US20030064153A1 - Method of depositing a metallic film on a substrate - Google Patents
Method of depositing a metallic film on a substrate Download PDFInfo
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- US20030064153A1 US20030064153A1 US10/081,426 US8142602A US2003064153A1 US 20030064153 A1 US20030064153 A1 US 20030064153A1 US 8142602 A US8142602 A US 8142602A US 2003064153 A1 US2003064153 A1 US 2003064153A1
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 238000000151 deposition Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 239000012159 carrier gas Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- 229910004200 TaSiN Inorganic materials 0.000 claims description 4
- 229910008482 TiSiN Inorganic materials 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 238000000231 atomic layer deposition Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004377 microelectronic Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017489 Cu I Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/257—Refractory metals
- C03C2217/259—V, Nb, Ta
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/282—Carbides, silicides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Definitions
- the present invention relates to a method of depositing a metallic film on a substrate using atomic layer deposition (ALD).
- ALD atomic layer deposition
- This method uses a carrier gas to deposit a selected source metal on a substrate in a reaction chamber. Excess source metal is removed using a pulse of an inert gas such as nitrogen. A reducing agent is then pulsed into the reaction chamber followed by a pulse of purge gas such as nitrogen. This series of steps is then repeated for other selected source metals of interest, for each layer of source metal that is to be deposited onto the substrate. This process may be used for the deposition of conformal seed layers for subsequent electrodeposition of thicker films for microelectronic interconnect applications.
- Electrodeposition of copper for the fabrication of microelectronic device interconnects has been used in the prior art.
- a wafer Prior to electrodeposition or electroplating, a wafer requires a thin layer of copper (Cu) which is known as a seed layer. Versions of sputtering have been employed in the prior art to deposit seed layers. As the dimensions of microelectronic devices shrink, new ways are needed of depositing a uniform seed layer in high aspect ratio trenches and vias of damascene structures.
- Prior art in the ALD of copper films consists of using a platinum under layer with hydrogen as a reducing agent, or elemental zinc vapor as a reducing agent. The copper film produced with these methods has high resistivity, rough texture, and contains large amounts of impurities. Hence, these methods are not suitable for microelectronic applications.
- the present invention provides an ALD method for sequentially depositing monolayers of highly conformal, continuous smooth metallic films.
- the thickness of the deposition can be controlled by controlling the number of deposition cycles.
- the chemistry employed for ALD can also be used for CVD of metallic films, where are the chemicals will be introduced to the reaction cell at the same time.
- An invention is described for conformally depositing nanoscale metallic films, such as copper, silver, gold, cobalt, or nickel using ALD of selected monolayers.
- Deposition of copper film is currently of significant interest for making interconnects in microelectronic devices because of its low resistivity that results in higher speed and its high resistance to electromigration that enhances its reliability.
- Other applications of copper include circuit board fabrication, catalyst preparation, and architectural coatings.
- This invention uses a reaction between a reducing agent and a copper compound to produce a high purity, low resistance copper film over a wide range of substrates.
- the copper source can be hydrated (hexafluoroacetylacetonate) copper II (Cu(hfac) 2 .XH 2 O) or other copper beta-diketonates. These copper compounds can be reduced into metallic copper using a second chemical component that is referred to as a reducing agent.
- a reducing agent Several reducing agents were investigated of which ethanol, isopropanol, and formaldehyde based solution produced bright and shiny copper colored films.
- the formaldehyde based solution (combination of specific percentages of formaldehyde, water and alcohol) produced the best films with resistivites ( ⁇ 1.72 ⁇ -cm) close to bulk values (1.67 ⁇ -cm), as shown in FIG. 4, which is of extreme importance for the advanced ultra large scale integration (ULSI) fabrication.
- a reducing agent and source metal are introduced into the reaction cell that contained the substrate.
- the substrate may be placed on a heated platform that could be heated up to 450° C.
- the sources were transported with a carrier gas.
- the reducing agent was transported by a carrier gas that was bubbled through it.
- To transport Cu (hfac) 2 H 2 was first bubbled through water and then over the Cu compound.
