WO2009116347A1 - 基材上にバリア兼シード層が形成された電子部材 - Google Patents
基材上にバリア兼シード層が形成された電子部材 Download PDFInfo
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- WO2009116347A1 WO2009116347A1 PCT/JP2009/052917 JP2009052917W WO2009116347A1 WO 2009116347 A1 WO2009116347 A1 WO 2009116347A1 JP 2009052917 W JP2009052917 W JP 2009052917W WO 2009116347 A1 WO2009116347 A1 WO 2009116347A1
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- WIPO (PCT)
- Prior art keywords
- thin film
- barrier
- electronic member
- alloy thin
- seed layer
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 41
- 239000000956 alloy Substances 0.000 claims abstract description 41
- 239000010409 thin film Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 19
- 239000010937 tungsten Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims description 32
- 230000004888 barrier function Effects 0.000 claims description 27
- 239000010408 film Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 44
- 239000000758 substrate Substances 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 3 -Sulfopropyl Chemical group 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- VZCCTDLWCKUBGD-UHFFFAOYSA-N 8-[[4-(dimethylamino)phenyl]diazenyl]-10-phenylphenazin-10-ium-2-amine;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(N=C2C(C=C(N)C=C2)=[N+]2C=3C=CC=CC=3)C2=C1 VZCCTDLWCKUBGD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- 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
- H01L21/2855—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 physical means, e.g. sputtering, evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to an electronic member in which a barrier / seed layer of ULSI fine copper wiring is formed on a substrate.
- a method is known in which a seed layer is provided by electroless copper plating and copper is formed by electrolytic copper plating.
- electroless copper plating is performed on a mirror surface such as a semiconductor wafer, it has been difficult to obtain sufficient adhesion to the deposited plating film. Moreover, the reactivity of plating was low, and it was difficult to perform uniform plating over the entire surface of the substrate.
- a barrier metal layer such as tantalum nitride by an electroless plating method, there is a problem that it is difficult to form a uniform plating and adhesion is not sufficient.
- the present inventors have already added a water-soluble nitrogen-containing polymer having a small weight average molecular weight (Mw) as an additive to the electroless copper plating solution, while attaching a catalytic metal to the substrate of the object to be plated before dipping the plating solution.
- Mw weight average molecular weight
- a uniform thin film having a film thickness of 15 nm or less can be formed on a mirror surface such as a wafer by miniaturization (Patent Document 1).
- the inventors of the present invention after forming a catalyst metal on the outermost surface in advance, are immersed in a plating solution to adsorb a polymer on the catalyst metal through nitrogen atoms. It was shown that the deposition rate was suppressed, and the crystal became very fine so that a uniform thin film having a thickness of 6 nm or less could be formed on a mirror surface such as a wafer.
- a barrier layer for preventing copper diffusion is previously formed separately from the catalyst metal layer. Therefore, before the copper seed layer is formed, two layers of the barrier layer and the catalytic metal layer are formed. The problem was found to be difficult to apply.
- Patent Documents 2 and 3 In order to eliminate the complexity of forming the two layers prior to the formation of the copper seed layer, the present inventors formed a single layer consisting of a specific alloy thin film having both barrier ability and catalytic ability, and further electroless It has been found that by using displacement plating and reduction plating together during plating, the copper seed layer formed thereon can be thinly and uniformly formed, and an application has already been filed (Patent Documents 2 and 3).
- Patent Document 4 includes at least one layer including a ruthenium-based material or a ruthenium-based alloy as a barrier layer, and at least one element from Group IV, Group V, or Group VI of the periodic table or a combination thereof.
- a laminated material having a laminated barrier layer structure in which one layer is provided and obtained by applying electrolytic copper plating directly on a layer containing a ruthenium-based material or a ruthenium-based alloy is described.
- As the layer containing a ruthenium-based material or a ruthenium-based alloy a ruthenium layer is used. Since the ruthenium layer has poor adhesion to the substrate layer, the periodic table of groups IV, V, VI, VI between the substrate and the ruthenium layer is used.
