FR2871937A1 - Formation of insulating nanostructured materials by controlled growth on a semiconductor material for the fabrication of capacitance devices such as Dynamic Random Access Memory - Google Patents

Formation of insulating nanostructured materials by controlled growth on a semiconductor material for the fabrication of capacitance devices such as Dynamic Random Access Memory Download PDF

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FR2871937A1
FR2871937A1 FR0406550A FR0406550A FR2871937A1 FR 2871937 A1 FR2871937 A1 FR 2871937A1 FR 0406550 A FR0406550 A FR 0406550A FR 0406550 A FR0406550 A FR 0406550A FR 2871937 A1 FR2871937 A1 FR 2871937A1
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growth
hafnium
isotopes
lutetium
ternary
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FR2871937B1 (en
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Lionel Girardie
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Lionel Girardie
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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    • C23CCOATING 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
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    • H01L27/1085Multistep manufacturing methods for structures comprising one transistor one-capacitor memory cells with at least one step of making the capacitor or connections thereto

Abstract

The formation of dielectric material nanostructured above a semiconductor material consists of a cycle of molecular reactions and saturation of the surfaces : The formation of dielectric material nanostructured above a semiconductor material consists of a cycle of molecular reactions and saturation of the surfaces comprises the following successive and indissociable stages: (A) growth with a factor alpha 1 a quarter of a mono-layer MC0 of the quaternary compound containing the oxynitrides with a base of the isotopes of germanium, hafnium, lutetium and lanthanides; (B) growth with a factor alpha 2 of a mono-layer MC1 of the binary or ternary or quaternary compound containing the oxides and oxynitrides with a base of the isotopes of hafnium, lutetium and lanthanides; (C) growth with a factorbeta 1 of a quarter of a mono-layer MC2 of the binary or ternary or quaternary compound containing oxides and oxynitrides with a base of the isotopes of hafnium, lutetium, lanthanides, titanium and aluminium; (D) growth with a factor alpha 3 of a quarter of a mono-layer MC1 of the binary or ternary or quaternary compound containing the oxides and oxynitrides with a base of the isotopes of hafnium, lutetium and lanthanides; (E) growth with a factor beta 2 of a mono-layer of the binary or ternary or quaternary compound containing the oxides and oxynitrides with a base of the isotopes of hafnium, lutetium, lanthanides, titanium and aluminium; (F) growth with a factor delta 1 of a quarter of a mono-layer MC3 of the quaternary compound containing the oxynitrides with a base of the isotopes of silicon, germanium, hafnium, lutetium, lanthanides, titanium, tantalum, tungsten, ruthenium, rhenium, cobalt, molybdenum, nickel and aluminium.

Description

Technique for forming nanostructured insulating materials

  Field: This invention deals with a technique for forming nanostructured materials to fabricate various devices such as: Dynamic Dynamic Access Memory MMTemory (DRAM) with capacitive zone in trench form in a semiconductor substrate such as silicon (Si) , germanium (Ge), gallium nitride (GaN) or an organosilicate polymer.

  É DRAM type dynamic memory with capacitive zone in the form of a hemispherical cylinder on a semiconductor substrate based on silicon (Si), germanium (Ge), gallium nitride (GaN) or an organosilicate polymer.

  Dynamic DRAM type memory with capacitive zone in the form of a pedestal on a semiconductor substrate based on silicon (Si), germanium (Ge), gallium nitride (GaN) or an organosilicate polymer.

  On-board memory type eDRAM with capacitive area on a semiconductor substrate based on silicon (Si), germanium (Ge), gallium nitride (GaN) or an organosilicate polymer.

  ^ Non-volatile memory type MRA, 1 (Magnetoresistive Random Access Memory) with magnetoresistance zone on a semiconductor substrate such as silicon (Si), germanium (Ge), gallium nitride (GaN) or an organosilicate polymer .

  Non-volatile Ferom type memory (Ferromagnetic Random Access Memory) with capacitive area on a semiconductor substrate based on silicon (Si), germanium (Ge), gallium nitride (GaN) or an organosilicate polymer.

  ^ Capacitive pass-through with decoupling effect of electronic signals or high-frequency filter in devices of analog and mixed-signal, radio-frequency or digital type technologies.