- the substrates include glass plates and silicon wafers that were coated with (blank or patterned) TaN, TiN, and Ta. Best film adhesion was achieved over TaN and Tin at about 300° C. However, at about 350° C., adhesion was excellent on all these substrates. Similar method can be adopted for other technologically important metallic thin films.
- FIG. 1 is a flow diagram of one preferred embodiment of a system suitable for practicing the method of the present invention.
- FIG. 2 is a block diagram of a first embodiment of the present invention.
- FIG. 3 is a block diagram of a second embodiment of the present invention.
- FIG. 4 is a graph depicting resistivity versus thickness for a Cu film applied using a preferred embodiment of the present invention.
- FIGS. 5 a and 5 b are scanning electron microscope cross sectional views of a Cu film deposited in trenches using a preferred method of the present invention.
- FIG. 6 is a graph depicting pulsing durations for a preferred embodiment of the present invention.
- the present invention is directed toward an ALD method of depositing a metallic film on a substrate.
- This invention comprises placing a substrate 12 comprising an upper surface, a lower surface, and silicon in a reaction cell or chamber 14 , wherein at least one of said surfaces is coated with a coating 16 selected from the group consisting of TaN, TiN, Ta, WN, WCN, TaSiN, and TiSiN, as shown in FIG. 1 and in block 10 of FIG. 2.
- the coating on the substrate is patterned.
- the reaction chamber is a Microchemistry F-120 ALD reactor.
- the substrate is a silicon wafer.
- the substrate is a glass plate.
- the silicon wafers are precoated with a layer of SiO 2 , having a thickness in the range of 5-100 nanometers followed by a six barrier layer comprising Ta, TaN, or TiN having a thickness in the range of 5-100 nanometers.
- the substrate is placed on a heated platform. In another preferred embodiment the substrate is heated to a temperature of at least 150° C.
- the invention further comprises injecting a source metal into the reaction chamber or cell through the use of the carrier gas that is bubbled into the reaction chamber during a first pulse.
- this pulse is 1-20 seconds in duration, as shown in FIG. 1 and in block 20 of FIG. 2.
- the carrier gas is bubbled through water into the cell.
- the substrate is heated to a temperature of at least 210° C. prior to introducing the source metal.
- a copper source metal was heated to approximately 75° C.
- the carrier gas is an inert gas. In another preferred embodiment, the carrier gas is argon. In another preferred embodiment, the carrier gas is hydrogen. In a preferred embodiment, the reducing agent is selected from a group consisting of alcohols and aldehydes. In another preferred embodiment, the reducing agent is selected from the group consisting of ethanol, isopropanol, and formaldehyde.
- the source metal comprises a copper I (Cu I) or a copper II (Cu II) compound.
- Cu II sources are more thermally stable than Cu I sources and are thus better suited for ALD processes.
- the source metal comprises a hydrated Cu II compound, or other copper beta-diketonates.
- the source metal comprises an anhydrous copper compound.
- the source metal comprises a silver I or a silver II compound.
- the source metal comprises a silver II compound.
- An inert gas is then injected into the cell during a second pulse.
- this pulse is 1-10 seconds in duration as shown in block 30 of FIG. 2.
- the inert gas pulsing step is used to purge excess source metal.
- the inert gas is selected from a group consisting of nitrogen, argon and helium.
- the invention further comprises injecting a reducing agent into the cell during a third pulse. In a preferred embodiment, this pulse is 1-10 seconds in duration, as shown in block 40 of FIG. 2. In a preferred embodiment, the reducing agent is in a vapor form.
- the invention further comprises injecting an inert gas into the cell during the a fourth pulse. In a preferred embodiment, this pulse is 1-10 seconds in duration, as shown in block 50 of FIG. 2. This inert gas pulse is used to remove excess reducing agent.
- the inert gas is selected from a group consisting of nitrogen, argon and helium. In a preferred embodiment, where the source metal comprises silver, the inert gas of the second and fourth pulsing steps is argon.
