WO2000013207A2 - Method for forming a metal film - Google Patents
Method for forming a metal film Download PDFInfo
- Publication number
- WO2000013207A2 WO2000013207A2 PCT/KR1999/000500 KR9900500W WO0013207A2 WO 2000013207 A2 WO2000013207 A2 WO 2000013207A2 KR 9900500 W KR9900500 W KR 9900500W WO 0013207 A2 WO0013207 A2 WO 0013207A2
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- WIPO (PCT)
- Prior art keywords
- metal film
- metal layer
- source
- catalyst metal
- catalyst
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 75
- 239000002184 metal Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 78
- 229910052763 palladium Inorganic materials 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 39
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018182 Al—Cu Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NGMRHZNERZGMEZ-UHFFFAOYSA-N alumane N,N-dimethylmethanamine Chemical compound [H][Al]([H])[H].CN(C)C NGMRHZNERZGMEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- SHEGNBCAYSUQEV-UHFFFAOYSA-N [Cu+].CC(C)=C(C)[SiH3] Chemical compound [Cu+].CC(C)=C(C)[SiH3] SHEGNBCAYSUQEV-UHFFFAOYSA-N 0.000 description 1
- 229910000086 alane Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
Definitions
- the present invention relates to a method for forming a film, and more particularly, to a method for forming a metal film for use in semiconductor devices on a substrate.
- metal films are used for circuit interconnections.
- One of the materials widely used in forming such a metal film is aluminum, and tungsten is used for specific applications.
- copper the second most conducting metal, will be increasingly used henceforth instead of aluminum.
- Circuit interconnection formation is divided into two categories: formation of contacts and formation of interconnection.
- problems have arisen with the conventional circuit interconnection formation, particularly in the formation of narrow lines or metal contacts.
- One of the problems is that the formation of a metal film of uniform thickness over an uneven surface becomes more difficult with the tight design rule.
- metal films deposited by a conventional method can not completely fill a contact or via hole having a high aspect ratio without voids.
- a contact or via hole having a high aspect ratio can completely be filled with a perfect step coverage.
- (l,l,l,5,5,5-hexafluoro-2,4-pentanedionato) copper(I)-trimethylvinylsilane was used as a deposition source and the deposition temperature was in the range of 171-183°C.
- the process comprises the steps of: oxidizing the surface of a diamond substrate; dipping the substrate into an aminosilane solution to fix amino groups on the surface of the substrate; irradiating the substrate through a mask with ultraviolet (UV) light to selectively remove the fixed amino groups from the substrate, resulting in a fixed amino group pattern; fixing palladium catalyst on the pattern; and chemical vapor depositing a copper film only on the pattern.
- UV ultraviolet
- O. Gottsleben et al. formed a palladium metal layer by decomposing precursors using a laser
- O. Lehmann et al. also used laser photo- CVD in their method.
- formation of a uniform catalyst layer on an uneven surface is impossible because the inner side surface of a hole or a groove can not be evenly irradiated.
- V. Bhaskaran et al. in an article entitled "Palladium Thin Films Grown by CVD from (l,l,l,5,5,5-hexafluoro-2,4-pentanedionato)Palladium(II)", published on p85 of Chemical Vapor Deposition, Vol. 3, No.
- the article is accompanied by a photograph showing the cross section of a palladium layer which is deposited on grooves of a width of 0.5 ⁇ m and a depth of 2.0 ⁇ m. Referring to the photograph, it is found that the palladium layers deposited on the top of grooves are more than five times thicker than those deposited on the underside.
- the present invention provides a method for forming a metal film, comprising the steps of: (a) forming a catalyst metal layer on a substrate using thermal chemical vapor deposition to facilitate formation of the metal film; (b) preparing at least one source of the metal film as a gas phase; and (c) applying the gas phase source to the catalyst metal layer to form a metal film thereon.
- palladium or platinum may be used as the catalyst metal for facilitating formation of a metal film comprising aluminum or copper.