  ^ Technology Field Effect Transistor CMOS (Complementary Metal Oxide Semiconductor) ^ Capacitive sensor for various applications Background Art: The manufacture of DRAM type memories uses a material deposited by ALD (Atomic Layer Deposition) which is alumina Al2O3. Knowing that to manufacture a DRAM memory, two technological sectors are possible by: 1. Trench capacitive area under the control transistor Technological sector (nm) 90 65 45 32 25 Year of production 2004 2007 2010 2013 2016 CET (Capacitance Equivalent 50 38 22 14 10 Thickness) in Angstrom It is therefore possible to obtain the equivalent thickness of silicon dioxide for the required capacitances up to the 90nm die. The alumina thickness deposited by ALD is then 6 nm. It would be possible to reduce this thickness up to 3 nm to reach the desired electrical thicknesses but the leakage currents would be greater than 1 fento amperes per capacitive cell and therefore new materials must be developed. II. Cylindrical or pedestal capacitive area Technological sector (nm) 90 65 45 32 25 Year of production 2004 2007 2010 2013 2016 EOT (Equivalent Oxide 23 8 6 6 5 Thickness) in Angstrom The technological leap required to reach the thicknesses 65 nm and beyond is so important that it becomes essential to find new materials that meet the different criteria that are more plural than for the trench die. Since the control transistor is manufactured before the capacitive cell, the set of processing treatments for the dielectric materials must be strictly compatible with the maximum operating temperature of the transistor junctions, namely 700 C. Moreover, the leakage currents of the capacitive cell of MIR (lletal Insulator Metal) structure are critical and are intimately related to the grains of the dielectric material that if this material takes a crystalline form at a temperature close to 700 C, the reliability of the cell is not tested and the currents leakage increase through the grain boundaries. Therefore, the alumina substitute material must have an amorphous structure at 700 C and a relative permittivity greater than 20.

  There are different ceramics that can be deposited by ALD and thus make it possible to laminate the layers of different materials such as nanolamines (Example: HAO or LAO) while HfxAlyOz is a mixed oxide made of two distinct and unrelated monolayers of HfO2 and Al2O3 manufactured as a nano-laminate according to the conventional ALD cycle growth process as described in patents FR 2,834,387, FR 2,834,242, FR 2,842,829 and CIP US10 / 425,415.

  Materials Hf02 HAO HfxAlyOz HSON LAO Permittivity by ALD at 300 C 20 12 20 13 20 11 14 18 - 25 EOT (Equivalent Oxide 28 25 23 17 16 Thickness) in Angstrom for leakage current at 1V of 1.E-7 A / cm2 But these materials have properties that are not compatible with the manufacturing criteria of DRANI and passive capacitive components namely that it is very difficult to obtain smaller electrical thicknesses for leakage currents of less than 100 nA / cm 2 at +/- -1V and also a material such as hafnium dioxide (14fO2) takes a crystalline phase from 550 C, which has the effect of influencing the leakage currents and generally the reliability of the device thus manufactured.

  Compatibility problem of ceramic materials deposited by ALD such as nano-laminates of THO, HAO or LAO type or mixed oxide films such as HfxAlyOz for nanoelectronics applications such as DRAM, eDRAM and passive components. Conical crystallites are formed in the materials previously mentioned in standard ALD cycles because of the nucleases that form and cause both vertical and horizontal nucleation with a kinetics of 0.2 nm / second or 20% faster than growth. average of a film by ALD. These crystallites are therefore crystalline islands and cause defects in the structure of the material in nano-laminates or mixed oxides by stacking faults and oxygen vacancies as well as dislocations in T, which has the effect of reducing from 30 to 50% electrical performance but the most decisive consequences in the implementation of these materials are a clear decrease in reliability. A reliability parameter such as TDDB (Time-Dependent Dielectric Breakdown) is very much affected by these structural defects of materials during electrical stress of temperature reliability because the temperature catalyzes according to a kinetics of Arrhenius law: this translates into the Gaps motions, resulting in the breaking of bonds between the metal atom and oxygen and as crystalline areas in an amorphous structure have different crystal binding energies of amorphous structure bonding energies with dipoles different from the amorphous zone, there is a chain of reactions causing a diffusion of defects at the grain boundaries and resulting in a flow of atoms.

  The TDDB test is a major step in the process of qualifying integrated devices such as DRAMs or eDRAMs, MOSFET transistors and any passive component used as a filter. Knowing that the breakdown field is inversely proportional to the square root of the relative permittivity and that a dipole depends on the ionic character in a crystal, the nano-laminated materials HAO or LAO or mixed oxide films such as HfxAlyOz having structural defects in the three axes are sensitive to the metal-ion shifts which are the consequence of an electric field> 5 MV / cm: this phenomenon results in the breaking of bonds, which leads to a so-called Boltzmann process of catching gaps. However, in the aforementioned materials, the crystallite zones are large and therefore the higher the number of coordinates for a crystallite, the more the breakdown field will be weak in intensity and for increasingly lower frequencies. It should be noted that the density of ionic bonds in materials such as nano-laminates of the THO, HAO or LAO type or the mixed oxide films of the HfxAlyOz type is very high and thus the covalent and metallic bonds are extremely weak.

  Another phenomenon related to the various radiations and in particular the neutrinos and the cosmic radiations have an impact on the operation of the integrated devices and in particular on any capacitive zone. Molecules used in the precursors used in the elaboration of materials must possess certain properties of thermal neutron capture. These phenomena are unacceptable for the implementation of existing material forming techniques in the production of the devices concerned and therefore, new materials development techniques are necessary.

