WO2009116346A1 - 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 PDF

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WO2009116346A1
WO2009116346A1 PCT/JP2009/052916 JP2009052916W WO2009116346A1 WO 2009116346 A1 WO2009116346 A1 WO 2009116346A1 JP 2009052916 W JP2009052916 W JP 2009052916W WO 2009116346 A1 WO2009116346 A1 WO 2009116346A1
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thin film
electronic member
barrier
alloy thin
noble metal
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PCT/JP2009/052916
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English (en)
French (fr)
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関口　淳之輔
伊森　徹
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日鉱金属株式会社
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Priority to US12/449,128 priority Critical patent/US8004082B2/en
Priority to CN200980101582.XA priority patent/CN101911264B/zh
Priority to JP2009523096A priority patent/JP4531114B2/ja
Priority to EP09721258.3A priority patent/EP2237312B1/en
Publication of WO2009116346A1 publication Critical patent/WO2009116346A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • H01L21/02—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
    • 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
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
    • 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
    • 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
    • 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.
  • An object of the present invention is to provide a technique for further streamlining the above method and forming ULSI fine copper wiring by a simpler method.
  • 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 base material, the alloy thin film containing 60 atomic% or more of tungsten and noble metal. An electronic member having a composition of 5 atomic% or more and 40 atomic% or less. (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 platinum, gold, silver, and palladium.
  • 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 platinum, gold, silver, palladium, and the like, and one or more metals selected from these metals are used. Among them, the use of platinum and palladium is preferable, and palladium is particularly preferable.
  • the composition ratio of tungsten in the alloy thin film of tungsten and noble metal is desirably 60 atomic% or more, and the composition ratio of noble metal is desirably 5 atomic% or more and 40 atomic% or less.
  • 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.
  • noble metal may be mixed into the copper plating film, in which case the resistance of the copper plating film is increased. Or since the composition ratio of tungsten is too small, the function as a barrier layer becomes insufficient.
  • a more preferable composition ratio of the noble metal is 10 atom% or more and 30 atom% or less, and a more preferable composition ratio of tungsten is 70 atom% or more and 90 atom% or less.
  • 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 an 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 Alternatively, by performing a combination of these processes, 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 a noble metal (palladium) and tungsten. The alloy film serves as a barrier. Copper wiring was formed by electroplating as a seed 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 a noble metal (palladium) and tungsten.
  • the alloy film serves as a barrier.
  • Copper wiring was formed by electroplating as a seed 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 and the diffusion of the noble metal into the copper plating layer were confirmed by AES depth profile measurement.
  • the barrier property was determined by the presence or absence of the diffusion phenomenon of copper into the tungsten alloy film, and the diffusion of the noble metal into the copper plating layer was determined by the presence or absence of the diffusion phenomenon of the noble metal component into the copper 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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Abstract

　本発明は、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。 　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６０原子％以上、貴金属を５原子％以上４０原子％以下とする組成である電子部材。前記貴金属としては、白金、金、銀、パラジウムから選ばれる１種または２種以上の金属が好ましい。

