WO2010114386A1 - Couches minces contenant de l'oxyde de molybdène - Google Patents

Couches minces contenant de l'oxyde de molybdène Download PDF

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WO2010114386A1
WO2010114386A1 PCT/NO2010/000120 NO2010000120W WO2010114386A1 WO 2010114386 A1 WO2010114386 A1 WO 2010114386A1 NO 2010000120 W NO2010000120 W NO 2010000120W WO 2010114386 A1 WO2010114386 A1 WO 2010114386A1
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precursor
thin film
pulse
steps
reactor
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WO2010114386A8 (fr
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Ola Nilsen
Helmer FJELLVÅG
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Universitetet I Oslo
Diskus, Madeleine
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

Definitions

  • the present invention relates to a method for producing thin films containing molybdenum oxide with the atomic layer deposition (ALD) technique and thin films obtained by this method.
  • ALD atomic layer deposition
  • Molybdenum oxide (MoO 3 ) is a transition metal investigated particularly for its electrochromic properties as described by S. S. Mahajan, S.H. Mujawar, P. S. Shinde, A.I. Inamdar, P.S. Patil, Applied Surface Science 254 (2008) 5895-5898, and for its broad industrial applications in electronic devices, but also for its interesting catalytic properties as discussed by Sobia Ashraf, Christopher S. Blackman, Geoffrey Hyett and Ivan P. Parkin, J. Mater. Chem., 2006, 16, 3575-3582.
  • MoO 3 thin films have been deposited by many different techniques, including CVD (chemical vapour deposition) as disclosed by Sobia Ashraf et al. and PVD (physical vapour deposition) described by M. S. Burdis and J. R. Siddle, Thin Solid Films, 1994, 237, 320.
  • ALD atomic layer deposition
  • MoxN is described by L. Hiltunen, M. Leskela, M. Makela, L. Niinist ⁇ , E. Nykanen, and P.Soininen, Thin Solid Films 166, (1988) 149 and by M. Juppo, M. Ritala, and M. Leskela, J. Electrochem. Soc. 147 (2000) 3377. Deposition of Mo is discussed by M. Juppo, M. Vehkamaki, M. Ritala, and M. Leskela, J. Vac. Sci. Technol. A 16 (1998) 2845.
  • the application of carbonyl compounds as precursors for ALD has generally been considered too limited thermally stable to be utilised in ALD growth, as disclosed in US2009/0029036.
  • the object of the present invention is accordingly to find a way to deposit thin films of oxides containing molybdenum by the ALD technique.
  • ALD atomic layer deposition
  • ALCVD atomic layer chemical vapour deposition
  • ALE atomic layer epitaxy
  • a thin film is produced by the ALD technique by using different types of precursors.
  • the precursors are pulsed sequentially into the reaction chamber where it reacts with a surface; each pulse is followed by a purging time with an inert gas or an evacuation of the reactor. In this way gas phase reactions are eliminated and film is constructed by precursor units in the order that they are pulsed.
  • This technique makes it possible to change building units at the resolution of one monolayer, and therefore enables production of artificial structures of films with different types of organic and inorganic building units.
  • the present invention provides a method for depositing a thin film comprising molybdenum oxide on a surface of a substrate by ALD technique where the method comprises the steps of: a) reacting a pulse of a halogen- free Mo-precursor with the surface; b) purging with an inert gas or pump down of reactor; c) reacting a pulse of an oxygen containing precursor with the surface; and d) purging with an inert gas or pump down of reactor; thereby obtaining a molybdenum oxide containing film.