  DESCRIPTION OF THE INVENTION The present invention describes embodiments of materials for the applications previously described by a technique of nanostructuring the material from miscible elements forming stable compounds. The nanostructure thus obtained offers new properties of temperature stability through various electrical tests and unprecedented crystalline properties by the new strip structure of the material that is the result of controlled molecular reactions.

  An example of a process is given in annex (1/2) in FIG. 1 on an ALD reactor as described in FIG. 1 of the annex (1/2) in a reactor as described in FIG. molecules the tetrakis ligand amino-ethyl-methyl for the metal Hafnium whose general architecture is given in Figure 3 of the appendix (2/2). The operating principle of an ALD reactor as described in FIG. 2 is based on a reactor operating in two phases. The first phase of increasing the temperature of the vaporization zone by an oven that is to say heating walls, which surround the block. The metal precursor dosage bulb is generally at most 10 mL and at least 1 mL and the inlet and outlet of any body entering the ampoule is electronically managed by the upstream and downstream valves. A precursor may be of solid or liquid nature and depending on its state, the vaporization principle is different. If the precursor is in a liquid state when it is placed in a container pressurized with helium, for example, this precursor, such as an alkylamide, is heated in its container before it is introduced per unit of time into the ampoule subjected to constant pressure with the outlet valve. The unit of time is usually the millisecond. The temperature to which is subjected is the precursor depends on each molecule and its state of purification and its method of manufacture which can vary according to the sources: the temperature is an essential parameter which is a function of the enthalpy of vaporization of the molecule which constitutes the precursor.

  Two equations govern the thermodynamics of this process by: Vp = n * k / T, n: density of the dose in the vial, k: Boltzmann's mass, T: temperature The gradient formed by the source zone of vaporization and the zone diffusion thus creates a gradient partial pressure of the transported fluid: Ln Vp = -AH / RT + AS / R, OH: evaporation enthalpy (kJ / mol), OS: entropy of vaporization (k.mol / J), R : constant of perfect gases.

  The typical precursor of the present invention has the molecule defined by the present invention which may be Metal (R-R '- AMD) 3 with R, R' as alkyl groups and the metal may be lutetium, yttrium, lanthanum, cerium , praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, germanium, as shown in Figure 4 of Annex 2/2. If the metal is Lanthanum, the dose is 5.10-2 mol / cm 2 for a vaporization temperature of 75 C at 100 m Torr and a bonding coefficient of 5.10-2 corresponding to the probability of molecular bonding by surface type, ie the ratio between non-adsorbed binder on adsorbed binder per unit of injected dose.

  Since the precursor is subjected to a given temperature, at a given pressure in a known volume, the mass contained in the ampoule before dosing by partial injection of a time unit in millisecond is consequently determined and therefore the density by the number of mol per unit area. A carrier gas such as argon allows injection into the reactor through an injector whose choice depends on the type of molecule vaporization. Generally the substrate is subjected to a centrifugal effect by rotation of the support foot. After each introduction into the reaction chamber, a metered and sublimed metal precursor or another fluid in the vaporization state such as heavy water D20 or a gas formed such as ozone 03, is systematically followed by pumping at a very high flow rate. 500 cm3 / min of the reactor with an inert gas such as argon or nitrogen. This pumping is essential to complete the molecular reactions on the surface of the substrate and to prevent other reactions of reaction products undergo physorptions.

  Any molecule involved in developing the nanostructured materials of the present invention are made from heavy isotopes for metals. For example, the hafnium metal has six isotopes (174, 176, 177, 178, 179, 180) and each of the isotopes of hafnium have different abundances but particular properties of radiation and thermal neutron. For example, the isotope Hf 174 has a thermal neutron section profile evaluated at 400 whereas Hf 180 has a thermal neutron section profile of 10. This property is essential for combating the effects of cosmic radiation in a storage cell. as a DRAM memory cell or a MOSFET transistor. Therefore, the present invention is based on the use of isotopes of the metals involved in the nanostructuring technique presented in this specification.

  Nanostructuring allows the interfaces to be controlled at the angstrom and to constrain materials to bond by dimer formation through polymerization reactions and surface saturation, which leads to the creation of a new order in each nanostructure of which each element is bound by covalently binding strong energies. A major interest in nanostructuring for the formation of thermally stable compounds is based on new band structures with a conduction bandwidth and valence band greater than 2 eV, which can not be the case with conventional ceramics as nano-laminates HAO or LAO or mixed oxide films such as HfxAlyOz.

  Nanostructuring has a major industrial interest in the development of new properties thanks to band structures comparable to silicon thermal oxide but with permittivities very much greater than 20. There is no transition between layers or component films each nanostructure, but a single film only a few nanometers thick but composed of thick nanostructures of 4 or 10 Angstroms. All the nanostructures are strongly bound by strong bonds, which modifies the ionic behavior of the materials, tending to move at very high frequencies the movements of atoms.

