WO2014118750A1 - Composés contenant du manganèse, leur synthèse et utilisation dans un dépôt de film contenant du manganèse - Google Patents

Composés contenant du manganèse, leur synthèse et utilisation dans un dépôt de film contenant du manganèse Download PDF

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WO2014118750A1
WO2014118750A1 PCT/IB2014/058714 IB2014058714W WO2014118750A1 WO 2014118750 A1 WO2014118750 A1 WO 2014118750A1 IB 2014058714 W IB2014058714 W IB 2014058714W WO 2014118750 A1 WO2014118750 A1 WO 2014118750A1
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manganese
compound
simn
group
formula
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PCT/IB2014/058714
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English (en)
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Satoko Gatineau
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L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Priority to JP2015555838A priority Critical patent/JP2016513087A/ja
Publication of WO2014118750A1 publication Critical patent/WO2014118750A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers

Definitions

  • Manganese-containing compounds their synthesis, and their use for the deposition of manganese-containing films are disclosed.
  • CVD Chemical Vapor Deposition
  • ALD Atomic Layer Deposition
  • Manganese-containing films are becoming important for a variety of electronics and electrochemical applications.
  • manganese silicate MnSiOx
  • the adhesion property of copper and MnSiO x was found to be strong enough to meet semiconductor industry requirement for interconnections.
  • Manganese-metal alloys like Mn-Cu, Mn-Pt may serve as seed layers.
  • Deposition using alkyl or halide silyl manganese pentacarbonyl precursors are also known for forming manganese-containing films. See, e.g., Kodas et al., The chemistry of metal CVD, 9.2 Classification of precursors, pp. 431 -433; Aylett et al., Chemical vapor deposition of transition-metal silicides by pyrolysis of silyl transition-metal carbonyl compound, J.C.S. Dalton, pp.2058-2061 (1977); Schmitt et al., Synthesis and applications of metal silicide nanowires, Journal of material chemistry, 20, pp. 223-235 (2010);. Higgins et al., Higher manganese silicide nanowires of nowotny chimney ladder phase, Journal of American chemical society 130, pp. 16086-16094 (2008).
  • alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl.
  • cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
  • hydrocarbon means a functional group containing exclusively hydrogen and carbon atoms.
  • the functional group may be saturated (containing only single bonds) or unsaturated (containing double or triple bonds).
  • the abbreviation "Me” refers to a methyl group
  • the abbreviation “Et” refers to an ethyl group
  • the abbreviation “Pr” refers to any propyl group (i.e., n-propyl or isopropyl);
  • the abbreviation “iPr” refers to an isopropyl group
  • the abbreviation “Bu” refers to any butyl group (n-butyl, iso-butyl, t-butyl, sec-butyl);
  • the abbreviation “tBu” refers to a tert-butyl group
  • the abbreviation “sBu” refers to a sec-butyl group
  • the abbreviation “iBu” refers to an iso-butyl group
  • the abbreviation “ph” refers to a phenyl group
  • the abbreviation “Cp” refers to cyclopentadieny
  • the disclosed compounds may have one or more of the following aspects:
  • NMe 3 selected from the group consisting of NMe 3 , NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 0, and Et 2 0;
  • a manganese-containing compound is introduced into a reactor having a substrate disposed therein. At least part of the manganese-containing compound is deposited onto the substrate to form the manganese-containing film.
