CN1867703A - Electroplating compositions and methods for electroplating - Google Patents
Electroplating compositions and methods for electroplating Download PDFInfo
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- CN1867703A CN1867703A CN200480029839.2A CN200480029839A CN1867703A CN 1867703 A CN1867703 A CN 1867703A CN 200480029839 A CN200480029839 A CN 200480029839A CN 1867703 A CN1867703 A CN 1867703A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electrodes Of Semiconductors (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Disclosed are electroplating compositions and methods for filling recessed microstructures of a microelectronic workpiece, such as a semiconductor wafer, with metallization. The electroplating compositions may comprise a mixture of copper and sulfuric acid wherein the ratio of copper concentration to sulfuric acid concentration is equal to from about 0.3 to about 0.8 g/L (grams per liter of solution). The disclosed electroplating compositions may also comprise a mixture of copper and sulfuric acid wherein the copper concentration is near its solubility limit when the sulfuric acid concentration is from about 65 to about 150 g/L. Such electroplating compositions may also include conventional additives, such as accelerators, suppressors, halides and/or levelers. Methods for electrochemically depositing conductive materials in features, such as trenches and/or contact holes formed on semiconductor workpieces are disclosed, including methods suited for use in multiple anode reactors using the disclosed electroplating solutions.
Description
Right of priority
The application requires to be filed in the U.S. Patent application No.10/688 on October 16th, 2003,420 right of priority, and this patent application is introduced for your guidance in full.
Technical field
The present invention generally relate to electroplating composition and parts as the groove (trench) that on semiconductor workpiece, forms and/or contact hole in the method for deposits conductive material.
Background technology
With microelectronic workpiece such as semiconductor wafer or semiconductor wafer substrate production semiconductor integrated circuit and other microelectronics goods, often be necessary on workpiece, to provide metal level to be used as interconnect metallization, different components is electrically connected to each other in unicircuit.
At first in semiconducter device, generated electrical interconnection easily by using sputter or similar techniques to go up the deposited conductor layer at semiconductor workpiece (as wafer).The unnecessary part of conductive layer uses the pattern mask of being made by photo-resist or analogous material to remove by chemical dry ecthing method.
Device more early uses aluminum or aluminum alloy to constitute wired circuit.Yet in order to catch up with the semiconducter device that becomes increasingly complex, it is more and more littler that the wiring in the semiconducter device is compelled to do.This causes higher current density conversely and because the life-span has been shortened in electromigration.In addition, the circuit of contraction causes RC (impedance/electric capacity) delay that higher resistance increases.
In order to eliminate that too much RC postpones and because the device fault that electromigration produces, the metal such as the copper that have excellent conductivity and high electromigration immunity (electromigration resistance) have been used for constituting wiring.Yet carrying out dry etching on the copper of whole work-piece surface deposition or copper alloy is very difficult (as above-mentioned method).Therefore, used the novel method that is called the damascus steel complete processing.To the copper wiring, constitute initial groove or raceway groove according to the predetermined pattern that is used in the workpiece surface connect up.In dual damascus steel complete processing, in workpiece, also carve contact hole or through hole (vias), so that layer of metal is connected with top or following metal level.Then these grooves and/or contact hole are filled copper or copper alloy.This method has been eliminated by etching and has been removed the process that conductor layer does not need part, and the surface that only needs polishing workpiece is to remove the plated metal of overload.
Yet narrower because wiring width becomes in the present designs, the such wire laying slot and/or the shape of contact hole have quite high aspect ratio (degree of depth of groove and/or contact hole is to the ratio of width).Device function parts (features) make the sputtering method with conventional metal refining be difficult in functional component surface filling planar metal layer as the small size of groove and/or contact hole (for example, less than 1 μ m or even be lower than 0.25 μ m).Chemical vapour deposition (CVD) has been used to deposit different materials, is very difficult but produce suitable steam material with copper or copper alloy.
The metalliding of workpiece immersion plating liquid also has been used for groove and/or contact hole are filled needed electro-conductive material, and representational is copper or copper alloy.Before electroplating process, electrochemical plating typically need be on workpiece the successive electroconductibility kind crystal layer (seed layer) of deposition of thin.Planting crystal layer is made of conducting metal such as copper usually.Usually the following plating of finishing required metal applies electrical bias on kind of crystal layer then, and workpiece such as wafer substrates are exposed to contain will be on kind of crystal layer in the electroplate liquid of galvanized metal ion, electroplates on kind of crystal layer in the presence of electrical bias.