  A technique for forming nanostructured dielectric material above a semiconductor material is characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps: Growth of a factor a quarter a mono-layer MCO quaternary compound comprising oxynitrides based on isotopes of germanium, hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, d europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium.

  Growth of a factor a2 a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium.

  Growth by a factor r1 a quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum.

  - Growth by a factor a3 a quarter of a monolayer 1MIC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium. Growth of a factor (32 a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum Growth of a factor 8i a quarter of a mono layer (MC3) of quaternary compound comprising oxynitrides based on isotopes of silicon, germanium, hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, tantalum, tungsten, ruthenium, rhenium, cobalt, molybdenum, nickel, aluminum.

  A technique for forming nanostructured dielectric material above a semiconductor material 15 according to another embodiment is characterized in that it consists of a cycle of molecular reactions and saturation of the surfaces comprising the successive and indissociable stages: Growth from a factor to a quarter of an MCO mono-layer of quaternary compound comprising oxynitrides based on isotopes of germanium, hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium.

  Growth of a factor a2 a monolayer 1MIC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium.

  Growth of a factor yi of a monolayer MC12 of an at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, of praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum.

  Growth of a factor a3 a quarter of a mono-layer MCi of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium.

  Growth of a factor (32 a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum Growth by a factor S1 a quarter of a monolayer (MC3) quaternary compound comprising oxynitrides based on isotopes of silicon, germanium, hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, tantalum, tungsten, ruthenium, rhenium, cobalt, molybdenum, nickel, 'aluminum.

  A nanostructured dielectric material forming technique above a conductive material is characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable stages: Growth of a factor and a monolayer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum. Growth of a factor (3 a quarter of a monolayer MC2 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  Growth of a factor a2 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a R2 factor a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  - Growth of a factor a3 a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a factor (33 a quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  Growth of a factor a4 a quarter of a monolayer MC1 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a 134 factor a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  Growth of a factor as a mono-layer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a factor N4 3un quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  A nanostructured dielectric material forming technique above a conductive material according to another embodiment is characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps o Growth of a factor a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  o Growth of a factor yi of a monolayer MC12 of an at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium , praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum.

  o Growth by a factor pz a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  o Growth of a factor a3 a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  o Growth of a y2 factor of an MC12 monolayer of an at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum and cerium , praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum.

  o Growth of a g4 factor a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  o Growth of a factor with a mono-layer MCI of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium , promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum. o Growth of a factor in a quarter of a mono-layer MC2 of compound

  binary or ternary or quaternary comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  A nanostructured dielectric material forming technique above a conductive material is characterized in that it consists of a cycle of molecular reactions and saturation of the surfaces comprising the successive and indissociable stages: Growth from a factor to a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum. Growth of a factor R1 a quarter of a monolayer MC2 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  Growth of a factor a2 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth by a factor f32 a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium. 10 15

  Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growing by a factor f33 a quarter of a mono-layer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  A technique for forming a nanostructured dielectric material above a conductive material, characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable stages: Growth of a factor ai a single-layer MCI of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a factor yi of a monolayer MC12 of an at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, of praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum.

  Growth by a factor 32 of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds including oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, aluminum.

  Growth of a factor of one-third to one-third of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium, lanthanum, cerium and praseodymium , neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, titanium.

  A growth of at least one quarter of MC1 or MC2 monolayer of binary or ternary or quaternary compound is characterized in that it consists of a cycle of chemisorption and polymerization reactions in a pressurized chamber. at a pressure of between 0.5 Torr and 5 mTorr and at a temperature of between 25 ° C. and 250 ° C. to reach a given thickness resulting from the saturation of the chemisorption and polymerization reactions according to the corresponding growth factor a, 13, S at the number of growth cycle and taking the values 1 or 2 or 3 according to the total thickness of the material and whose cycle of stages comprises successive and indissociable steps: Under constant pressure atmosphere of a gas selected from the nitrogen, argon, deuterium, tritium or helium, raised from ambient temperature to a temperature of between 50 C and 250 C for at least 30 seconds and not more than 3 minutes, Inject dosed ion of a reagent. the state of vaporization with a carrier gas such as helium or argon for at least one thousandth of a second and at most 30 seconds, - Under an atmosphere of a helium or argon gas, suction by pumping of the chamber for one thousandth of a second and at most 30 seconds, - metered injection of a reactant such as ozone or heavy water of the D2O type but preferably T2O in the vaporization state with a carrier gas such as nitrogen or argon for at least one thousandth of a second and not more than 30 seconds. Under a nitrogen gas or argon gas, the chamber is pumped for one thousandth of a second and at most 30 seconds.

