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US20030124267A1 - Method for manufacturing metal film having high purity - Google Patents

Method for manufacturing metal film having high purity Download PDF

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US20030124267A1
US20030124267A1 US10/320,580 US32058002A US2003124267A1 US 20030124267 A1 US20030124267 A1 US 20030124267A1 US 32058002 A US32058002 A US 32058002A US 2003124267 A1 US2003124267 A1 US 2003124267A1
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Younsoo Kim
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SK Hynix Inc
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical 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
    • C23C16/18Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45527Atomic 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

Definitions

  • Methods for manufacturing metal films are disclosed, and more particularly, methods for manufacturing a cobalt film, a rhodium film or an iridium film are disclosed wherein the films have a high purity via a Chemical Vapor Deposition (hereinafter, referred to as ‘CVD’) process without using reaction gas at a low deposition temperature.
  • CVD Chemical Vapor Deposition
  • the conventional CVD methods uses source in gas state to grow thin films.
  • the thin films are deposited using metal precursor in solid source or metal precursor in liquid source due to difficulties in vaporizing those materials.
  • the above process is performed in a device comprising a source supply, a vaporizer and a reactor.
  • the sources from the source supply are injected in the vaporizer.
  • the temperature of the vaporizer is maintained at temperature higher than vaporization temperatures of the sources and lower than reaction temperatures or deposition temperatures of the sources. Therefore, the injected metal precursor in solid or liquid sources are vaporized instantly in the vaporizer maintained at high temperature.
  • the vaporized source is injected into the reactor by carrier gas and reacts with reaction gas to form a desired thin film on a semiconductor substrate.
  • precursors such as MX or MX 3 where M is cobalt, iridum or rhodium having oxidation number of metal of +1 or +3 is used as precursors, and wherein oxygen or hydrogen is used as reaction gas, and wherein X is anion ligand.
  • oxygen reacts with the metal precursor MX or MX 3 to reduce or oxidize metal.
  • oxygen reacts with anion ligand X to make the side-product.
  • neutral side-product made from oxidation-reduction reaction may be removed using a vacuum.
  • anion or cation side-products remain in the films because they difficult to remove.
  • the oxygen reacts with metal precursor MX or MX 3 under gaseous atmosphere to cause decomposition reaction, by which lump of inactive materials such as carbonate or oxide are formed on the films to generate particles.
  • the deposition temperature should be greater than 700° C. to activate hydrogen, which causes the metal precursor MX or MX 3 to self-decompose to form carbonate. As a result, impurities still remain in the films.
  • metal films are used as upper electrodes on oxide films such as Ta 2 O 5 film, BST film, PZT film or SBT film
  • oxide films such as Ta 2 O 5 film, BST film, PZT film or SBT film
  • hydrogen used under high temperature environment reduces the oxide film. As a result, desired electric characteristics cannot be obtained.
  • a cobalt film, rhodium film or iridium film wherein the films have a high purity via a CVD method at a low deposition temperature without using reaction gas such as oxygen or hydrogen by using a disproportionate reaction of a metal precursor wherein oxidation number of the metal is +1.
  • a disclosed method for manufacturing a metal film comprises:
  • the metal precursor having a structure formula M(L)X wherein the metal M has an oxidation number of +1 is explained.
  • the M which is metal, is preferably selected from the group consisting of cobalt, rhodium and iridium, the L is neutral ligand, and X is anion ligand.