  • the manganese-containing compounds have one of the following formulae:
  • the disclosed methods may have one or more of the following aspects:
  • neutral adduct ligands selected from the group consisting of NMe3, NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 0, and Et 2 0;
  • the manganese-containing compound having Formula II the manganese-containing compound being (CO)5MnSiH 2 Mn(CO)5, the manganese-containing compound being (CO) 5 MnSiMe 2 Mn(CO)5, the manganese-containing compound being (CO)5MnSiEt 2 Mn(CO)5, the manganese-containing compound being (CO) 5 MnSi(iPr) 2 Mn(CO)5, the manganese-containing compound being (CO) 5 MnSi(Ph) 2 Mn(CO)5, the manganese-containing compound being
  • the depositing step being chemical vapor deposition (CVD);
  • the depositing step being atomic layer deposition (ALD);
  • the depositing step being plasma enhanced chemical vapor deposition
  • PECVD PECVD
  • the depositing step being plasma enhanced atomic layer deposition (PEALD);
  • the depositing step being pulsed chemical vapor deposition (PCVD);
  • the depositing step being low pressure chemical vapor deposition (LPCVD);
  • the depositing step being sub-atmospheric chemical vapor deposition (SACVD);
  • the depositing step being atmospheric pressure chemical vapor depositi (APCVD);
  • the depositing step being spatial ALD
  • the depositing step being radicals incorporated deposition
  • the depositing step being super critical fluid deposition
  • the depositing step being a combination of two or more of CVD, ALD,
  • PECVD PEALD, PCVD, LPCVD, SACVD, APCVD, spatial ALD, radicals incorporated deposition, or super critical deposition;
  • the method being performed at a temperature between about 20°C and about 800°C;
  • the method being performed at a temperature between about 25°C and about 600°C; • the reactor having a pressure between approximately 0.1 Pa and
  • the manganese-containing film being manganese nitride (Mn x N y ), wherein x and y are each integers ranging inclusively from 1 to 3;
  • the manganese-containing film being manganese silicide (Mn x Si y ), wherein x and y are each integers ranging inclusively from 1 to 3;
  • the manganese-containing film being manganese silicide nitride (Mn x Si y N z ), wherein x, y, and z are each integers ranging inclusively from 1 to 3;
  • the manganese-containing film being manganese oxide (Mn x O y ), wherein x and y are each integers ranging inclusively from 1 to 3;
  • the manganese-containing film being manganese silicate (MnSiO x ), wherein x is an integer ranging inclusively from 1 to 3;
  • the manganese-containing film being manganese-doped indium arsenide (In, Mn)As;
  • the manganese-containing film being manganese-doped gallium arsenide (Ga, Mn)As;
  • the manganese-containing film being manganese-doped zinc oxide
  • the manganese-containing film being manganese-doped tin dioxide
  • reaction gas being a reducing agent selected from the group consisting of N 2 , H 2 , NH 3 , SiH 4 , Si 2 H 6 , Si 3 H 8 , (CH 3 ) 2 SiH 2 , (C 2 H 5 ) 2 SiH 2 , (CH 3 ) 3 SiH, (C 2 H 5 ) 3 SiH, [N(C 2 H 5 ) 2 ] 2 SiH 2 , N(CH 3 ) 3 , N(C 2 H 5 ) 3 , (SiMe 3 ) 2 NH, (CH 3 )HNNH 2 , (CH 3 ) 2 NNH 2 , phenyl hydrazine, B 2 H 6 , (SiH 3 ) 3 N, radical species of these reducing agents, and mixtures of these reducing agents; and • the reaction gas being an oxidizing reagent selected from the group consisting of 0 2 , 0 3 , H 2 0, H 2 0 2 , NO, NO 2, acetic acid,
  • the Formula I compound may include one or two neutral adduct ligands selected from the group consisting of NMe 3 , NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 O, and Et 2 O.
  • the ligand is NMe 3 or NEt 3 .
  • Exemplary Formula I compounds include, but are not limited to,
  • Exemplary Formula I I compounds include, but are not limited to,
  • the manganese-containing compounds may be synthesized by reacting Mn 2 (CO)i o with an excess amount of alkylsilane at -30°C. These reactants are commercially available. The mixture, with stirring, is warmed to room temperature to complete the reaction. During the reaction, hydrogen generation is observed. After 1 hour of stirring, excess alkylsilane is removed under vacuum at room temperature. The resulting dark color oil or solid is purified by vacuum distillation or sublimation.
  • the adduct may be synthesized by adding the manganese-containing compound to a solvent, such as toluene or dichloromethane. The resulting mixture is cooled to approximately -15°C. The adduct ligand is slowly added to the cooled mixture. The cooled adduct mixture is allowed to warm to room temperature (approximately 20°C), with continuous stirring. Excess adduct ligand is removed under vacuum. The resulting adduct product may be purified by distillation or sublimation.