  A growth of at least one quarter of an MCO or MC12 monolayer of at least ternary or quaternary compound is characterized in that it consists of a cycle of chemisorption and polymerization reactions in a pressurized chamber at a pressure between 0.5 Torr and 5 mTorr and at a temperature between 25 C and 250 C to reach a given thickness resulting from the saturation of the chemisorption and polymerization reactions according to the growth factor a or y corresponding to the number of growth cycle and taking the values 1 or 2 as a function of the total thickness of the material and whose stage cycle comprises the successive and indissociable stages: - under a constant-pressure atmosphere of a gas selected from nitrogen, argon, deuterium, tritium or helium, raised from room temperature to 25 C to 250 C for at least 30 seconds and not more than 3 minutes, Metered reagent injection 1 in the vaporization state with a carrier gas such as helium or argon for at least one thousandth of a second and not more than 30 seconds, - Under an atmosphere of a helium or argon gas, suction by pumping of the chamber for one thousandth of a second and at most 30 seconds, metering of a reagent 2 in the vaporization state with a carrier gas such as helium or argon for at least one thousandth of a second and at plus 30 seconds., - Under an atmosphere of helium or argon gas, suction by pumping the chamber for one thousandth of a second and at most 30 seconds, metered and simultaneous or combined injection of a reactant 1 such as ozone or heavy water type D20 but preferably T20 and a reactant 2 such as ammonia or hydrazine in the vaporization state with a carrier gas such as nitrogen or argon during at least one thousandth of a second and not more than 30 seconds, Under a nitrogen gas or argon gas, suction per mpage of the chamber for one thousandth of a second and at most 30 seconds.

  A metered injection of reagent 1 or 2 is characterized in that it consists of a dosage of at least one nanomole per square centimeter and at most ten micron-mole per square centimeter of liquid organic metal precursors to radical type alkyl amide or (R-R '- AMD) 3 with R, R' as alkyl groups for any metal including hafnium, lutetium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum, germanium and having all of the following properties: the vaporization temperature must be lower at 1250C but preferentially below 110C the reagent can react only by catalysis and by thermal action without any reaction of decomposition - Gibbs free energy of the reaction of the reagent with the surface on which it is projected, must be strictly negative - the reaction Thermolysis of the reagent must not release more than one reactive ion composed of carbon and hydrogen in a temperature range of 25 C to 250 C.

  probability of molecular bonding on lipophilic surface less than or equal to 0.08 A monolayer MC12 is characterized in that the at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, yttrium , lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, titanium, aluminum is very preferably made of concentration gradient and inverse gradient concentration films of each element of the combination of binary or ternary or quaternary compounds comprising oxides, nitrides and oxynitrides based on isotopes of hafnium, zirconium, lutetium, yttrium, aluminum, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, of ytterbium, titanium.

  The examples which follow are given at a growth factor of 1 and therefore to reach thicknesses of 60 Angstroms, therefore the growth factors for the examples given are 4.

  Example of a nanostructured material forming method (Annex 1/2) for producing a pedestal-type capacitive cell of MIM structure for the 65 nm wafer die 200 mm in diameter.

  Rise in temperature for 100 seconds to reach 385 C and argon injection at 340 cm3 / min and pressure at 20 mTorr Argon injection at 350 cm3 / min for 1 second Helium injection at 180 cm3 / min for 250 msec and Hf [N (Et-Me)] 4 mTorr of pressure Argon injection at 350 cm3 / min for 600 msec Injection of D20 at 380 cm3 / min with 150 cm3 / min of nitrogen for 1000 msec Injection of argon at 350 cm3 / min for 1 second Helium injection at 150 cm3 / min for 350 msec (milli seconds) and La (Me-Et - AMD) 3 40 mTorr of pressure Argon injection at 350 cm3 / min for 500 msec Helium injection at 180 cm3 / min for 350 msec and Hf [N (Et-Me)] 4 mTorr of pressure - Argon injection at 350 cm3 / min for 1 second Ozone injection at 380 cm3 / min with 150 cm3 / min of nitrogen and 200 cm3 / min of NH3 for 2500 msec - Argon injection at 350 cm3 / min for 2500 msec For a thick nanostructure growth in total of 60 Angstroms, the value of the E OT taken from the voltage capacitance diagram is 8.17 Angstroms for an insulating material LaaHfbOcNd.

  A second example of a process for forming a nanostructured material for manufacturing a capacitive pedestal type cell with a MIM structure for the 65 nm wafer die 200 mm in diameter.

