- the oxidizing ions are 0 + ions
- the source produces ions whose kinetic energy is a few keV / q (q being the number of charges per ion), generally from 1 to 20 keV / q, and the values of the extraction voltages are of the order a few kilovolts; the density of the ion beam at the level of the interaction with the substrate is between 10 12 and 10 14 ⁇ ons / cm 2 .s;
- a fine selection of the ions in speed and in direction is carried out by filtering means of bandpass or highpass type with electric field, which selects the ions according to their kinetic energy, coupled to collimation means, which eliminate ions whose lateral velocity is greater than a certain threshold, constituted for example by a series of diaphragms of the order of a millimeter in diameter.
- the invention provides a method of growing a thin layer of silicon oxide on the surface of a silicon substrate oriented along the plane 100, consisting in completing a step of cleaning said surface with a passivation stage of this surface using a hydrogenation forming a monolayer of hydrogen, to produce under vacuum ions of a rare gas moderately and uniformly charged, the charge per ion being taken in the interval varying between +1 and +14 , and to direct them towards said surface while controlling their kinetic energy so that their speed is substantially zero when approaching said surface, so as to cause an opening of the pendant Si-H bonds at said surface, and to introduce under vacuum oxygen gas controlled in pressure so as to fill the open bonds, the silicon substrate being maintained at a temperature below 500 ° C.
- the hydrogenation can be carried out using a hydrofluoric acid and ammonium ion bath.
- the passivation thus obtained is of the type used by the company BELL TELEPHONE Inc.
- This process is self-stopping because the phase of opening of the bonds on the hydrogen monolayer is self-stopping. Indeed, the electrostatic charges generated by the continuous supply of new ions are neutralized by electrons from the semiconductor substrate. Then, the oxidation layer can only form on the pendant bonds from the hydrogen monolayer.
- the production of the thin layer of Si0 2 is controlled by the following parameters: production of ions by application of an extraction voltage at the output of an ion source, control of the ions in the direction by magnetic sorting as a function of the mass / charge ratio, then deceleration of these ions when approaching the silicon surface by the application of a deceleration voltage;
- the source produces ions of kinetic energy of a few keV / q (q being the number of charges per ion), generally from 1 to 20 keV / q; the density of incident ions at the interaction level is between 10 12 and 10 14 ions / cm 2 , s;
- means for fine selection of the ions in terms of speed and direction are constituted by a bandpass or high-pass type filter with an electric field, which selects the ions according to their kinetic energy, coupled to collimation means, which remove ions whose lateral velocity is above a certain threshold;
- the collimation means consist of a series of diaphragms of the order of a millimeter in diameter; the values of the extraction and deceleration voltages are of the order of a few kV;
- the process is controlled by the charge of the selected ions, the density of these ions at the level of the interaction, and the temperature of the substrate.
- a device for controlling the position of the ion beam is arranged in the path of the beam;
- the ions are rare gas ions, in particular Argon ions whose uniform charge is broadly between +1 and +14; -
- the silicon substrate is maintained under vacuum to receive a deposit of refractory oxide according to known methods.
- the invention also relates to a three-chamber machine for producing a grid of integrated electronic component, implementing the method of the invention.
- a machine has an entry airlock that can be used, if necessary, as an RIE vacuum etching enclosure. Etching can also be carried out in another reaction chamber.
- the airlock serves as an inlet to a first reactor, dedicated to producing the thin layer of Si0 2 , and for transferring the silicon substrate thus oxidized from the first reactor to a second reactor dedicated to the deposition of the refractory metal oxide. This deposition is carried out by conventional sputtering means or by IBD.
- FIG. 2 a sectional view of a MOS type transistor whose gate oxide consists of a thin layer of Si0 2 , formed according to the method of the invention, and a thicker layer d 'refractory metal oxide;
- FIG. 3 a graph of the growth in the thickness of the layer of Si0 2 as a function of time according to a preferential oxidation process of the invention;
- FIG. 5 the block diagram of a machine with two reactors for producing a grid of integrated electronic component, implementing the method of one invention.
- the MOS transistor illustrated in FIG. 2 comprises, in addition to the field oxide, the source, the drain and the channel of the silicon substrate already represented in FIG. 1 with the same reference signs, a grid 21.
- This grid generally made of polycrystallm silicon, according to the invention comprises a thin layer 31 of S ⁇ 0 2 , of equal thickness to about 5 ⁇ in the illustrated example, underlying a a layer 32 of titanium oxide T ⁇ 0 2 , of thickness equal to approximately 20 ⁇ .