- the above four pulsing steps may be used to deposit one monolayer using the method of the present invention. These four steps may be repeated for various selected source metals to deposit subsequent monolayers on the substrate. A preferred embodiment of the pulsing steps of the present invention is illustrated in the graph of FIG. 6.
- Cu(hfac) 2 is introduced in a pulse that is 2-3 seconds in duration, carried by H 2 gas that has been bubbled through water. This is followed by a pulse of nitrogen gas of approximately one second in duration. The nitrogen pulse is used to remove any excess Cu(hfac) 2 and its byproducts.
- a pulse of reducing agent of approximately one second in duration is then introduced into the reaction chamber, using an H 2 carrier gas. The pulse duration can be varied by adjusting the carrier gas flow rate.
- the reducing agent reacts with and reduces cooper oxide to copper.
- another pulse of nitrogen of approximately one second in duration is then introduced into the reaction chamber to remove excess reducing agent as well as the reducing reaction byproducts. Using this method, the film thickness is controlled by repeating this sequence for a desired number of cycles.
- FIGS. 5 a and 5 b depict scanning electron microscope cross sectional views of an electrode deposited copper layer entrenches. As shown in FIGS. 5 a and 5 b , the deposited copper completely fills these structures leaving no observable voids.
- the invention is also directed toward a method for etching copper films on a substrate.
- This process is the reverse chemistry of the deposition process invented.
- This method comprises placing a substrate having a temperature in the range of 120° C. to 300° C. and comprising and upper surface, a lower surface, and silicon in a reaction cell where at least one of the surfaces is coated with a copper layer, as shown in block 60 of FIG. 3.
- the invention further comprises injecting an oxidizing agent into the cell through the use of a carrier gas for a first pulse of 1-20 seconds duration, as shown in block 70 of FIG. 3.
- the oxidizing agent is a gas comprising oxygen.
- the oxidizing agent is water in a gaseous phase.
- This embodiment of the invention further comprises injecting a nitrogen purge pulse into the cell during a second pulse of 1-10 seconds duration, as shown in block 80 of FIG. 3.
- a reducing agent is then injected into the cell during a third pulse of 1-10 seconds duration, as shown in block 90 of FIG. 3.
- the reducing agent is hydrogen hexafluoroacetylacetonate (H(hfac)).
- the invention further comprises injecting nitrogen into the cell during a fourth pulse of 1-20 seconds duration, as shown in block 100 of FIG. 3.
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Abstract
The present invention relates to a method of depositing a metallic film on a substrate. This method uses a carrier gas to deposit a source metal in the presence of a reducing agent such that the rate of deposition can be controlled by controlling the flow rate of the carrier gas, the substrate temperature, the pulse widths of the metal source and reducing agents, and the number of deposition phases.
Description
- This application is a continuation-in-part of application Ser. No. 09/968,370, filed on Oct. 1, 2001.
- 2. Field of Invention
- The present invention relates to a method of depositing a metallic film on a substrate using atomic layer deposition (ALD). This method uses a carrier gas to deposit a selected source metal on a substrate in a reaction chamber. Excess source metal is removed using a pulse of an inert gas such as nitrogen. A reducing agent is then pulsed into the reaction chamber followed by a pulse of purge gas such as nitrogen. This series of steps is then repeated for other selected source metals of interest, for each layer of source metal that is to be deposited onto the substrate. This process may be used for the deposition of conformal seed layers for subsequent electrodeposition of thicker films for microelectronic interconnect applications.
- 2. Description of the Prior Art
- Electrodeposition of copper for the fabrication of microelectronic device interconnects has been used in the prior art. Prior to electrodeposition or electroplating, a wafer requires a thin layer of copper (Cu) which is known as a seed layer. Versions of sputtering have been employed in the prior art to deposit seed layers. As the dimensions of microelectronic devices shrink, new ways are needed of depositing a uniform seed layer in high aspect ratio trenches and vias of damascene structures. Prior art in the ALD of copper films consists of using a platinum under layer with hydrogen as a reducing agent, or elemental zinc vapor as a reducing agent. The copper film produced with these methods has high resistivity, rough texture, and contains large amounts of impurities. Hence, these methods are not suitable for microelectronic applications.