  Rise in temperature for 100 seconds to reach 450 C and argon injection at 340 cm3 / min and pressure at 35 mTorr Argon injection at 350 cm3 / min for 1 second - Helium injection at 180 cm3 / min for 250 msec (milli seconds) and Hf [N (Et-25 Me)] 4 -1 mTorr of pressure Argon injection at 350 cm3 / min for 1 second Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen 1 second argon Injection at 350 cm3 / min for 1 second Helium injection at 180 cm3 / min for 250 msec (miii second) and Hf [N (Et-30 Me)] 4 1 mTorr pressure - Injection Argon at 350 cm3 / min for 1 second - Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1 second Argon injection at 350 cm3 / min for 1 second Helium injection at 180 cm3 / min for 250 msec (milli seconds) and Hf [N (Et-35 Me)] 4 1 mTorr of pressure Argon injection at 350 cm3 / min for 1 second Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1 second Injectio Argon at 350 cm3 / min for 1 second Helium injection at 150 cc / min for 350 msec (milli second) and La (Me-Et 40 - AMMD) 3 1 mTorr of pressure Argon injection at 350 cm 3 / min for 500 msec Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec Injection of argon at 350 cm3 / min for 1300 msec Injection of helium at 180 cm3 / min for 250 msec (milli second) and Hf [N (Et-Me)] 4 1 mTorr of pressure Argon injection at 350 cm3 / min for 1 second - Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen during 1 second argon Injection at 350 cm3 / min for 1 second Injection of 150 cm3 / min of nitrogen and 200 cm3 / min of NH3 for 1500 msec Injection of argon at 350 cm3 / min for 2000 msec Injection of helium at 150 cm3 / min for 350 msec (milli second) and La (Me-Et AMD) 3 1 mTorr of pressure Injection of argon at 350 cm3 / min for 500 msec Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec Injection of a rpm at 350 cc / min for 1300 msec Helium injection at 150 cc / min for 350 msec (milli second) and La (Me-Et-AMD) 3 -1 mTorr pressure - Argon injection at 350 cc / min for 500 msec Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec Injection of argon at 350 cm3 / min for 1300 msec Injection of helium at 150 cm3 / min for 350 msec (milli second ) and the (Me-Et-AMD) 3 1 mTorr pressure Injection of argon at 350 cm3 / min for 500 msec - Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec Injection d Argon at 350 cm3 / min for 1300 msec Helium injection at 180 cm3 / min for 250 msec (milli second) and Hf [N (Et-Me)] 4 1 mTorr of pressure Argon injection at 350 cm3 / min for 1 second - Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1 second Injection of argon at 350 cm3 / min for 1 second Injection of helium at 150 cm3 / min for 350 msec (milli second ) and the (Me-Et - AMD) 3 1 m Torr pressure Argon injection at 350 cm3 / min for 500 msec Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec - Injection of argon at 350 cm3 / min for 1300 msec - Injection of 150 cm3 / min of nitrogen and 200 cm3 / min of NH3 for 1500 msec Argon injection at 350 cm3 / min for 2000 msec A third example of a process for forming nanostructured material to manufacture a capacitive cell of pedestal and structure type MIM for the 45 nm wafer die 300 mm in diameter.

  - Rise in temperature for 100 seconds to reach 450 C and argon injection at 340 cm3 / min and pressure at 35 mTorr Argon injection at 350 cm3 / min for 1 second Helium injection at 150 cm3 / min for 350 msec (: miii second) and La (Nfe-Et - AMD) 3 40 mTorr of pressure Injection of argon at 350 cm3 / min for 500 msec Injection of helium at 180 cm3 / min for 350 msec and Hf [N (and -Me)] 4 mTorr of pressure Argon injection at 350 cm3 / min for 1 second Ozone injection at 380 cm3 / min with 150 cm3 / min of nitrogen and 200 cm3 / min of NH3 for 2500 msec Injection d Argon at 350 cm3 / min for 2500 msec Helium injection at 150 cm3 / min for 350 msec (milli second) and La (Me-Et - AMD) 3 -1 mTorr of pressure - argon injection at 350 cm3 / min for 500 msec - Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec - Injection of argon at 350 cm3 / min for 1300 msec Injection of helium at 150 cm3 / min for 350 msec (milli second) and of the (Me-Et-AMD) 3 1 mTorr of pressure Argon injection at 350 cm3 / min for 500 msec Injection of 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec Injection of argon at 350 cm3 / min for 1300 msec Injection of helium at 150 cm3 / min for 350 msec (millisecond) and La (Me-Et - AMD) 3 1 mTorr of pressure Injection of argon at 350 cm3 / min for 500 msec - Injection from 03 to 380 cm3 / min with 150 cm3 / min of nitrogen for 1250 msec - Injection of argon at 350 cm3 / min for 1300 msec Injection of helium at 180 cm3 / min for 350 msec and HE [N ( Et-Me)] 4 mTorr pressure - Argon injection at 350 cm3 / min for 1 second Helium injection at 150 cm3 / min for 350 msec (min second) and La (Me-Et - AMD) 3 40 mTorr of pressure Injection of argon at 350 cm3 / min for 500 msec Injection of ozone at 380 cm3 / min with 150 cm3 / min of nitrogen and 200 cm3 / min of NH3 for 2500 msec Injection of argon at 350 cm3 / min for 2500 msec For nanostructu growth At 60 Angstroms, the ESO value from the voltage capacitance diagram is 8.17 Angstroms for a LaaHfbOcNd insulating material.

