CN104878420A - Methods For Electrochemical Deposition Of Multi-component Solder Using Cation Permeable Barrier - Google Patents

Methods For Electrochemical Deposition Of Multi-component Solder Using Cation Permeable Barrier Download PDF

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Publication number
CN104878420A
CN104878420A CN201510089333.0A CN201510089333A CN104878420A CN 104878420 A CN104878420 A CN 104878420A CN 201510089333 A CN201510089333 A CN 201510089333A CN 104878420 A CN104878420 A CN 104878420A
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China
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ion
process fluid
technique
catholyte
cation
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马文·L·伯恩特
罗斯·古莎
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Applied Materials Inc
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Applied Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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

Abstract

Processes and systems for electrochemical deposition of a multi-component solder by processing a microfeature workpiece with a first processing fluid and an anode are described. Microfeature workpieces are electrolytically processed using a first processing fluid, an anode, a second processing fluid, and a cation permeable barrier layer. The cation permeable barrier layer separates the first processing fluid from the second processing fluid while allowing certain cationic species to transfer between the two fluids.

Description

Cation permeable blocking layer is used to carry out the method for the electrochemical deposition of multicomponent solder
Technical field
Embodiments of the invention relate to the electrolysis treatment of microfeature workpieces and utilize the electrolysis treatment technique on cation permeable blocking layer.
Background technology
Such as semiconductor device, imager, indicating meter, membrane head, micromechanics, MEMS (micro electro mechanical system) (microelectromechanical systems; MEMS) and micro-characterizing arrangement of the large through hole (largethrough-wafers via) through wafer and so on typically use from several machines of workpiece deposition and/or etching material on microfeature workpieces and/or middle manufacture.Many micro-characterizing arrangement at present need interconnection structure and other very little submicron-scale features (such as 45 nanometer to 250 nanometers), and described interconnection structure and other very little submicron-scale features are by being formed deposition of material in minor groove or hole.For being electrolysis treatment by deposition of material to the useful especially technique of in minor groove and/or through hole, such as, electroplate.Typical case's electrolysis treatment technology comprises electroplating technology and etch process, and by copper, nickel, lead, gold and silver, tin, platinum and other deposition of materials on microfeature workpieces, described etch process removes metal from microfeature workpiece surface to described electroplating technology.
In some plating or etch process, sequestrant or complexing agent deposit in order to affect metal ion or remove residing electromotive force from microfeature workpiece surface on microfeature workpiece surface.Other compositions that can be present in process fluid (processing fluid) comprise the catalyzer of the result that can affect plating or electroetch process, inhibitor and leveler (leveler).Although the material energy favourable influence plating of these types or electroetch process, the use of these materials is not immaculate.Such as, these compositions are likely owing to react with electrode used in electrolysis process or other interact and have detrimentally affect to electrolysis process.
Another difficulty be deposited into by metal in narrow deep trench or through hole is difficult to fill little feature completely and in metal refining, do not produce space or other heterogeneities.Such as, when in groove metal being deposited into the characteristic dimension with 45 nanometer to 250 nanometers, ultra-thin kind of crystal layer can be used, but carefully must guarantee in groove, there be the body metal of sufficient clearance spaces for depositing subsequently.In addition, because the quality of the kind crystal layer of deposition may be uneven, therefore ultra-thin kind of crystal layer may have problems.Such as, ultra-thin kind of crystal layer may have space or other uneven physical propertys, and described space or physical property can cause being deposited on the ununiformity in the material on kind of crystal layer.These difficulties are by overcoming with under type: strengthening (enhance) is planted crystal layer or directly formed kind of crystal layer over the barrier layer to provide the suitable kind of crystal layer being well suited for depositing metal in the little groove of characteristic dimension or hole.A kind of technology for strengthening kind of crystal layer or directly forming kind of crystal layer over the barrier layer uses the treatment soln plated material with low conductivity.This kind of low conductivity process fluid has relatively low hydrogen ion (H +) concentration, namely relatively high pH value.For using low conductivity process fluid to form the electrochemical process be applicable to of suitably kind crystal layer in United States Patent (USP) case the 6th, open in 197, No. 181, by reference described United States Patent (USP) case is incorporated herein at this.
The process fluid of low conductivity/high ph-values is used to electroplate on kind of crystal layer or there is other difficulty by material Direct Electroplating to blocking layer.Such as, when using high ph-values process fluid, generally inert anode is needed, because high ph-values trends towards passivation sacrificial anode.This kind of passivation can produce metal hydroxide particles and/or fragment, and described particle and/or fragment can produce defect in micro-feature.Not immaculate to the use of inert anode.Present inventor notices, and when using inert anode, the resistivity of deposition material is significantly improving after relative minority object plate cycle.A kind of mode that this resistivity of opposing deposition material increases changes process fluid continually; But this solution increases the running cost of technique.
Therefore, the existing electrolysis process needed for the treatment of microfeature workpieces, described technique reduces the detrimentally affect produced by the existence of complexing agent and/or other additives, and also the deposition characteristics of such as resistivity and so on is maintained required scope Inner.
At wafer level packaging (wafer level packaging; WLP) electrochemical deposition (electrochemicaldeposition; ECD), in, the Xi-Yin (Sn-Ag) close to congruent melting is the selected alloy covering (capping) at present for lead free solder bumps and copper post.In current zinc-plated silver process, liquid tin ion doping enriched material is added into catholyte, to replenish the tin ion consumed in depositing operation.But tin ion enriched material trends towards more than solid tin costly, and due to the additive in enriched material, cause reducing the control of stability, and catholyte shortening in work-ing life.
Therefore, there are the needs to a kind of electrochemical deposition method, described method is used for plating more than a kind of metal such as multicomponent solder on microfeature workpieces, and described method uses the main ion source being easier to control than the liquid state doping enriched material being added into catholyte.The embodiment of disclosure case is for addressing this need and other needs.
Summary of the invention
Embodiment described herein relate to for electrolysis treatment microfeature workpieces with by deposition of material in microfeature workpiece surface or the technique from microfeature workpiece surface removing materials.Technique described herein can produce the settling showing characteristic (such as resistivity value) within the required range after the plate cycle through more number of times.Embodiment described herein also relates to the dysgenic technique reducing and produced by the complexing agent in order to exist in the process fluid of electrolysis treatment microfeature workpieces and/or other additives.In certain embodiments, described technique uses low conductivity/high ph-values process fluid, and can not cause forming defect in the deposited material because of there is metal hydroxide particles or fragment in the process fluid contacted with microfeature workpieces.Microfeature workpieces processor will find, some technique described herein caters to the need because described technique produce productive rate higher can receive sediments product, and change process fluid without the need to cost intensive ground is frequent.It is desirable for reducing that the disadvantageous effect that produces also can be regarded as by the user of electrolysis treatment described herein by the existence of process fluid complexing agent and/or other additives.
In one embodiment, microfeature workpiece surface contact first process fluid, described first process fluid comprises the first process fluidic species, such as positively charged ion, negatively charged ion and complexing agent.Comparative electrode contact second process fluid, and electrochemical reaction occurs in comparative electrode place.Described technique stops non-cationic species (such as anionic species) to process the movement between fluid at the first process fluid and second effectively.In certain embodiments, the first process fluid can be low pH value treatment fluid, and the second process fluid can be high ph-values process fluid, and positively charged ion can for will be deposited on the metal ion on microfeature workpiece surface, and comparative electrode energy can noble electrode.
In another embodiment, microfeature workpiece surface contact first process fluid, described first process fluid comprises and will be deposited on the metal ion on microfeature workpiece surface.In addition, the first process fluid comprises complexing agent and the negatively charged ion relative with metal ion.Inert anode contact second process fluid, and produce oxygenant at inert anode place.Described technique processes between fluid at the first process fluid and second and uses cation permeable blocking layer.Described cation permeable blocking layer allows positively charged ion (such as hydrogen ion) to arrive the second process fluid by the first process fluid.In this embodiment, the metal ion deposition in the first process fluid at microelectronic workpiece on the surface.In certain embodiments, the first process fluid and the second process fluid can be high ph-values process fluid.
In another embodiment, microfeature workpiece surface contact first process fluid, described first process fluid comprises the metal ion that will be deposited on microelectronic workpiece surface.In this embodiment, inert anode contact second process fluid, the second described process fluid comprises buffer reagent and pH value adjusting agent, and cation permeable blocking layer processes between fluid at the first process fluid and second.
Can perform in the system for electrolysis treatment microfeature workpieces in the technique of above-outlined.Described system comprises chamber, and described chamber has the processing unit for receiving the first process fluid and the comparative electrode unit for receiving the second process fluid.Comparative electrode is arranged in comparative electrode unit, and cation permeable blocking layer is between processing unit and comparative electrode unit.Described system also comprises complexing agent source.Described chamber comprises the metal ion source be communicated with processing unit or comparative electrode unit fluid further, and the pH value adjusting agent source be communicated with processing unit fluid.
By using technique described above and system described above, the metal of such as copper, nickel, lead, gold and silver, tin, platinum, ruthenium, rhodium, iridium, osmium, rhenium and palladium and so on can be deposited on microfeature workpiece surface.These surface energy take the form on kind of crystal layer or blocking layer.
Process example described above and system can for by electroplating material to microfeature workpiece surface, or for from microfeature workpiece surface electrograving or except plating material.When described technique is used for plated material, microfeature workpieces will serve as negative electrode, and comparative electrode will serve as anode.On the contrary, when performing except plating, microfeature workpieces will serve as anode, and comparative electrode will serve as negative electrode.
Thus, in another embodiment, microfeature workpiece surface contact first process fluid, described first process fluid comprises the relative ion of the metal on hydrogen ion and surface.Cathode contacts second processes fluid, and described second process fluid also comprises hydrogen ion, and cation permeable blocking layer processes between fluid at the first process fluid and second.Chemical species in second process fluid reduce, and acid are introduced the first process fluid to provide hydrogen ion.Hydrogen ion from the first process fluid arrives the second process fluid by cation permeable blocking layer.According to this embodiment, the metal of electrolytic decomposition (be namely oxidized and remove plating) microfeature workpiece surface.
The technique summarized in last paragraph can perform in the system for electrolysis treatment microfeature workpieces, and described system comprises chamber, and described chamber has the processing unit for receiving the first process fluid and the comparative electrode unit for receiving the second process fluid.Cation permeable blocking layer is positioned between processing unit and comparative electrode unit.The pH value adjusting agent source that described system is included in the negative electrode in comparative electrode unit, the hydrogen ion source be communicated with processing unit fluid further and is communicated with comparative electrode unit fluid.
Described above for from the technique of microfeature workpiece surface removing materials and system by using, can by the metal of such as copper, nickel, lead, gold and silver, tin and platinum and so on from microfeature workpiece surface except plating.
According to another embodiment of the present invention, provide a kind of technique, described technique is used for processing fluid and the comparative electrode electrolysis treatment microfeature workpieces as working electrode with first.Described technique generally comprises and makes the first process fluid contact microfeature workpiece surface, and described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises at least one metallic cation, negatively charged ion and complexing agent.Described technique comprises further makes the second process fluid contact comparative electrode, thus produces electrochemical reaction at comparative electrode place, and by metallic cation electrolytic deposition on microfeature workpiece surface.Described technique comprises prevention negatively charged ion and complexing agent species substantially further and processes the movement between fluid at the first process fluid and second.
According to another embodiment of present disclosure, provide a kind of technique, described technique is used for processing fluid and the comparative electrode electrolysis treatment microfeature workpieces as working electrode with first.Described technique generally comprises and makes the first process fluid contact microfeature workpiece surface, described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises at least one metallic cation, negatively charged ion and is selected from least one organic composition of the group be made up of following material: catalyzer, inhibitor and leveler.Described technique comprises further makes the second process fluid contact comparative electrode, thus produces electrochemical reaction at comparative electrode place, and by metallic cation electrolytic deposition on microfeature workpiece surface.Described technique comprises further provides cation exchange membrane (membrane), processes the movement between fluid to stop anionic species and at least one organic composition substantially at the first process fluid and second.