- the formation of catalyst metal layers can be repeated to increase the deposition rate of the metal film. If more than two source gases are required to form the catalyst metal layer, it is desirable to supply the source gases sequentially on the substrate, not to supply the source gases simultaneously thereon, to obtain a catalyst metal layer with a superior step coverage. Additionally, during or after the deposition of the metal film, it is also desirable to diffuse the catalyst metal into the metal film to form an alloy film.
- FIGS. 1A to ID show the steps of forming a metal film in accordance with an embodiment of the present invention.
- a silicon substrate 10 to form a metal film thereon is prepared first. Then, as shown in FIG. 1A, a palladium thin layer 20 is formed on the silicon substrate by supplying both (l,l,l,5,5,5-hexafluoro-2,4- pentanedionato)Palladium(II) and hydrogen gas sequentially on the silicon substrate.
- platinum may be employed instead of the palladium.
- a Pd-Al alloy or a Pd-Cu alloy provides the following advantages. If pure aluminum is employed to form interconnection of semiconductor devices, low current density should be maintained to avoid an electromigration- induced open circuit. Accordingly, in a conventional method, an Al-Cu alloy, in which aluminum contains a small amount of copper, is used as an interconnection material to decrease electromigration. The Pd-Al alloy can decrease electromigration thus increase the durability of the metal interconnection, to a degree equal or superior to the Al-Cu alloy. A Pd-Al alloy displays other desirable properites. K. P. Rodbell et al.
- the palladium layer 20 is formed as thin as possible with a uniform thickness to provide higher current density, because the sheet resistance of catalyst metal is generally higher than that of aluminum or copper for use in the interconnection.
- a uniform thickness palladium layer is formed by atomic layer deposition in which source compound gases are sequentially supplied on the silicon substrate maintained at a temperature lower than the thermal decomposition temperatures of source compound gases.
- the deposition rate of atomic layer deposition is significantly low compared with that of conventional deposition where source gases are simultaneously supplied.
- a low deposition rate is advantageous because a thin palladium catalyst layer is required.
- the sources required to form an aluminum film are prepared as gases. After formation of a palladium catalyst layer, the source gases are applied to the palladium catalyst layer to form an aluminum film 20 thereon, as shown in FIG.
- the palladium catalyst is diffused into the aluminum film by applied heat, forming an Al-Pd alloy. If the Al-Pd alloy is used as an interconnection metal material, no additional process is needed to prevent electromigration or oxidation of the interconnection metal film and turn-around-time can be considerably reduced.
- the Al-Pd alloy can be formed in a different way when the heat applied during the chemical deposition of aluminum film is insufficient for the diffusion of the palladium catalyst. In this case, additional heat treatment is conducted after the formation of aluminum film. And then, formation of an additional palladium catalyst layer 22 and an additional aluminum film 32 is sequentially repeated as shown in FIG. 1C and ID.
- the multiple palladium catalyst layers are used upon consideration of the study of O. Lehmann and M. Stuke. They reported that the thickness of aluminum film formed on the palladium layer did not increase and came to saturation with increasing contact time between a liquid aluminum source and the palladium layer. It is supposed that this results from the reduction in catalytic effect of the palladium catalyst underlying the metal film. In an effort to overcome the above problem, multiple palladium catalyst layers are used to the overall deposition rate of the metal film.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A method for forming a metal film for use in semiconductor devices on a substrate. A catalyst metal layer for facilitating formation of a metal film is formed first on a substrate using thermal chemical vapor deposition. Then, at least one source of the metal film is prepared as a gas phase. The metal film is formed on the catalyst metal layer by applying the gas phase source to the catalyst metal layer. According to the present invention, a metal film of uniform thickness can be formed on an uneven substrate surface or on a hole with a high aspect ratio.
Description
METHOD FOR FORMING A METAL FILM
TECHNICAL FIELD
The present invention relates to a method for forming a film, and more particularly, to a method for forming a metal film for use in semiconductor devices on a substrate.