  The advantage of using as a precursor of La, a lanthanum tris (N, N 'methylethylacetarnidinate) molecule 40 in substitution of lanthanum tris (N, N' isopropylacetamidinate) which sublimates at 80 C under a pressure of 40 mTorr, but the cabbage of the molecule La (Me-Et-AMD) 3 resides in the alkyl chain and thus the binder of this bidentate and monoleptic molecule, but the binder chosen to manufacture the nano-materials thus formed. by the nanostructuration makes it possible to obtain a liquid precursor at the vaporization temperature at 1 Tor near the vaporization temperature of the hafnium liquid precursor by hafnium tetrakis ethy-methyl-amino. Moreover, these molecules do not have pyrophoric reactions and therefore comply with the most stringent safety rules in use in the years 2005 to 2015.

  Furthermore, nitrogen compounds are essential in the formation of stable nano-materials for insulators because nitrogen stabilizes the compound by resistance to oxygen migration and by the systematic taking of interstices and a resistance action to the formation of nucleases during temperature rise. These nano-materials based on compounds such as LaaHfbOcNd are a major invention in the semiconductor industry.

20 25 30 35

Claims (10)

  1. A nanostructured dielectric material forming technique above a semiconductor material characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps: a. Growth of a factor a quarter of a monolayer MCO quaternary compound comprising oxynitrides based on isotopes of germanium, hafnium, lutetium, lanthanides.
  b. Growth of a factor a2 a monolayer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides.
  vs. Growth of a factor (31 a quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  d. Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides.
  e. Growth of a factor (32 a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, indium, lanthanides, titanium, aluminum.
  f. Growth of a factor S1 a quarter of a monolayer (MC3) of quaternary compound comprising oxynitrides based on isotopes of silicon, germanium, hafnium, lutetium, lanthanides, titanium, tantalum, tungsten, ruthenium, rhenium, cobalt, molybdenum, nickel, aluminum.
  2. A nanostructured dielectric material forming technique above a semiconductor material according to another embodiment characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps a. Growth of a factor a quarter of a monolayer MCO quaternary compound comprising oxynitrides based on isotopes of germanium, hafnium, lutetium, lanthanides.
  b. Growth of a factor a2 a monolayer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides.
  vs. Growth of a yt factor of a monolayer MC12 of a least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, indium, lanthanides, titanium, aluminum.
  d. Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides. -18 -
  e. Growth of a Pz factor a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  f. Growth of a factor 8i a quarter of a mono-layer (MC3) of quaternary compound comprising oxynitrides based on isotopes of silicon, germanium, hafnium, lutetium, lanthanides, titanium, tantalum, tungsten, ruthenium, rhenium, cobalt, molybdenum, nickel, aluminum.
  3. A nanostructured dielectric material forming technique above a conductive material characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps: a. Growth of a factor al a mono-layer MCI of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  b. Growth of a factor Pt a quarter of a monolayer MC2 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  vs. Growth by a factor of a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides and aluminum.
  d. Growth of a factor 2 MC2 mono-layer of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, indium, lanthanides, titanium, aluminum.
  e. Growth of a factor a3 a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  f. Growth by a factor of one quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  boy Wut. Growth of a factor a4 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  h. Growth of a R4 factor a mono-layer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  i. Growth of a factor as a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  j. Growth of a factor R4 a quarter of a mono-layer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum. -1e-
  4. A nanostructured dielectric material forming technique above a conductive material according to another embodiment characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable steps: a. Growth of a factor ai a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  b. Growth of a yl factor of a monolayer MC12 of a least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  vs. Growth of a factor [32] a mono-layer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, indecium, lanthanides, titanium, aluminum.
  d. Growth of a factor a3 a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  e. Growth of a y2 factor of a monolayer MC12 of a least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  f. Growth of a monolayer MC2 of a binary or ternary or quaternary compound comprising the oxides and oxynitrides based on the isotopes of hafnium, lutetium, lanthanides, titanium, aluminum and titanium.
  boy Wut. Growth of a factor a5 a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  h. Growth of a factor (34 a quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  5. A nanostructured dielectric material forming technique over a conductive material characterized in that it consists of a cycle of molecular reactions and saturation of the surfaces comprising the successive and indissociable steps: a. Growth of a factor ai a mono-layer MC1 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  b. Growth of a factor RI a quarter of a mono-layer MC2 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  vs. Growth of a factor a2 a quarter of a monolayer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  - 2.0-- d. Growth of a factor (3z a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  e. Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  f. Growth of a factor R3 a quarter of a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  6. A technique for forming a nanostructured dielectric material above a conductive material, characterized in that it consists of a cycle of molecular reactions and surface saturation comprising the successive and indissociable stages: Growth from a factor to a mono- MC1 layer of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  Growth of a factor yi of a monolayer MC12 of an at least ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  Growth of a factor (3z a monolayer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  Growth of a factor a3 a quarter of a mono-layer MC1 of binary or ternary or quaternary compounds comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, aluminum.