  • the steps a) to d) are repeated to obtain the desired thickness of the film.
  • the method may further comprise deposition of one or more other compounds one or more times between or after the steps a) to d) are performed.
  • the method is performed within the temperature range between 140°C and 200°C, more preferably about 157-175°C.
  • the method further comprises the steps of e) reacting a pulse of a cobalt precursor with the surface, wherein the cobalt precursor is selected from the group comprising Co(thd) 2 , Co(Cp) 2 , Co(alkyl substituted Cp) 2 , Co(acac) 2 and Co(PrAMD); f) purging with an inert gas or pump down of reactor; g) reacting a pulse of an oxygen containing precursor with the surface; and h) purging with an inert gas or pump down of reactor; thereby obtaining a complex Mo-Co-O containing film.
  • the cobalt precursor is selected from the group comprising Co(thd) 2 , Co(Cp) 2 , Co(alkyl substituted Cp) 2 , Co(acac) 2 and Co(PrAMD
  • f) purging with an inert gas or pump down of reactor g) reacting a pulse of an oxygen containing precursor with the surface; and h) purging with an
  • steps a)-d) and e)-f) may be respectively repeated an individually selected number of times and where all the steps are repeated to grow the thin film.
  • thd stands for 2,2,6,6-tetramethylheptane-3,5-dione
  • Cp stands for cyclopentadienyl
  • acac stands for acetylacetonato
  • PrAMD stands for N 1 N'- diisopropylacetamidinato.
  • Alkyl substituted Cp means Cp substituded 1-5 times with C 1-6 alkyl.
  • the obtained thin film is annealed at a temperature above 400°C, preferably between 500°C and 1000°C, more preferred about 500°C-600°C.
  • the present invention further provides a thin film comprising MoO 3 obtained by the method according to the present invention.
  • the molybdenum oxides are deposited by the ALD technique using the Mo(CO) 6 precursor (molybdenum hexacarbonyl) in combination with an oxygen containing precursor.
  • the process is performed through self limiting gas-to-surface reactions.
  • the reaction steps of the method according to the present invention leads to the formation of MoO 3 on the surface of the substrate.
  • the process is repeated until desired thickness is achieved.
  • the Mo(CO) 6 precursor is introduced into the ALD reactor from an external reservoir using additional inert carrier gas flow, such as nitrogen, argon, helium or similar.
  • additional inert carrier gas flow such as nitrogen, argon, helium or similar.
  • the precursor was maintained at room temperature.
  • the oxygen containing precursor according to the present invention is selected from the group consisting of O 3 , H 2 O, a mixture of O 3 and H 2 O, plasma oxygen, N 2 O, NO, NO 2 or H 2 O 2 .
  • O 3 is used as the oxygen containing precursors.
  • the process does also work for deposition using solely H 2 O as the oxygen containing precursor, but a notably smaller growth rate was experienced.
  • a mixture of O 3 and H 2 O is used as the oxygen containing precursor.
  • the growth rate may vary dependent on the selected oxygen containing precursor.
  • the deposition approach has been to use individual cycles of the Mo-process as described above and similar processes for deposition of the other metal elements.
  • Figure 1 Shows ALD growth rates OfMoO 3 as function of the deposition temperature.