BACKGROUND ART
In the manufacture of semiconductor devices, metal films are used for circuit interconnections. One of the materials widely used in forming such a metal film is aluminum, and tungsten is used for specific applications. However, it is expected that copper, the second most conducting metal, will be increasingly used henceforth instead of aluminum.
Circuit interconnection formation is divided into two categories: formation of contacts and formation of interconnection. As the sizes of integrated circuit structures have continued to become smaller and smaller, problems have arisen with the conventional circuit interconnection formation, particularly in the formation of narrow lines or metal contacts. One of the problems is that the formation of a metal film of uniform thickness over an uneven surface becomes more difficult with the tight design rule. Another problem is that metal films deposited by a conventional method can not completely fill a contact or via hole having a high aspect ratio without voids.
However, if the deposition rate of a film is controlled only by the rate of surface chemical reaction independent of the mass transport rate at which the deposition sources travel to the surface of the substrate, a contact or via hole having a high aspect ratio can completely be filled with a perfect step coverage.
It is well known in the field of chemistry that higher chemical reaction rate at the same temperature or the same reaction rate at lower temperature can be accomplished with the use of a catalyst. However, up to now examples of catalyst applications in forming metal films of semiconductor devices have been limited to few cases. For example, S. J. Potochnik et al., in an article entitled "Selective Copper Chemical Vapor Deposition (CVD) Using Pd-activated Organosilane Films",
published on pl841 of Langmuir, Vol. 11, No. 6, in 1994, reported that a copper metal film could selectively be chemical-vapor-deposited only on portions of a diamond substrate where a palladium ion catalyst is introduced. In the process, (l,l,l,5,5,5-hexafluoro-2,4-pentanedionato) copper(I)-trimethylvinylsilane was used as a deposition source and the deposition temperature was in the range of 171-183°C. The process comprises the steps of: oxidizing the surface of a diamond substrate; dipping the substrate into an aminosilane solution to fix amino groups on the surface of the substrate; irradiating the substrate through a mask with ultraviolet (UV) light to selectively remove the fixed amino groups from the substrate, resulting in a fixed amino group pattern; fixing palladium catalyst on the pattern; and chemical vapor depositing a copper film only on the pattern. They also reported the process was applied to a substrate such as silicon or quartz instead of the diamond substrate. However, their process requires solution treatments to introduce the patterned palladium catalyst onto the substrate, causing difficulties when incorporated with other vacuum process.
O. Gottsleben et al., in an article entitled "Two-step Generation of Aluminum Microstructures on Laser-generated Pd Pre-nucleation Patterns Using Thermal CVD from (Trimethylamine)trihydridoaluminum", published on p201 of Advanced Materials, Vol. 3, No. 4, in 1991, reported that aluminum microstructures were selectively formed only on a palladium catalyst metal pattern using chemical vapor deposition using (trimethylamine)trihydridoaluminum as a CVD source. In this process, the palladium catalyst metal pattern was generated by an UV excimer laser.
O. Lehmann et al. applied liquid triethylamine alane to a KrF-laser patterned palladium catalyst layer formed on an alumina substrate, forming an aluminum film selectively on the patterned palladium catalyst layer. (Reference : O. Lehmann and M. Stuke, "Liquid Precursor Two-step Aluminum Thin-film Deposition on KrF-laser patterned palladium", Applied Physics Letters, Vol. 61, No. 17, p 2027, 1992.)
As described above, O. Gottsleben et al. formed a palladium metal layer by decomposing precursors using a laser, and O. Lehmann et al. also used laser photo- CVD in their method. However, according to the above methods, formation of a uniform catalyst layer on an uneven surface is impossible because the inner side surface of a hole or a groove can not be evenly irradiated.