  e. Growth of a factor p3 a quarter of a mono-layer MC2 of binary or ternary or quaternary compound comprising oxides and oxynitrides based on isotopes of hafnium, lutetium, lanthanides, titanium, aluminum.
  7. Technique for forming nanostructured dielectric material above a conductive or semiconductor material according to the preceding claims, characterized in that a growth of at least a quarter of monolayer MC1 or MC2 of binary or ternary or quaternary compound consists of a cycle of chemisorption and polymerization reactions in a pressurized chamber at a pressure of between 0.5 Torr and 5 mTorr and at a temperature of between 25 ° C. and 250 ° C. to reach a given thickness resulting from the saturation of the reaction reactions. chemisorption and polymerization according to the growth factor a, (i, 8 corresponding to the number of growth cycle and taking the values 1 or 2 or 3 as a function of the total thickness of the material and whose cycle of steps comprises the steps successive and indissociable: a) Under a constant pressure atmosphere of a gas selected from nitrogen, argon, deuterium, tritium or helium , raising the ambient temperature to a temperature of between 50 C and 250 C for at least 30 seconds and not more than 3 minutes, a. b. vs. d. -
  b. Metered injection of a reagent in the vaporization state with a carrier gas such as helium or argon for at least one thousandth of a second and at most 30 seconds, c. Under an atmosphere of helium or argon gas, pump suction of the chamber for one thousandth of a second and at most 30 seconds, d. Metered injection of a reactant such as ozone or heavy water of the D2O type but preferably T2O in the vaporization state with a carrier gas such as nitrogen or argon for at least one thousandth of a second and at most 30 seconds, e. Under an atmosphere of a nitrogen gas or argon, aspiration by pumping the chamber for a thousandth of a second and at most 30 seconds.
  8. A nanostructured dielectric material forming technique above a conductive or semiconductor material according to claims 1,2,3,4,5,6 characterized in that a growth of at least a quarter of mono-layer MCO or MC12 of at least ternary or quaternary compound consists of a cycle of chemisorption and polymerization reactions in a pressurized chamber at a pressure between 0.5 Torr and 5 mTorr and at a temperature between 25 C and 250 C for to achieve a given thickness resulting from the saturation of the chemisorption and polymerization reactions according to the growth factor a or y corresponding to the number of growth cycle and taking the values 1 or 2 as a function of the total thickness of the material and whose cycle of stages includes successive and indissociable steps: a. Under a constant-pressure atmosphere of a gas selected from nitrogen, argon, deuterium, tritium or helium, raised from room temperature to a temperature between 25 C and 250 C for at least 30 seconds and not more than 3 minutes, b. Metered injection of a reagent 1 in the vaporization state with a carrier gas such as helium or argon for at least one thousandth of a second and at most 30 seconds, c. Under an atmosphere of helium or argon gas, pump suction of the chamber for one thousandth of a second and at most 30 seconds, d. Metered injection of a reagent 2 in the vaporization state with a carrier gas such as helium or argon for at least one thousandth of a second and at most 30 seconds, e. Under an atmosphere of helium or argon gas, pump suction of the chamber for one thousandth of a second and at most 30 seconds, f. Injection dosed and simultaneous or combined a reactant 1 as ozone or heavy water of the type D2O but preferably T2O and a reactant 2 such as ammonia or hydrazine in the state of vaporization with a carrier gas as nitrogen or argon for at least one thousandth of a second and not more than 30 seconds, g. Under an atmosphere of a nitrogen gas or argon, aspiration by pumping the chamber for a thousandth of a second and at most 30 seconds.
  9. A nanostructured dielectric material forming technique above a conductive or semiconductor material according to claims 7 and 8 characterized in that a growth of at least a quarter of mono-layer MCO, MC1, MC2 or MC12 consists of in that a metered injection of reagent 1 or 2 is an assay of at least one nano-mole per square centimeter and at most ten micron-moles per square centimeter of alkyl amide-type liquid organic metal precursors or ( RR '- AMD) 3 with R, R' as alkyl groups for any metal including lutetium, lanthanides, aluminum, germanium and having all of the following properties: the vaporization temperature must be less than I25 C but preferably lower at 110 C the reagent can react only by catalysis and by thermal action without any reaction of decomposition Gibbs free energy of the reaction of the reagent with the surface on which it is projected, must be strictly negative the reaction of thermolysis of the reagent must not release more than one reactive ion composed of carbon and hydrogen in a temperature range from 25 C to 250 C probability of molecular bonding on lipophilic surface less than or equal to 0.08
10. Technique for forming nanostructured dielectric material over a conductive or semiconductor material according to claims 2, 4, 6, characterized in that an MC12 monolayer is produced very preferably of concentration gradient films and inverse gradient concentration of each element of the combination of binary or ternary or quaternary compounds comprising oxides, nitrides and oxynitrides based on isotopes of hafnium, zirconium, lutetium, lanthanides, aluminum, titanium. I0
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US20030207097A1 (en) * 2001-12-31 2003-11-06 Memscap Le Parc Technologique Des Fountaines Multilayer structure used especially as a material of high relative permittivity
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