Can use the electroplating composition that contains copper (as copper sulfate) and acid or conducting salt (as sulfuric acid).Adding acid in electroplating composition provides the ionic conductivity of essential high density to obtain high distributed force (throwing power) as sulfuric acid." distributed force " is meant electroplating composition ability of metal refining equably on workpiece such as crystalline substrates.Electrode reaction is not participated in acid, but provides the conformability covering on the surface of workpiece, because acid has reduced resistivity in electroplating composition.If composition contains the copper of lower concentration and the acid of high density, improved the distributed force of composition like this.
The problem that traditional electroplate liquid runs into is the influence that also is subjected to mass transport (mass transport) in the groove of high aspect ratio and/or the deposition process in the contact hole, i.e. except the large size of electrical domain (in bigger functional component device is general), metal diffusing enters the kinetics that has influenced deposition reaction in groove and/or the contact hole.Therefore, do not consider to be applied to the voltage or the current density of plate surface, the plating ionic speed that deposits to workpiece surface can limit electroplating velocity.Produce covering that the high conductivity electroplating composition (as the composition of high acid concentration) of well distributed power do not obtain and on device filling filled smaller functional component, for example groove of sub-micron and/or contact hole.This often causes the decline of deposition quality and causes filling defect, and representational is space (void).When using such composition to fill relatively little groove and/or contact hole, often produce the space.In order to obtain high-quality deposition, deposition process high mass transport speed must be arranged and in minor groove and/or contact hole or near the respond low elimination factor of substrate concentration.Yet transfer rate is subjected to the restriction of low relatively concentration of metal ions in typical peracidity plating bath.
The transfer of metal ion to be plated is directly relevant with the concentration of plated metal in the electroplating composition.Higher concentration of metal ions makes metal transfer in the higher and depletion layer frictional belt of cathode surface (promptly) higher concentration of metal ions be arranged to the speed in the little functional component, the deposition of the faster and better quality of the speed that therefore can obtain.
Yet, having when the electroplating composition that uses distributed force and overlay film homogeneity excellence in the groove of substrate of bigger aspect ratio and/or the contact hole and filling copper, as mentioned above, the filling capacity of composition is very poor.Before groove and/or contact hole filling, the inlet of groove and/or contact hole is often blocked, therefore easily produces the space.Other factors also can produce the space, for example plant heterogeneous nucleation phenomenon, inadequate nucleation and the big crystallization in electroplating process of crystal layer in electroplating process.Regrettably, use typical low sour high metal plating compositions to produce relatively poor distributed force and repressed additive activity, in functional component, produce not galvanized zone.
The space of significant number and/or uneven deposition cause that typically deleterious electroconductibility reduces and weak electromigration immunity (electromigration resistance).In some cases, space and/or heterogeneity are can be enough big and cause and open circuit and device fault.
Briefly, known as those of ordinary skill in the art, if electroplating composition contains the copper of lower concentration and the acid of high density, then electroplating composition has the polarized action that high electroconductibility is become reconciled, and has therefore improved distributed force.In contrast, if electroplating composition has the acid of the copper and the lower concentration of high density, the transfer that the metal ion of known compositions has.In other words, there is the metal ion of enough concentration that functional component is filled well at the groove of high aspect ratio and/or the bottom of contact hole.
The trial of using conventional electroplating composition (promptly containing the copper of lower concentration and the acid of high density or the composition that vice versa) to address the above problem is not entirely satisfactory.For example, used different additives, as specific inhibitor, accelerator and/or the leveling agent (leveler) of different concns.Other used additives comprise halide-ions, as muriate.Employed additive has low copper concentration and high acid concentration or fixed on the contrary mutually according to electroplating composition, as the technician is known usually in this area.Under given voltage, some additive can reduce the sedimentation rate of atoms metal, has therefore suppressed deposition process, and other additives can increase the sedimentation velocity of metal ion under given voltage, so has accelerated sedimentation rate.Regrettably, the existing plating composition does not also solve functional component fully and fills problem when relating to metal ion wherein and shift the relative high aspect ratio functional component of the restriction that is subjected to a certain degree.
Summary of the invention
As described in detail below, electroplating composition of the present invention and electro-plating method provide the filling capacity of surprising excellence, and guaranteed that the high aspect ratio functional component to sub-micron has the copper deposition of the excellence of filling capacity from bottom to top, has reduced the existence in space like this or has removed the space substantially fully.