  • a solvent such as toluene or dichloromethane
  • a manganese-containing compound is introduced into a reactor having a substrate disposed therein. At least part of the manganese-containing compound is deposited onto the substrate to form the manganese-containing film.
  • the man anese-containing compounds have one of the following formulae:
  • the Formula I compound may include one or two neutral adduct ligands selected from the group consisting of NMe 3 , NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 0, and Et 2 0.
  • the ligand is NMe3 or NEt 3 .
  • Exemplary Formula I compounds include, but are not limited to,
  • Exemplary Formula II compounds include, but are not limited to,
  • At least part of the disclosed manganese-containing compounds may be deposited onto a substrate to form the manganese-containing films by chemical vapor deposition (CVD), atomic layer deposition (ALD), or other types of depositions that are related to vapor coating such as plasma enhanced CVD (PECVD), plasma enhanced ALD (PEALD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD deposition (SACVD) or atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, also known as catCVD, in which a hot wire seres as a catalyst for the deposition process), spatial ALD, hot-wire
  • ALD HWALD
  • radicals incorporated deposition radicals incorporated deposition
  • super critical fluid deposition or combinations thereof Preferably, the deposition method is CVD, ALD or PE-ALD.
  • the disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel display devices.
  • the method includes introducing the vapor of at least one manganese-containing compound disclosed above into a reactor having at least one substrate disposed therein and depositing at least part of the manganese-containing compound onto the at least one substrate to form a manganese-containing layer using a vapor deposition process.
  • the temperature and the pressure within the reactor and the temperature of the substrate are held at conditions suitable for formation of the
  • a reaction gas may also be used to help in formation of the manganese-containing layer.
  • the reactor may be any enclosure or chamber of a device in which deposition methods take place, such as, without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, or other such types of deposition systems. All of these exemplary reactors are capable of serving as an ALD or CVD reactor.
  • the reactor may be maintained at a pressure ranging from about 0.5 mTorr to about 20 Torr.
  • the temperature within the reactor may range from about room temperature (20°C) to about 600°C.
  • the temperature may be optimized through mere experimentation to achieve the desired result.
  • the temperature of the reactor may be controlled by either controlling the temperature of the substrate holder (called a cold wall reactor) or controlling the temperature of the reactor wall (called a hot wall reactor) or combination of both methods.
  • Devices used to heat the substrate are known in the art.
  • the reactor wall may be heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition.
  • a non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 20°C to approximately 600°C.
  • the deposition temperature may range from approximately 20°C to approximately 550°C.
  • the deposition temperature may range from approximately 100°C to approximately 600°C.
  • the substrate may be heated to a sufficient temperature to obtain the desired manganese-containing layer at a sufficient growth rate and with desired physical state and composition.
  • a non-limiting exemplary temperature range to which the substrate may be heated includes from 100°C to 600°C.
  • the temperature of the substrate remains less than or equal to 500°C.
  • the substrate upon which the manganese-containing layer will be deposited will vary depending on the final use intended.
  • the substrate may be chosen from oxides which are used as dielectric materials in MIM, DRAM, or FeRam technologies (for example, Zr0 2 based materials, Hf0 2 based materials, ⁇ 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based layers (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer.
  • oxides which are used as dielectric materials in MIM, DRAM, or FeRam technologies (for example, Zr0 2 based materials, Hf0 2 based materials, ⁇ 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based layers (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer.
  • Other substrates may be used in the manufacture of semiconductors, photovoltaics, LCD
  • substrates include, but are not limited to, solid substrates such as copper and copper based alloy, metal nitride-containing substrates (for example, TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); insulators (for example, SiO 2 , Si 3 N 4 , SiON, HfO 2 , Ta 2 O 5 , ZrO 2 , TiO 2 , AI 2 O 3 , and barium strontium titanate); or other substrates that include any number of combinations of these materials.