- Chemical vapor deposition techniques have been used to deposit metallic substances, such as copper, on substrates. In CVD methods all of the reactants are present in the reaction chamber at a single time. In contrast to CVD methods, in ALD methods a single source metal is introduced into a reaction chamber at a given time for deposition. The deposition temperatures required for ALD are slightly less than those required for CVD. With the advent of nanotechnology, there is an increasing need to develop methods for depositing nanoscale metallic films on substrates for use in producing items such as state of the art microelectronic devices, circuit boards, and architectural coatings.
- The present invention provides an ALD method for sequentially depositing monolayers of highly conformal, continuous smooth metallic films. The thickness of the deposition can be controlled by controlling the number of deposition cycles. The chemistry employed for ALD can also be used for CVD of metallic films, where are the chemicals will be introduced to the reaction cell at the same time.
- An invention is described for conformally depositing nanoscale metallic films, such as copper, silver, gold, cobalt, or nickel using ALD of selected monolayers. Deposition of copper film is currently of significant interest for making interconnects in microelectronic devices because of its low resistivity that results in higher speed and its high resistance to electromigration that enhances its reliability. Other applications of copper include circuit board fabrication, catalyst preparation, and architectural coatings.
- This invention uses a reaction between a reducing agent and a copper compound to produce a high purity, low resistance copper film over a wide range of substrates. The copper source can be hydrated (hexafluoroacetylacetonate) copper II (Cu(hfac)2.XH2O) or other copper beta-diketonates. These copper compounds can be reduced into metallic copper using a second chemical component that is referred to as a reducing agent. Several reducing agents were investigated of which ethanol, isopropanol, and formaldehyde based solution produced bright and shiny copper colored films. The formaldehyde based solution (combination of specific percentages of formaldehyde, water and alcohol) produced the best films with resistivites (˜1.72 μΩ-cm) close to bulk values (1.67 μΩ-cm), as shown in FIG. 4, which is of extreme importance for the advanced ultra large scale integration (ULSI) fabrication.
- A reducing agent and source metal are introduced into the reaction cell that contained the substrate. The substrate may be placed on a heated platform that could be heated up to 450° C.
- The sources were transported with a carrier gas. The reducing agent was transported by a carrier gas that was bubbled through it. To transport Cu (hfac)2, H2 was first bubbled through water and then over the Cu compound.
- The substrates include glass plates and silicon wafers that were coated with (blank or patterned) TaN, TiN, and Ta. Best film adhesion was achieved over TaN and Tin at about 300° C. However, at about 350° C., adhesion was excellent on all these substrates. Similar method can be adopted for other technologically important metallic thin films.
- This technique was also utilized to deposit several other metallic films. High purity silver films were deposit on glass and Si coated with TaN, TiN, and Ta (patterned and blank) where Ag source was trimethylphosphine (hexafluoroacetylacetonate) Ag(I). The reducing agents were again alcohol and formaldehyde based solution, as described above. The resistivity of films were about 1.7 μΩ-cm. Other metallic films that were similarly deposited include gold using Me2Au(hfac) and Me2Au(tfac), Pt from hexafluoroacetylacetonate Pt (II), and Co from hexfluoroacetylacetonate Co (III). The reducing agents were same mentioned above.
- FIG. 1 is a flow diagram of one preferred embodiment of a system suitable for practicing the method of the present invention.
- FIG. 2 is a block diagram of a first embodiment of the present invention.
- FIG. 3 is a block diagram of a second embodiment of the present invention.
- FIG. 4 is a graph depicting resistivity versus thickness for a Cu film applied using a preferred embodiment of the present invention.
- FIGS. 5a and 5 b are scanning electron microscope cross sectional views of a Cu film deposited in trenches using a preferred method of the present invention.
- FIG. 6 is a graph depicting pulsing durations for a preferred embodiment of the present invention.