- a layer containing at least one element from the group or a combination thereof is provided, and the barrier layer has at least a two-layer structure.
- JP 2008-223100 A International Publication No. 2009/016979 Pamphlet International Publication No. 2009/016980 Pamphlet Special table 2008-538591
- the inventors tried to make the alloy thin film having the barrier function itself function as a seed layer.
- the alloy thin film was obtained.
- the present inventors have found that it is possible to directly perform electrolytic copper plating without forming a seed layer by electroless plating or the like, and it is possible to form a ULSI fine copper wiring.
- the present invention (1) An electronic member in which an alloy thin film of tungsten and noble metal used as a barrier and seed layer for ULSI fine copper wiring is formed on a substrate, the alloy thin film containing 50 atomic% or more of tungsten and noble metal. An electronic member having a composition of 5 atomic% to 50 atomic%. (2) The electronic member according to (1), wherein the alloy thin film further contains less than 5 atomic% of a metal having a specific resistance value of 20 ⁇ ⁇ cm or less. (3) The electronic member according to (1) or (2), wherein the noble metal is one or more metals selected from ruthenium, rhodium, and iridium.
- the alloy thin film of tungsten and noble metal on the base material sufficiently functions as a barrier and seed layer, a process of forming a conventional electroless plating film on the alloy thin film layer is not required.
- the ULSI fine copper wiring can be formed by directly performing the electrolytic copper plating. Therefore, the film thickness can be reduced, and the present invention can be applied to damascene copper wiring that is increasingly miniaturized.
- the present invention is an electronic member in which an alloy thin film of tungsten and a noble metal is formed on a base material as a barrier / seed layer when ULSI fine copper wiring is formed by electrolytic copper plating.
- Tungsten has a barrier function against copper and has a low specific resistance value of 5.65 ⁇ ⁇ cm, but its surface is easily oxidized in the atmosphere. Therefore, in the case of a thin film, the surface is oxidized to increase the resistance, and the resistance is too high as a seed layer for electroplating, and uniform copper electroplating cannot be performed and cannot be used.
- the oxidation resistance of the tungsten surface is improved, the barrier property is improved, the resistance is reduced, and direct copper electroplating can be performed.
- the noble metal examples include ruthenium, rhodium, iridium and the like, and one or two or more metals selected from these metals are used. Among them, the use of rhodium and ruthenium is preferable, and ruthenium is particularly preferable.
- the composition ratio of tungsten in the alloy thin film of tungsten and noble metal is desirably 50 atomic% or more, and the composition ratio of noble metal is desirably 5 atomic% or more and 50 atomic% or less. If the precious metal content is less than 5 atomic%, the effect of suppressing oxidation is small, the resistance is not sufficiently lowered, and it becomes difficult to form a copper film uniformly on the alloy thin film by electrolytic copper plating. On the other hand, if it exceeds 50 atomic%, the composition ratio of tungsten is too small, and the function as a barrier layer becomes insufficient.
- a more preferable composition ratio of the noble metal is 10 atom% or more and 40 atom% or less, and a more preferable composition ratio of tungsten is 60 atom% or more and 90 atom% or less.
- Ruthenium has poor adhesion to the base material layer (Si, SiO 2 ), and when the ruthenium layer is provided directly on the base material, the ruthenium layer is easily peeled off, which causes a problem.
- the adhesion between the base material and the alloy thin film is improved, and there is no problem.
- Metals having barrier properties other than tungsten such as tantalum and titanium have a high degree of surface oxidation or high resistance because the oxide film is passivated, and are not suitable for use as a seed layer for electroplating.
- the alloy thin film may further contain a metal other than tungsten and a noble metal as long as it does not affect the barrier properties and plating properties.
- the alloy thin film is a metal having a specific resistance of 20 ⁇ ⁇ cm or less. If present, it may contain less than 5 atomic%. By containing these metals, electromigration resistance may be improved. Examples of metals having a specific resistance value of 20 ⁇ ⁇ cm or less include aluminum (specific resistance value 2.655 ⁇ ⁇ cm), magnesium (specific resistance value 4.45 ⁇ ⁇ cm), tin (specific resistance value 11.0 ⁇ ⁇ cm).