  • the actual substrate utilized may also depend upon the specific compound embodiment utilized. In many instances though, the preferred substrate utilized will be selected from Si and SiO 2 substrates.
  • the disclosed manganese-containing compounds may be supplied either in neat form or in a blend with a suitable solvent, such as ethyl benzene, xylene, mesitylene, decane, dodecane, to form a precursor mixture.
  • a suitable solvent such as ethyl benzene, xylene, mesitylene, decane, dodecane
  • the disclosed compounds may be present in varying concentrations in the solvent.
  • One or more of the neat compounds or precursor mixtures are introduced into a reactor in vapor form by conventional means, such as tubing and/or flow meters.
  • the vapor form of the neat compound or precursor mixture may be produced by vaporizing the neat compound or precursor mixture through a conventional vaporization step such as direct vaporization, distillation, by bubbling, or by using a sublimator such as the one disclosed in PCT Publication
  • the neat compound or precursor mixture may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor.
  • the neat compound or precursor mixture may be vaporized by passing a carrier gas into a container containing the neat compound or precursor mixture or by bubbling the carrier gas into the neat compound or precursor mixture.
  • the carrier gas may include, but is not limited to, Ar, He, N 2 ,and mixtures thereof. The carrier gas and compound are then introduced into the reactor as a vapor.
  • the container of the neat compound or precursor mixture may be heated to a temperature that permits the neat compound or precursor mixture to be in its liquid phase and to have a sufficient vapor pressure.
  • the container may be maintained at temperatures in the range of, for example, approximately 0°C to approximately 200°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
  • the manganese-containing compound may be mixed with a reaction gas inside the reactor.
  • the reaction gas may include a reducing reagent which is selected from, but not limited to, N 2 , H 2 , NH 3 , SiH 4 , Si 2 H 6 , Si 3 H 8 , (CH 3 ) 2 SiH 2 , (C 2 H 5 ) 2 SiH 2 , (CH 3 ) 3 SiH, (C 2 H 5 ) 3 SiH, [N(C 2 H 5 ) 2 ] 2 SiH 2 , N(CH 3 ) 3 , N(C 2 H 5 ) 3 , (SiMe 3 ) 2 NH, (CH 3 )HNNH 2 , (CH 3 ) 2 NNH 2 , phenyl hydrazine, B 2 H 6 , (SiH 3 ) 3 N, radical species of these reducing agents, and mixtures of these reducing agents.
  • the reducing reagent is H 2 .
  • the reaction gas may include an oxidizing reagent which is selected from, but not limited to, 0 2 , O3, H 2 0, H 2 0 2 , acetic acid, formalin, para-formaldehyde, radical species of these oxidizing agents, and mixtures of these oxidizing agents.
  • the oxidizing reagent is H 2 0.
  • the reaction gas may be treated by plasma in order to decompose the reaction gas into its radical form.
  • the plasma may be generated or present within the reaction chamber itself. Alternatively, the plasma may generally be at a location removed from the reaction chamber, for instance, in a remotely located plasma system.
  • One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
  • the reaction gas may be introduced into a direct plasma reactor, which generates plasma in the reaction chamber, to produce the plasma-treated reaction gas in the reaction chamber.
  • direct plasma reactors include the TitanTM PECVD System produced by Trion Technologies.
  • the reaction gas may be introduced and held in the reaction chamber prior to plasma processing. Alternatively, the plasma processing may occur
  • In-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder.
  • the substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs.
  • Typical applied powers in in-situ plasma generators are from approximately 50W to approximately 1000 W.
  • the disassociation of the reaction gas using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reaction gas disassociation as a remote plasma system, which may be beneficial for the deposition of
  • the plasma-treated reaction gas may be produced outside of the reaction chamber.
  • the MKS Instruments' ASTRONi ® reactive gas generator may be used to treat the reaction gas prior to passage into the reaction chamber. Operated at 2.45 GHz, 7kW plasma power, and a pressure ranging from
  • the reaction gas O 2 may be decomposed into two O " radicals.