- the thin layer of S ⁇ 0 2 produced according to the preferred method of the invention, has a surface condition with a very low roughness, and a substantially constant thickness due to the homogeneity of oxidation obtained in accordance with the invention.
- the silicon substrate 100 is firstly etched in a bath of hydrofluoric acid. This pickling is followed by rinsing with deionized water by permutation.
- the substrate is placed in a vacuum reactor pushes between 10 "8 and 10 " 11 mbar by known pumping means.
- the native oxide which could remain on the substrate is severe by RIE etching in a vacuum enclosure, well known to those skilled in the art, then, without breaking the vacuum chain, the substrate is introduced into the reactor to proceed to the growth of the actual thin oxide layer.
- This reactor is equipped with an ion beam source
- An ion source can be an electron cyclotron resonance type source
- ECR initials of Electron Cyclotron Resonance in English terminology
- the ions being confined in a plasma heated by radiofrequency waves.
- the source produces ions with low kinetic energy, of a few keV / q (q being the number of charges per ion), generally from 1 to 20 keV / q, 10 keV / q in the example of implementation.
- the kinetic energy of extraction is regulated by applying an extraction voltage, which is equal to 10 kV in the present case.
- the source setting parameters are further adjusted to provide the desired ion flow rate.
- the dimensions of the extracted ion beam are also adjusted by appropriate means, known to those skilled in the art, to define, with the flow rate, the density of the ion beam at the level of the substrate, that is to say a - say the number of ions per unit of area and time.
- the extracted ions are sorted, according to their mass / charge ratio, by a sorting magnet associated with the source.
- a “scanner” analyzer in Anglo-Saxon denomination
- This scanner is formed of a wire, a grid or plates which collects the charges in two main and orthogonal directions, in order to allow a counting of the charges in these two directions. This counting then makes it possible to measure the intensity profiles and to identify the position of the beam.
- a light detector comprising such a scanner and to establish the intensity profile and the position of the beam from the number of photons emitted by the ions captured on the wire, the grid or the plates.
- the ions are more precisely selected by means of ion selection, consisting of:
- a series of diaphragms with a diameter of the order of a millimeter, arranged a few tens of centimeters from each other: these means eliminate the ions whose lateral velocity component, perpendicular to the general direction of the beam, is greater than a given value, corresponding here to a kinetic energy of 1 eV / q.
- the silicon substrate is maintained at a temperature below 500 ° C, of the order of 300 ° C for example, using a suitable heating system.
- An electric deceleration field slows down the ions as they approach the silicon surface until they reach kinetic energy close to zero.
- This electric field is produced in the middle of a flat capacitor formed by an electrode and the substrate between which a deceleration voltage is applied.
- This voltage adjusted by a potentiometer, is generally adjusted between 1 and 20 kV, 10 kV in our example, to give each ion 0 + an energy between a few eV / q and 0.
- the majority of the interactions of the ions with the substrate takes place at about ten Angstroms above the surface of the substrate.
- the density of the ions in the area where they interact with the surface is controlled by the flow of the ion source and by the dimensions of the beam in that area.
- the emission rate is adjusted by appropriate means known to those skilled in the art, and the beam is focused at the level of the interaction zone by means of unipolar electrostatic lenses or by the use of electric fields or magnetic.
- the reaction mechanism which occurs during this interaction is an extraction of electrons from the silicon surface, causing the opening of the Si-Si bonds to the surface of the treated surface, and therefore the formation of pendant bonds. These pendant bonds are then filled with 0 + ions to form a surface layer of Si0 2 . Heating the silicon substrate facilitates the opening of the connections, the formation of the pending connections and the filling of these connections.
- the oxidation of the silicon substrate takes place in two phases, as illustrated diagrammatically in FIG. 3 by the growth curve over time t of the thickness e of oxidized silicon:
- a first phase A up to point P o corresponding to rapid oxidation during t 0 (for example a few seconds), during which the surface silicon bonds open to form pendant bonds, filled with 0 + ions as explained above;
- the monolayer formed on the surface has a thickness e o , of approximately 3 to 5 ⁇ in the embodiment;
- P 0 values of e o and to
- shape of the asymptotic branch in phase B are directly dependent on the density of the ions, between 10 12 to 10 14 ⁇ ons / cm 2 .s, and on the temperature silicon, between 200 and 500 ° C.
- the 0 + ion beam has an intensity of 10 ⁇ A and a section of 1 cm 2 ;
- the density of incident ions is 6.10 13 ⁇ ons / cm 2 .s, which allows to oxidize 1 cm 2 of substrate after a duration of about 4 seconds;
- the temperature is taken equal to 300 ° C.