- Indium (resistivity value 8.37 ⁇ ⁇ cm), molybdenum (resistivity value 5.2 ⁇ ⁇ cm), niobium (resistivity value 12.5 ⁇ ⁇ cm), zinc (resistivity value 5.92 ⁇ ⁇ cm), Examples include nickel (specific resistance value 6.84 ⁇ ⁇ cm), cobalt (specific resistance value 6.24 ⁇ ⁇ cm), chromium (specific resistance value 12.9 ⁇ ⁇ cm), and the like.
- the thickness of the alloy thin film is preferably 10 nm or less. By reducing the film thickness of the alloy thin film, application to damascene copper wiring with a line width of several tens of nanometers becomes possible.
- the alloy thin film is preferably formed by sputtering which allows easy control of the alloy film composition. By using a sputtering alloy target containing tungsten and a noble metal, a thin film of an alloy of tungsten and noble metal can be formed by sputtering film formation on a substrate.
- the base material on which the alloy thin film is formed is preferably a Si wafer or a semiconductor wafer such as a Si wafer having at least a portion of SiO 2 formed on the surface, and is subjected to acid treatment, alkali treatment, surfactant treatment, ultrasonic cleaning.
- the substrate can be cleaned and wettability can be improved.
- a ULSI fine copper wiring can be further provided on the alloy thin film by electroplating to form an electronic member.
- an electrolytic copper plating film is formed using the alloy thin film as a barrier / seed layer, an electronic member free from defects such as voids and seams can be obtained.
- the wiring portion is preferably copper or an alloy containing copper as a main component, and more preferably copper.
- the electrolytic copper plating solution is not particularly limited as long as it is a composition generally used for embedding damascene copper wiring.
- copper sulfate and sulfuric acid as main components chlorine, polyethylene glycol, bis (2 disulfide) (3 -Sulfopropyl) Liquid containing disodium, Janus green, etc.
- conditions, such as temperature, pH, and a current density at the time of performing an electrolytic copper plating it can carry out on the same conditions as the normal electrolytic copper plating for copper wiring.
- Example 1 An SiO 2 film is formed on a Si substrate, and a 10 nm-thickness alloy thin film having a composition shown in Table 1 is prepared on the surface using a sputtering alloy target made of noble metal (ruthenium) and tungsten. The alloy film is used as a barrier / seed. Copper wiring was formed by electroplating as a layer. Sputter film formation was performed after pre-sputtering for 15 minutes by generating plasma with an argon pressure of 0.8 Pa and an output of 50 W.
- a sputtering alloy target made of noble metal (ruthenium) and tungsten.
- the alloy film is used as a barrier / seed.
- Copper wiring was formed by electroplating as a layer.
- Sputter film formation was performed after pre-sputtering for 15 minutes by generating plasma with an argon pressure of 0.8 Pa and an output of 50 W.
- the composition of the electroplating solution is copper sulfate 0.25 mol / L, sulfuric acid 1.8 mol / L, hydrochloric acid 1.4 mmol / L, trace additive (bis (3-sulfopropyl) disodium disulfide, polyethylene glycol, Janus Green
- the plating conditions were 30 seconds at a bath temperature of 25 ° C. and a current density of 0.2 A / dm 2 .
- the barrier property after vacuum annealing at 400 ° C. for 30 minutes was confirmed by AES depth profile measurement. The barrier property was determined by the presence or absence of a diffusion phenomenon of copper into the tungsten alloy film. Appropriateness of electrolytic copper plating is acceptable when the bright copper plating film is uniformly deposited on the entire surface, non-depositing when the matte rough plating film is seen, and non-depositing film. did. The results are shown in Table 1.
- Example 2 to 7 Comparative Examples 1 to 3 A copper wiring was formed and evaluated in the same manner as in Example 1 except that the composition of the alloy thin film in Example 1 was changed as shown in Table 1. The results are shown in Table 1.