According to another embodiment again of present disclosure, provide a kind of technique, described technique is used for processing fluid and the comparative electrode electrolysis treatment microfeature workpieces as working electrode with first.Described technique comprises makes the first process fluid contact microfeature workpiece surface, and described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises metallic cation, negatively charged ion and complexing agent.Described technique comprises further makes the second process fluid contact comparative electrode, thus produces electrochemical reaction at comparative electrode place, and by metallic cation electrolytic deposition on microfeature workpiece surface.Described technique is included in the first process fluid and second further and processes between fluid and provide cation permeable blocking layer, to stop negatively charged ion and complexing agent species to process the movement between fluid at the first process fluid and second substantially, wherein said cation permeable blocking layer is directed with the configuration of general horizontal.
According to another embodiment of present disclosure, provide a kind of technique, described technique is used for the microfeature workpieces of the comparative electrode electrolysis treatment in the second process fluid as the working electrode in the first process fluid.Described technique generally comprises: make the first process fluid contact microfeature workpiece surface, and described first process fluid comprises the first metallic cation; Make the second process fluid contact comparative electrode, described second process fluid comprises the second metallic cation and has the pH value in about 1 to about 3 scope; There is provided cation permeable blocking layer between fluid by processing at the first process fluid and second and allow the second metallic cation to process fluid from second to move to the first process fluid, but stop the first metallic cation to move to the second process fluid from the first process fluid substantially, wherein the second metallic cation is through cation permeable blocking layer from the second process fluid to the prevailing quality transmission of the first process fluid; And by the first metallic cation and the second metallic cation electrolytic deposition on microfeature workpiece surface.
According to another embodiment of present disclosure, provide a kind of technique, described technique is for using the first process fluid and comparative electrode electrolysis treatment as the microfeature workpieces of working electrode.Described technique comprises: the first process fluid is contacted with microfeature workpiece surface, and described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises the first metallic cation; Second process fluid is contacted with comparative electrode, and described second process fluid has the pH value in about 1 to about 3 scope; Electrochemical reaction is produced to produce the second metallic cation at comparative electrode place; There is provided cation exchange membrane to move to the first process fluid to allow the second metallic cation when electrolysis treatment microfeature workpieces from the second process fluid, but stop the first metallic cation to move to the second process fluid from the first process fluid substantially; And when not electrolysis treatment microfeature workpieces, make the second process fluid and membrane separation.
According to another embodiment of the present invention, provide a kind of technique, described technique is for using the first process fluid and anode electrolysis process as the microfeature workpieces of negative electrode.Described technique generally comprises: make the first process fluid contact microfeature workpiece surface, and described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises the first metallic cation; Make the second process fluid contact anode, described second process fluid has the pH value in about 1 to about 3 scope; Consumable anode is to produce the second metallic cation; Cation exchange membrane is provided to move to the first process fluid to allow the second metallic cation from the second process fluid, but stop the first metallic cation to move to the second process fluid from the first process fluid substantially, wherein said second process fluid is not mixed and is joined (dose) in the first process fluid; And by the first metallic cation and the second metallic cation electrolytic deposition on microfeature workpiece surface.
According to any technique described herein, cation permeable blocking layer can be cationic exchange membrane.
According to any technique described herein, described technique can be included in comparative electrode place further and produce electrochemical reaction to produce the second metallic cation.
According to any technique described herein, working electrode can be negative electrode, and comparative electrode can be anode.
According to any technique described herein, the first process fluid can be furnished with the first metallic cation.
According to any technique described herein, comparative electrode can be expendable electrode.
According to any technique described herein, one of in the first process fluid and the second process fluid or both can mix and be furnished with the second metallic cation.
According to any technique described herein, one of in the first process fluid and the second process fluid or mix in both and allocate the main source that the second metallic cation may not be the second metallic cation in the first process fluid into.
According to any technique described herein, the first metal cation concentration in the first process fluid can in the scope of about 0.1g/L to about 5.0g/L.
According to any technique described herein, the group of the following scope composition of the optional freedom of the second metal cation concentration in the first process fluid: about 40g/L is to about 80g/L, about 40g/L to about 120g/L and about 40g/L to about 150g/L.
According to any technique described herein, the pH value of the second process fluid can higher than the pH value of the first process fluid.
According to any technique described herein, the group of the optional freedom of the pH value following scope composition of the second process fluid: about 1.0 to about 2.0, about 1.2 to about 1.8, about 1.5 to about 2.2, be greater than about 2.0, about 1.0 to about 3.0 and about 2.0 to about 3.0.
According to any technique described herein, the group of the optional freedom of the pH value following scope composition of the first process fluid: be less than or equal to 1.0 and be less than or equal to 0.5 and in 0 to 1.0 scope.
According to any technique described herein, the group of the following ion composition of the optional freedom of the first metallic cation: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion.
According to any technique described herein, the group of the following ion composition of the optional freedom of the second metallic cation: cupric ion, lead ion, tin ion, bismuth ion, indium ion, silver ions, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion.
According to any technique described herein, described technique can comprise deposition the 3rd metallic cation further, and described 3rd metallic cation is selected from the group be made up of following ion: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion, nickel ion.
According to any technique described herein, described technique can comprise the common deposition of deposition (co-deposited) metal further.
According to any technique described herein, the first process fluid can comprise antioxidant.
According to any technique described herein, the second process fluid can comprise antioxidant.
According to any technique described herein, wherein the second process fluid can not be mixed and allocate in the first process fluid.
Accompanying drawing explanation
When by reference to the accompanying drawings, will understand technique described herein better by reference to following detailed description, therefore the aforementioned aspects of technique described herein and many attendant advantages will be easier to understand, in the accompanying drawings:
Fig. 1 is the schematic diagram of the reactor for performing technique described herein;
Fig. 2 is the schematic diagram using inert anode described herein to carry out chemical action and the chemical reaction occurred in an embodiment of the technique of plated metal;
Fig. 3 is the schematic diagram using sacrificial anode described herein to carry out chemical action and the chemical reaction occurred in another embodiment of the technique of plated metal;
Fig. 4 A to Fig. 4 C is the schematic diagram for an embodiment of electrolysis treatment kind crystal layer in technique described herein;
Fig. 5 A and Fig. 5 B is the schematic diagram for electrolysis treatment blocking layer embodiment in technique described herein;
Fig. 6 is to electroplate the schematic diagram of chemical action and the chemical reaction occurred in an embodiment of the technique of two kinds of metals described herein at use inert anode;
Fig. 7 is to electroplate the schematic diagram of chemical action and the chemical reaction occurred in an embodiment of the technique of two kinds of metals described herein in use sacrificial anode;
Fig. 8 is the schematic diagram of the reactor for performing technique described herein;
Fig. 9 is the schematic diagram of instrument, and described instrument comprises the chamber for performing technique described herein;
Figure 10 is the schematic diagram of chemical action and the chemical reaction occurred in an embodiment for the technique except metallizing described herein;
Figure 11 is the figure of the relation represented between the molconcentration (molar concentration) of tin ion in anolyte and anolyte pH value;
Figure 12 A and Figure 12 B is the figure of the relation represented in catholyte and anolyte between pH value and tin concentration; And
Figure 13 represents based on the figure of the relation of MSA concentration between pH value and specific conductivity in anolyte.
Embodiment
As used herein, term " microfeature workpieces " or " workpiece " refer to substrate, and microdevice on the substrate and/or middle formation.This kind of substrate comprises semiconductor substrate (such as silicon wafer and gallium arsenide wafer), non-conductive (nonconductive) substrate (such as pottery or glass substrate) and electrically-conductive backing plate (such as wafers doped).The example of microdevice comprises microelectronic circuit or parts, micro-mechanical device, microelectromechanicdevices devices, micro-optic device, thin film recording head, data storage elements, microfluidic device and other packaged units.
Hereinafter about by Metal plating description on microfeature workpieces, concrete with reference to copper as the example electroplating metal ion on microfeature workpieces.Be in order to exemplary object to the reference of cupric ion, it should be understood that following description is not limited to cupric ion.Gold ion, tin ion, silver ions, platinum ion, lead ion, cobalt ion, zine ion, nickel ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion and palladium ion are comprised to the example of useful other metal ions of technique described herein.
Hereinafter about by more than in a kind of Metal plating description on microfeature workpieces, concrete with reference to tin-silver solder system as electroplating on microfeature workpieces to form the example of the metal ion of composite deposition thing.Be in order to exemplary object to the reference of deposit tin-silver solder, it should be understood that description is not restricted to tin and silver ions.
For hereinafter about from microfeature workpieces except in the description of metallizing, concrete with reference to copper as can from the example of microfeature workpieces except the metal ion of plating.Be in order to exemplary object to the reference of copper, it should be understood that and be not restricted to removing of copper about the description except plating.The example of other metals that can remove from microfeature workpieces according to embodiment described herein comprises gold ion, tin ion, silver ions, platinum ion, lead ion, cobalt ion, zine ion, nickel ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion and palladium ion.
Technique described herein can perform in plating or except plating in reactor, and described reactor is such as hereinafter with reference to the reactor that figure 1 describes.Referring to Fig. 1, electrochemical deposition chamber 400 comprises processing unit 404 and the comparative electrode unit 410 below processing unit 404, upper processing unit 404 comprises the first process fluid 406 (catholyte in such as electroplating technology and the anolyte removed in depositing process), comparative electrode unit 410 comprises the second process fluid 412 (anolyte in such as electroplating technology or the catholyte removed in depositing process), and the second process fluid 412 can be different from the first process fluid 406 in composition and/or characteristic.Processing unit 404 receives working electrode 408 (such as microfeature workpieces) and the first process fluid 406 is delivered to working electrode 408.Comparative electrode unit 410 comprises comparative electrode 414, and comparative electrode 414 and second processes fluid 412 and contacts.When copper will be deposited on working electrode 408, working electrode 408 is negative electrode comparative electrode 414 will be anode.Thus, in plating application, the first process fluid 406 is catholytes, and the second process fluid 412 is anolytes.Catholyte 406 comprises the composition of ionic species form usually, such as acid ion and metal ion, as hereinafter described in more detail.
Generally speaking, catholyte comprises the composition of ionic species form, such as acid ion (such as H +), hydroxyl ion and metal ion, and the complexing agent of complex compound can be formed with metal ion.Catholyte also can comprise organic composition, such as improves the catalyzer of electroplating technology result, inhibitor and leveler.In addition, catholyte can comprise pH value adjusting agent to affect the pH value of catholyte.Anolyte generally also comprises ionic species, such as acid ion (such as H +), hydroxyl ion and metal ion.Catholyte also can comprise pH value adjusting agent.Additional detail about the various compositions in catholyte and anolyte is hereinafter provided.
When removing copper facing from working electrode 408, working electrode 408 will be anode, and comparative electrode 414 is negative electrode.Thus, in applying except plating, the first process fluid 406 is anolytes, and the second process fluid 412 is catholytes.
Reactor 400 processes between fluid 412 at the first process fluid 406 and second and also comprises atresia cation permeable blocking layer 402.Atresia cation permeable blocking layer 402 allows positively charged ion (such as H +with Cu 2+) through blocking layer, suppress simultaneously or stop non-cationic composition (such as organic composition (such as catalyzer, inhibitor and leveler) and anionic component) to process between fluid at the first process fluid and second substantially to pass.Pass by suppressing or stoping non-cationic composition to process between fluid 412 at the first process fluid 406 and second substantially, the detrimental action to deposition material, the negatively charged ion that described harmful non-cationic composition is such as harmful to or the organic bath composition caused by the existence of (unwanted) non-cationic composition harmful in the first process fluid 406 can be avoided.Therefore, the first process fluid 406 and second is processed fluid 412 and separates by atresia cation permeable blocking layer 402, so that first processes fluid 406 and can have and process the different chemical feature of fluid 412 and characteristic from second.Such as, first process fluid 406 and second process the chemical composition of fluid 412 can be different, first process fluid 406 and second process fluid 412 pH value can different and first process fluid 406 and second process the concentration having composition in fluid 412 can be different.