- the step of cleaning the silicon substrate is completed by a passivation step of the surface by hydrogenation using a bath of hydrofluoric acid and ammonium ions.
- the silicon surface is then covered with a single layer of hydrogen forming Si-H bonds.
- the presence of hydrogen on the surface delays the formation of the native oxide, which leaves sufficient time to introduce the substrate, after hydrogenation, into the reactor to carry out the oxidation.
- Means for the production of weakly or moderately expanded ions, for example Ar 8+ are provided in place of the means for producing 0 + ions in the reactor described above. The means for applying voltage, selecting ions, and temperature are retained.
- the Argon ions generated with an energy as low as that of the 0 + ions of the previous example, are directed towards the surface of the silicon substrate and decelerate on approaching this surface under the conditions described above.
- the applied deceleration voltage makes it possible to prevent any penetration or any contact of the ions with the silicon surface.
- the value of the deceleration voltage regulates the approach distance of the ions and the size of the electron extraction zone.
- Argon ions approaching the silicon surface extract electrons from the hydrogenated monolayer, causing the appearance of pendant hydrogen bonds.
- the Argon ions are then retroreflected by electrostatic repulsion due to the creation of positive electrostatic charges with respect to these ions during the extraction of the electrons.
- the oxidation is then done by introducing oxygen gas into the vacuum enclosure, under a partial pressure between 10 ⁇ 5 and 10 "9 mbar, equal to 10 " 7 mbar in the embodiment. Each time you open a hydrogen bonding, filling with oxygen is carried out under these pressure conditions. Heating the silicon substrate to 300 ° C facilitates oxidation.
- the phenomenon is self-stopping because the oxidation reaction slows down and stops by itself when there are no more hanging hydrogen bonds to be replaced by oxygen bonds on the surface. Indeed, as illustrated by FIG. 4, once a surface layer of S ⁇ 0 2 41 has been formed on the silicon substrate 40, the electrostatic charges generated by the arrival of new Argon Ar 8+ 42 ions are neutralized by the extraction of electrons 43 from deep layers of the silicon substrate 40. These electrons are transported through the surface layer 41 by an effect of the "tunnel effect" type.
- the layer of monomolecular S ⁇ 0 2 formed has a thickness of the order of 3 to 5 ⁇ .
- the control and the duration of the oxidation are regulated by the choice of the charge of the argon ions, +4 to +8, the density of these ions, preferably from 10 12 to 10 14 ions / cm 2 , the residual pressure and the temperature of the silicon substrate, between 200 and 500 ° C.
- the Ar +8 ion beam forms a current of intensity equal to 80 ⁇ A with a section of 1 cm 2 ; the density of incident ions is 6.10 13 ⁇ ons / cm 2 .s, which makes it possible to oxidize 1 cm 2 of substrate after a duration t of approximately 1 second; and
- the temperature is taken equal to 300 ° C.
- This airlock of the silicon substrate also ensures the transfer of the oxidized substrate from the first reactor to the second reactor where the deposition of the oxide grid is produced by conventional means, sputtering or by ion bombardment under oxidizing condition.
- the assembly of the two reactors and the airlock forms a machine 50.
- the RIE etching step in order to eliminate the native oxide layer can be carried out in the airlock or in a third reactor (not shown).
- the process can use 0 ++ ions, or ions from other oxidizing agents, such as ions from water vapor or other oxidizing gases.
- oxidizing agents such as ions from water vapor or other oxidizing gases.