  • solvent used in the M(L)X solution is selected from the group consisting of C 1 -C 20 alkane, C 2 -C 20 alkene, C 2 -C 20 alkyne, C 1 -C 20 alcohol, C 2 -C 20 ether, C 2 -C 20 carboxylic acid, C 3 -C 20 ester, C 3 -C 20 ⁇ -diketone, C 1 -C 20 amine, C 6 -C 20 arene, C 4 -C 20 cyclic alkane, C 3 -C 20 cyclic ether, C 1 -C 20 alkane substituted with halogen, C 2 -C 20 alkene substituted with halogen, C 2 -C 20 alkyne substituted with halogen, C 1 -C 20 alcohol substituted with halogen, C 2 -C 20
  • the neutral ligand L is selected from the group consisting of CO, CS, CS 2 , RCN, RNC, OR 2 , SR 2 , NR 3 , PR 3 , NR 2 R′, PR 2 P′, ROR′, RSR′, C 2 -C 20 alkylidene, C 2 -C 20 alkylidyne, C 4 -C 20 cyclic alkylidene, C 4 -C 20 diene, C 6 -C 20 triene, C 4 -C 20 cyclic diene, C 2 -C 20 cyclic triene, C 6 -C 20 arene, C 2 -C 20 ether, C 1 -C 20 amine, C 3 -C 20 cyclic ether, RCN substituted with halogen, RNC substituted with halogen, OR 2 substituted with halogen, SR 2 substituted with halogen, NR 3 substituted with halogen, PR 3 substituted with halogen, NR
  • the anion ligand X is selected from the group consisting of H, F, Cl, Br, I, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, ⁇ -diketonate, cyclopentadienyl, C 1 -C 8 alkylcylcopentadienyl, C 1 -C 10 alkyl substituted with halogen, C 2 -C 10 alkenyl substituted with halogen, C 1 -C 8 alkoxy substituted with halogen, C 6 -C 12 aryl substituted with halogen, ⁇ -diketonate substituted with halogen, cyclopentadienyl substituted with halogen and C 1 -C 8 alkylcylcopentadienyl substituted with halogen.
  • the metal precursor M(L)X further comprises the neutral ligand L in an amount ranging from 0.1 to 50 wt %. Also, the metal precursor further comprises HX in an amount ranging from 0.1 to 50 wt %.
  • X is the above-described anion ligand.
  • the step (b) is performed at the presence of a catalyst selected from the group consisting of HF, HCl, HBr, HI, F 2 , C 12 , Br 2 , I 2 , C 1 -C 10 alkane substituted with halogen, C 2 -C 10 alkane substituted with halogen, C 1 -C 8 alkoxide substituted with halogen, C 6 -C 12 arene substituted with halogen, ⁇ -diketonate substituted with halogen, cyclopentadiene substituted with halogen and C 1 -C 8 alkylcyclopentadiene.
  • a catalyst selected from the group consisting of HF, HCl, HBr, HI, F 2 , C 12 , Br 2 , I 2 , C 1 -C 10 alkane substituted with halogen, C 2 -C 10 alkane substituted with halogen, C 1 -C 8 alkoxide substituted with halogen, C 6
  • the metal precursor M(L)X may be easily deposited as metal film according to the following disproportionate reaction.
  • the M(L)X may be deposited at relatively low temperature because electrons are exchanged between the same metals.
  • FIGS. 1 and 2 are cross-sectional diagrams illustrating the reaction mechanisms of the metal film deposition according to this disclosure.
  • metal precursor 2 such as pure solid state of M(L)X or a M(L)X solution having a molarity ranging from 0.05 M to 10M is sent from a source supply to a vaporizer using carrier gas such as argon or nitrogen.
  • carrier gas such as argon or nitrogen.
  • the metal precursor 2 is vaporized in the vaporizer and then provided to a reactor to be adsorbed on a surface of a semiconductor substrate 1 pre-heated to a temperature ranging from 100 to 900° C.
  • the adsorbed metal precursor 2 absorbs heat from the surface of the substrate 1 pre-heated to a temperature ranging from 100 to 900° C., and then decomposes according to the above-described reaction formulas. As a result, metal films 3 are formed.
  • M is a metal, preferably cobalt, rhodium or iridium
  • L is neutral ligand
  • X is anion ligand.
  • the side-products (MX 3 ) 4 and neutral ligand (L) 5 generated from the process are easily pumped out using vacuum due to their high vapor pressure.