  • Figure 2 Shows the results of QCM measurements of the depositions of Mo-oxide.
  • Figure 3 Shows ALD growth rates of MoO 3 as function of the duration of the Mo- precursor pulse.
  • Figure 4 X-Ray diffraction pattern OfMoO 3 thin film on a substrate Si(111).
  • Figure 5 XRD diffractogram of the MoO 3 sample annealed at 600 0 C under air.
  • Figure 6 Co content (as measured by XRF) versus fraction of Co pulses in Mo-Co-O films.
  • FIG. 7 Shows the catalytic activity in ammonia decomposition reaction of reduced
  • Thin films containing molybdenum oxide have been deposited using a F- 120 Sat reactor (ASM Microchemistry) and Mo(CO) 6 (Molybdenum hexacarbonyls) as the metal containing precursor and a mixture of O 3 and H 2 O as the oxygen containing precursor.
  • the ozone was made by feeding 99.999% O 2 into an OT-020 ozone generator from Ozone Technology, giving an ozone concentration of 15 vol.% according to specifications.
  • An ozone flow of ca. 500 cm 3 /min was used during the ozone pulses.
  • a background pressure of 3.5 mbar was obtained by applying a N 2 carrier gas flow of 300 cm 3 min '.
  • the carrier gas was produced in a Schmidlin UHPN3001 N 2 purifier with a claimed purity of 99.999% with regard to N 2 +Ar content.
  • the films were deposited on substrates of Si(111) single crystals which were used as obtained from the manufacturer.
  • the film is grown through alternating pulses of these precursors separated by purging by inert gas. The process is repeated until the desired film thickness is achieved. The process proved to give a growth rate of ca. 0.07 nm/cycle in the temperature range 157 — 175 °C. Above this temperature the precursor decomposes and provides uncontrolled growth. Below this range the reactivity OfMo(CO) 6 is too low for formation of film. This is illustrated on figure 1 showing the average growth rate over 1000 cycles at different temperatures.
  • This example applies Mo(CO) 6 as the Mo-containing precursor. This will react through self- limiting gas-to-surface reactions with an oxidizing gas such as O 3 and form MoO 3 .
  • the oxygen containing gas as a parameter has also been studied at 167°C by QCM (quarts crystal microbalance).
  • QCM quarts crystal microbalance
  • composition of one the films obtained at 167°C have been measured by X-ray photoelectron spectroscopy (XPS) recorded on a Kratos Axis Ultra Instrument, a conventional Al Ka anode was used at 15 kV and 10 mA as the source of X-ray radiation.
  • the pressure in analysis chamber during the analyses was around 5*10 "9 Torr.
  • the energy scale was calibrated by adjusting the C(Is) binding energy for the omnipresent air-borne hydrocarbons at 284.6 eV.
  • the obtained graphs fitted perfectly well with the theoretical graphs OfMoO 3 proving the films to be of near stoichiometric MoO 3 .
  • Thin film thicknesses have been measured by X-ray reflectometry (XRR) using a Siemens D5000 X-ray diffractometer equipped with a G ⁇ bel-mirror which provides parallel Cu Ka radiation. The setup was also used to measure conventional X-ray diffraction (XRD) in reflection mode. X-ray diffraction analysis proved the films to be as deposited films to be amorphous for depositions in the range 152 to 173 0 C when deposited on Si(111) using 1000 cycles and a mix of water and ozone as the oxygen source.
  • Figure 4 is an example of the results obtained.
  • Figure 4 shows the X-Ray diffraction pattern obtained for the film obtain at the following pulsing scheme 0.8 s Mo(CO) 6 followed by a purge of 1.1 s and 5.0 s of a mixture of ozone and water followed by a purge of 3.0 s.