V. Bhaskaran et al., in an article entitled "Palladium Thin Films Grown by CVD from (l,l,l,5,5,5-hexafluoro-2,4-pentanedionato)Palladium(II)", published on p85 of Chemical Vapor Deposition, Vol. 3, No. 2, in 1997, reported that a pure palladium layer was obtained by applying both (l,l,l,5,5,5-hexafluoro-2,4- pentanedionato)Palladium(II) and hydrogen gas to a silicon single crystal substrate heated at a temperature between 80-200°C. The purity of palladium layer was such that carbon, fluorine, or oxygen was not detected when investigated by Auger electron spectroscopy. In the process, nitrogen gas was used as a carrier gas of a sublimated palladium source compound instead of hydrogen gas to avoid the violent reaction between hydrogen gas and palladium source compound. However, in this case, they reported that the inside of gas conduit, where the palladium source compound carried nitrogen gas and hydrogen gas meet, should be frequently cleaned because palladium layers are deposited thereon. In general, superior step coverage is not expected to occur under violent chemical vapor reaction conditions. The article is accompanied by a photograph showing the cross section of a palladium layer which is deposited on grooves of a width of 0.5 μm and a depth of 2.0μm. Referring to the photograph, it is found that the palladium layers deposited on the top of grooves are more than five times thicker than those deposited on the underside.
DISCLOSURE OF INVENTION
Accordingly, it is an object of the present invention to provide a method for forming a metal film of uniform thickness despite unevenness of a substrate surface.
In order to accomplish the aforementioned object, the present invention provides a method for forming a metal film, comprising the steps of: (a) forming a catalyst metal layer on a substrate using thermal chemical vapor deposition to facilitate formation of the metal film; (b) preparing at least one source of the metal film as a gas phase; and (c) applying the gas phase source to the catalyst metal layer to form a metal film thereon.
In the embodiments of the present invention, palladium or platinum may be used as the catalyst metal for facilitating formation of a metal film comprising aluminum or copper. The formation of catalyst metal layers can be repeated to increase the deposition rate of the metal film. If more than two source gases are
required to form the catalyst metal layer, it is desirable to supply the source gases sequentially on the substrate, not to supply the source gases simultaneously thereon, to obtain a catalyst metal layer with a superior step coverage. Additionally, during or after the deposition of the metal film, it is also desirable to diffuse the catalyst metal into the metal film to form an alloy film.
BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1A to ID show the steps of forming a metal film in accordance with an embodiment of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
In the practice of the invention, a silicon substrate 10 to form a metal film thereon is prepared first. Then, as shown in FIG. 1A, a palladium thin layer 20 is formed on the silicon substrate by supplying both (l,l,l,5,5,5-hexafluoro-2,4- pentanedionato)Palladium(II) and hydrogen gas sequentially on the silicon substrate. In other embodiment, platinum may be employed instead of the palladium.
In particular, a Pd-Al alloy or a Pd-Cu alloy provides the following advantages. If pure aluminum is employed to form interconnection of semiconductor devices, low current density should be maintained to avoid an electromigration- induced open circuit. Accordingly, in a conventional method, an Al-Cu alloy, in which aluminum contains a small amount of copper, is used as an interconnection material to decrease electromigration. The Pd-Al alloy can decrease electromigration thus increase the durability of the metal interconnection, to a degree equal or superior to the Al-Cu alloy. A Pd-Al alloy displays other desirable properites. K. P. Rodbell et al. reported that it is resistant to metal corrosion during a reactive ion etching process in "The Microstructure, Mechanical Stress, Texture and Electromigration Behavior of Al-Pd alloys", Journal of Electronic Materials, Vol. 22, No. 6, p 597, 1993. Additionally, P. Atanasova et al. reported that a Cu-0.5% Pd alloy effectively prevented the oxidation of copper without causing any effects on electrical conductivity. (Reference : P. Atanasova, V. Bhaskaran, T. Kodas and M. Hampden- Smith, an article entitled "Oxidation Resistance of Copper Alloy Thin Films Formed by CVD" published in a book "Advanced Metallization for Future ULSI", Materials