  • solvent is preferably C 1 -C 20 alkane, C 2 -C 20 alkene, C 2 -C 20 alkyne, C 1 -C 20 alcohol, C 2 -C 20 ether, C 2 -C 20 carboxylic acid, C 3 -C 20 ester, C 3 -C 20 ⁇ -diketone, C 1 -C 20 amine, C 6 -C 20 arene, C 4 -C 20 cyclic alkane, C 3 -C 20 cyclic ether, C 1 -C 20 alkane substituted with halogen, C 2 -C 20 alkene substituted with halogen, C 2 -C 20 alkyne substituted with halogen, C 1 -C 20 alcohol substituted with halogen, C 2 -C 20 ether substituted with halogen, C 2 -C 20 carboxylic acid substituted with halogen, C 3 -C 20 ester substituted withd with
  • the neutral ligand L 5 is preferably CO, CS, CS 2 , RCN, RNC, OR 2 , SR 2 , NR 3 , PR 3 , NR 2 R′, PR 2 P′, ROR′, RSR′, C 2 -C 20 alkylidene, C 2 -C 20 alkylidyne, C 4 -C 20 cyclic alkylidene, C 4 -C 20 diene, C 6 -C 20 triene, C 4 -C 20 cyclic diene, C 2 -C 20 cyclic triene, C 6 -C 20 arene, C 2 -C 20 ether, C 1 -C 20 amine, C 3 -C 20 cyclic ether, RCN substituted with halogen, RNC substituted with halogen, OR 2 substituted with halogen, SR 2 substituted with halogen, NR 3 substituted with halogen, PR 3 substituted with halogen, NR 2 R′ substitute
  • the anion ligand X is preferably H, F, Cl, Br, I, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, ⁇ -diketonate, cyclopentadienyl, C 1 -C 8 alkylcylcopentadienyl, C 1 -C 10 alkyl substituted with halogen, C 2 -C 10 alkenyl substituted with halogen, C 1 -C 8 alkoxy substituted with halogen, C 6 -C 12 aryl substituted with halogen, ⁇ -diketonate substituted with halogen, cyclopentadienyl substituted with halogen or C 1 -C 8 alkylcylcopentadienyl substituted with halogen.
  • additional neutral ligand (L) 5 in an amount ranging from 0.1 to 50 wt % may be added in the metal precursor.
  • reaction speed is increased due to catalyst reaction.
  • a catalyst is preferably HF, HCl, HBr, HI, F 2 , Cl 2 , Br 2 , I 2 , C 1 -C 10 alkane substituted with halogen, C 2 -C 10 alkane substituted with halogen, C 1 -C 8 alkoxide substituted with halogen, C 6 -C 12 arene substituted with halogen, ⁇ -diketonate substituted with halogen, cyclopentadiene substituted with halogen or C 1 -C 8 alkylcyclopentadiene.
  • metal films having high purity may be deposited without impurities such as carbon, hydrogen or oxygen by using disproportionate reaction at low temperature because side-products such as L and MX 3 , which are neutral materials having high vapor pressure, are easily removed from a reactor by vacuum without remaining in the films. Additionally, almost no particles are generated because a reaction gas is not used.

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Abstract

Methods for manufacturing metal films, and more particularly, to a method for manufacturing a cobalt film, a rhodium film or an iridium film having high purity via a CVD method without using reaction gas at low deposition temperature. Metal films having high purity may be deposited without impurities such as carbon, hydrogen or oxygen by using disproportionate reaction at low temperature because side-products such as L and MX3, which are neutral materials having high vapor pressure, are easily removed from a reactor by vacuum without remaining in the films. Additionally, almost no particles are generated because reaction gas is not used.

Description

    BACKGROUND
  • 1. Technical Field [0001]
  • Methods for manufacturing metal films are disclosed, and more particularly, methods for manufacturing a cobalt film, a rhodium film or an iridium film are disclosed wherein the films have a high purity via a Chemical Vapor Deposition (hereinafter, referred to as ‘CVD’) process without using reaction gas at a low deposition temperature. [0002]
  • 2. Description of the Related Art [0003]
  • Generally, when semiconductor devices are manufactured, various processes are employed to form thin films. Particularly, a CVD process which provides improved step coverage and deposition rate of films is used to obtain uniform thin films. [0004]
  • In the CVD process, thin films or epitaxial layers are formed on semiconductor substrates from decomposed gaseous compounds by chemical reaction. Here, the formation process of the thin films is carried out using reaction gas which is injected into a reaction chamber from outside, not using materials on the semiconductor substrates. [0005]
  • The conventional CVD methods uses source in gas state to grow thin films. However, in case of high dielectric material or wiring materials, the thin films are deposited using metal precursor in solid source or metal precursor in liquid source due to difficulties in vaporizing those materials. [0006]
  • The above process is performed in a device comprising a source supply, a vaporizer and a reactor. The sources from the source supply are injected in the vaporizer. The temperature of the vaporizer is maintained at temperature higher than vaporization temperatures of the sources and lower than reaction temperatures or deposition temperatures of the sources. Therefore, the injected metal precursor in solid or liquid sources are vaporized instantly in the vaporizer maintained at high temperature. Then, the vaporized source is injected into the reactor by carrier gas and reacts with reaction gas to form a desired thin film on a semiconductor substrate. [0007]
  • In the conventional CVD method for manufacturing metal films such as iridium film or rhodium film, precursors such as MX or MX[0008] 3 where M is cobalt, iridum or rhodium having oxidation number of metal of +1 or +3 is used as precursors, and wherein oxygen or hydrogen is used as reaction gas, and wherein X is anion ligand.