  • the remote plasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
  • the reaction gas may include a second precursor which is selected from, but not limited to, metal alkyls, such as (CH3)3AI, metal amines, such as
  • the manganese-containing compound and one or more reaction gases may be introduced into the reactor simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations.
  • the manganese-containing compound may be introduced in one pulse and two additional precursors may be introduced together in a separate pulse [modified atomic layer deposition].
  • the reactor may already contain the reaction gas prior to introduction of the manganese-containing compound.
  • the manganese-containing compound may be introduced to the reactor continuously while other reaction gases are introduced by pulse
  • the reaction gas may be passed through a plasma system localized or remotely from the reactor, and decomposed to radicals.
  • a pulse may be followed by a purge or evacuation step to remove excess amounts of the component introduced.
  • the pulse may last for a time period ranging from about 0.01 s to about 30 s, alternatively from about 0.3 s to about 3 s, alternatively from about 0.5 s to about 2 s.
  • the manganese-containing compound and one or more reaction gases may be simultaneously sprayed from a shower head under which a susceptor holding several wafers is spun (spatial ALD).
  • the vapor phase of a manganese-containing compound is introduced into the reactor, where it is contacted with a suitable substrate. Excess manganese-containing compound may then be removed from the reactor by purging and/or evacuating the reactor. An oxidizing reagent is introduced into the reactor where it reacts with the absorbed manganese-containing compound in a self-limiting manner. Any excess oxidizing reagent is removed from the reactor by purging and/or evacuating the reactor. If the desired layer is a manganese oxide layer, this two-step process may provide the desired layer thickness or may be repeated until a layer having the necessary thickness has been obtained.
  • the manganese-containing layers resulting from the processes discussed above may include pure manganese, manganese nitride (Mn x N y ), manganese silicide (Mn x Si y ), manganese silicide nitride (Mn x Si y N z ), manganese oxide (Mn x O y ), manganese silicate (MnSiO x ), manganese-doped indium arsenide ⁇ (ln,Mn)As ⁇ , manganese-doped gallium arsenide ⁇ (Ga,Mn)As ⁇ , manganese-doped zinc oxide ⁇ (Mn)ZnO ⁇ , and manganese-doped tin dioxide ⁇ (Mn)Sn02 ⁇ , wherein x and y are integers which each inclusively ranges from 1 to 3.
  • x and y are integers which each inclusively ranges from 1 to 3.
  • composition may be obtained.
  • the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure.
  • further processing such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure.
  • the manganese-containing film may be exposed to a temperature ranging from approximately 200°C to approximately 1000°C for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, a H-containing atmosphere, a N-containing atmosphere, an O-containing atmosphere, or combinations thereof.
  • the inert atmosphere a H-containing atmosphere, a N-containing atmosphere, an O-containing atmosphere, or combinations thereof.
  • the annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, is expected to effectively reduce any carbon and nitrogen contamination of the manganese-containing film. This in turn is expected to improve the resistivity of the film.
  • the disclosed manganese-containing compounds may be used as doping or implantation agents.
  • the disclosed manganese-containing compounds may be used as doping or implantation agents.
  • manganese-containing precursors may be deposited on top of the film to be doped, such as an indium arsenide (InAs) film, a gallium arsenide (GaAs) film (a zinc oxide (ZnO) film, or a tin dioxide (Sn02) film.
  • InAs indium arsenide
  • GaAs gallium arsenide
  • ZnO zinc oxide
  • Sn02 tin dioxide
  • high energy ion implantation using a variable energy radio frequency quadrupole implanter may be used to dope the manganese of the
  • manganese-containing compound into a film. See, e.g., Kensuke et al., JVSTA 16(2) Mar/Apr 1998, the implantation method of which is incorporated herein by reference in its entirety.
  • plasma doping, pulsed plasma doping or plasma immersion ion implantation may be performed using the disclosed manganese-containing compounds. See, e.g., Felch et al., Plasma doping for the fabrication of ultra-shallow junctions Surface Coatings Technology, 156 (1 -3) 2002, pp. 229-236, the doping method of which is incorporated herein by reference in its entirety. Examples
  • Mn 2 (CO)io will be added to a 100 ml_ flask. Liquid SiH 2 Et 2 will slowly be dropped into the flask at -30°C. The mixture will be allowed to warm to room temperature with continuous stirring to complete reaction. Hydrogen gas was generated after 5 min stirring. After 1 hour of stirring, excess SiH 2 Et 2 was removed as a gas under vacuum at room temperature. The product may be purified by distillation under vacuum.
