EP1482073A2 - Procédé pour la fabrication de couches en métal ultra-minces et homogènes - Google Patents

Procédé pour la fabrication de couches en métal ultra-minces et homogènes Download PDF

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Publication number
EP1482073A2
EP1482073A2 EP04011671A EP04011671A EP1482073A2 EP 1482073 A2 EP1482073 A2 EP 1482073A2 EP 04011671 A EP04011671 A EP 04011671A EP 04011671 A EP04011671 A EP 04011671A EP 1482073 A2 EP1482073 A2 EP 1482073A2
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EP
European Patent Office
Prior art keywords
metal layer
metal
layer
ultra
deposition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04011671A
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German (de)
English (en)
Inventor
Gerneot Dr. Steinlesberger
Manfred Dr. Engelhardt
Eugen Dr. Unger
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Infineon Technologies AG
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Infineon Technologies AG
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Publication date
Application filed by Infineon Technologies AG filed Critical Infineon Technologies AG
Publication of EP1482073A2 publication Critical patent/EP1482073A2/fr
Withdrawn legal-status Critical Current

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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only

Definitions

  • the present invention relates to a method for training an ultra-thin homogeneous metal layer, which in particular is able to form as a basic metallization Contact points or contact pads or wiring on one integrated electronic component such as microchips or Serve microarrays, wherein at least on a substrate (10) a first metal layer (20) is deposited in regions and then a second one at least in some areas Metal layer (30) is produced, the component (s) of the second metal layer (30) has a more positive redox potential than the component (s) of the first metal layer (20) (t / en) and the ultra-thin homogeneous deposition of the second Metal layer (30) by means of wet chemical, electroless, electrochemical redox processes, if necessary under simultaneous activation of the surface of the first Metal layer (20), by element exchange of one or several metal salts as an oxidizing agent with at least the uppermost metal atom layer of the first metal layer (20) as Reducing agent takes place.
  • Base metallization (seed layer) on the corresponding Substrate are applied.
  • the specific resistance and the The morphology of the base metallization determines the properties which then for the formation of appropriate contact points or contact pads or rewiring electrochemically deposited copper layer.
  • a barrier layer between the Base metallization and the insulator for example Lower silica or dielectrics Dielectric constant
  • Barrier layer and base metallization are usually in two independent steps using physical Vapor deposition or chemical deposition ("Chemical Vapor Deposition ", CVD).
  • CVD chemical Vapor Deposition
  • a method to solve the problems described above is the introduction of another Process step in which a non-homogeneous Base metallization is optimized ("seed repair"). Such a additional process step is always costly.
  • a method for Formation of an ultra-thin homogeneous metal layer is particularly capable of forming as a basic metallization of contact points or contact pads or wiring an integrated electronic component, such as one Microchip to serve provided, wherein on a substrate (10) at least in some areas a first metal layer (20) is deposited and then at least subsequently a second metal layer (30) is produced in regions, wherein the component (s) of the second metal layer (30) more positive redox potential than the component (s) of the first Metal layer (20) exhibit (t / en) and the ultra-thin homogeneous Deposition of the second metal layer (30) by means of wet chemical, electroless, electrochemical redox processes, if necessary with simultaneous activation of the surface the first metal layer (20), by exchanging elements from one or more metal salts as an oxidizing agent with at least the uppermost metal atom layer of the first metal layer (20) as Reducing agent takes place.
  • the method according to the invention is generally the generation of ultra-thin homogene
  • the first metal layer is used in the method according to the invention even as a reducing agent.
  • This first layer of metal is made by a corresponding precursor compound (s), i.e. (A) Oxidizing agent (s) such as metal salt (s), the second metal layer to be deposited at least in the top metal atom layer oxidized, the corresponding from ions formed in the first metal layer go into solution and simultaneously depositing the second metal layer the corresponding precursor compound (s) by reduction he follows.
  • Redox process can usually take place on the surface activated the first metal layer at the same time. This can for example when removing a passivating oxide layer done on the first metal layer.
  • Such activation can, for example, in the process according to the invention
  • Treatment with hydrofluoric acid (HF) can be achieved, which in corresponding concentration in addition to the above-mentioned Precursor compound (s) of the second metal layer in the solution for the wet chemical, currentless, electrochemical Redox processes according to the method of the present invention is available.
  • HF hydrofluoric acid
  • Wet chemical deposition of the second metal layer requires a chemical potential gradient between one Metal salt of the metal forming the second metal layer and the metal of the previously applied first metal layer, the serves as a barrier layer.
  • the interaction of kinetics and Thermodynamics is an essential factor, which is this Influenced by the redox reaction, the base metal of the Barrier layer oxidized, while the metal cations from the Metal salt of the metal forming the second metal layer be reduced and thus by exchanging at least the topmost metal atom layer of the first metal layer thereon form an ultra-thin metal layer (second metal layer).
  • the first Metal layer preferably made of at least one component, selected from tantalum, titanium or aluminum or their Alloys with e.g. Magnesium, built up, their production by means of physical vapor deposition or chemical Deposition (CVD) can take place.
  • CVD chemical Deposition
  • Elements or alloys can be used, provided that they are Fulfill the barrier function and a correspondingly more negative one Redox potential than that forming the second metal layer Have metal.
  • the method according to the invention is based on the generation of a ultra-thin metal layer or base metallization Element exchange using a wet chemical, electroless, electrochemical redox process.