Research Society, 1996 of K. N. Tu, J. W. Mayer, J. M. Poate and L. J. Chen.) Therefore, if palladium catalyst is diffused into an interconnection metal film to form an alloy during or after the deposition of the metal film, additional process is not needed to prevent electromigration or oxidation of the interconnection metal film. In the embodiment of the present invention, the palladium layer 20 is formed as thin as possible with a uniform thickness to provide higher current density, because the sheet resistance of catalyst metal is generally higher than that of aluminum or copper for use in the interconnection. For this purpose, a uniform thickness palladium layer is formed by atomic layer deposition in which source compound gases are sequentially supplied on the silicon substrate maintained at a temperature lower than the thermal decomposition temperatures of source compound gases. In this process, only surface reaction is utilized while chemical vapor reaction between source gases is prevented. In general, the deposition rate of atomic layer deposition is significantly low compared with that of conventional deposition where source gases are simultaneously supplied. However, in this embodiment, such a low deposition rate is advantageous because a thin palladium catalyst layer is required. In view of the report of S. J. Potochnik et al. that palladium ion catalyst of less than one atomic layer induces effective chemical deposition of copper, a palladium thin layer of several atomic layers is expected to provide sufficient catalytic effects. The sources required to form an aluminum film are prepared as gases. After formation of a palladium catalyst layer, the source gases are applied to the palladium catalyst layer to form an aluminum film 20 thereon, as shown in FIG. IB. In the course of chemically depositing the aluminum film, the palladium catalyst is diffused into the aluminum film by applied heat, forming an Al-Pd alloy. If the Al-Pd alloy is used as an interconnection metal material, no additional process is needed to prevent electromigration or oxidation of the interconnection metal film and turn-around-time can be considerably reduced. The Al-Pd alloy can be formed in a different way when the heat applied during the chemical deposition of aluminum film is insufficient for the diffusion of the palladium catalyst. In this case, additional heat treatment is conducted after the formation of aluminum film. And then, formation of an additional palladium catalyst layer 22 and an additional aluminum film 32 is sequentially repeated as shown in FIG. 1C and ID. As such, the multiple palladium catalyst layers
are used upon consideration of the study of O. Lehmann and M. Stuke. They reported that the thickness of aluminum film formed on the palladium layer did not increase and came to saturation with increasing contact time between a liquid aluminum source and the palladium layer. It is supposed that this results from the reduction in catalytic effect of the palladium catalyst underlying the metal film. In an effort to overcome the above problem, multiple palladium catalyst layers are used to the overall deposition rate of the metal film.
Claims
1. A method for forming a metal film comprising the steps of:
(a) forming a catalyst metal layer on a substrate using thermal chemical vapor deposition to facilitate formation of said metal film;
(b) preparing at least one source of said metal film as a gas phase; and
(c) applying said gas phase source to said catalyst metal layer to form a metal film thereon.
2. The method of claim 1, wherein said catalyst metal layer comprises palladium or platinum.
3. The method of claim 1 , wherein said metal film comprises aluminum or copper.
4. The method of claim 1, after the step (c), further comprising the steps of:
(d) forming another catalyst metal layer on said metal film;
(e) preparing at least one source of said metal film as a gas phase; and
(f) applying said gas phase source to said another catalyst metal layer to form another metal film thereon.
5. The method of claim 4, wherein the steps (d) to (f) are repeated at least one number of times.
6. The method of claim 1, wherein the deposition source of said catalyst metal layer comprises at least two source gases, said source gases being alternately applied to said substrate to reach a desired thickness during the step (a).
7. The method of claim 2, wherein the deposition source of said catalyst metal layer comprises at least two source gases, said source gases being alternately applied to said substrate to reach a desired thickness during the step (a).
8. The method of claim 3, wherein the deposition source of said catalyst metal layer comprises at least two source gases, said source gases being alternately applied to said substrate to reach a desired thickness during the step (a).
9. The method of claim 4, wherein the deposition source of said catalyst metal layer comprises at least two source gases, said source gases being alternately applied to the underlying structure to reach a desired thickness during the step (d).
10. The method of claim 5, wherein the deposition source of said catalyst metal layer comprises at least two source gases, said source gases being alternately applied to the underlying structure to reach a desired thickness during the step (d).
11. The method of claim 1, wherein the step (c) includes diffusing said catalyst metal layer into said metal film to form an alloy film.