- the production of ions can be stopped when the oxygen gas is sent or can be continued until the end of the oxidation.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000617484A JP2002544665A (ja) | 1999-05-07 | 2000-05-03 | シリコン基板表面上への酸化珪素薄膜の成長方法及び2つの反応器を有する装置 |
AU45741/00A AU4574100A (en) | 1999-05-07 | 2000-05-03 | Method for the growth of a thin silicon oxide layer on a silicon substrate surface and double reactor machine |
EP00927311A EP1183717A1 (fr) | 1999-05-07 | 2000-05-03 | Procede de croissance d'une couche d'oxyde de silicium de faible epaisseur sur une surface de substrat de silicium et machine a deux reacteurs |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9905834A FR2793349B1 (fr) | 1999-05-07 | 1999-05-07 | Procede de croissance d'une couche d'oxyde de silicium de faible epaisseur sur une surface de substrat de silicium et machine a deux reacteurs de mise en oeuvre |
FR99/05834 | 1999-05-07 |
Publications (1)
Publication Number | Publication Date |
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WO2000068981A1 true WO2000068981A1 (fr) | 2000-11-16 |
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PCT/FR2000/001181 WO2000068981A1 (fr) | 1999-05-07 | 2000-05-03 | Procede de croissance d'une couche d'oxyde de silicium de faible epaisseur sur une surface de substrat de silicium et machine a deux reacteurs |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1183717A1 (fr) |
JP (1) | JP2002544665A (fr) |
AU (1) | AU4574100A (fr) |
FR (1) | FR2793349B1 (fr) |
WO (1) | WO2000068981A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005013349A2 (fr) * | 2003-07-31 | 2005-02-10 | Fsi International, Inc. | Croissance controlee de couches d'oxyde uniformes, en particulier de couches ultraminces |
WO2006016986A2 (fr) * | 2004-07-09 | 2006-02-16 | The Trustees Of Dartmouth College | Sélecteur de masse électronique en parcours |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013116595A1 (fr) * | 2012-02-03 | 2013-08-08 | Seagate Technology Llc | Procédés de formation de couches |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2757881A1 (fr) * | 1996-12-31 | 1998-07-03 | Univ Paris Curie | Procede de traitement d'une surface d'un semi-conducteur, dispositif correspondant et semi-conducteur associe |
-
1999
- 1999-05-07 FR FR9905834A patent/FR2793349B1/fr not_active Expired - Fee Related
-
2000
- 2000-05-03 AU AU45741/00A patent/AU4574100A/en not_active Abandoned
- 2000-05-03 EP EP00927311A patent/EP1183717A1/fr not_active Withdrawn
- 2000-05-03 WO PCT/FR2000/001181 patent/WO2000068981A1/fr not_active Application Discontinuation
- 2000-05-03 JP JP2000617484A patent/JP2002544665A/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2757881A1 (fr) * | 1996-12-31 | 1998-07-03 | Univ Paris Curie | Procede de traitement d'une surface d'un semi-conducteur, dispositif correspondant et semi-conducteur associe |
Non-Patent Citations (3)
Title |
---|
AL-BAYATI A H ET AL: "HOMOEPITAXY AND CONTROLLED OXIDATION OF SILICON AT LOW TEMPERATURESUSING LOW-ENERGY ION BEAMS", JOURNAL OF VACUUM SCIENCE AND TECHNOLOGY: PART B,US,AMERICAN INSTITUTE OF PHYSICS. NEW YORK, vol. 13, no. 4, pages 1639-1644, XP000542861, ISSN: 0734-211X * |
CHANANA R K ET AL: "Electrical properties of 6.3 nm rf oxygen plasma oxide grown near room temperature with in situ dry cleaning of Si surface", SOLID STATE ELECTRONICS,GB,ELSEVIER SCIENCE PUBLISHERS, BARKING, vol. 38, no. 5, 1 May 1995 (1995-05-01), pages 1075 - 1080, XP004013317, ISSN: 0038-1101 * |
HECHT M H ET AL: "OXIDATION OF SILICON WITH A 5 EV O- BEAM", APPLIED PHYSICS LETTERS,US,AMERICAN INSTITUTE OF PHYSICS. NEW YORK, vol. 54, no. 5, 30 January 1989 (1989-01-30), pages 421 - 423, XP000025804, ISSN: 0003-6951 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005013349A2 (fr) * | 2003-07-31 | 2005-02-10 | Fsi International, Inc. | Croissance controlee de couches d'oxyde uniformes, en particulier de couches ultraminces |
WO2005013349A3 (fr) * | 2003-07-31 | 2005-05-12 | Fsi Int Inc | Croissance controlee de couches d'oxyde uniformes, en particulier de couches ultraminces |
US7235495B2 (en) | 2003-07-31 | 2007-06-26 | Fsi International, Inc. | Controlled growth of highly uniform, oxide layers, especially ultrathin layers |
WO2006016986A2 (fr) * | 2004-07-09 | 2006-02-16 | The Trustees Of Dartmouth College | Sélecteur de masse électronique en parcours |
WO2006016986A3 (fr) * | 2004-07-09 | 2006-11-23 | Dartmouth College | Sélecteur de masse électronique en parcours |
Also Published As
Publication number | Publication date |
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FR2793349A1 (fr) | 2000-11-10 |
FR2793349B1 (fr) | 2003-06-27 |
JP2002544665A (ja) | 2002-12-24 |
EP1183717A1 (fr) | 2002-03-06 |
AU4574100A (en) | 2000-11-21 |
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