  • According to the reaction mechanism, when metal films are deposited, oxygen reacts with the metal precursor MX or MX[0009] 3 to reduce or oxidize metal. In addition, oxygen reacts with anion ligand X to make the side-product. Here, neutral side-product made from oxidation-reduction reaction may be removed using a vacuum. However, anion or cation side-products remain in the films because they difficult to remove.
  • Decomposition reaction of oxygen and ligand is complicated and fast. As a result, impurities such as carbon, hydrogen and oxygen remain in metal films. Those impurities diffuse into other films during the subsequent thermal process or deposition process, thereby deteriorating characteristics of film. [0010]
  • In addition, in the conventional CVD method using oxygen, the oxygen reacts with metal precursor MX or MX[0011] 3 under gaseous atmosphere to cause decomposition reaction, by which lump of inactive materials such as carbonate or oxide are formed on the films to generate particles.
  • Accordingly, in order to solve the problem in the CVD method using the oxygen, hydrogen which is a reduction gas may be used instead of oxygen. However, the deposition temperature should be greater than 700° C. to activate hydrogen, which causes the metal precursor MX or MX[0012] 3 to self-decompose to form carbonate. As a result, impurities still remain in the films.
  • When metal films are used as upper electrodes on oxide films such as Ta[0013] 2O5 film, BST film, PZT film or SBT film, hydrogen used under high temperature environment reduces the oxide film. As a result, desired electric characteristics cannot be obtained.
  • SUMMARY OF THE DISCLOSURE
  • Accordingly, methods for manufacturing a cobalt film, rhodium film or iridium film are disclosed wherein the films have a high purity via a CVD method at a low deposition temperature without using reaction gas such as oxygen or hydrogen by using a disproportionate reaction of a metal precursor wherein oxidation number of the metal is +1. [0014]
  • A disclosed method for manufacturing a metal film comprises: [0015]
  • (a) vaporizing a metal precursor M(L)X, where M is a metal, L is a neutral ligand and X is an anion ligand, wherein the metal M has an oxidation number of +1; [0016]
  • (b) adsorbing the vaporized metal precursor on a semiconductor substrate heated to a temperature ranging from 100 to 900° C. to deposit metal layer on the substrate; and [0017]
  • (c) pumping out the side-product generated during the step (b). [0018]
  • First, the metal precursor having a structure formula M(L)X wherein the metal M has an oxidation number of +1 is explained. Here, the M, which is metal, is preferably selected from the group consisting of cobalt, rhodium and iridium, the L is neutral ligand, and X is anion ligand. [0019]
  • Pure solid state of M(L)X or M(L)X solution having a molarity ranging from 0.05 to 10M is used for metal precursor. Here, solvent used in the M(L)X solution is selected from the group consisting of C[0020] 1-C20 alkane, C2-C20 alkene, C2-C20 alkyne, C1-C20 alcohol, C2-C20 ether, C2-C20 carboxylic acid, C3-C20 ester, C3-C20 β-diketone, C1-C20 amine, C6-C20 arene, C4-C20 cyclic alkane, C3-C20 cyclic ether, C1-C20 alkane substituted with halogen, C2-C20 alkene substituted with halogen, C2-C20 alkyne substituted with halogen, C1-C20 alcohol substituted with halogen, C2-C20 ether substituted with halogen, C2-C20 carboxylic acid substituted with halogen, C3-C20 ester substituted with halogen, C3-C20 β-diketone substituted with halogen, C1-C20 amine substituted with halogen, C6-C20 arene substituted with halogen, C4-C20 cyclic alkane substituted with halogen and C3-C20 cyclic ether substituted with halogen.