During copper electroplating technology hereinafter describes, for the purpose of consistence, working electrode 408 will be referred to as negative electrode, and comparative electrode 414 will be referred to as anode.Equally, the first process fluid 406 will be referred to as catholyte, and the second process fluid 412 will be referred to as anolyte.When reactor 400 for electrolysis treatment microfeature workpieces with metal ions on microfeature workpieces time, between anode 414 and negative electrode 408, apply electromotive force.Cupric ion in catholyte is consumed by the deposition of cupric ion on negative electrode.Meanwhile, anode becomes and carries positive charge, and negatively charged ions is attracted to anode surface.Such as, the hydroxyl ion in anolyte attracted to anode, reacts to discharge oxygen, and produce water at described anode place.Previous reaction produces the charge gradient in anolyte, has unbalanced positive charge species, and have negative charge species in catholyte solution in anolyte solution.This charge unbalance impels positive charge positively charged ion to be sent to catholyte 406 through cation permeable blocking layer 402 from anolyte 412.There is electrochemical reaction (such as loss or obtain electronics) at negative electrode 408 place, cause metal ion reduce on the surface of negative electrode 408 (namely obtaining electronics) be metal.
During electroplating technology, reactor 400 maintains the concentration of metal ion in catholyte 406 in the following ways effectively.When metal ion deposition is on the surface of negative electrode 408, except arrive the metal ion of catholyte 406 through anolyte 412 except, from metal ion source 130, extra metal ion can also be introduced catholyte 406, metal ion source 130 is communicated with processing unit 404 fluid.As hereinafter explained in more detail, by metal salt solution being delivered to processing unit 404 to provide these metal ions.Processing unit 404 also can with the fluid communication needing other compositions supplemented.In a similar manner, comparative electrode unit 410 can with the fluid communication needing the composition supplemented.Such as, comparative electrode unit 410 can be communicated with pH value adjusting agent source 132 fluid.Equally, processing unit 404 and electrode unit 410 all can comprise pipeline or other structures remove part catholyte 406 for from processing unit 404, or removes segment anode electrolytic solution 412 from comparative electrode unit 410.
Anode 414 can be sacrificial anode or inert anode.Exemplary sacrificial anode and inert anode are described in more detail hereinafter.
Cation permeable blocking layer 402 moves to provide multiple advantage by stoping some anionic species and organic composition substantially between catholyte and anolyte.Such as, the organic composition from catholyte can not flow through anode and resolve into the product that can hinder electroplating technology.The second, because organic composition does not arrive anolyte from catholyte, therefore consume organic composition, so that cost is lower and be easier to the concentration controlling organic composition in catholyte with comparatively slow rate.3rd, reduce or eliminate because anode and organic composition react and produce the risk of passivation.In addition, the existence on cation permeable blocking layer reduces the chance of metal fragment or small-particle arrival workpiece, described metal fragment or small-particle are produced by anode passivation (when sacrificial anode is combined with the anolyte of high ph-values, low conductivity, low acidity), at described workpiece place, described fragment or particle may have disadvantageous effect to metal refining.Use another advantage of cation membrane to be stop the gas produced at anode to enter catholyte, described gas may contact with workpiece surface in catholyte.
Hereinafter with reference Fig. 2 be described in the processing unit 404 of Fig. 1 with the Exemplary chemical effect that exists in the comparative electrode unit 410 of Fig. 1.It should be understood that, by describing the chemical reaction believed and occur in reactor 400, technique described herein is not restricted to the technique that these reactions occur.
Fig. 2 schematically illustrates the operational instances of reactor 400, and cation permeable blocking layer 422 and inert anode 424 are combined with the catholyte 426 of low conductivity/high ph-values and the anolyte 428 of low conductivity/high ph-values by described operation.In the following description, the catholyte 426 in processing unit 430 comprises metal ion (M +) (such as cupric ion (Cu 2+)), the relative ion (X of metal ion -) (such as vitriol radical ion (SO 4 2-)), (such as resolve into hydrogen ion (H with the complexing agent (CA) of metal ion-chelant, pH value buffer reagent +) and H 2bO 3 -boric acid (H 3bO 3)) and pH value adjusting agent (such as resolve into hydroxyl ion (OH -) and TMA +tetramethylammonium hydroxide (tetramethylammonium hydroxide; TMAH)).Can select specific hydrogen ion concentration and the pH value of catholyte 426 when taking into account Traditional Factors, the concentration of the complex ability of described factor such as complexing agent, the surge capability of buffer reagent, concentration of metal ions, volatile organic matter, mixture are at sedimentation potential, the solubleness of catholyte component, the stability of catholyte, the spread coefficient of sedimental required characteristic sum metal ion of certain ph.The anolyte 428 of the low conductivity in electrode unit 432, low acidity comprises aqueous acid, such as, resolve into hydrogen ion (H +) and vitriol radical ion (SO 4 2-) sulfuric acid.Anolyte 428 also can comprise buffer reagent.The better hydrogen ion concentration being greater than catholyte 426 of the hydrogen ion concentration of anolyte 428, although this and nonessential, as hereafter explained in more detail.This species diversity impels hydrogen ion from anolyte 428 to the movement of catholyte 426.In order to cause this raising of hydrogen ion concentration in catholyte 426, pH value adjusting agent can be added into catholyte 426.Hydrogen ions from anolyte 428 arrives catholyte 426 through cation permeable blocking layer 422, and described hydrogen ion is supplemented in the oxidation at anode 424 place by water in anolyte 428, and described oxidation produces hydrogen ion.
During plate cycle, between negative electrode 434 and inert anode 424, apply electromotive force.Be electroplated on negative electrode 434 along with reducing metal ions, hydrogen ion (H +) in anolyte 428, be gathered in cation permeable blocking layer 422 first surface 436 near.The charge gradient caused and concentration gradient make positive charge hydrogen ion move to the second surface 438 on cation permeable blocking layer 422 from the first surface 436 on cation permeable blocking layer 422, described second surface 438 Contact cathod electrolytic solution 426.During plate cycle, positive charge hydrogen ion maintains the charge balance of reactor 400 to the transmission of catholyte 426 from anolyte 428.The charge gradient produced owing to applying electromotive force between negative electrode 434 and anode 424 also hinders positively charged ion to be sent to the migration of anolyte 428 through cation permeable blocking layer 422 from catholyte 426, and described cat ions is as metal ions M +with the positively charged ion of pH value adjusting agent.For avoiding the relative ion (X of metal ion -) and the positively charged ion of pH value adjusting agent gather in catholyte, these ionic specieses and cationic species can be removed from catholyte 426.
Continue referring to Fig. 2, during plate cycle, as explained above, the metal ion in catholyte 426 in the reduction of negative electrode 434 place, and is deposited as metal.The metal ion consumed due to plating is by adding metal-salt (MX) solution to catholyte 426 and being supplemented.
Although in order to promote that hydrogen ion transmits to catholyte 426 from anolyte 428 through cation permeable barrier film 422, preferably operate reactor 400 when the hydrogen ion concentration of anolyte 428 is greater than the hydrogen ion concentration of catholyte 426, but also the hydrogen ion concentration in anolyte 428 may operate reactor 400 when being less than in catholyte 426 hydrogen ion concentration.Hydrogen ion is from anolyte 428 to the motivating force of the transmission of catholyte 426 to provide this kind of hydrogen ion concentration gradient reduction to be promoted, so that transmit other cationic species that may exist in catholyte 426, to provide necessary charge balance.This metallic cation promotes by the charge gradient between anode 424 and negative electrode 434 from the transmission of catholyte 426 anode electrolytic solution 428.In this case, in order to maintain the hydrogen ion concentration of the hydrogen ion concentration in anolyte 428 lower than catholyte 426, pH value adjusting agent may be needed to be added into anolyte 428.
Also cation permeable blocking layer and sacrificial anode metal refining can be used.Referring to Fig. 3, this figure illustrates reactor 450, and reactor 450 comprises cation permeable blocking layer 452, sacrificial anode 454, low conductivity/high ph-values catholyte 456 and low conductivity/high ph-values anolyte 458.For the embodiment of Fig. 3, the composition of catholyte 456 can have the composition being similar to the catholyte 426 described with reference to figure 2.Anolyte 458 comprises the metal ion (M decomposed by sacrificial anode 454 +) and hydrogen ion (H +).Anolyte 458 also can comprise the degradation production of buffer reagent and pH value adjusting agent.Goodly make positive metal atoms ion (M +) and positive charge hydrogen ion (H +) be conveyed through cation permeable blocking layer 452 on the contrary.Thus, anolyte 458 is preferably the anolyte of low acidity/high ph-values, there is not the hydrogen ion concentration gradient that can promote that hydrogen ion moves from anolyte 458 to catholyte 456 between catholyte 456 and anolyte 458.In addition, by suppressing positive charge hydrogen ion from anolyte 458 to the transmission of catholyte 456, more constant catholyte pH value can be maintained, and the demand of adding pH value regulator in subtend catholyte can be reduced.As mentioned above, this measure simplifies the maintenance of catholyte, and contributes to maintaining the relatively stable of catholyte specific conductivity during the plate cycle repeated.
Continue referring to Fig. 3, during plate cycle, between negative electrode 460 and anode 454, apply electromotive force.Metal is in the oxidation of anode 454 place, and metal ion (M +) in anolyte, be gathered in cation permeable blocking layer 452 first surface 462 near.The charge gradient caused makes positive metal atoms positively charged ion (M +) second surface 464 on cation permeable blocking layer 452 is shifted to from the first surface 462 on cation permeable blocking layer 452.During plate cycle, positive metal atoms ion maintains the charge balance of reactor 450 to the transmission of catholyte 456 from anolyte 458.Be understood that, hydrogen ion also will be transferred to catholyte 456 from anolyte 458 through cation exchange membrane 452, and the amount that this kind transmits is determined by the hydrogen ion concentration gradient part between anolyte 458 as above and catholyte 456.During plate cycle, the metal ion (M in catholyte 456 +) reduce at negative electrode 460 place and be deposited as metal.
The technique described herein microfeature workpieces that carries out processing can be used can to comprise different structures in its surface, and described structure can through electrolysis treatment with deposition material over the structure.Such as, semiconductor microactuator microfeature workpiece can comprise kind of crystal layer or blocking layer.Referring to Fig. 4 A to Fig. 4 C, provide a sequence of steps, described sequence of steps is for using process electrolyte process kind crystal layer described herein.
Referring to Fig. 4 A, this figure illustrates the viewgraph of cross-section as the microstructure of groove 105, to be metallized with block (bulk metallization) filling groove 105, and the viewgraph of cross-section of described microstructure will be used for describing use technique described herein to strengthen kind of a crystal layer.As shown in the figure, thin barrier layer 110 (such as titanium nitride or tantalum nitride) is deposited on semiconductor device surface, or as shown in Figure 4 A, thin barrier layer 110 is deposited on dielectric layer 108 (such as silicon-dioxide).Any known technology (such as chemical vapour deposition (chemicalvapor deposition; Or physical vapor deposition (physical vapor deposition CVD); PVD)) can be used for deposited barrier layer 110.