Description

基材上にバリア兼シード層が形成された電子部材
　本発明は、基材上に、ＵＬＳＩ微細銅配線のバリア兼シード層が形成された電子部材に関する。
　ＵＬＳＩ微細銅配線（ダマシン銅配線）の銅の成膜方法として、無電解銅めっきによりシード層を設け、電気銅めっきにより銅を成膜する方法が知られている。
　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。
　本発明者らは、既に、無電解銅めっき液に添加剤として重量平均分子量（Ｍｗ）の小さい水溶性窒素含有ポリマーを加え、一方被めっき物の基板にはめっき液浸漬前に触媒金属を付着させるか、あるいは触媒金属をあらかじめ最表面に成膜した後、めっき液に浸漬させて該触媒金属上に窒素原子を介してポリマーを吸着させることによりめっきの析出速度が抑制され、かつ結晶が非常に微細化して膜厚１５ｎｍ以下の均一な薄膜がウェハーのような鏡面上に形成可能となることを見出した（特許文献１）。また本発明者らは、前記発明の実施例において、触媒金属をあらかじめ最表面に成膜した後、めっき液に浸漬させて該触媒金属上に窒素原子を介してポリマーを吸着させることによりめっきの析出速度が抑制され、かつ結晶が非常に微細化して膜厚６ｎｍ以下の均一な薄膜がウェハーのような鏡面上に形成可能となることを示した。
　このような方法、すなわちダマシン銅配線形成において、触媒金属を成膜した後に無電解めっきにより銅シード層を設ける場合は、銅拡散防止のためのバリア層が触媒金属層とは別に予め形成されていることが必要であり、従って、銅シード層を成膜する前にバリア層と触媒金属層の二層もの層を形成することになるため、膜厚を厚くできない超微細配線では実工程への適用が困難であるという問題が判明した。
　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）。
特開２００８－２２３１００号公報 国際公開第２００９／０１６９７９号パンフレット 国際公開第２００９／０１６９８０号パンフレット
　しかしながら、この方法においても、ＵＬＳＩ微細銅配線（ダマシン銅配線）の形成のためには、バリア能と触媒能とを兼ね備えた合金薄膜の形成工程と、その上に無電解めっきによりシード層を形成する工程を経て電気銅めっきにより銅配線の形成工程が必要である。
　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。
　本発明者らは、鋭意検討した結果、このバリア機能を有する合金薄膜自体をシード層として機能させることを試みたところ、バリア機能を有するタングステンと貴金属との合金薄膜とすることにより、この合金薄膜上に無電解めっき等によるシード層形成をせずに直接電気銅めっきを施すことができ、ＵＬＳＩ微細銅配線を形成することが可能であることを見出し、本発明に至った。
　すなわち、本発明は、
（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６０原子％以上、貴金属を５原子％以上４０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、白金、金、銀、パラ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。
　本発明によれば、基材上のタングステンと貴金属との合金薄膜がバリア兼シード層として十分に機能するため、この合金薄膜層の上に従来の無電解めっき膜を形成する工程を必要とせずに、直接電気銅めっきを施すことによりＵＬＳＩ微細銅配線を形成することができる。したがって、膜厚を薄くすることができ、ますます微細化が進むダマシン銅配線に適用が可能となる。
　本発明は、基材上に、電気銅めっきによりＵＬＳＩ微細銅配線を形成する際のバリア兼シード層として、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。
　貴金属としては、白金、金、銀、パラジウムなどが挙げられ、これらの金属から選ばれる１種または２種以上の金属を使用するが、中でも白金、パラジウムの使用が好ましく、パラジウムが特に好ましい。
　タングステンと貴金属との合金薄膜におけるタングステンの組成比は６０原子％以上、貴金属の組成比は５原子％以上、４０原子％以下が望ましい。貴金属が５原子％より少ないと酸化抑制効果が少なく、十分に抵抗が下がらず、合金薄膜上に電気銅めっきにより均一に銅膜を成膜しにくくなる。また４０原子％より多くなると、貴金属が銅めっき膜中に混入するおそれがあり、その場合銅めっき膜の抵抗が高くなる。あるいは、タングステンの組成比が少なすぎるため、バリア層としての機能が不十分となる。貴金属のより好ましい組成比は１０原子％以上３０原子％以下であり、タングステンのより好ましい組成比は７０原子％以上９０原子％以下である。
　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。
　また、前記合金薄膜は、バリア性、めっき性に影響を与えない範囲であれば、更にタングステンと貴金属以外の金属を含んでいても良く、例えば、比抵抗値が２０μΩ・ｃｍ以下である金属であれば５原子％未満含んでいても良い。これらの金属を含有させることにより、エレクトロマイグレーション耐性が向上する場合がある。
　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。
　前記合金薄膜の厚みは１０ｎｍ以下が好ましい。合金薄膜の膜厚を薄くすることにより、線幅数十ｎｍレベルのダマシン銅配線への適用が可能となる。
　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。
　本発明において合金薄膜を形成する基材は、Ｓｉウェハー、あるいは表面にＳｉＯ２が少なくとも一部形成されたＳｉウェハーなどの半導体ウェハーが好ましく、酸処理、アルカリ処理、界面活性剤処理、超音波洗浄あるいはこれらを組み合わせた処理を実施することで、基材のクリーニング、濡れ性向上を図ることができる。
　本発明において、前記合金薄膜上に、さらに、ＵＬＳＩ微細銅配線を電気めっきにより設け、電子部材とすることができる。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た場合、ボイド・シーム等の欠陥の発生しない電子部材が得られる。
　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。
　次に本発明を実施例によって説明するが、本発明はこれらの実施例によって限定される物ではない。
実施例１
　Ｓｉ基板上にＳｉＯ２を形成し、その上にに貴金属（パラジウム）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及び貴金属の銅めっき層への拡散を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、貴金属の銅めっき層への拡散は、貴金属成分の銅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２～７、比較例１～３
　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。
Figure JPOXMLDOC01-appb-T000001

Claims (5)

  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６０原子％以上、貴金属を５原子％以上４０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％未満含む請求の範囲第１項記載の電子部材。
  3. 　前記貴金属が、白金、金、銀、パラ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。
  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。
  5. 　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。
PCT/JP2009/052916 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 WO2009116346A1 (ja)

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