  • The neutral ligand L is selected from the group consisting of CO, CS, CS[0021] 2, RCN, RNC, OR2, SR2, NR3, PR3, NR2R′, PR2P′, ROR′, RSR′, C2-C20 alkylidene, C2-C20 alkylidyne, C4-C20 cyclic alkylidene, C4-C20 diene, C6-C20 triene, C4-C20 cyclic diene, C2-C20 cyclic triene, C6-C20 arene, C2-C20 ether, C1-C20 amine, C3-C20 cyclic ether, RCN substituted with halogen, RNC substituted with halogen, OR2 substituted with halogen, SR2 substituted with halogen, NR3 substituted with halogen, PR3 substituted with halogen, NR2R′ substituted with halogen, PR2P′ substituted with halogen, ROR′ substituted with halogen, RSR′ substituted with halogen, C2-C20 alkylidene substituted with halogen, C2-C20 alkylidyne substituted with halogen, C4-C20 cyclic alkylidene substituted with halogen, C4-C20 diene substituted with halogen, C6-C20 triene substituted with halogen, C4-C20 cyclic diene substituted with halogen, C2-C20 cyclic triene substituted with halogen, C6-C20 arene substituted with halogen, C2-C20 ether substituted with halogen, C1-C20 amine substituted with halogen and C3-C20 cyclic ether substituted with halogen. Here, R and R′ are individually selected from the group consisting of H, C1-C10 alkyl and C1-C10 alkyl substituted with halogen.
  • The anion ligand X is selected from the group consisting of H, F, Cl, Br, I, C[0022] 1-C10 alkyl, C2-C10 alkenyl, C1-C8 alkoxy, C6-C12 aryl, β-diketonate, cyclopentadienyl, C1-C8 alkylcylcopentadienyl, C1-C10 alkyl substituted with halogen, C2-C10 alkenyl substituted with halogen, C1-C8 alkoxy substituted with halogen, C6-C12 aryl substituted with halogen, β-diketonate substituted with halogen, cyclopentadienyl substituted with halogen and C1-C8 alkylcylcopentadienyl substituted with halogen.
  • The metal precursor M(L)X further comprises the neutral ligand L in an amount ranging from 0.1 to 50 wt %. Also, the metal precursor further comprises HX in an amount ranging from 0.1 to 50 wt %. Here, X is the above-described anion ligand. [0023]
  • The step (b) is performed at the presence of a catalyst selected from the group consisting of HF, HCl, HBr, HI, F[0024] 2, C12, Br2, I2, C1-C10 alkane substituted with halogen, C2-C10 alkane substituted with halogen, C1-C8 alkoxide substituted with halogen, C6-C12 arene substituted with halogen, β-diketonate substituted with halogen, cyclopentadiene substituted with halogen and C1-C8 alkylcyclopentadiene.
  • The metal precursor M(L)X may be easily deposited as metal film according to the following disproportionate reaction. In addition, the M(L)X may be deposited at relatively low temperature because electrons are exchanged between the same metals.[0025]
  • Metal reaction formula: 3M+→2M+M3+
  • Overall reaction formula: 3M(L)X→2M+MX3+3L
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIGS. 1 and 2 are cross-sectional diagrams illustrating the reaction mechanisms of the metal film deposition according to this disclosure.[0026]
  • DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS
  • The CVD method performed according to the above-described reaction principle will be explained referring to FIGS. 1 and 2. [0027]
  • Referring to FIG. 1, [0028] metal precursor 2 such as pure solid state of M(L)X or a M(L)X solution having a molarity ranging from 0.05 M to 10M is sent from a source supply to a vaporizer using carrier gas such as argon or nitrogen. The metal precursor 2 is vaporized in the vaporizer and then provided to a reactor to be adsorbed on a surface of a semiconductor substrate 1 pre-heated to a temperature ranging from 100 to 900° C.
  • Referring to FIG. 2, the [0029] adsorbed metal precursor 2 absorbs heat from the surface of the substrate 1 pre-heated to a temperature ranging from 100 to 900° C., and then decomposes according to the above-described reaction formulas. As a result, metal films 3 are formed. Here, M is a metal, preferably cobalt, rhodium or iridium, L is neutral ligand and X is anion ligand. The side-products (MX3) 4 and neutral ligand (L) 5 generated from the process are easily pumped out using vacuum due to their high vapor pressure.