After the deposition on blocking layer 110, ultra-thin copper kind crystal layer 115 deposits on the barrier layer 110.Resulting structures is illustrated in Fig. 4 B.Also can use gas phase deposition technology, such as CVD or PVD, form kind of a crystal layer 115.Or, form kind of crystal layer 115 by Direct Electroplating on the barrier layer 110.Because groove 105 size is less, the technology therefore for the formation of ultra-thin kind of crystal layer 115 should be able to form kind of a crystal layer when not closing little geometrical shape groove.For avoiding closed little geometrical shape groove, planting crystal layer 115 should be thin as far as possible, still provides applicable substrate, to deposit block metal on the substrate simultaneously.
Ultra-thin kind of crystal layer 115 is used to introduce the multiple shortcomings of himself.Such as, ultra-thin kind of crystal layer may not coated blocking layer in an uniform way.Such as, on trenched side-wall, the space at such as 120 places or discontinuous kind of crystal layer region may be present in ultra-thin kind of crystal layer 115.Technique described herein can be used for strengthening kind of crystal layer 115 to fill the space or discontinuity zone 120 that find in ultra-thin kind of crystal layer 115.Referring to Fig. 4 C, in order to reach this strengthening, process microfeature workpieces like that as described herein, with the metal 118 being exposed to the deposited on portions more of space or discontinuous part 120 on the blocking layer 110 at ultra-thin kind of crystal layer 115 and/or lower floor.
This kind of crystal layer strengthening is better lasting until reach side-wall step covering, and namely the ratio of nominal (nominal) thickness of the kind crystal layer 115 at bottom kind crystal layer 115 thickness of sidewall areas and the side place arranged outside of workpiece reaches the value of at least 10%.Side-wall step covering is better is at least about 20%.Preferably, this side-wall step coverage values is present in in fact all groove structures of microfeature workpieces; But should admit, some groove structure may not reach this side-wall step value.
Microfeature workpiece surface can be blocking layer by the another type feature that technique described herein carries out electrolysis treatment.Because some metal trends towards diffusing to the electrology characteristic also changing the semiconductor device formed in a substrate in silicon knot, therefore use blocking layer.The blocking layer of being made up of the material of such as titanium, titanium nitride, tantalum, tantalum nitride, tungsten and tungsten nitride and so on often covered on silicon knot and any middle layer before depositing metal layers.Referring to Fig. 5 A, this figure illustrates the viewgraph of cross-section as the microstructure of groove 205, and groove 205 will be metallized by block and fill, and the viewgraph of cross-section of described microstructure will use technique described herein to make metal level be formed directly into blocking layer for describing.As shown in Figure 5 A, thin barrier layer 210 is deposited on semiconductor device on the surface, or as shown in Figure 5 A, is deposited on dielectric layer 208 (such as silicon-dioxide).CVD or PVD deposition techniques blocking layer 210 can be used, as above as described in reference Fig. 4 A.After deposited barrier layer 210, process microfeature workpieces as described herein, to form metallicity 215 on blocking layer 210.Resulting structures can then through processing to deposit block metal (not shown) with filling groove 205 further.
The pH value of process fluid described herein can be changed to acidity from alkalescence.It is different that the low ph value (pH<7) that low conductivity described herein/high ph-values process fluid and such as acid electroplating are bathed and so on processes fluid.H useful in high ph-values process fluid +concentration can become with providing the described process fluid of more than 7 pH value, better more than 8 pH value and best more than 9 pH value, and the process fluid of these pH value is examples of useful high ph-values process fluid.
As mentioned above, technique described herein can be used for the metal electroplated beyond copper removal, such as gold and silver, platinum, nickel, tin, lead, ruthenium, rhodium, iridium, osmium, rhenium and palladium.Metal ion useful in catholyte can be provided by metal salt solution.Illustrative metal salt comprises gluconate, prussiate, sulfamate, Citrate trianion, fluoroborate, pyrophosphate salt, vitriol, muriate, sulfide, oxymuriate, sulphite, nitrate, nitrite and mesylate.For electroplating the exemplary concentration ranges of the metal-salt in the catholyte of application from about 0.03M to about 0.25M.
The ability of plated metal ion can be subject to the impact of complexing agent chelated metal ions.When copper is electroplated, represent higher sedimentation potential with the cupric ion of quadrol complexing agent chelating compared with the cupric ion without chelating.For with metal ion-chelant and the complexing agent forming complex compound comprise and have at least a part to have chemical structure COOR 1-COHR 2r 3chemical compound, wherein R 1the organic group covalently bonded to carboxyl (COO) or hydrogen, R 2hydrogen or organic group, R 3hydrogen or organic group.The specific examples of such complexing agent comprises citric acid and Citrate trianion, tartrate and tartrate, diethyl tartrate, tartrate diisopropyl ester and dimethyl tartrate.The useful complexing agent of another type comprises and comprises nitrogenous chelate group R-NR 2-R 1compound, wherein R is any alkyl, aryl or polymer chain, and R1 and R2 is H, alkyl or aryl organic group.The specific examples of the complexing agent of these types comprises quadrol, ethylenediamine tetraacetic acid (EDTA) and edetate, ring draws amine, porphyrin, dipyridyl, pyrroles, thiophene and polyamines.In plating embodiment, the applicable proportional range of the concentration of metal ions in catholyte and complexing agent concentration can from 1:25 to 25:1; Such as, 1:10 to 10:1 or 1:5 to 5:1.
Useful pH value adjusting agent comprises can adjust the material that the first process fluid and second processes fluid pH value, such as, pH value is adjusted to more than 7 to about 13, and more specifically, about more than 9.0.When quadrol or citric acid are used as the complexing agent of cupric ion, the pH value of about 9.5 is available.When ethylenediamine tetraacetic acid (EDTA) is used as the complexing agent of cupric ion, the pH value of about 12.5 is applicable.The example of the pH value adjusting agent be applicable to comprises alkaline reagents, such as potassium hydroxide, ammonium hydroxide, tetramethyl ammonium hydroxide, sodium hydroxide and other alkali metal hydroxides.Have consumption and the concentration of pH value adjusting agent will depend on the level that required pH value adjusts and other factors, the volume such as processing fluid and other compositions processed in fluid.Useful pH value adjusting agent also comprises the material that the first process fluid and the second pH value processing fluid can be adjusted to less than 7.
For acidic treatment fluid (low ph value, high conductivity, peracidity), useful pH value adjusting agent comprises the material that the first process fluid and the second pH value processing fluid can be adjusted to less than 7.The useful complexing agent of acidic treatment fluid comprises pyrophosphate salt, citric acid, quadrol, ethylenediamine tetraacetic acid (EDTA), poly-imines and polyamines.
Alkalescence comprises with the useful buffer reagent of acidic treatment fluid material pH value being maintained relative constancy state, preferably maintains the level promoting to form complex compound and required complex species.Boric acid is the example of above-mentioned applicable buffer reagent.Other useful buffer reagents comprise acetate/acetic and phosphoric acid salt.Buffer reagent is for electroplating exemplary concentration ranges in the catholyte of application from about 0.001M to about 0.5M.The Examples of buffers concentration range of anolyte is from about 0.001M to about 1.0M.
Catholyte can comprise other additives, such as reduces the additive of fluid resistivity, such as ammonium sulfate; And improve the additive of settling conformality, such as ethylene glycol.In plating application, the exemplary concentration ranges of resistivity agent in catholyte is from about 0.01M to about 0.5M.Affect for agent for conformality, exemplary concentration ranges is from about 0 to 1.0M.
Catholyte also can comprise other additives, such as suppresses metal crystal nuclei growth on itself, allows metal to be deposited on additive on processed blocking layer or additive combination simultaneously.By using this kind of additive or additive combination, metal refining nucleation over the barrier layer can be promoted, and nonmetal own growth.By promoting to deposit the nucleation of metal over the barrier layer but not metal crystal nuclei own growth, conformal (being namely lining in described feature equably) and the continuous metal deposition of small size (such as thickness) can be promoted.
Useful cation permeable blocking layer generally has selectivity for positive charge ion (such as hydrogen ion and metal ion); Therefore, hydrogen ion and metal ion transportable through useful cation permeable blocking layer.
Useful cation permeable blocking layer comprises non-porous barrier layer, such as semi-permeable cation exchange membrane.Semi-permeable cation exchange membrane allows positively charged ion pass but do not allow non-cationic species (such as negatively charged ion) to pass.The first process fluid 406 in the reactor 400 of the atresia feature suppression Fig. 1 on blocking layer and the second fluid processed between fluid 412 flow.Thus, the charge unbalance between electromotive force, process fluid and/or the material concentration difference in process fluid can order about positively charged ion through cation permeable blocking layer.Compared with Porous barriers, the feature of non-porous barrier layer is have minimum or almost do not have porosity (porosity) or unlimited space.In conventional associated with electroplating reactors, when the pressure reduction of both sides, blocking layer is less than about 6psi, non-porous barrier layer does not generally allow fluid to flow.Because non-porous barrier layer does not have open region in fact, so suppression fluid is through non-porous barrier layer.But water is conveyed through non-porous barrier layer by infiltration and/or electric osmose.When the molconcentration in the first process fluid and the second process fluid is different substantially, can permeate.When water passes non-porous barrier layer with the form carrying belt electron ion of hydration ball, there is electric osmose.When the first process fluid and the second process fluid have same molconcentration and do not have electric current to pass through process fluid, the fluid flowing by non-porous barrier layer between the first process fluid and the second process fluid is prevented from substantially.
Non-porous barrier layer can be hydrophilic, so that the bubble processed in fluid does not make each several part on blocking layer dry, the drying on blocking layer is lowered through the specific conductivity on blocking layer.The example on useful cation permeable blocking layer comprises commercially available cation permeable barrier film.Such as, Tokuyama company manufactures and supplies the multiple multiple hydro carbons barrier film for electric osmose and related application, and trade mark is Neosepta tM.Perfluorinated cation barrier film generally can be buied from DuPont company, as Nafion tMbarrier film N-117, N-450, or buy from Asahi Glass company (Japan), trade mark is Flemion tM, as Fx-50, F738 and F893 type barrier film.Also production range is widely based on the ion exchange membrane of polystyrene in Asahi Glass company, and trade mark is Selemion tM, described ion exchange membrane removes very effectively (cation membrane CMV, CMD and CMT and anion membrane AMV, AMT and AMD) electrolytic solution concentrate/desalination and organism.Manufacture other companies (Solvay (France), Sybron chemical company (U.S.), Ionics (U.S.) and FuMA science and technology (Germany) etc.) of similar ion exchange membrane in addition.Also can use bipolarity barrier film, such as AQ-BA-06 and AQ-BA-04 type, described bipolarity barrier film such as can be buied from Aqualitics company (U.S.) and Asahi Glass company.
Except above-mentioned non-porous barrier layer, cation permeable blocking layer also Porous barriers.Porous barriers comprises a large amount of open region or hole, and described open region or hole allow fluid to pass through Porous barriers.Cationic materials and non-ionic material can both pass through Porous barriers; But if the size of some material allows Porous barriers to suppress it to pass through, then some material described is limited or limited by possibility.Although useful Porous barriers can limit the chemistry transmission (by diffusion and/or convection current) of some materials in the first process fluid and the second process fluid, but during applying the electric field associated with electrolysis treatment, described Porous barriers allows the migration (current strengthening passes through) of cationic species.When electrolysis treatment, useful Porous barriers enables cationic species migrate across Porous barriers, limits the diffusion between anolyte with catholyte of larger organic composition and other non-cationic compositions substantially simultaneously or mixes (namely through the transmission on blocking layer).Thus, Porous barriers allows the different chemical maintaining anolyte and catholyte to form.Porous barriers should be chemically compatible in longer operating time section with process fluid.The Porous barriers example be applicable to comprises sintered glass (frit be such as made up of the meticulous glass powder of roasting), porous ceramics (such as alumina and zirconium white), silica aerogel, organism aerogel (such as resorcinol formaldehyde aerogels) and porous polymeric materials, such as launches the porous ceramics be applicable to comprises the P-6-C level porous ceramics can buied from Colorado CoorsTek of Golden.The example of Porous barriers is applicable sponge plastics, such as Kynar tM, sintering polyethylene or polypropylene.The material be applicable to can have the porosity (void fraction) of by volume about 25% to 85%, and mean pore size scope is from about 0.5 micron to about 20 microns.This porous plastic materials can be buied from the Poretex company in Georgia State, USA Fairburn city.These sponge plastics can be made up of three independent material layers, and described material layer comprises the thin small-bore material be clipped between two thicker larger aperture sheet materials (sheet).The product example that can be used for the middle layer with small-bore is the CelGard manufactured by CelGard company tM2400, CelGard company is the branch office of the Hoechst (Hirst company) in Xia Luote city, North Carolina.The skin of sandwich structure can be the material of the polyethylene sheets of such as hyperfine level sintering and so on, and described sheet material can be buied from Poretex company.Porous block layer material allows fluid to flow through described material itself in response to the using of pressure be often subject in electrochemical treatment technique, and such as, described pressure range is generally about 6psi or lower.