  • the deposition temperature was 167 0 C, a total of 1000 cycles was used and the substrate was Si(111). Shown in grey is the theoretical diffraction peaks of any crystalline Mo-oxide film and in black is the experimental diffraction graph obtained.
  • the diffraction peak at 28° belongs to the substrate Si(111), and one can easily see that the Mo-oxide film is amorphous.
  • films were annealed for 15 minutes under air at 200 0 C, 300 0 C, 400 0 C, 500 0 C and 600 0 C.
  • Annealing at 200 0 C, 300 0 C and 400 0 C did not result in crystallisation of the annealed Mo-oxide films, whereas annealing at 500 0 C and above resulted in a crystalline film.
  • Figure 5 shows the diffractogram of the resulting crystallisation of a film obtained after annealing at 600 °C in air for 15 min.
  • the crystalline phase is identified as the orthorhombic ⁇ -MoO 3 phase (Inorganic File, Plate 18-1418, Mineral Power Diffraction File, 1986).
  • the doted lines show the theoretical diffraction peaks which are not possible to observe due to too low intensity from the diffracting film.
  • the present invention relates to the deposition of complex oxide thin films comprising molybdenum. This embodiment is illustrated by the deposition of Co-Mo-oxide with different compositions.
  • the Mo(CO) 6 was maintained at room temperature and pulsed using 1.4 s followed by 1.1 s of purge (N 2 ).
  • the oxygen containing gas was a mixture of H 2 O and O 3 employed with a pulse of 5.0 s followed by a 1.5 s of purge.
  • the Co(thd) 2 was sublimed at 115 0 C and delivered by a pulse of 1.5 s followed by a purge of 0.3 s. Thereafter a pulse of 0.5 s of O 3 was introduced as the oxygen containing gas, followed by a purge of 1.5 s.
  • the substrate was Si (111).
  • Table 1 clearly shows that films with different content are obtain with the different pulsing patterns.
  • Figure 6 shows the Co content (as measured by XRF) versus fraction of Co pulses in Mo-Co-O films grown on Si(111) at 165 0 C.
  • the precursor systems used are Mo(CO) 6 + (O 3 /H 2 O) and Co(thd) 2 + O 3 at 167 0 C.
  • Examples of possible interesting complex oxides include: Fe 2 MoO 4 , Al 2 [MoO 4 J 3 , BaMoO 4 , CaMoO 4 , Cu 3 Mo 2 O 9 , CuMoO 4 , Eu 2 Mo 3 Oi 2 , La 2 MoO 6 , Li 2 MoO 4 , MgMoO 4 , MnMoO 4 , Nd 2 Mo 2 O 7 , MoNiO 4 , MoSb 2 O 6 , V 2 MoO 8 , WMo 4 Oi 4 , Y 2 Mo 2 O 7 , Yb 2 Mo 2 O 7 , Zn 2 Mo 3 O 8 , and Zr[MoO 4 J 2 .
  • Catalytic testing The ammonia decomposition reaction was carried out on a CoMo-thin film catalyst coated on quartz substrate.
  • the catalyst coated quartz substrate was cut into small pieces that could fit in the quartz reactor with an inner diameter 0.3 cm.
  • Prior to catalytic testing the thin film catalyst was reduced under the flow of pure hydrogen at 600 0 C for 2 h. The temperature was raised from RT to 600 0 C at a heating rate of 5 °C/min. The flow of hydrogen is 10 ml/min. After reduction, the reactor was cooled down to RT (5 °C/min) with continuous Ar flush (25 ml/min).
  • Temperature programmed ammonia decomposition over the thin film catalyst was done by flowing NH 3 (25 ml/min) and Ar (25 ml/min) from RT to 900 0 C at a heating rate of 5 °C/min.
  • the effluent gas was analyzed using a micro GC (Model: Agilent 3000 Micro GC) equipped with Molecular sieve column/PLOTU pre-column (Ar carrier gas) for detecting N 2 and H 2 and PLOTU column/PLOTQ pre-column (He carrier gas) for detecting NH 3 .
  • the columns were equipped with TCD detectors.