  • When the M(L)X solution is used as the metal precursor, solvent is preferably C[0030] 1-C20 alkane, C2-C20 alkene, C2-C20 alkyne, C1-C20 alcohol, C2-C20 ether, C2-C20 carboxylic acid, C3-C20 ester, C3-C20 β-diketone, C1-C20 amine, C6-C20 arene, C4-C20 cyclic alkane, C3-C20 cyclic ether, C1-C20 alkane substituted with halogen, C2-C20 alkene substituted with halogen, C2-C20 alkyne substituted with halogen, C1-C20 alcohol substituted with halogen, C2-C20 ether substituted with halogen, C2-C20 carboxylic acid substituted with halogen, C3-C20 ester substituted with halogen, C3-C20 β-diketone substituted with halogen, C1-C20 amine substituted with halogen, C6-C20 arene substituted with halogen, C4-C20 cyclic alkane substituted with halogen or C3-C20 cyclic ether substituted with halogen.
  • The neutral ligand L[0031] 5 is preferably CO, CS, CS2, RCN, RNC, OR2, SR2, NR3, PR3, NR2R′, PR2P′, ROR′, RSR′, C2-C20 alkylidene, C2-C20 alkylidyne, C4-C20 cyclic alkylidene, C4-C20 diene, C6-C20 triene, C4-C20 cyclic diene, C2-C20 cyclic triene, C6-C20 arene, C2-C20 ether, C1-C20 amine, C3-C20 cyclic ether, RCN substituted with halogen, RNC substituted with halogen, OR2 substituted with halogen, SR2 substituted with halogen, NR3 substituted with halogen, PR3 substituted with halogen, NR2R′ substituted with halogen, PR2P′ substituted with halogen, ROR′ substituted with halogen, RSR′ substituted with halogen, C2-C20 alkylidene substituted with halogen, C2-C20 alkylidyne substituted with halogen, C4-C20 cyclic alkylidene substituted with halogen, C4-C20 diene substituted with halogen, C6-C20 triene substituted with halogen, C4-C20 cyclic diene substituted with halogen, C2-C20 cyclic triene substituted with halogen, C6-C20 arene substituted with halogen, C2-C20 ether substituted with halogen, C1-C20 amine substituted with halogen or C3-C20 cyclic ether substituted with halogen. Here, R and R′ are preferably H, C1-C10 alkyl or C1-C10 alkyl substituted with halogen.
  • The anion ligand X is preferably H, F, Cl, Br, I, C[0032] 1-C10 alkyl, C2-C10 alkenyl, C1-C8 alkoxy, C6-C12 aryl, β-diketonate, cyclopentadienyl, C1-C8 alkylcylcopentadienyl, C1-C10 alkyl substituted with halogen, C2-C10 alkenyl substituted with halogen, C1-C8 alkoxy substituted with halogen, C6-C12 aryl substituted with halogen, β-diketonate substituted with halogen, cyclopentadienyl substituted with halogen or C1-C8 alkylcylcopentadienyl substituted with halogen.
  • In order to stabilize the metal precursor M(L)X during the deposition process of the [0033] metal films 3, additional neutral ligand (L) 5 in an amount ranging from 0.1 to 50 wt % may be added in the metal precursor. HX (X=anion ligand) in an amount ranging from 0.1 to 50 wt % may be added in the metal precursor to achieve the same objective.
  • Additionally, when materials including halogen are added, reaction speed is increased due to catalyst reaction. [0034]
  • Here, a catalyst is preferably HF, HCl, HBr, HI, F[0035] 2, Cl2, Br2, I2, C1-C10 alkane substituted with halogen, C2-C10 alkane substituted with halogen, C1-C8 alkoxide substituted with halogen, C6-C12 arene substituted with halogen, β-diketonate substituted with halogen, cyclopentadiene substituted with halogen or C1-C8 alkylcyclopentadiene.
  • As discussed earlier, metal films having high purity may be deposited without impurities such as carbon, hydrogen or oxygen by using disproportionate reaction at low temperature because side-products such as L and MX[0036] 3, which are neutral materials having high vapor pressure, are easily removed from a reactor by vacuum without remaining in the films. Additionally, almost no particles are generated because a reaction gas is not used.

Claims (12)

What is claimed is:
1. A method for manufacturing a metal film comprising:
(a) vaporizing a metal precursor M(L)X, where M is a metal, L is a neutral ligand and X is an anion ligand, wherein the metal M has an oxidation number of +1;
(b) adsorbing the vaporized metal precursor on a semiconductor substrate heated to a temperature ranging from 100 to 900° C. to deposit metal layer on the substrate; and
(c) pumping out the side-product generated during the step (b).