Also non-expendable anode and/or dimensionally stable anode is referred to as the inert anode in technique described herein, and described inert anode is such, namely, when applying electromotive force between the anode contacting electrolyte solution and negative electrode, the chemical species of described inert anode do not decompose.The exemplary materials of inert anode comprises platinum, ruthenium, ruthenium oxide, iridium and other precious metals.
Be such for the sacrificial anode in technique described herein, namely when applying electromotive force between the anode contacting electrolyte solution and negative electrode, the chemical species forming described anode decompose.The exemplary materials of sacrificial anode will comprise deposition those materials on microfeature workpieces, such as copper, tin, silver, lead, nickel, cobalt, zinc and analogous material.
Can select when taking into account Traditional Factors to process fluid temperature (F.T.), the complex ability of described factor such as complexing agent, the surge capability of buffer reagent, concentration of metal ions, volatile organic matter concentration, complexing metal are at sedimentation potential, the solubleness of process fluid integral part, the spread coefficient of process fluid stability, required Sediment Characteristics and metal ion of certain ph.Generally speaking, be applicable from the temperature range of about 20 DEG C to 35 DEG C, although also the temperature higher or lower than this scope can be used.
As mentioned above, in electroplating technology situation, the oxidation at anode place of hydroxyl ion or water produces oxygen, and described oxygen can be oxidized the composition in catholyte.When not having cation permeable blocking layer, the composition oxidation in electrolytic solution also can directly occur at anode place.Composition oxidation in electrolytic solution is undesirable, because think that oxydised component promotes the change of metal deposit characteristic (such as resistivity).As mentioned above, by using cation permeable blocking layer, the transfer of oxygen from anolyte to catholyte produced at anode place is reduced to minimum and/or stops, and therefore, these oxygen can not be oxidized the composition existed in catholyte.State as discussed above, a kind of method solving the problem composition in process fluid being oxidized at the oxygen of anode place generation is that frequent replacing processes fluid.Owing to processing fluid relevant time and cost to changing continually, technique described herein provides a kind of attractive alternative method by allowing process fluid to be used for many plate cycle without the need to more bringing.Use cation permeable blocking layer also isolates the non-cationic composition (such as complexing agent) in anode and catholyte, otherwise, described non-cationic composition also may adversely affect in the oxidation of anode place the ability that catholyte deposition has the feature of acceptable matter, such as falls into the electrical resistivity properties in tolerance interval.
Use in technique described herein another advantage on cation permeable blocking layer be blocking layer stop anode place produce oxygen or hydrogen gas bubbles be transferred to catholyte.Bubble in catholyte is undesirable, because described bubble can produce space or hole in deposition characteristics.
In description above, copper has been used as can in order to strengthening kind of crystal layer or the Material examples directly forming metallicity over the barrier layer.But, be understood that, the ultimate principle of technique described herein and described technique also can be applied to other metal or alloy in the block deposition of additional metal or the use over the barrier layer before Direct Electroplating metal in ultra-thin metal layer strengthening, and can be applied to the deposition of other objects.Such as, gold is usually used in membrane head, and applies for Group III-V semiconductor.Muriate or sulphite can be used as relative ion and carry out electrogilding ion.The same with copper, gold ion and hydrogen ion will migrate across cation permeable blocking layer, as described in a case of copper above.In gold plating embodiment, potassium hydroxide can be used as pH value adjusting agent to be reduced to resist the pH value caused to the migration of catholyte from anolyte due to hydrogen ion in catholyte.If needed, then can add reagent to resist the loss of hydrogen ion from anolyte in anode electrolytic solution.The same with above-mentioned copper example, in the golden embodiment using inert anode, the sulfurous acid gold or gold trichloride with gold sodium sulfide or sulfurous acid gold potassium form can be added into catholyte, with the gold of supplementary deposition.
As previously mentioned, technique described above can for depositing more than a metal ion species on microfeature workpiece surface.Such as, technique described above can be used for depositing multicomponent solder, such as tin-silver solder.The multicomponent metal system of the other types of process deposits described above can be used to comprise tin-copper, tin-silver-copper, lead-Xi, Ni-Fe and tin-copper-antimony.Be different from some the copper feature formed on microfeature workpiece surface, solder characteristics trends towards for package application, and large compared with micro-feature of copper thus.Due to the large-size of described solder characteristics, such as 10 microns to 200 microns, solder characteristics is more responsive to the bubble existed in process fluid, and described bubble may be trapped and affect the quality of solder deposits.Tin-silver solder system is the plating example of multivalent state metal.Generally speaking, multivalent state metal can be electroplated under its most stable state.Because be directly proportional to for reducing required electronics for depositing electric charge needed for any metal, the metal be therefore near the valence state of neutral state consumes less energy when being reduced to metal.Unfortunately, the most metals be near the valence state of neutral state is unstable inherently, is therefore worth the plating of producing to carry out.By using the technique for plated metal ion described above, comprising the electroplating solution being in this metal inherently under unsteady state and can be applied in effective technique, to deposit required metal.By using the technique for metal refining described above, metal species unstable are inherently less to be oxidized, thus provides the technique of more worth production.
By illustrating, the preferred Sn of most of Xi-Yin electroplating solution (II) is as zinc-plated species.For this multicomponent electroplating system, the control of tin and silver ions is needed accurately.Multicomponent electroplating system can use inert anode or sacrificial anode.Use sacrificial anode to produce stability problem, described problem is caused by the plating of a kind of metal in metal or described a kind of metal and anodic reaction, and described problem also produces the problem about the ability of supplementary metal equably.On the other hand, use inert anode to avoid foregoing problems, but introduce the new problem be associated with the oxygen produced by the oxidation at inert anode place of water or hydroxyl ion.This kind of oxygen other compositions not only in oxidable plating bath, also required species (such as Sn (II)) can be oxidized to more stable species (such as Sn (IV) ion), described more stable species are more difficult to be electroplated onto on workpiece.
Referring to Fig. 6, this figure provides the operation chart of reactor 610, and cation permeable blocking layer 624 and inert anode 622 and be suitable for deposit tin-silver solder first are processed fluid 614 and second and process fluid 620 and be combined by described operation.In the following description, the process fluid 614 in processing unit 612 is catholytes, and described catholyte comprises: metal ions M 1 +and M 2 +, such as Sn 2+and Ag +ion; The relative ion X of metal ion 1 -and X 2 -, such as mesylate CH 3sO 3 -; And with the complexing agent CA of metal ion, hydrogen ion and hydroxyl ion chelating 1and CA 2, such as proprietary organic additive.As above when copper is electroplated discussed, the specific hydrogen ion concentration in catholyte 614 can be selected, the spread coefficient of the solubleness of the complex ability of described factor such as complexing agent, the surge capability of buffer reagent, concentration of metal ions, volatile organic matter concentration, complex compound alloy deposition current potential under certain ph, catholyte liquid composition, the stability of catholyte, sedimental required characteristic sum metal ion when taking into account Traditional Factors.
Above under copper electro-plating situation about H +the relative concentration of the buffer reagent in the concentration in anolyte and catholyte, anolyte and catholyte, the use of pH value adjusting agent, the supplementing of metal ion, the reduction reaction of negative electrode and the discussion of anodic oxidation reactions are equally applicable to Xi-Yin system.The most desirable specific operation condition is relevant with used specified chemical effect.
The same with copper electroplating technology, the electromotive force applied between negative electrode 616 and anode 622 causes tin ion and silver ions to reduce at negative electrode 616 place, and is deposited on negative electrode 616.Hydrogen ion (H +) be gathered in anolyte cationic permeability barriers 624 first surface 632 near.The same with copper system, water is converted into hydrogen ion (H at positive charge inert anode 622 place +) and oxygen.The charge gradient produced impels positive charge hydrogen ion (H +) second surface 634 on cation permeable blocking layer 624 is moved to from the first surface 632 on cation permeable blocking layer 624.During plate cycle, positive charge hydrogen ion maintains the charge balance of reactor 610 to the transfer of catholyte 614 from anolyte 620.As indicated in figure 6, the hydrogen ion concentration in anolyte 620 is higher than the hydrogen ion concentration in catholyte 614.This concentration gradient also impels hydrogen ion to shift to catholyte 614 from anolyte 620 through cation permeable blocking layer 624.Be deposited on tin on negative electrode 616 and silver ions to be supplemented by adding tin methane sulfonate and methylsulfonic acid silver solution in catholyte.During plate cycle, owing to adding tin MSA and silver-colored MSA, the MSA ion be incorporated in catholyte 614 gathers, and finally must remove MSA ion.A part of catholyte can be removed to solve MSA ion gathering in catholyte from processing unit 612.
Or, under the hydrogen ion concentration in catholyte 614 is greater than the condition of the hydrogen ion concentration in anolyte 620, tin and/or silver ions can be added into anolyte 620.Under these conditions, hydrogen ion suppresses from anolyte 620 to the movement of catholyte 614 by hydrogen ion concentration gradient, and the metal ion in anolyte is transferred to catholyte, and helps the charge balance maintaining reactor.Under these conditions, can take steps to alleviate and be oxidized by the metal ion in anolyte 620 any problem produced.
Referring to Fig. 7, in different embodiments, sacrificial anode 722 is used also can to realize the plating of two kinds of metals (such as tin and silver).Referring to Fig. 7, the catholyte 714 in processing unit 712 is similar to the catholyte described with reference to Fig. 6.In the figure 7 in illustrated technique, from source 700 by metal ions M 2 +introduce processing unit 712, by the oxidation of the metal of composition sacrificial anode 722 by metal ions M 1 +be supplied to comparative electrode unit 718.Metal ions M in anolyte 716 1 +move in catholyte 714 through cation permeable blocking layer 720.Metal ions M 1 +mobile help the charge balance maintaining reactor 730.In addition, metal ions M 1 +from anolyte 716 to the movement of catholyte 714 also by the metal ions M anolyte 716 and catholyte 714 1 +concentration gradient and promoting, the metal ions M namely in anolyte 716 1 +concentration is greater than the metal ions M in catholyte 714 1 +concentration.Metal ions M 1 +with M 2 +can reduce at negative electrode 724 place, and be deposited on negative electrode 724, as described in above with reference to Fig. 6.According to this embodiment, complexing agent (CA) is present in catholyte 714, in catholyte 714, and complexing agent energy and metal ions M 1 +with M 2 +complexing.The pH value adjusting agent be applicable to and pH value buffer reagent can exist and/or can be added in catholyte and anolyte.By the positive metal atoms ion M in comparative electrode unit 718 1 +the charge balance maintained in reactor 730 in processing unit 712 is transferred to through cation permeable barrier film 720.In this system, hydrogen ion is suppressed (to be conducive to M to provide charge balance from anolyte 716 to the movement of catholyte 714 by providing in catholyte 714 higher than the hydrogen ion concentration in anolyte 716 1 +transfer).In this system, metal ions M 2 +do not contact anode 722, depend on metal ions M 2 +with metal ions M 1 +sedimentation potential, metal ions M 2 +at anode 722, place may adversely deposit.