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- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
従来、半導体ウェハーのような鏡面上に無電解銅めっきを行った場合、析出しためっき膜に十分な密着性を得るのは困難であった。また、めっきの反応性が低く、基板全面に均一なめっきを行うことも困難であった。従来は、例えば、窒化タンタルなどのバリアメタル層上に無電解めっき法で銅シード層を形成する場合、めっきを均一に形成することが難しく密着力が十分でないという問題があった。
こうした銅シード層の成膜に先立つ二つの層形成の煩雑さを解消するため、本発明者らはバリア能と触媒能とを兼ね備えた特定の合金薄膜からなる単一層を形成し、さらに無電解めっき時に置換めっきおよび還元めっきを併用することにより、その上に形成する銅シード層の膜厚を薄く均一に形成できることを見出し、すでに出願した(特許文献2、特許文献3)。
また、上記特許文献4記載の積層材料においても、バリア層を積層構造とすることが必要である。
本発明は、前記方法を更に合理化し、より簡易な方法によりULSI微細銅配線を形成する技術を提供することを目的とするものである。
(1)基材上に、ULSI微細銅配線のバリア兼シード層として使用するタングステンと貴金属との合金薄膜が形成された電子部材であって、該合金薄膜がタングステンを50原子%以上、貴金属を5原子%以上50原子%以下とする組成である電子部材。
(2)前記合金薄膜が、更に比抵抗値が20μΩ・cm以下である金属を5原子%未満含む前記(1)記載の電子部材。
(3)前記貴金属が、ルテニウム、ロジウム、イリジウムから選ばれる1種または2種以上の金属である前記(1)または(2)記載の電子部材。
(4)前記合金薄膜をバリア兼シード層として電気銅めっき膜を成膜し、ULSI微細銅配線を形成した前記(1)~(3)のいずれか一項に記載の電子部材。
(5)前記基材が半導体ウェハーである前記(1)~(4)のいずれか一項に記載の電子部材。
からなる。
タングステンは銅に対するバリア機能を有し、比抵抗値が5.65μΩ・cmと低めであるが、大気中で表面が酸化されやすい。そのため、薄膜とした場合は表面が酸化されて抵抗が高くなり、電気めっき用のシード層としては抵抗が高すぎて、均一な電気銅めっきができず、使用することができない。貴金属との合金とすることにより、タングステン表面の耐酸化性が向上し、バリア性の向上、抵抗減となり、直接電気銅めっきを行うことができるようになる。
タングステン以外のバリア性を有する金属(タンタル、チタン等)は、表面酸化度合いが大きいか、または酸化膜が不働態化しているため抵抗が高く、電気めっき用シード層としての使用に適さない。
比抵抗値が20μΩ・cm以下である金属としては、例えば、アルミニウム(比抵抗値2.655μΩ・cm)、マグネシウム(比抵抗値4.45μΩ・cm)、スズ(比抵抗値11.0μΩ・cm)、インジウム(比抵抗値8.37μΩ・cm)、モリブデン(比抵抗値5.2μΩ・cm)、ニオブ(比抵抗値12.5μΩ・cm)、亜鉛(比抵抗値5.92μΩ・cm)、ニッケル(比抵抗値6.84μΩ・cm)、コバルト(比抵抗値6.24μΩ・cm)、クロム(比抵抗値12.9μΩ・cm)等が挙げられる。
前記合金薄膜は、合金膜組成制御が容易なスパッタリングで形成することが好ましい。タングステンと貴金属を含むスパッタリング合金ターゲットを用い、基材上にスパッタ成膜することにより、タングステンと貴金属との合金薄膜を形成することができる。
配線部は銅又は銅を主成分とする合金であることが好ましく、銅がより好ましい。電気銅めっき液は、一般にダマシン銅配線埋め込み用に使用されている組成であればよく、特に限定されないが、例えば主成分として硫酸銅及び硫酸、微量成分として塩素、ポリエチレングリコール、二硫化ビス(3-スルホプロピル)二ナトリウム、ヤヌスグリーンなどを含んだ液を用いることができる。また、電気銅めっきを行う際の、温度、pH、電流密度等の条件についても、通常の銅配線用電気銅めっきと同様の条件で行うことができる。
実施例1