  • Mn 2 (CO)io will be added to a 100 mL flask. Liquid Si(H)Et 3 will slowly be dropped into the flask at -30°C. The mixture will be allowed to warm to room temperature with continuous stirring to complete reaction. Hydrogen gas will be generated during stirring. After 1 hour stirring, excess SiHEt 3 will be removed as a gas under vacuum at room temperature. The product may be purified by distillation under vacuum.
  • Mn 2 (CO)io will be added to a 100 mL flask. Liquid Si(H)iPr 3 will slowly be dropped into the flask at -30°C. The mixture will be allowed to warm to room temperature with continuous stirring to complete reaction. Hydrogen gas will be generated during stirring. After 1 hour stirring, excess SiHEt 3 will be removed as a gas under vacuum at room temperature. The product may be purified by distillation under vacuum.
  • Mn 2 (CO)io will be added to a 100 ml_ flask. Liquid SiH 2 Et 2 will slowly be dropped into the flask at -30°C. The mixture will be allowed to warm to room temperature with continuous stirring to complete reaction. Hydrogen gas will be generated after 5 min stirring. After 1 hour of stirring, excess SiH 2 Et 2 will be removed as a gas under vacuum at room temperature. This method is the same method used to synthesize (CO) 5 MnSi(H)Et 2 in the example above.
  • any of the disclosed compounds may be used to deposit Mn x Si y films using ALD techniques known in the art and H 2 as a reaction gas.
  • any of the disclosed compounds may be used to deposit Mn films using plasma enhanced ALD techniques known in the art and H 2 and NH 3 as reaction gases.
  • any of the disclosed compounds may be used to deposit MnSiOx films using CVD techniques known in the art using O 2 or H 2 O as a reaction gas.
  • any of the disclosed compounds may be used to deposit Mn x N y films using CVD techniques known in the art using NH 3 as a reaction gas.
  • any of the disclosed compounds may be used to deposit Mn x Si y N z films using CVD techniques known in the art using NH3 as a reaction gas.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des composés contenant du manganèse, leur synthèse et leur utilisation pour le dépôt de films contenant du manganèse. Les composés contenant du manganèse décrits ont la formule suivante : I dans laquelle chacun parmi R, R 2 et R 3 est indépendamment choisi parmi hydrogène ou des hydrocarbures linéaires, cycliques ou ramifiés, à la condition que R, R 2 et R 3 représentent un groupe hydrocarboné en C3-C4 lorsque R =R 2 =R 3 et que chacun parmi R 4 et R 5 est indépendamment choisi parmi un groupe hydrocarboné linéaire, cyclique ou ramifié.
PCT/IB2014/058714 2013-01-31 2014-01-31 Composés contenant du manganèse, leur synthèse et utilisation dans un dépôt de film contenant du manganèse WO2014118750A1 (fr)

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US9786760B1 (en) 2016-09-29 2017-10-10 International Business Machines Corporation Air gap and air spacer pinch off
CN110482675A (zh) * 2019-08-25 2019-11-22 山东理工大学 一种用硅酸锰处理亚甲基蓝废水的方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016172792A1 (fr) * 2015-04-30 2016-11-03 Seastar Chemicals Inc. Composés organométalliques utiles pour le dépôt chimique en phase
US11498938B2 (en) 2015-04-30 2022-11-15 Seastar Chemicals Ulc Organometallic compounds useful for chemical phase deposition
US9786760B1 (en) 2016-09-29 2017-10-10 International Business Machines Corporation Air gap and air spacer pinch off
CN110482675A (zh) * 2019-08-25 2019-11-22 山东理工大学 一种用硅酸锰处理亚甲基蓝废水的方法

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