2. The method according to claim 1, wherein the metal M is selected from the group consisting of cobalt, rhodium and iridium.
3. The method according to claim 1, wherein the metal precursor is pure solid state of M(L)X or a M(L)X solution having a molarity ranging from 0.05 to 10M.
4. The method according to claim 3, wherein solvent used in the M(L)X solution is selected from the group consisting of C1-C20 alkane, C2-C20 alkene, C2-C20 alkyne, C1-C20 alcohol, C2-C20 ether, C2-C20 carboxylic acid, C3-C20 ester, C3-C20 β-diketone, C1-C20 amine, C6-C20 arene, C4-C20 cyclic alkane, C3-C20 cyclic ether, C1-C20 alkane substituted with halogen, C2-C20 alkene substituted with halogen, C2-C20 alkyne substituted with halogen, C1-C20 alcohol substituted with halogen, C2-C20 ether substituted with halogen, C2-C20 carboxylic acid substituted with halogen, C3-C20 ester substituted with halogen, C3-C20 β-diketone substituted with halogen, C1-C20 amine substituted with halogen, C6-C20 arene substituted with halogen, C4-C20 cyclic alkane substituted with halogen and C3-C20 cyclic ether substituted with halogen.
5. The method according to claim 1, wherein the neutral ligand L is selected from the group consisting of CO, CS, CS2, RCN, RNC, OR2, SR2, NR3, PR3, NR2R′, PR2P′, ROR′, RSR′, C2-C20 alkylidene, C2-C20 alkylidyne, C4-C20 cyclic alkylidene, C4-C20 diene, C6-C20 triene, C4-C20 cyclic diene, C2-C20 cyclic triene, C6-C20 arene, C2-C20 ether, C1-C20 amine, C3-C20 cyclic ether, RCN substituted with halogen, RNC substituted with halogen, OR2 substituted with halogen, SR2 substituted with halogen, NR3 substituted with halogen, PR3 substituted with halogen, NR2R′ substituted with halogen, PR2P′ substituted with halogen, ROR′ substituted with halogen, RSR′ substituted with halogen, C2-C20 alkylidene substituted with halogen, C2-C20 alkylidyne substituted with halogen, C4-C20 cyclic alkylidene substituted with halogen, C4-C20 diene substituted with halogen, C6-C20 triene substituted with halogen, C4-C20 cyclic diene substituted with halogen, C2-C20 cyclic triene substituted with halogen, C6-C20 arene substituted with halogen, C2-C20 ether substituted with halogen, C1-C20 amine substituted with halogen and C3-C20 cyclic ether substituted with halogen, where R and R′ are individually selected from the group consisting of H, C1-C10 alkyl and C1-C10 alkyl substituted with halogen.
6. The method according to claim 1, wherein the anion ligand X is selected from the group consisting of H, F, Cl, Br, I, C1-C10 alkyl, C2-C10 alkenyl, C1-C8 alkoxy, C6-C12 aryl, β-diketonate, cyclopentadienyl, C1-C8 alkylcylcopentadienyl, C1-C10 alkyl substituted with halogen, C2-C10 alkenyl substituted with halogen, C1-C8 alkoxy substituted with halogen, C6-C12 aryl substituted with halogen, β-diketonate substituted with halogen, cyclopentadienyl substituted with halogen and C1-C8 alkylcylcopentadienyl substituted with halogen.
7. The method according to claim 1, wherein the metal precursor further comprises a neutral ligand in an amount ranging from 0.1 to 50 wt %.
8. The method according to claim 1, wherein the metal precursor further comprises HX in an amount ranging from 0.1 to 50 wt % wherein X is an anion ligand.
9. The method according to claim 1, wherein step (b) is performed at the presence of a catalyst selected from the group consisting of HF, HCl, HBr, HI, F2, Cl2, Br2, I2, C1-C10 alkane substituted with halogen, C2-C10 alkane substituted with halogen, C1-C8 alkoxide substituted with halogen, C6-C12 arene substituted with halogen, β-diketonate substituted with halogen, cyclopentadiene substituted with halogen and C1-C8 alkylcyclopentadiene.
10. The method according to claim 1, wherein parts (a) to (c) are performed using a CVD(chemical vapor deposition) method.