Be contemplated that except metal ions M 1 +positively charged ion in addition such as can arrive catholyte 714 from anolyte 716 through cation permeable blocking layer 720 by the above-mentioned hydrogen ion concentration gradient of reversion.When hydrogen ion concentration gradient is reversed, the hydrogen ion concentration of such as anolyte is greater than the hydrogen ion concentration of catholyte, and hydrogen ion will be easier to shift from anolyte 716 to catholyte 714.In addition, be contemplated that except M 1 +outside other metal ions also can be added into anolyte 716, and can to shift to catholyte 714 from anolyte 716 through cation permeable blocking layer 720.
Applicable reactor for deposit tin ion and silver ions comprises the Raptor named by the Semitool company limited in Si Peier city of Montana, United States Cali tMreactor, or U.S. patent application case the 60/739th, the reactor of the type described in No. 343, described application case applies on November 23rd, 2005, and name is called " Apparatus and Method for Agitating Fluids and the Processing ofMicrofeature Workpieces (for stirring fluid and the apparatus and method for for microfeature workpieces process) ".
Come from microfeature workpieces except metallizing by being reversed in the electric field bias produced between microfeature workpieces and working electrode.Referring to Figure 10, provide the microfeature workpieces 516 of bearing metal M (such as copper) in its surface.Microfeature workpieces 516 contacts the first process fluid 514 in processing unit 512.Process fluid 514 comprises: metal ions M +, such as cupric ion; Complexing agent CA, such as ethylenediamine tetraacetic acid (EDTA); Metal-salt MX, such as copper sulfate or cupric phosphate; Complexation of metal ions M (CA) +; Hydroxyl ion; Buffer reagent; And relative ion X -, such as phosphoric acid salt or sulfate ion.Processing unit 512 is separated by cation permeable barrier film 524 and comparative electrode unit 518.Comparative electrode unit 518 comprises comparative electrode 522 and the second process fluid 520.In depositing process, microfeature workpieces 516 (i.e. working electrode) is anode, and comparative electrode 522 is negative electrodes.Processing unit 512 is also communicated with hydrogen ion source 532 fluid with complexing agent CA source 530.Comparative electrode unit 518 is communicated with pH value adjusting agent source 550 fluid.By applying electromotive force between anode 516 and negative electrode 522, hydrogen ion reduces at negative electrode 522 place to produce hydrogen.Burning on microfeature workpieces 516 surface, causes metal ion to be removed from microfeature workpiece surface.Charge balance in reactor 540 is shifted through cation permeable barrier film 524 anode electrolytic solution 514 from catholyte 520 by hydrogen ion and maintains.
Catholyte 520 in comparative electrode unit 518 comprises hydrogen ion, hydroxyl ion, buffer reagent and relative ion X -.The pH value adjusting agent be added in comparative electrode unit 518 can both be relative ion X -source is again hydrogen ion (H +) source.Pass in time, metal ions M +concentrations build-up in anolyte 514.Thus, anolyte 514 periodic purge with supplement can be required.Charge balance in reactor 540 is shifted to catholyte 520 from anolyte 514 by hydrogen ion and maintains.In order to promote that hydrogen ion passes cation permeable blocking layer 524 to the movement of catholyte 520 from anolyte 514 further, hydrogen ion concentration gradient can be set up between anolyte 514 and catholyte 520.In other words, the hydrogen ion concentration in anolyte 514 can higher than the hydrogen ion concentration in catholyte 520.Although metal ions M +likely also shift from anolyte 514 to catholyte 520, but the movement of the better nonmetallic ion mainly through hydrogen ion maintains charge balance.If need to make metal ion serve as main charge carriers to maintain the charge balance in reactor 540, then suppress hydrogen ion to pass the movement on cation permeable blocking layer 524 by ortho-hydrogen ionic concn, namely the hydrogen ion concentration of catholyte is greater than the hydrogen ion concentration of anolyte.
Referring to Fig. 8, this figure illustrates the more detailed schematic diagram of a kind of design of reactor 8, and material for using cation permeable blocking layer by metal Direct Electroplating over the barrier layer, or is deposited directly on workpiece by reactor 824 in other cases.Reactor 824 comprises container 802, treatment chamber 810 and anode chamber 820, and treatment chamber 810 is configured to guiding first and processes fluid and flow to treatment zone 812, anode chamber 820 be configured to comprise to process with first that fluid partitioning opens second process fluid.In the first process fluid in processing unit 810 and anode chamber 820 second is processed fluid partitioning and opens by cation permeable blocking layer 830.Reactor 824 comprises work holder 840 further, and work holder 840 has multiple electrical contact 842 and applies electromotive force for the workpiece 844 being mounted to work holder 840.Work holder 840 can be portable head, and described portable head is configured to workpiece 844 to be positioned in the treatment zone 812 of processing unit 810, and work holder 840 can be configured to rotational workpieces 844 in treatment zone 812.The work holder be applicable to, in United States Patent (USP) case the 6th, 080, No. 291, the 6th, 527, No. 925, the 6th, 773, No. 560, and U.S. patent application case the 10/497th, is described in No. 460, above-mentioned whole case to be incorporated to herein with reference to mode.
Reactor 824 comprises the bracing member 850 in treatment chamber 810 and the comparative electrode 860 in anode chamber 820 further.Bracing member 850 makes cation permeable blocking layer 830 and workpiece treatment zone 812 be separated by a controlled distance.This feature provides the better control of the electric field to treatment zone 812 place, because the distance between cation permeable blocking layer 830 and workpiece treatment zone 812 affects the intensity of field for the treatment of zone 812.Bracing member 850 generally contacts the first surface 832 on cation permeable blocking layer 830, to make the distance between first surface 832 with treatment zone 812 identical substantially in whole treatment chamber 810.Another feature of bracing member 850 is that described bracing member also makes cation permeable blocking layer 830 shape, and does not assemble to make bubble along second side 834 on cation permeable blocking layer 830.
Bracing member 850 is configured to guiding first and processes the first surface 832 of fluid stream F1 transverse flow through cation permeable blocking layer 830, and vertical current is to treatment zone 812.Bracing member 850 controls the first process fluid stream F1 in treatment chamber 810 thus, to provide required mass transfer characteristics in treatment zone 812.Bracing member 850 also makes the electric field in treatment chamber 810 shape.
The second surface 834 on comparative electrode 860 and cation permeable blocking layer 830 separately so that the second process fluid stream F2 is with the relatively high speed law ground outwards mobile second surface 834 across cation permeable blocking layer 830.Second process fluid stream F2 removes oxygen bubbles and/or particle from cation permeable blocking layer 830.Reactor 824 comprises the restrictor 870 around comparative electrode 860 further.Restrictor 870 is porous materials, and described porous material produces back pressure to provide Uniform Flow between comparative electrode 860 and the second surface 834 on cation permeable blocking layer 830 in anode chamber 820.Therefore, can maintain electric field consistently, because restrictor 870 relaxes the velocity slope in the second process fluid, bubble and/or particle may be assembled in described second process fluid.The configuration of comparative electrode 860 and restrictor 870 also maintains the pressure in anode chamber 820 at electroplating, cation permeable blocking layer 830 is compressed bracing member 850 by described pressure, to give profile (contour) needed for cation permeable blocking layer 830.
By following steps operant response device 824: workpiece 844 is positioned in treatment zone 812; Guide the first process fluid stream F1 through treatment chamber 810; And guide the second process fluid stream F2 through anode chamber 820.When the first process fluid and the second process fluid flow through reactor 824, by electrical contact 842 and comparative electrode 860, electromotive force is put on workpiece 844, to set up electric field in treatment chamber 810 and in anode chamber 820.
For using another available reactor of process deposits metal described herein to be described in No. 2005/0087439th, U.S. patent application case, specially described application case is incorporated to herein with reference to mode.
Can be integrated in processing tool for the one or more reactor in the reactor of electrolysis treatment microfeature workpieces or the system that comprises this reactor, described processing tool can perform multiple method on workpiece.A this kind of processing tool is the electroplating device can buied from the Semitool company limited in Si Peier city of Montana, United States Cali.Referring to Fig. 9, this kind of processing tool can comprise multiple treatment station 910, and one or more in described treatment station are designed to the electrolysis treatment performing microfeature workpieces as described above.Other treatment station be applicable to comprise one or more cleaning/drying station, and for performing other stations of wet chemical treatment.Described instrument also comprises mechanical manipulator component 920, and mechanical manipulator component 920 is carried on central orbit 925 and is delivered to various treatment station for by workpiece from i/o sites+.
Further describe for by more than the technique of a kind of metal ion deposition on microfeature workpiece surface.Such as, described technique can be used for deposition multicomponent solder.Although described above is the exemplary tin-silver solder electroplating technology using cation permeable blocking layer, additional metal and the treatment condition of solder plating are hereafter described.Other limiting examples of multicomponent solder can comprise tin-silver-copper, Sn-Bi, tin-indium, tin-copper, Sn-Bi-indium and Sn-Bi-zirconium.
Technique described herein can be used for the electrochemical deposition of two or more metal ion species.In an embodiment of present disclosure, the solder of deposition comprises at least first and second metal ion.The group that below the optional freedom of first metal ion, various ionic group becomes: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion etc.Equally, the group that below the optional freedom of the second metal ion, various ionic group becomes: cupric ion, lead ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion, nickel ion etc.
In ternary alloy, solder deposits can comprise the 3rd metal ion, and described 3rd metal ion is also selected from the group become by following various ionic group: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion, nickel ion etc.
According to an embodiment of present disclosure, generally comprise as the working electrode in the first process fluid and the second technique processing the microfeature workpieces of the comparative electrode in fluid for electrolysis treatment: make the first process fluid contact microfeature workpiece surface, described first process fluid comprises the first metallic cation; And making the second process fluid contact comparative electrode, described second process fluid comprises the second metallic cation.Described technique comprises further: allow the second metallic cation to move from the second process fluid to the first process fluid, but stops the first metallic cation substantially from the first process fluid to the movement of the second process fluid.Described technique comprises further by first and second metallic cation electrolytic deposition on microfeature workpiece surface.
In exemplary tin described above-silver solder deposition, the first process fluid is catholyte, and the second process fluid is anolyte.Negative electrode is workpiece, and anode is sacrificial anode or inert anode, as hereafter discussed in more detail.
Stop the first metallic cation can comprise from the first process fluid to the movement of the second process fluid: to be combined cation permeable blocking layer and process fluid to second with the charge balance be applicable to move to stop the first metallic cation process fluid from first, but allow the second metallic cation to process from second fluid to process fluid movement to first.Useful cation permeable blocking layer comprises non-porous barrier layer, such as semi-permeable cation exchange membrane.Discuss applicable cation permeable barrier film hereinbefore.
As discussed above with reference to Fig. 7, use sacrificial anode 722 can realize the plating of two kinds of metals, such as tin and silver.(referring to Fig. 6 and above for the relevant discussion of the technique of use inert anode).Referring to Fig. 7, the catholyte 714 in processing unit 712 is similar to the catholyte described with reference to Fig. 6.In the figure 7 in illustrated technique, from source 700 by metal ions M 2 +introduce processing unit 712, by the oxidation of the metal of composition sacrificial anode 722 by metal ions M 1 +be supplied to comparative electrode unit 718.Metal ions M in anolyte 716 1 +move in catholyte 714 through cation permeable blocking layer 720.Metal ions M 1 +mobile help the charge balance maintaining reactor 730.In addition, metal ions M 1 +also can by the metal ions M anolyte 716 and catholyte 714 to the movement of catholyte 714 from anolyte 716 1 +concentration gradient and promoting, the metal ions M namely in anolyte 716 1 +concentration can be greater than the metal ions M in catholyte 714 1 +concentration.But, if metal ions M 1 +main drive be electric current, but not concentration gradient, then this metal concentration gradient between anolyte and catholyte may and nonessential.With regard to this respect, the metal ions M in anolyte 716 1 +concentration can be less than the metal ions M in catholyte 714 1 +concentration.
