US20030124267A1 - Method for manufacturing metal film having high purity - Google Patents
Method for manufacturing metal film having high purity Download PDFInfo
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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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- 239000002184 metal Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 142
- 239000002243 precursor Substances 0.000 claims description 29
- 239000003446 ligand Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 150000001450 anions Chemical group 0.000 claims description 14
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 7
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 150000004703 alkoxides Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 47
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 150000002367 halogens Chemical group 0.000 description 95
- 239000010408 film Substances 0.000 description 34
- 239000010409 thin film Substances 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Images
Classifications
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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
- C23C16/06—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
-
- 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
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
- 1. Technical Field
- 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.
- 2. Description of the Related Art
- 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.
- 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.
- 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.
- 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.
- In the conventional CVD method for manufacturing metal films such as iridium film or rhodium film, precursors such as MX or MX3 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 MX3 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.
- In addition, in the conventional CVD method using oxygen, the oxygen reacts with metal precursor MX or MX3 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 MX3 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 Ta2O5 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.
- 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.
- A disclosed method for manufacturing a metal film comprises:
- (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).
- 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.
- 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 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.
- 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. 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, 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.
- 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.
- The step (b) is performed at the presence of a catalyst selected from the group consisting of HF, HCl, HBr, HI, F2, 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.
- Metal reaction formula: 3M+→2M+M3+
- Overall reaction formula: 3M(L)X→2M+MX3+3L
- FIGS. 1 and 2 are cross-sectional diagrams illustrating the reaction mechanisms of the metal film deposition according to this disclosure.
- The CVD method performed according to the above-described reaction principle will be explained referring to FIGS. 1 and 2.
- Referring to FIG. 1,
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. Themetal precursor 2 is vaporized in the vaporizer and then provided to a reactor to be adsorbed on a surface of asemiconductor substrate 1 pre-heated to a temperature ranging from 100 to 900° C. - Referring to FIG. 2, the
adsorbed metal precursor 2 absorbs heat from the surface of thesubstrate 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 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 or C3-C20 cyclic ether substituted with halogen.
- The neutral ligand L5 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, 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 or C1-C8 alkylcylcopentadienyl substituted with halogen.
- In order to stabilize the metal precursor M(L)X during the deposition process of the
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.
- Here, a catalyst is preferably 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 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 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 a reaction gas is not used.
Claims (12)
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)
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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 |
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KR100469126B1 (en) * | 2002-06-05 | 2005-01-29 | 삼성전자주식회사 | Method of forming a thin film with a low hydrogen contents |
KR20040035108A (en) * | 2002-10-18 | 2004-04-29 | 학교법인 포항공과대학교 | Method for forming functional thin film |
KR100664079B1 (en) * | 2005-11-04 | 2007-01-03 | 엘지전자 주식회사 | Catalyst supporting method for steam reforming of fuel cell |
TWI755607B (en) | 2018-06-22 | 2022-02-21 | 美商應用材料股份有限公司 | Catalyzed deposition of metal films |
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KR20030058040A (en) | 2003-07-07 |
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