12. The method of claim 11, wherein said catalyst metal layer comprises palladium.
13. The method of claim 11, wherein said metal film comprises aluminum or copper.
14. The method of claim 1, after the step (c), further comprising the step of diffusing said catalyst metal layer into said metal film to form an alloy film.
15. The method of claim 14, wherein said catalyst metal layer comprises palladium.
16. The method of claim 14, wherein said metal film comprises aluminum or copper.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2001045149A1 (en) * | 1999-12-15 | 2001-06-21 | Genitech Co., Ltd. | Method of forming copper interconnections and thin films using chemical vapor deposition with catalyst |
WO2001078123A1 (en) * | 2000-04-11 | 2001-10-18 | Genitech Co., Ltd. | Method of forming metal interconnects |
KR100403454B1 (en) * | 2000-06-20 | 2003-11-01 | 주식회사 하이닉스반도체 | Method of forming a metal wiring in a semiconductor device |
US6727169B1 (en) | 1999-10-15 | 2004-04-27 | Asm International, N.V. | Method of making conformal lining layers for damascene metallization |
US7438760B2 (en) | 2005-02-04 | 2008-10-21 | Asm America, Inc. | Methods of making substitutionally carbon-doped crystalline Si-containing materials by chemical vapor deposition |
US7608549B2 (en) | 2005-03-15 | 2009-10-27 | Asm America, Inc. | Method of forming non-conformal layers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6362099B1 (en) * | 1999-03-09 | 2002-03-26 | Applied Materials, Inc. | Method for enhancing the adhesion of copper deposited by chemical vapor deposition |
US7186630B2 (en) | 2002-08-14 | 2007-03-06 | Asm America, Inc. | Deposition of amorphous silicon-containing films |
US8278176B2 (en) | 2006-06-07 | 2012-10-02 | Asm America, Inc. | Selective epitaxial formation of semiconductor films |
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EP0448223A2 (en) * | 1990-02-19 | 1991-09-25 | Canon Kabushiki Kaisha | Process for forming metal deposited film containing aluminium as main component by use of alkyl aluminum hydride |
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EP0448223A2 (en) * | 1990-02-19 | 1991-09-25 | Canon Kabushiki Kaisha | Process for forming metal deposited film containing aluminium as main component by use of alkyl aluminum hydride |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6727169B1 (en) | 1999-10-15 | 2004-04-27 | Asm International, N.V. | Method of making conformal lining layers for damascene metallization |
US7102235B2 (en) | 1999-10-15 | 2006-09-05 | Asm International N.V. | Conformal lining layers for damascene metallization |
WO2001045149A1 (en) * | 1999-12-15 | 2001-06-21 | Genitech Co., Ltd. | Method of forming copper interconnections and thin films using chemical vapor deposition with catalyst |
US6720262B2 (en) | 1999-12-15 | 2004-04-13 | Genitech, Inc. | Method of forming copper interconnections and thin films using chemical vapor deposition with catalyst |
WO2001078123A1 (en) * | 2000-04-11 | 2001-10-18 | Genitech Co., Ltd. | Method of forming metal interconnects |
KR100403454B1 (en) * | 2000-06-20 | 2003-11-01 | 주식회사 하이닉스반도체 | Method of forming a metal wiring in a semiconductor device |
US7438760B2 (en) | 2005-02-04 | 2008-10-21 | Asm America, Inc. | Methods of making substitutionally carbon-doped crystalline Si-containing materials by chemical vapor deposition |
US9190515B2 (en) | 2005-02-04 | 2015-11-17 | Asm America, Inc. | Structure comprises an As-deposited doped single crystalline Si-containing film |
US7608549B2 (en) | 2005-03-15 | 2009-10-27 | Asm America, Inc. | Method of forming non-conformal layers |
Also Published As
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KR100332364B1 (en) | 2002-09-18 |
WO2000013207A3 (en) | 2000-06-02 |
KR20000018353A (en) | 2000-04-06 |
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