Electroplating composition and method can be used at device function parts plated metal, for example the semiconducter device groove and/or the contact hole of the high aspect ratio on the semiconductor workpiece.Composition disclosed by the invention and method can be applied to most of step of the metal level of making workpiece.For the ease of explaining, composition and method are at first discussed about the metallization of semiconductor wafer being processed into the functional component in unicircuit and other microelectronics functional components the time.Composition disclosed by the invention and method are not limited to such semiconductor wafer and functional component, but can use when relevant with the metallized semiconductor workpiece of any needs.Term " workpiece " is not limited to semiconductor wafer, but more be meant the substrate on first and second surfaces of common parallel flat, and relatively thin, comprise that semiconductor wafer, ceramic wafers and other constitute the substrate of microelectronic circuit or microelectronics functional component, data storage elements or layer and/or micromechanical component thereon.
Electroplating composition comprises copper and the acid that is under the relative concentration of before having avoided.Electroplating composition has produced the filling capacity of surprising excellence, particularly copper has reduced the existence in space like this or has eliminated the space basically fully the high aspect ratio functional component deposition capability from top to down of submicron-scale (as the groove of 0.12 μ m).In addition, electroplating composition is less to the corrosion of kind of crystal layer, and this has also produced excellent filling capacity.
Electroplating composition can comprise copper and vitriolic aqueous mixture, and wherein the concentration of copper is about 0.3 to about 0.8 to the ratio of sulfuric acid concentration (concentration is represented with g/L).They also can comprise copper and vitriolic aqueous mixture, wherein when vitriolic concentration is 65 to about 150g/L the concentration of copper near solubility limit.These compositions also can comprise conventional additive, for example accelerator, inhibitor, halogen and/or leveling agent.
Method disclosed by the invention is used electroplating composition deposited copper on semiconductor workpiece.These methods further guarantee the copper deposition from top to bottom to the excellence of the high aspect ratio functional component of sub-micron, have reduced the existence in space like this or have eliminated the space substantially fully.
Description of drawings
Fig. 1 has illustrated the solubleness of copper sulfate in sulfuric acid in the time of about 25 ℃.
Fig. 2 (a)-(e) is the picture of the scanning electronic microscope (SEM) of copper semiconductor interconnect, measure width from about 0.12 μ m to about 0.15 μ m, measured altitude is at half place of the interconnect height that constitutes with the different embodiments of electroplating composition, wherein the concentration of copper be different and acid concentration at about 80g/L.
The Presentation Function parts were filled result's lever diagram when Fig. 2 (f) was different acid of comparison/copper electroplating composition, and wherein the concentration of copper increases in the successive experiment.
Fig. 3 (a)-(d) is scanning electronic microscope (SEM) picture of copper semiconductor interconnect, measure the about 0.15 μ m of width, measured altitude is in half of the interconnect height of using different embodiments to constitute, wherein Suan concentration be different and the concentration of copper at about 20g/L (Fig. 3 (a)-(b)) and 50g/L (Fig. 3 (c)-(d)).
Fig. 3 (e) is the scanning electron microscope diagram sheet of interconnection channel before electroplating, and measures the about 0.023 μ m of width, and measured altitude is in half of interconnection channel height.
The functions parts were filled result's lever diagram when Fig. 3 (f) was different acid of comparison/copper electroplating composition, and wherein Suan concentration increases in successive is tested.
Fig. 4 (a)-4 (c) is the scanning electron microscope diagram sheet of copper semiconductor interconnect, and width is about 0.25 μ m, and measured altitude is in half of the interconnect height of using the prior art electroplating composition to constitute, and wherein the about 50g/L of copper concentration and acid concentration are at about 10g/L.
Fig. 4 (d)-4 (f) is the scanning electron microscope diagram sheet of copper semiconductor interconnect, measure width at about 0.25 μ m, measured altitude is in half of the interconnect height of using electroplating composition embodiment of the present invention to constitute, wherein the concentration of copper at about 50g/L and acid concentration at about 80g/L.
Fig. 5 (a) is the scanning electron microscope diagram sheet of copper semiconductor interconnect, measures width at about 0.2 μ m, and measured altitude is in half of the interconnect height of using the prior art electroplating composition to constitute, wherein the concentration of copper at about 20g/L and sour concentration at about 180g/L.