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Abstract

L'invention porte sur un procédé pour le dépôt d'une couche mince renfermant de l'oxyde de molybdène sur une surface d'un substrat par la technique de dépôt de couches atomiques ALD, le procédé comportant les étapes consistant : a) à faire réagir un jet discontinu de précurseur de Mo sans halogène avec la surface; b) à purger avec un gaz inerte ou vidanger le réacteur; c) à faire réagir un jet discontinu de précurseur contenant de l'oxygène avec la surface; et d) à purger avec un gaz inerte ou vidanger le réacteur; ce qui permet d'obtenir ainsi un film contenant de l'oxyde de molybdène. En outre, la présente invention porte sur des couches minces obtenues par ce procédé.
PCT/NO2010/000120 2009-03-30 2010-03-29 Couches minces contenant de l'oxyde de molybdène WO2010114386A1 (fr)

Applications Claiming Priority (2)

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NO20091287 2009-03-30
NO20091287 2009-03-30

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WO2010114386A1 true WO2010114386A1 (fr) 2010-10-07
WO2010114386A8 WO2010114386A8 (fr) 2011-09-29

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CN103668108A (zh) * 2013-12-10 2014-03-26 中国科学院微电子研究所 一种氧化物介质的原子层沉积方法
WO2014140863A2 (fr) * 2013-03-15 2014-09-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Molécules de bis(alkylimido)-bis(alkylamido)molybdène pour le dépôt de for de films contenant du molybdène
WO2016191432A1 (fr) * 2015-05-27 2016-12-01 Asm Ip Holding B.V. Synthèse et utilisation de précurseurs pour le dépôt de couches atomiques de couches minces à base de molybdène ou de tungstène
JP2017029878A (ja) * 2015-07-29 2017-02-09 株式会社東芝 複合触媒層の形成方法、電気化学反応装置用構造体、および光電気化学反応装置
WO2018213305A1 (fr) * 2017-05-15 2018-11-22 Starfire Energy Oxyde d'aluminium de baryum et de calcium décoré par du métal et matériaux apparentés pour la catalyse d'ammoniac (nh3)
US10787367B2 (en) 2017-05-26 2020-09-29 Starfire Energy Removal of gaseous NH3 from an NH3 reactor product stream
US20210047726A1 (en) * 2019-08-12 2021-02-18 Applied Materials, Inc. Molybdenum Thin Films By Oxidation-Reduction
US20210054500A1 (en) * 2019-08-23 2021-02-25 Asm Ip Holding B.V. Methods for forming a polycrystalline molybdenum film over a surface of a substrate and related structures including a polycrystalline molybdenum film
US11014866B2 (en) 2016-10-12 2021-05-25 Asm Ip Holding B.V. Synthesis and use of precursors for vapor deposition of tungsten containing thin films
CN113697857A (zh) * 2021-09-14 2021-11-26 河北地质大学 一种二维片状氧化钼纳米材料的制备方法及应用
CN114436338A (zh) * 2022-03-01 2022-05-06 青岛大学 一种铁钼双金属纳米酶及其制备方法和应用
US11492701B2 (en) 2019-03-19 2022-11-08 Asm Ip Holding B.V. Reactor manifolds
US11549179B2 (en) * 2020-05-19 2023-01-10 Tokyo Electron Limited Film forming method
WO2023086298A1 (fr) * 2021-11-10 2023-05-19 Entegris, Inc. Composés précurseurs de molybdène
US11791153B2 (en) 2020-02-10 2023-10-17 Asm Ip Holding B.V. Deposition of hafnium oxide within a high aspect ratio hole
US11807541B2 (en) 2016-03-01 2023-11-07 Starfire Energy Electrically enhanced Haber-Bosch (EEHB) anhydrous ammonia synthesis
US11830731B2 (en) 2019-10-22 2023-11-28 Asm Ip Holding B.V. Semiconductor deposition reactor manifolds