  • the second metal layer is by exchanging the top metal atom layers of the as Barrier layer serving first metal layer with metal atoms of the metal forming the second metal layer. Consequently becomes the separate separation conventionally provided of two metal layers (diffusion barrier and Base metallization) by only one deposition of the Barrier layer and a subsequent wet chemical Exchange reaction to form the ultra-thin, homogeneous second metal layer as the actual base metallization replaced.
  • the method according to the invention requires in advantageously no additional "seed repair" process step.
  • conventional deposition of a base metallization replaced an inexpensive wet chemical process.
  • the first metal layer which acts as a barrier layer, can for example in a thickness of 5 nm to 100 nm, preferred from 10 to 50 nm and more preferably from 10 to 20 nm, be applied.
  • the second metal layer which is used as the basic metallization for the subsequent electrochemical metal deposition for filling the trenches and holes to form contact points or Contact pads on, for example, a microchip is used preferably copper, silver, gold, platinum or nickel or corresponding alloys thereof.
  • the second metal layer can are contiguous or island-like.
  • wet chemical Deposition of this second metal layer can be done within the inventive method for the aforementioned metals conventionally used metal salts or Electrolyte compositions are used.
  • the second Metal layer can be deposited in such a way that it is only one or more layers of metal atoms. she can thus for example in a thickness of 0.5 nm to 10 nm, in particular 1 nm to 10 nm.
  • the substrate materials are not specifically limited.
  • the dielectrics such as SiO 2
  • the substrates can be unstructured. Usually, however, they are structured with the trenches or holes customary in the context of microchip production, for example by means of appropriate lift-off techniques or lithography techniques.
  • a first layer of metal made of tantalum, which serves as a barrier layer, and then one second metal layer made of copper, which in particular as Base metallization can serve.
  • the Base metallization by exchanging the top Ta atoms Atomic layers by copper atoms, which together form one for the subsequent electrochemical deposition of corresponding Suitable contact points or pads or wiring Form basic metallization.
  • first 20% hydrofluoric acid (HF) with 20 g / l CuSO 4 .5H 2 O can be prepared at room temperature, with which a substrate with a barrier layer already deposited thereupon takes a few seconds until a layer appears Darkening (copper deposition) is treated.
  • HF hydrofluoric acid
  • the wet chemical process can be divided into the following reaction steps within the scope of the process according to the invention: First the native, passivating tantalum oxide layer is removed with hydrofluoric acid according to the following reaction equations: Ta 2 O 5 + 10HF + 2F - ⁇ 5H 2 O + 2TaF 6 - Ta 2 O 5 + 10HF + 4F - ⁇ 5H 2 O + 2TaF 7 2- (both reactions are in balance)
  • copper is generated according to the invention: 2Ta + 5Cu 2+ ⁇ 2Ta 5+ + 5Cu (Redox potentials: Ta ⁇ Ta 2 O 5 : -0.75 V and Cu ⁇ Cu 2+ : +0.34 V)
  • the advantages of the method according to the invention are in the Saving costs through expensive process steps and Saving additional process steps to a faulty one Optimize base metallization.
  • Advantageously can in particular very much by the inventive method thin base metallizations for those to be applied subsequently Metallization systems are generated.
  • the thickness of the barrier or the barrier-to-base metallization ratio is over the concentration of the corresponding solutions in wet chemical Process and the parameters of the chemical reaction such as time and temperature adjustable.
  • a liability between the first Metal layer and the second metal layer favors what conducive to the reliability of Metallization systems and thus on the lifespan of corresponding, from the inventive method resulting products such as microchips or microarrays effect.
  • Figure 1a shows schematically one in the context of the invention Process used substrate with trench structure.
  • Figure 1b shows schematically the substrate of Figure 1a, on the the first metal layer has been applied.
  • Figure 1c shows schematically the substrate of Figure 1b, with on the first metal layer a homogeneous ultra-thin second Metal layer has been created.
  • FIG. 2 shows light micrographs in the upper row of a substrate (SiO 2 ) provided with a tantalum barrier layer before and after production of a thin copper layer, and enlarged scanning electron microscope photos of the corresponding tantalum and copper surfaces in the lower row.
  • FIG. 1a schematically shows a substrate (10) with a trench or contact hole structure. That in the method according to the invention
  • the substrate (10) used can be an insulator, for example (e.g. silicon dioxide or dielectrics with lower Dielectric constant) as part of an integrated electronic Component like a microchip or microarray.
  • Figure 1b shows schematically the substrate (10) with the on it deposited first metal layer (20), which as Serves as a barrier layer.
  • This first metal layer (20) is According to the invention from at least one metal, such as Tantalum, titanium or aluminum, preferably built up tantalum, their generation by physical vapor deposition or chemical deposition (CVD).
  • Figure 1c shows schematically the substrate (10) with the deposited first Metal layer (20) and the wet chemical applied thereon second metal layer (30).
  • the second metal layer (30) can for example made of copper, silver, gold, platinum or nickel, preferably copper, be built up and coherent or island-like.
  • Figure 2 shows light microscope images of the invention a tantalum barrier layer (40) coated substrates and a copper layer partially deposited on it like an island (50).
  • FIG. 2 shows Scanning electron microscope images of the tantalum layer (40a) and the copper layer (50a) is shown.
  • the different components the first metal layer (20) and the second metal layer (30) are different due to their Different surface morphologies.
  • the inventive method enables the otherwise usual, complex process steps of a separate Base metallization on, for example, integrated electronic components can be avoided.
  • the inventive method is not only for applications in Framework of the metallization of structured substrates limited, but is for all applications where thin Metal layers for further processes - but above all electrochemical deposition of various metals - are needed, usable and expandable.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Chemical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
EP04011671A 2003-05-26 2004-05-17 Procédé pour la fabrication de couches en métal ultra-minces et homogènes Withdrawn EP1482073A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10323905A DE10323905A1 (de) 2003-05-26 2003-05-26 Verfahren zur Erzeugung von ultradünnen homogenen Metallschichten
DE10323905 2003-05-26