Si基板上にSiO2を形成し、その上に貴金属(ルテニウム)とタングステンからなるスパッタリング合金ターゲットを用いて表1に示す組成の膜厚10nmの合金薄膜を作製し、その合金膜をバリア兼シード層として電気めっきにより銅配線を形成した。スパッタ成膜はアルゴン圧0.8Pa、50Wの出力でプラズマを発生させ、15分間のプレスパッタ後、実施した。電気めっき液の組成は、硫酸銅0.25mol/L、硫酸1.8mol/L、塩酸1.4mmol/L、微量添加剤(二硫化ビス(3-スルホプロピル)二ナトリウム、ポリエチレングリコール、ヤヌスグリーン)で、めっき条件は浴温25℃、電流密度0.2A/dm2で30秒間実施した。400℃×30分の真空アニール処理後のバリア性をAESデプスプロファイル測定により確認した。バリア性の判定は、銅のタングステン合金膜中への拡散現象の有無により判定した。電気銅めっきの可否は、外観上光沢銅めっき膜が全面に均一に析出しているものは可、無光沢の粗いめっき膜が見られるものを析出不均一、膜が未析出のものを不可とした。結果を表1に示す。
実施例1における合金薄膜の組成を表1記載のように変えた以外は実施例1と同様にして銅配線を形成し、評価した。結果を表1に示す。
Claims (5)
- 基材上に、ULSI微細銅配線のバリア兼シード層として使用するタングステンと貴金属との合金薄膜が形成された電子部材であって、該合金薄膜がタングステンを50原子%以上、貴金属を5原子%以上50原子%以下とする組成である電子部材。
- 前記合金薄膜が、更に比抵抗値が20μΩ・cm以下である金属を5原子%未満含む請求の範囲第1項記載の電子部材。
- 前記貴金属が、ルテニウム、ロジウム、イリジウムから選ばれる1種または2種以上の金属である請求の範囲第1項または第2項記載の電子部材。
- 前記合金薄膜をバリア兼シード層として電気銅めっき膜を成膜し、ULSI微細銅配線を形成した請求の範囲第1項~第3項のいずれか一項に記載の電子部材。
- 前記基材が半導体ウェハーである請求の範囲第1項~第4項のいずれか一項に記載の電子部材。
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US12/449,162 US8089154B2 (en) | 2008-03-19 | 2009-02-19 | Electronic component formed with barrier-seed layer on base material |
JP2009523097A JP4531115B2 (ja) | 2008-03-19 | 2009-02-19 | 基材上にバリア兼シード層が形成された電子部材 |
CN2009801015834A CN101911265B (zh) | 2008-03-19 | 2009-02-19 | 在基材上形成有阻挡层兼种子层的电子构件 |
KR1020107014415A KR101279716B1 (ko) | 2008-03-19 | 2009-02-19 | 기재상에 배리어 겸 시드층이 형성된 전자 부재 |
EP09721789.7A EP2237313B1 (en) | 2008-03-19 | 2009-02-19 | ELECTRONIC MEMBER WHEREIN a BARRIER-SEED LAYER IS FORMED ON a BASE layer |
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EP2237313B1 (en) | 2014-07-30 |
CN101911265A (zh) | 2010-12-08 |
EP2237313A1 (en) | 2010-10-06 |
KR101279716B1 (ko) | 2013-06-27 |
US8089154B2 (en) | 2012-01-03 |
JPWO2009116347A1 (ja) | 2011-07-21 |
JP4531115B2 (ja) | 2010-08-25 |
US20110006427A1 (en) | 2011-01-13 |
CN101911265B (zh) | 2012-07-04 |
TW200950051A (en) | 2009-12-01 |
EP2237313A4 (en) | 2012-08-01 |
KR20100090301A (ko) | 2010-08-13 |
TWI389284B (zh) | 2013-03-11 |
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