Metal ions M 1 +with M 2 +can reduce at negative electrode 724 place, and be deposited on negative electrode 724, as described above with reference to Fig. 6.According to this embodiment, complexing agent (CA) is present in catholyte 714, in catholyte 714, and complexing agent energy and metal ions M 1 +with M 2 +complexing.The pH value adjusting agent be applicable to and pH value buffer reagent can be present in and/or can be added in catholyte and anolyte.Charge balance in reactor 730 is by the positive metal atoms ion M in comparative electrode unit 718 1 +be maintained through cation permeable barrier film 720 is transferred in processing unit 712.In such a system, suppress (to be conducive to M higher than the hydrogen ion concentration in anolyte 716 by providing in catholyte 714 1 +transfer) hydrogen ion in order to provide charge balance from anolyte 716 to the movement of catholyte 714.In such systems, metal ions M 2 +do not contact anode 722, in anode 722 place metal ions M 2 +may undesirably deposit, this depends on metal ions M 2 +with metal ions M 1 +sedimentation potential.
When electric current runs, due to charge balance, the first metallic cation (such as silver ions) does not enter the second process fluid from the first process fluid through cation permeable blocking layer.But, when electric current off-duty, first process fluid and the second process fluid may need with separated from one another, to stop the first metallic cation from the first process fluid to the second process fluid migration, and stop proton (H+) ion from catholyte anode electrolytic solution adverse current (back draft).This kind separates the anolyte volume by reducing in anolyte chamber, to make the upper surface of anolyte no longer close contact barrier film and realizing.Put at this point, when electric current does not run in systems in which, can discharge from anolyte chamber to allow anolyte fluid by open valve.
By stoping the first metallic cation to the movement of the second process fluid, anode does not contact the ion of more precious metals ideally.Using in the non-limiting exemplary silver/tin alloy system consuming tin anode, if silver ions contact tin anode, then silver ions will be deposited on tin anode, and be extracted continuously from solution.Meanwhile, tin will be corroded, and tin ion will enter electrolytic solution by replacement(metathesis)reaction.Once silver metal is deposited on tin anode, then cannot electrolysis remove easily.If tin metal in the anode can with and be exposed to solution, the electromotive force applied can not have enough the positive to remove silver.
This replacement(metathesis)reaction in exemplary silver/tin alloy system, it is important for avoiding tin anode is contacted with the silver ions in bath.Therefore, the first metallic cation is stoped substantially from the first process fluid to the movement of the second process fluid.In an embodiment of present disclosure, cation selective membrane is for separating catholyte and anolyte.Described barrier film allows tin ion to arrive catholyte through anolyte, and with the tin consumed in supplementary sedimentation chemistry reaction, but described barrier film stops silver ions to arrive anolyte through catholyte substantially.
For pass the tin ion of barrier film arrival catholyte from anolyte for, tin ion must be main charge carriers.Due to based on the acidic levels in the chemical reaction system of acid, proton (H+) trends towards alternative tin ion becomes main charge carriers, unless pH value in anolyte is higher than pH value (making anolyte lack proton thus) in catholyte.Be generally less than 1.0 for the target ph in the catholyte of exemplary tin/silver alloys deposition, or be less than 0.5.This target ph in catholyte improves chemical specific conductivity and metal ion solubleness.And the pH value of anolyte is greater than the pH value of catholyte, to produce pH value gradient, making the second metallic cation (such as tin ion) replace proton becomes main charge carriers through barrier film.
Further complicated described chemical reaction, pH value close to 2 time, the tin solubleness in methylsulfonic acid (MSA) solution sharply declines.Therefore, in order to make anolyte have pH value higher than catholyte, applicable anolyte solution is maintained pH value higher than 1 but lower than 2.But, along with chemical reaction continues, the pH value being greater than 2 can be reached.According to the embodiment of present disclosure, the present inventor has found that the ratio of at least 30 to 40 to 1 of metal ion and proton in anolyte improves the mass transfer that metal ion passes barrier film.Referring to Figure 11, this figure illustrates the relation between the molconcentration of tin ion in anolyte and anolyte pH value, and preferred proportion may correspond to the pH value in about 1.8 to 2.0.In another embodiment, in anolyte metal ion and proton at least 100 to 1 ratio improve the mass transfer of metal ion through barrier film.Referring to Figure 11, this ratio may correspond in the pH value of about 2.2.
According to the embodiment of present disclosure, the additive in chemical reaction can allow the pH value of anolyte can close to 2.0, or even more than 2.0.Be applicable to additive can comprise stablizer, sequestrant, metal chelating agent and/or buffer reagent to contribute to making the ion in anolyte stay in the solution, even if pH value close to or more than 2.0.
In an embodiment of present disclosure, the target ph of anolyte is being greater than within 1.0 to the scope being less than 2.0.In another embodiment, the target ph of anolyte is within the scope of about 1.2 to about 1.8.In another embodiment, the target ph of anolyte is greater than about 2.0.In another embodiment, the target ph of anolyte is within the scope of about 2.0 to about 3.0.In another embodiment, the target ph of anolyte is within the scope of about 1.0 to about 3.0.
In another embodiment, the target ph of anolyte is within the scope of about 1.5 to about 2.2.In this pH value range, Sn (2+) ion in solution and the ratio of H+ ion (proton) are about 40 to about 100 to 1.In this pH value range, and under this ratio of tin and proton ion, the tolerance interval of barrier film efficiency can be reached, as hereinafter discussed in more detail.
For the catholyte chemical reaction of complementation, in an embodiment of present disclosure, the target ph of catholyte is less than 1.0, and is also less than the pH value of anolyte.
In different alloy plating systems, as described in No. US2012/0138471st, the U.S. Patent Publication case of being applied for by the people such as Mayer (hereinafter referred " Mayer "), due to the hardware differences in system, pH value gradient is non-essential.In Mayer publication, the fluid pump from anolyte is delivered to (such as referring to the pipeline 259 in Fig. 2 B, Fig. 3 and Fig. 4 of Mayer publication) in catholyte.Therefore, in exemplary tin/silver-colored system, the movement of tin ion is mainly through pipeline 259, and not through cation permeable barrier film.On the contrary, in the publication of Mayer, the purposes of barrier film stops silver ions to move in anolyte, deposits on tin anode to avoid silver ions.
In the system that Mayer instructs, in anolyte, tin ion concentration will be higher, and thus, anolyte will be used for mixing joining catholyte.Because other chemical compositions move when anolyte is mixed and joined catholyte (such as excessive water, proton and chemical additive) and assemble in catholyte, therefore the catholyte in Mayer system may need frequently to discharge and rebalancing, to return the parameter needed for it.Although it is effective for discharging and giving technique to Control of chemical reaction, this technique waste material also significantly improves system operation cost, particularly in (cost-sensitive) wafer level package application of cost sensitivity.
Because the main movement of tin ion is by pipeline 259 in Mayer system, but not through cation permeable barrier film, the tin ion therefore through barrier film transmits the pH value gradient do not needed anolyte and catholyte.Therefore, anolyte can maintain the pH value being similar to catholyte pH value.
Although Mayer discusses the pH value range of anolyte and is less than the example provided in 2.0, Mayer publication and has anolyte pH value far below 1.0, described pH value is in the scope of about 0 to about 0.5.Put, the exemplary anode electrolytic solution chemical in Mayer publication comprises the methylsulfonic acid (MSA) of 40g/L to 140g/L, 80g/L, 50g/L, 180g/L to 350g/L respectively at this point.During figure as Figure 13 Anodic electrolyte ph data represents provide, the MSA in anolyte chemical measures remarkably influenced pH value.Or even the MSA of 1.0g/L will make anolyte pH value far below 2.0.According to estimates, according to the MSA amount provided in the example in Mayer publication, the anolyte pH value in Mayer publication is by the scope of 0 to 0.5.
On the contrary, according to the embodiment of present disclosure, tin ion is through the leading ion of the mass transfer of cation membrane, therefore reduces in fact other chemical compositions from anolyte to the movement of catholyte, other chemical compositions described such as water, proton and chemical additive.
According to the embodiment of present disclosure, applicable cation membrane is chemically compatible with MSA, and effective to shifting tin ion.In one embodiment, barrier film has high current carrying capacity.Such as, tin-deposition of silver technique is everlasting in the scope of 30 amperes to 50 amperes and is operated, to reach high rate of deposition.Reach stable anolyte and catholyte and generally mean that a tin ion from anolyte has to pass through barrier film and enters catholyte for each tin atom on wafer of plating.
In the exemplary tin-silver solder deposition of the embodiment according to present disclosure, solder can be the solder close to congruent melting.Compared with any other mixture be made up of same recipe, congruent melting solder will solidify at a lower temperature.Congruent melting tin-silver solder has the silver content of 3.5%.Can in about 0.1% to about 5% silver content scope close to congruent melting, in about 0.5% to 5% silver content scope, in about 1% to about 3% silver medal scope, or in about 0.8% to about 5% silver content scope.
For realizing the tin-silver solder deposition close to congruent melting, the composition of catholyte can be included in about 40g/L to about 80g/L, about 40g/L to about 120g/L or about 40g/L to the tin ion concentration in the scope of about 150g/L.As described in more detail below, if anode is expendable tin anode, then the tin ion concentration in anolyte is similar to the tin ion concentration in catholyte substantially.
Equally, the composition of catholyte can comprise the concentration of silver ions be within the scope of about 0.1g/L to about 5.0g/L.Because silver ions mixes be assigned in catholyte, and system stops silver metal positively charged ion from the movement of catholyte anode electrolytic solution substantially, therefore have minimum in expection anolyte or there is no concentration of silver ions.
According to other embodiments of present disclosure, other Mn solder can comprise copper-Yin-Xi, Xi-Jin and Sn-Bi.Mn solder be the about +/-10% of congruent melting scope close to congruent melting scope.However, it is appreciated that solder characteristic changes along with composition change.Such as, desirable solder characteristic can comprise desirable grain pattern, uniform fusing point, ductility and lower brittleness.
Example
The composition of exemplary cathode electrolytic solution and anode electrolysis bath of liquid is provided in following table.Acid can be MSA.Obviously find out, according to data figured in Figure 13, the acid content in anolyte in the scope of 0.5g/L to 2.5g/L, to reach applicable anolyte pH value range.
Multicomponent solder is except having the metal of use electrochemical deposition process deposition, and multicomponent solder also can comprise other codeposition metals.Exemplary common metal refining can comprise a small amount of too electronegativity and cannot use the metal of ECD deposition techniques, and such as pressing deposit weight calculates, within the scope of about 1ppm to about 100ppm, or in about 0.1% to about 20% scope.One limiting examples, titanium and tantalum can be applicable codeposition metal.Other limiting examples comprise vanadium, chromium, zirconium, niobium, molybdenum, hafnium and tungsten.Although these metals of ECD deposition techniques cannot be used, if these metals are present in catholyte chemical, then these metals can be found in settling due to physical deposition effect.For reaching the common deposition composition of about 1ppm to about 100ppm, codeposition metal can be present in catholyte, and content is in the scope of about 0.1g/L to about 15g/L.