- The present invention is directed toward an ALD method of depositing a metallic film on a substrate. This invention comprises placing a substrate12 comprising an upper surface, a lower surface, and silicon in a reaction cell or
chamber 14, wherein at least one of said surfaces is coated with acoating 16 selected from the group consisting of TaN, TiN, Ta, WN, WCN, TaSiN, and TiSiN, as shown in FIG. 1 and inblock 10 of FIG. 2. In a preferred embodiment, the coating on the substrate is patterned. In one preferred embodiment, the reaction chamber is a Microchemistry F-120 ALD reactor. - In one preferred embodiment, the substrate is a silicon wafer. In another preferred embodiment, the substrate is a glass plate. In another preferred embodiment, the silicon wafers are precoated with a layer of SiO2, having a thickness in the range of 5-100 nanometers followed by a six barrier layer comprising Ta, TaN, or TiN having a thickness in the range of 5-100 nanometers. In another preferred embodiment, the substrate is placed on a heated platform. In another preferred embodiment the substrate is heated to a temperature of at least 150° C.
- The invention further comprises injecting a source metal into the reaction chamber or cell through the use of the carrier gas that is bubbled into the reaction chamber during a first pulse. In a preferred embodiment, this pulse is 1-20 seconds in duration, as shown in FIG. 1 and in
block 20 of FIG. 2. In a preferred embodiment, the carrier gas is bubbled through water into the cell. In one preferred embodiment, the substrate is heated to a temperature of at least 210° C. prior to introducing the source metal. In a preferred embodiment, a copper source metal was heated to approximately 75° C. - In a preferred embodiment, the carrier gas is an inert gas. In another preferred embodiment, the carrier gas is argon. In another preferred embodiment, the carrier gas is hydrogen. In a preferred embodiment, the reducing agent is selected from a group consisting of alcohols and aldehydes. In another preferred embodiment, the reducing agent is selected from the group consisting of ethanol, isopropanol, and formaldehyde.
- In one preferred embodiment the source metal comprises a copper I (Cu I) or a copper II (Cu II) compound. Cu II sources are more thermally stable than Cu I sources and are thus better suited for ALD processes. In another preferred embodiment, the source metal comprises a hydrated Cu II compound, or other copper beta-diketonates. In another preferred embodiment, the source metal comprises an anhydrous copper compound. In another preferred embodiment, the source metal comprises a silver I or a silver II compound. In another preferred embodiment, the source metal comprises a silver II compound.
- An inert gas is then injected into the cell during a second pulse. In a preferred embodiment, this pulse is 1-10 seconds in duration as shown in
block 30 of FIG. 2. The inert gas pulsing step is used to purge excess source metal. In a preferred embodiment, the inert gas is selected from a group consisting of nitrogen, argon and helium. - The invention further comprises injecting a reducing agent into the cell during a third pulse. In a preferred embodiment, this pulse is 1-10 seconds in duration, as shown in
block 40 of FIG. 2. In a preferred embodiment, the reducing agent is in a vapor form. The invention further comprises injecting an inert gas into the cell during the a fourth pulse. In a preferred embodiment, this pulse is 1-10 seconds in duration, as shown inblock 50 of FIG. 2. This inert gas pulse is used to remove excess reducing agent. In a preferred embodiment, the inert gas is selected from a group consisting of nitrogen, argon and helium. In a preferred embodiment, where the source metal comprises silver, the inert gas of the second and fourth pulsing steps is argon. - The above four pulsing steps may be used to deposit one monolayer using the method of the present invention. These four steps may be repeated for various selected source metals to deposit subsequent monolayers on the substrate. A preferred embodiment of the pulsing steps of the present invention is illustrated in the graph of FIG. 6.
- In a preferred embodiment, Cu(hfac)2 is introduced in a pulse that is 2-3 seconds in duration, carried by H2 gas that has been bubbled through water. This is followed by a pulse of nitrogen gas of approximately one second in duration. The nitrogen pulse is used to remove any excess Cu(hfac)2 and its byproducts. In this preferred embodiment, a pulse of reducing agent of approximately one second in duration is then introduced into the reaction chamber, using an H2 carrier gas. The pulse duration can be varied by adjusting the carrier gas flow rate. The reducing agent reacts with and reduces cooper oxide to copper. In this preferred embodiment, another pulse of nitrogen of approximately one second in duration is then introduced into the reaction chamber to remove excess reducing agent as well as the reducing reaction byproducts. Using this method, the film thickness is controlled by repeating this sequence for a desired number of cycles.