11. A CVD method using a precursor M(L)X as a source, where M is a metal, L is a neutral ligand and X is an anion ligand, wherein the metal has an oxidation number of +1.
12. The CVD method according to claim 11, the method being performed in the absence of oxygen or hydrogen as a reaction gas.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050014365A1 (en) * 2003-07-15 2005-01-20 Moon Kwang-Jin Methods of forming cobalt layers for semiconductor devices
CN100363529C (en) * 2005-09-19 2008-01-23 哈尔滨意锋稀土材料开发有限公司 Permeation promoter for organic RE chemical heat treatment and its application
US20100310562A1 (en) * 2007-11-20 2010-12-09 Bundesrepublik Deutschland letztvertreten durch das Robert Koch-Institut vertreten durch seinen System for delivery into xcr1 positive cell and uses thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100469126B1 (en) * 2002-06-05 2005-01-29 삼성전자주식회사 Method of forming a thin film with a low hydrogen contents
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6123876A (en) * 1995-04-04 2000-09-26 Canon Kabushiki Kaisha Metal-containing composition for forming electron-emitting device
US6242771B1 (en) * 1998-01-02 2001-06-05 Sharp Laboratories Of America, Inc. Chemical vapor deposition of PB5GE3O11 thin film for ferroelectric applications
US6284655B1 (en) * 1998-09-03 2001-09-04 Micron Technology, Inc. Method for producing low carbon/oxygen conductive layers
US6365502B1 (en) * 1998-12-22 2002-04-02 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method
US6491978B1 (en) * 2000-07-10 2002-12-10 Applied Materials, Inc. Deposition of CVD layers for copper metallization using novel metal organic chemical vapor deposition (MOCVD) precursors
US20030049932A1 (en) * 2001-08-30 2003-03-13 Weimin Li Technique for high efficiency metalorganic chemical vapor deposition
US6627995B2 (en) * 2000-03-03 2003-09-30 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09205070A (en) * 1996-01-25 1997-08-05 Sony Corp Plasma cvd system and semiconductor device having metal film formed thereby
KR100243267B1 (en) * 1996-11-22 2000-02-01 윤종용 Thin film forming method and semiconductor device having the thin film
KR100275752B1 (en) * 1998-11-18 2000-12-15 윤종용 Manufacturing method of concave capacitor having adhesion spacers
WO2001088972A1 (en) * 2000-05-15 2001-11-22 Asm Microchemistry Oy Process for producing integrated circuits

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6123876A (en) * 1995-04-04 2000-09-26 Canon Kabushiki Kaisha Metal-containing composition for forming electron-emitting device
US6242771B1 (en) * 1998-01-02 2001-06-05 Sharp Laboratories Of America, Inc. Chemical vapor deposition of PB5GE3O11 thin film for ferroelectric applications
US6284655B1 (en) * 1998-09-03 2001-09-04 Micron Technology, Inc. Method for producing low carbon/oxygen conductive layers
US6365502B1 (en) * 1998-12-22 2002-04-02 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method
US6627995B2 (en) * 2000-03-03 2003-09-30 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method
US6491978B1 (en) * 2000-07-10 2002-12-10 Applied Materials, Inc. Deposition of CVD layers for copper metallization using novel metal organic chemical vapor deposition (MOCVD) precursors
US20030049932A1 (en) * 2001-08-30 2003-03-13 Weimin Li Technique for high efficiency metalorganic chemical vapor deposition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050014365A1 (en) * 2003-07-15 2005-01-20 Moon Kwang-Jin Methods of forming cobalt layers for semiconductor devices
US7211506B2 (en) 2003-07-15 2007-05-01 Samsung Electronics Co., Ltd. Methods of forming cobalt layers for semiconductor devices
CN100363529C (en) * 2005-09-19 2008-01-23 哈尔滨意锋稀土材料开发有限公司 Permeation promoter for organic RE chemical heat treatment and its application
US20100310562A1 (en) * 2007-11-20 2010-12-09 Bundesrepublik Deutschland letztvertreten durch das Robert Koch-Institut vertreten durch seinen System for delivery into xcr1 positive cell and uses thereof
US10703817B2 (en) 2007-11-20 2020-07-07 Bundesrepublik Deutschland Letzvertreten Durch Das Robert Koch-Institut Vertreten Durch Seinen Praesidenten System for delivery into XCR1 positive cell and uses thereof

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