As discussed above, anode can be the sacrificial anode for providing metal ion source in anode electrolytic solution.Sacrificial anode is used to have several advantage.Such as, the cost of tin concentrated solution is high more than the cost of tin sacrificial anode.And sacrificial anode is continuous print, stable self-acting control metal ion source.Put, the concentration of metal ion in anolyte is controlled at this point, because each ion to deposition, an ion is consumed, and an ion is through barrier film, and an ion is dissolved in solution.Analyze (being mainly tin and acid concentration) by bath, faraday inductive law can be made to follow the tracks of the ion transmission through barrier film produced relative to the losses of ions (plating) in catholyte and the ion in anolyte.
Be provided in Figure 12 A and Figure 12 B by utilizing the test-results that exemplary tin/deposition of silver system draws of expendable tin anode.As visible in Figure 12 A, when the anolyte pH value in exemplary tin/deposition of silver system is close to about 0.8 (chart moves from left to right), the tin concentration in catholyte and anolyte starts to depart from expection concentration.Equally, when pH value from 0.8 continue rise and close to 1 time, the tin concentration in catholyte start improve.If two observationss all indicate pH value enough high, then tin ion becomes main charge carriers, and starts to arrive catholyte from anolyte through barrier film.
As visible in Figure 12 B, Figure 12 B be pH value in catholyte and anolyte and between tin concentration the figure of relation represent, if the anolyte pH value in exemplary tin/deposition of silver system maintains the pH value higher than 1, then the tin concentration in catholyte can maintain the concentration close to aimed concn.This observed result represents that the tin consumed in catholyte is supplemented through barrier film from anolyte by tin ion.
Contrary with sacrificial anode, metal ion is mixed in the system of being assigned to there is shortcoming.Such as, metal ion is mixed be assigned in anolyte or catholyte time, technology controlling and process is the formula of reviewing (retroactive), causes zigzag concentration profile thus.And metal ion enriched material can comprise other compositions, so that metal ion is kept in the solution.Because tin ion is consumed, therefore other compositions described are assembled, thus impact bath stability and bath life-span.
As mentioned above, use in technique described herein another advantage on cation permeable blocking layer be blocking layer stop anode place produce oxygen or hydrogen gas bubbles be transferred to catholyte.Bubble in catholyte is undesirable, because described bubble may produce space or hole in deposition characteristics.
In the idealized system using sacrificial anode, charge balance is such: for the metal ion of each deposition, and an ion arrives catholyte from anolyte through barrier film, and equally, consumes an ion from sacrificial anode.However, it is appreciated that, the system that can not always realize ideal.Such as, proton can replace metal ion to move through barrier film.Although the pH value gradient between anolyte and catholyte is designed so that metal ion (such as tin ion) in mass transfer in the highest flight, proton has more movability, less, and is easier to mobile than metal ion.Due to the movability of described proton, any proton of near diaphragm all can pass barrier film by loaded current.
In an embodiment of present disclosure, the efficiency of 85% can be reached.In another embodiment of present disclosure, the efficiency of 90% can be reached.In another embodiment of present disclosure, the efficiency of 95% can be reached.
Although sacrificial anode can be metal ion source, sacrificial anode may not be only metal ion source.Put at this point, except the existence of the metal ion from sacrificial anode, extra metal ion source can be mixed and be assigned in catholyte.In an embodiment of present disclosure, main metal ion source is from sacrificial anode.In an embodiment of present disclosure, main metal ion source comes from mixing in catholyte and joins.
In addition, when system start, may need to mix for cycle chemistry to join metal ion source.
According to another embodiment of present disclosure, main metal ion source can be mixing in anolyte and joins.Put, technique can comprise sacrificial anode or inert anode at this point.
From Sn (II) to Sn, the tin oxidation of (IV) is the total problem of the chemical comprising tin ion, and this problem causes the minimizing of tin ion for electroplating in chemical.Antioxidant is comprised to alleviate tin oxidation by making chemical.Therefore, according to another embodiment of present disclosure, described system comprises a kind of method for alleviating oxidation.Antioxidant can be the chemical antioxidants in solution, and described antioxidant is sacrificial oxygenant, exhausts any oxygen in system before oxygen stannic oxide in systems in which.
Other antioxidants producing antioxygenation in systems in which can comprise removal unit, for removing the oxygen in catholyte and/or anolyte; Maybe can comprise the nitrogen entering catholyte and/or anolyte in the form of bubbles to inject.Catholyte may be easier to oxygenizement occurs than anolyte, because catholyte chamber can be opened to air, thus allows more polyoxy to be dissolved in solution.
Although illustrate and describe the preferred embodiments of the present invention, will understand, and multiple change can be made in the present invention under the prerequisite of the spirit and scope that do not deviate from present disclosure.

Claims (22)

1., for processing a technique for the microfeature workpieces of the working electrode in fluid as first by the comparative electrode electrolysis treatment in the second process fluid, said method comprising the steps of:
A () makes the surface of microfeature workpieces described in described first process fluid contact, described first process fluid comprises the first metallic cation;
B () makes comparative electrode described in the second process fluid contact, described second process fluid comprises the second metallic cation and has the pH value in the scope of about 1 to about 3;
C () to provide cation permeable blocking layer to allow described second metallic cation to process fluid from described second to process fluid to described first and move by processing at described first process fluid and described second between fluid, but stop described first metallic cation substantially from described first process fluid to the movement of described second process fluid, wherein said second metallic cation is through from described second process fluid to the prevailing quality transmission of described first process fluid that described cation permeable blocking layer carries out; And
(d) by described first metallic cation and described second metallic cation electrolytic deposition on the described surface of described microfeature workpieces.
2. technique as claimed in claim 1, wherein said cation permeable blocking layer is cation exchange membrane.
3. technique as claimed in claim 1, is included in described comparative electrode place further and produces electrochemical reaction to produce described second metallic cation.
4. technique as claimed in claim 1, wherein said working electrode is negative electrode and described comparative electrode is anode.
5. technique as claimed in claim 1, wherein said first process fluid is mixed and is furnished with described first metallic cation.
6. technique as claimed in claim 1, wherein said comparative electrode is expendable electrode.
7. technique as claimed in claim 1, one or two in wherein said first process fluid and described second process fluid can be mixed and be furnished with described second metallic cation.
8. technique as claimed in claim 7, mixes the main source of joining the second metallic cation described in the not described first process fluid of described second metallic cation in one or two wherein in described first process fluid and described second process fluid.
9. technique as claimed in claim 1, described first metal cation concentration in wherein said first process fluid is in the scope of about 0.1g/L to about 5.0g/L.
10. technique as claimed in claim 1, described second metal cation concentration in wherein said first process fluid is selected from the group be made up of following scope: about 40g/L is to about 80g/L, about 40g/L to about 120g/L and about 40g/L to about 150g/L.
11. techniques as claimed in claim 1, the pH value of wherein said second process fluid processes the pH value of fluid higher than described first.
12. techniques as claimed in claim 1, the pH value of wherein said second process fluid is selected from the group be made up of following scope: about 1.0 to about 2.0, about 1.2 to about 1.8, about 1.5 to about 2.2, be greater than about 2.0, about 1.0 to about 3.0 and about 2.0 to about 3.0.
13. techniques as claimed in claim 12, the pH value of wherein said first process fluid is selected from the group be made up of following scope: be less than or equal to 1.0, be less than or equal to 0.5 and in the scope of 0 to 1.0.
14. technique as claimed in claim 1, wherein said first metallic cation is selected from the group be made up of following ion: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion.
15. techniques as claimed in claim 1, wherein said second metallic cation is selected from the group be made up of following ion: cupric ion, lead ion, tin ion, bismuth ion, indium ion, silver ions, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion.
16. techniques as claimed in claim 1, comprise the 3rd metallic cation further, described 3rd metallic cation is selected from the group be made up of following ion: cupric ion, lead ion, gold ion, tin ion, silver ions, bismuth ion, indium ion, platinum ion, ruthenium ion, rhodium ion, iridium ion, osmium ion, rhenium ion, palladium ion and nickel ion.
17. techniques as claimed in claim 1, comprise the metal of codeposition further.
18. techniques as claimed in claim 1, wherein said first process fluid comprises antioxidant.
19. techniques as claimed in claim 1, wherein said second process fluid comprises antioxidant.
20. techniques as claimed in claim 1, wherein said second process fluid is not mixed and is allocated in described first process fluid.
21. 1 kinds for by the first process fluid and comparative electrode electrolysis treatment as the technique of the microfeature workpieces of working electrode, described technique comprises the following steps:
A () makes the surface of microfeature workpieces described in described first process fluid contact, described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises the first metallic cation;
B () makes comparative electrode described in the second process fluid contact, described second process fluid has the pH value in the scope of about 1 to about 3;
C () produces electrochemical reaction to produce the second metallic cation at described comparative electrode place;
(d) provide cation exchange membrane with allow during microfeature workpieces described in electrolysis treatment described second metallic cation from described second process fluid to described first process fluid move, but stop substantially described first metallic cation from described first process fluid to described second process fluid movement; And
E (), when not described in electrolysis treatment during microfeature workpieces, makes described second process fluid separate with described barrier film.
22. 1 kinds for the first process fluid and anode electrolysis process as the technique of the microfeature workpieces of negative electrode, described technique comprises the following steps:
A () makes the surface of microfeature workpieces described in described first process fluid contact, described first process fluid comprises the first process fluidic species, and described first process fluidic species comprises the first metallic cation;
B () makes anode described in the second process fluid contact, described second process fluid has the pH value in the scope of about 1 to about 3;
C () consumes described anode to produce the second metallic cation;
D () provides cation exchange membrane to move to described first process fluid from described second process fluid to allow described second metallic cation, but stop described first metallic cation substantially from described first process fluid to the movement of described second process fluid, wherein said second process fluid is not mixed and is fitted in described first process fluid; And
(e) by described first metallic cation and described second metallic cation electrolytic deposition on the described surface of described microfeature workpieces.
CN201510089333.0A 2014-02-28 2015-02-27 Methods For Electrochemical Deposition Of Multi-component Solder Using Cation Permeable Barrier Pending CN104878420A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112601840A (en) * 2018-08-28 2021-04-02 学校法人工学院大学 Method for producing composition for forming metal film, method for producing metal film, metal film laminate, and apparatus for producing composition for forming metal film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893886A (en) * 1981-11-30 1983-06-03 Tokuyama Soda Co Ltd Electroplating method
CN101476150A (en) * 2008-12-29 2009-07-08 广州电器科学研究院 Device and method for electroplating Sn-Cu alloy
CN102534740A (en) * 2010-12-01 2012-07-04 诺发系统有限公司 Electroplating apparatus and process for wafer level packaging
CN103060871A (en) * 2007-12-04 2013-04-24 株式会社荏原制作所 Plating apparatus and plating method
CN103422140A (en) * 2012-05-15 2013-12-04 株式会社荏原制作所 Plating apparatus and plating solution management method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236159B2 (en) * 1999-04-13 2012-08-07 Applied Materials Inc. Electrolytic process using cation permeable barrier
US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893886A (en) * 1981-11-30 1983-06-03 Tokuyama Soda Co Ltd Electroplating method
CN103060871A (en) * 2007-12-04 2013-04-24 株式会社荏原制作所 Plating apparatus and plating method
CN101476150A (en) * 2008-12-29 2009-07-08 广州电器科学研究院 Device and method for electroplating Sn-Cu alloy
CN102534740A (en) * 2010-12-01 2012-07-04 诺发系统有限公司 Electroplating apparatus and process for wafer level packaging
CN103422140A (en) * 2012-05-15 2013-12-04 株式会社荏原制作所 Plating apparatus and plating solution management method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112601840A (en) * 2018-08-28 2021-04-02 学校法人工学院大学 Method for producing composition for forming metal film, method for producing metal film, metal film laminate, and apparatus for producing composition for forming metal film
CN112601840B (en) * 2018-08-28 2023-10-31 学校法人工学院大学 Method for producing composition for forming metal film, method for producing metal film, metal film laminate, and apparatus for producing composition for forming metal film

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