- The present invention is applicable to the electrodeposition of copper films to be used as seed layers. FIGS. 5a and 5 b depict scanning electron microscope cross sectional views of an electrode deposited copper layer entrenches. As shown in FIGS. 5a and 5 b, the deposited copper completely fills these structures leaving no observable voids.
- The invention is also directed toward a method for etching copper films on a substrate. This process is the reverse chemistry of the deposition process invented. This method comprises placing a substrate having a temperature in the range of 120° C. to 300° C. and comprising and upper surface, a lower surface, and silicon in a reaction cell where at least one of the surfaces is coated with a copper layer, as shown in
block 60 of FIG. 3. - The invention further comprises injecting an oxidizing agent into the cell through the use of a carrier gas for a first pulse of 1-20 seconds duration, as shown in block70 of FIG. 3. In one preferred embodiment, the oxidizing agent is a gas comprising oxygen. In another preferred embodiment the oxidizing agent is water in a gaseous phase.
- This embodiment of the invention further comprises injecting a nitrogen purge pulse into the cell during a second pulse of 1-10 seconds duration, as shown in
block 80 of FIG. 3. A reducing agent is then injected into the cell during a third pulse of 1-10 seconds duration, as shown inblock 90 of FIG. 3. In a preferred embodiment, the reducing agent is hydrogen hexafluoroacetylacetonate (H(hfac)). - The invention further comprises injecting nitrogen into the cell during a fourth pulse of 1-20 seconds duration, as shown in
block 100 of FIG. 3. - The foregoing disclosure and description of the invention are illustrative and explanatory. Various changes in the size, shape, and materials, as well as in the details of the illustrative construction may be made without departing from the spirit of the invention.
Claims (24)
1. A method of depositing a metallic film on a substrate comprising:
a. placing a substrate comprising an upper surface, a lower surface, and silicon in a reaction cell, wherein at least one of said surfaces is coated with a coating selected with from the group consisting of TaN, TiN, Ta, WN, WCN, TaSiN, and TiSiN;
b. injecting a source metal into the cell through the use of a carrier gas that is bubbled through water into the cell during a first pulse of 1-20 seconds duration;
c. injecting an inert gas into the cell during a second pulse of 1-10 seconds duration;
d. injecting a reducing agent into the cell during a third pulse of 1-10 seconds duration; and
e. injecting an inert gas into the cell during a fourth pulse of 1-10 seconds duration.
2. The method of claim 1 , wherein the reducing agent is selected from the group consisting of alcohols and aldehydes.
3. The method of claim 1 , wherein the source metal comprises a copper II compound.
4. The method of claim 3 , wherein the source metal is a hydrated copper II compound.
5. The method of claim 1 , wherein the carrier gas is an inert gas.
6. The method of claim 1 , wherein the carrier gas is argon.
7. The method of claim 1 , wherein the carrier gas is hydrogen.
8. The method of claim 1 , wherein the source metal comprises an anhydrous copper compound.
9. The method of claim 1 , wherein the source metal comprises a copper beta-diketonates.
10. The method of claim 1 , wherein the source metal comprises a silver I compound.
11. The method of claim 1 , wherein the source metal comprises a silver II compound.
12. The method of claim 1 , wherein the source metal comprises a copper I compound.
13. The method of claim 1 , wherein said inert gas is selected from a group consisting of nitrogen, argon and helium.
14. The method of claim 1 wherein said coating has a thickness in the range of 5-100 nanometers.
15. A method for etching copper films on a substrate comprising:
a. placing a substrate having a temperature in the range of 120° C. to 300° C. and comprising an upper surface, a lower surface, and silicon in a reaction cell, wherein at least one of said surfaces is coated with a copper layer.
b. injecting an oxidizing agent into the cell through the use of a carrier gas during a first pulse of 1-20 seconds duration;
c. injecting purge pulse comprising an inert gas into the cell during a second pulse of 1-10 seconds duration;
d. injecting a reducing agent into the cell during a third pulse of 1-10 seconds duration; and
e. injecting an inert gas into the cell during a fourth pulse of 1-10 seconds duration.