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WO2012027575A1 (fr) * 2010-08-27 2012-03-01 Sigma-Aldrich Co. Llc Précurseurs de molybdène (iv)‑amide et leur utilisation dans le dépôt de couches atomiques
US9802220B2 (en) 2010-08-27 2017-10-31 Merck Patent Gmbh Molybdenum (IV) amide precursors and use thereof in atomic layer deposition
WO2014140863A2 (fr) * 2013-03-15 2014-09-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Molécules de bis(alkylimido)-bis(alkylamido)molybdène pour le dépôt de for de films contenant du molybdène
WO2014140672A1 (fr) * 2013-03-15 2014-09-18 L'air Liquide, Societe Anonyme Pour I'etude Et I'exploitation Des Procedes Georges Claude Molécules de bis(alkylimido)-bis-(alkylamido) molybdène pour le dépôt de films contenant du molybdène
WO2014140863A3 (fr) * 2013-03-15 2015-01-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Molécules de bis(alkylimido)-bis(alkylamido)molybdène pour le dépôt de for de films contenant du molybdène
KR20150126857A (ko) * 2013-03-15 2015-11-13 레르 리키드 쏘시에떼 아노님 뿌르 레뜌드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 몰리브데넘-함유 필름의 증착을 위한 비스(알킬이미도)-비스(알킬아미도)몰리브데넘 분자
KR101627988B1 (ko) 2013-03-15 2016-06-07 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 몰리브데넘-함유 필름의 증착을 위한 비스(알킬이미도)-비스(알킬아미도)몰리브데넘 분자
TWI596099B (zh) * 2013-03-15 2017-08-21 液態空氣喬治斯克勞帝方法研究開發股份有限公司 用於含鉬薄膜之沉積之雙（烷基亞胺基）－雙（烷基醯胺基）鉬分子
CN103668108A (zh) * 2013-12-10 2014-03-26 中国科学院微电子研究所 一种氧化物介质的原子层沉积方法
US11047042B2 (en) 2015-05-27 2021-06-29 Asm Ip Holding B.V. Synthesis and use of precursors for ALD of molybdenum or tungsten containing thin films
WO2016191432A1 (fr) * 2015-05-27 2016-12-01 Asm Ip Holding B.V. Synthèse et utilisation de précurseurs pour le dépôt de couches atomiques de couches minces à base de molybdène ou de tungstène
US11624112B2 (en) 2015-05-27 2023-04-11 Asm Ip Holding B.V. Synthesis and use of precursors for ALD of molybdenum or tungsten containing thin films
JP2017029878A (ja) * 2015-07-29 2017-02-09 株式会社東芝 複合触媒層の形成方法、電気化学反応装置用構造体、および光電気化学反応装置
US11807541B2 (en) 2016-03-01 2023-11-07 Starfire Energy Electrically enhanced Haber-Bosch (EEHB) anhydrous ammonia synthesis
US11667595B2 (en) 2016-10-12 2023-06-06 Asm Ip Holding B.V. Synthesis and use of precursors for vapor deposition of tungsten containing thin films
US11014866B2 (en) 2016-10-12 2021-05-25 Asm Ip Holding B.V. Synthesis and use of precursors for vapor deposition of tungsten containing thin films
US11325105B2 (en) 2017-05-15 2022-05-10 Starfire Energy Metal-decorated barium calcium aluminum oxide and related materials for NH3 catalysis
US11772071B2 (en) 2017-05-15 2023-10-03 Starfire Energy Metal-decorated barium calcium aluminum oxide and related materials for NH3 catalysis
WO2018213305A1 (fr) * 2017-05-15 2018-11-22 Starfire Energy Oxyde d'aluminium de baryum et de calcium décoré par du métal et matériaux apparentés pour la catalyse d'ammoniac (nh3)
US10787367B2 (en) 2017-05-26 2020-09-29 Starfire Energy Removal of gaseous NH3 from an NH3 reactor product stream
US11492701B2 (en) 2019-03-19 2022-11-08 Asm Ip Holding B.V. Reactor manifolds
US11891690B2 (en) * 2019-08-12 2024-02-06 Applied Materials, Inc. Molybdenum thin films by oxidation-reduction
US20210047726A1 (en) * 2019-08-12 2021-02-18 Applied Materials, Inc. Molybdenum Thin Films By Oxidation-Reduction
US11827978B2 (en) 2019-08-23 2023-11-28 Asm Ip Holding B.V. Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film
US11898242B2 (en) 2019-08-23 2024-02-13 Asm Ip Holding B.V. Methods for forming a polycrystalline molybdenum film over a surface of a substrate and related structures including a polycrystalline molybdenum film
US20210054500A1 (en) * 2019-08-23 2021-02-25 Asm Ip Holding B.V. Methods for forming a polycrystalline molybdenum film over a surface of a substrate and related structures including a polycrystalline molybdenum film
US11830731B2 (en) 2019-10-22 2023-11-28 Asm Ip Holding B.V. Semiconductor deposition reactor manifolds
US11791153B2 (en) 2020-02-10 2023-10-17 Asm Ip Holding B.V. Deposition of hafnium oxide within a high aspect ratio hole
US11549179B2 (en) * 2020-05-19 2023-01-10 Tokyo Electron Limited Film forming method
CN113697857B (zh) * 2021-09-14 2023-01-24 河北地质大学 一种二维片状氧化钼纳米材料的制备方法及应用
CN113697857A (zh) * 2021-09-14 2021-11-26 河北地质大学 一种二维片状氧化钼纳米材料的制备方法及应用
WO2023086298A1 (fr) * 2021-11-10 2023-05-19 Entegris, Inc. Composés précurseurs de molybdène
CN114436338B (zh) * 2022-03-01 2023-07-25 青岛大学 一种铁钼双金属纳米酶及其制备方法和应用
CN114436338A (zh) * 2022-03-01 2022-05-06 青岛大学 一种铁钼双金属纳米酶及其制备方法和应用

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