Publications (1)

Publication Number Publication Date
EP1482073A2 true EP1482073A2 (fr) 2004-12-01

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EP04011671A Withdrawn EP1482073A2 (fr) 2003-05-26 2004-05-17 Procédé pour la fabrication de couches en métal ultra-minces et homogènes

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US (1) US6946386B2 (fr)
EP (1) EP1482073A2 (fr)
DE (1) DE10323905A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6696746B1 (en) * 1998-04-29 2004-02-24 Micron Technology, Inc. Buried conductors
KR100574560B1 (ko) * 2004-12-31 2006-04-27 동부일렉트로닉스 주식회사 반도체 소자의 금속배선 형성 방법
EP1909320A1 (fr) * 2006-10-05 2008-04-09 ST Microelectronics Crolles 2 SAS Barrière de diffusion du cuivre
US7759241B2 (en) * 2006-09-15 2010-07-20 Intel Corporation Group II element alloys for protecting metal interconnects
KR101516215B1 (ko) 2013-11-15 2015-05-04 한국지질자원연구원 장력계를 포함하는 시추시스템 및 이를 이용한 정확한 시추의 판단방법

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824599A (en) * 1996-01-16 1998-10-20 Cornell Research Foundation, Inc. Protected encapsulation of catalytic layer for electroless copper interconnect
US6268289B1 (en) * 1998-05-18 2001-07-31 Motorola Inc. Method for protecting the edge exclusion of a semiconductor wafer from copper plating through use of an edge exclusion masking layer
US6479902B1 (en) * 2000-06-29 2002-11-12 Advanced Micro Devices, Inc. Semiconductor catalytic layer and atomic layer deposition thereof
JP2002053971A (ja) * 2000-08-03 2002-02-19 Sony Corp めっき方法及びめっき構造、並びに半導体装置の製造方法及び半導体装置
US6511912B1 (en) * 2000-08-22 2003-01-28 Micron Technology, Inc. Method of forming a non-conformal layer over and exposing a trench
US20020064592A1 (en) * 2000-11-29 2002-05-30 Madhav Datta Electroless method of seed layer depostion, repair, and fabrication of Cu interconnects
ATE466975T1 (de) * 2000-12-13 2010-05-15 Imec Verfahren zur herstellung eines elektroplattierungsbad und zugehöriges kupfer- plattierungsverfahren
US6977224B2 (en) * 2000-12-28 2005-12-20 Intel Corporation Method of electroless introduction of interconnect structures

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DE10323905A1 (de) 2005-01-05
US6946386B2 (en) 2005-09-20

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