16. The method of claim 15 , wherein the reducing agent is hydrogen hexafluoroacetylacetonate (H (hfac)).
17. The method of claim 15 , wherein the oxidizing agent is a gas comprising oxygen.
18. The method of claim 15 , wherein the oxidizing agent is water in a gaseous phase.
19. The method of claim 15 , wherein said inert gas is selected from a group consisting of nitrogen, argon and helium.
20. A method of depositing a metallic film on a substrate comprising:
a. placing a substrate comprising an upper surface, a lower surface, and silicon in a reaction cell, wherein at least one of said surfaces is coated with a coating having a thickness in the range of 5-100 nanometers, and selected with from the group consisting of TaN, TiN, Ta, WN, WCN, TaSiN, and TiSiN;
b. injecting a source metal into the cell through the use of an inert carrier gas that is bubbled through water into the cell during a first pulse of 1-20 seconds duration;
c. injecting an inert gas into the cell during a second pulse of 1-10 seconds duration;
d. injecting a reducing agent selected from the group consisting of alcohols and aldehydes into the cell during a third pulse of 1-10 seconds duration; and
e. injecting an inert gas into the cell during a fourth pulse of 1-10 seconds duration.
21. A method of depositing a metallic film on a substrate comprising:
a. placing a substrate comprising an upper surface, a lower surface, and silicon in a reaction cell, wherein at least one of said surfaces is coated with a coating selected with from the group consisting of TaN, TiN, Ta, WN, WCN, TaSiN, and TiSiN;
b. injecting a source metal into the cell through the use of a carrier gas that is bubbled through water into the cell during a first pulse;
c. purging excess source metal by injecting an inert gas into the cell during a second pulse;
d. injecting a reducing agent into the cell during a third pulse; and
e. removing excess reducing agent by injecting an inert gas into the cell during a fourth pulse.
22. The method of claim 21 , wherein the reducing agent is selected from the group consisting of alcohols and aldehydes.
23. The method of claim 21 , wherein the carrier gas is an inert gas.
24. The method of claim 21 , wherein said source metal is selected from a group consisting of a silver I compound, a silver II compound, a copper I compound, a copper II compound, and a copper beta-diketonates.
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US10/081,426 US20030064153A1 (en) | 2001-10-01 | 2002-02-22 | Method of depositing a metallic film on a substrate |
US10/838,275 US7204935B2 (en) | 2001-10-01 | 2004-05-04 | Method of etching a metallic film on a substrate |
Applications Claiming Priority (2)
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US09/968,370 US20020039622A1 (en) | 2000-10-02 | 2001-10-01 | Method of depositing a metallic film on a substrate |
US10/081,426 US20030064153A1 (en) | 2001-10-01 | 2002-02-22 | Method of depositing a metallic film on a substrate |
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US10/838,275 Expired - Fee Related US7204935B2 (en) | 2001-10-01 | 2004-05-04 | Method of etching a metallic film on a substrate |
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US20050186342A1 (en) * | 2004-02-19 | 2005-08-25 | Nanosolar, Inc. | Formation of CIGS absorber layer materials using atomic layer deposition and high throughput surface treatment |
US20050191803A1 (en) * | 1997-11-05 | 2005-09-01 | Tokyo Electron Limited | Method of forming a metal film for electrode |
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US20100301478A1 (en) * | 2007-12-05 | 2010-12-02 | Thomas Waechtler | Substrate Having a Coating Comprising Copper and Method for the Production Thereof by Means of Atomic Layer Deposition |
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Also Published As
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US7204935B2 (en) | 2007-04-17 |
US20040200414A1 (en) | 2004-10-14 |
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