Fig. 5 (b) is the scanning electron microscope diagram sheet of copper semiconductor interconnect, measure width at about 0.2 μ m, measured altitude is in half of the interconnect height of using electroplating composition embodiment of the present invention to constitute, wherein the concentration of copper at about 50g/L and sour concentration at about 80g/L.
Fig. 6 (a) is the scanning electron microscope diagram sheet of copper semi-conductor through hole, measures width at about 0.16 μ m, and measured altitude is in half of the through hole height that uses the prior art electroplating composition to constitute, wherein the concentration of copper at about 20g/L and sour concentration at about 180g/L.
Fig. 6 (b) is the scanning electron microscope diagram sheet of copper semi-conductor through hole, measure width at about 0.16 μ m, passage in height is in half of the through hole height that uses electroplating composition embodiment of the present invention to form, wherein copper concentration at about 40g/L and acid concentration at about 100g/L.
Fig. 7 (a) is the sectional view of representational electromachining station (electroprocessing station), and this plating station has the Processing Room that can use electroplating composition or the reactor that uses in machining tool (processing tool).
Fig. 7 (b) be typically can the Applied Electrochemistry composition Processing Room or the representational sectional view of the part of reactor.
Fig. 8 (a)-8 (d) is typical process flow diagram flow chart, has illustrated in metallized a lot of possibility modes of using electroplating composition of the present invention and method to finish semiconductor workpiece some.
Fig. 9 (a) and (b) illustrated two machining tools that typically can use electroplating composition
Detailed Description Of The Invention
Copper and acid are as the conventional electroplating composition of vitriolic, contain low relatively acid concentration and high relatively copper concentration is arranged simultaneously to reduce end effect (terminal effect) and suitable filling capacity is provided, perhaps containing high relatively acid concentration has low relatively copper concentration simultaneously, the distributed force that has of electroplating composition like this.Electroplating composition of the present invention is not followed these general general knowledge.Instead, their copper concentration of containing equates with acid concentration.
In special embodiment, comprise copper and vitriolic aqueous mixture according to the electroplating composition of the present invention's preparation, wherein copper concentration is about 0.3 to about 0.8g/L to the ratio of sulfuric acid concentration (all concentration of representing with g/L of listing refer to grams per liter solution).In other special embodiments, electroplating composition comprises copper and vitriolic mixture, and wherein copper concentration is about 0.4 to about 0.7g/L to the ratio of sulfuric acid concentration.In other other embodiment, electroplating composition comprises copper and vitriolic mixture, and wherein copper concentration is about 0.5 to about 0.6g/L to the ratio of sulfuric acid concentration.
In other embodiments, electroplating composition comprises copper and vitriolic aqueous mixture, and wherein the concentration of copper is about 60% in its solubility limit to about 90% in composition, and vitriolic concentration about 65 to about 150g/L.In other other embodiments, electroplating composition comprises copper and vitriolic aqueous mixture, wherein in composition copper concentration for about 60% in its solubility limit to about 90% sulfuric acid concentration about 70 to about 120g/L.In other special embodiments, composition comprise concentration in about copper of 35 to about 60g/L and concentration at about 65 to about 150g/L vitriolic aqueous mixture.In other embodiments, composition comprise concentration in about copper of 45 to about 55g/L and concentration at about 75 to about 120g/L vitriolic aqueous mixture.
Although have acid in the above open scope and any electroplating composition of copper can produce excellent filling capacity, comprise that the electroplating composition of vitriolic waterborne compositions of the copper of the sulfuric acid of the copper of about 40g/L and about 100g/L or about 50g/L and about 80g/L is particularly useful.Other representational embodiments comprise the copper of about 60g/L and sulfuric acid or the copper of about 47g/L and the vitriolic aqueous mixture of about 70g/L of about 65g/L.
For example, the source of the copper that uses in the electroplating composition of the present invention can be mantoquita such as copper sulfate, cupric fluoborate, copper gluconate, thionamic acid copper, sulfonic acid copper, cupric pyrophosphate, cupric chloride, cupric cyanide, their combination etc.Although copper sulfate is at first mentioned, should be understood that the copper in any suitable source can use here in disclosed composition.
Electroplating composition can comprise and mix or replace other mineral acids of vitriolic such as fluoroboric acid and similarly acid with sulfuric acid, organic acid such as methylsulfonic acid (MSA), thionamic acid, Padil, their combination etc., mineral acid and organic acid combination.Electroplating composition can comprise other additive such as inhibitor, accelerator and leveling agent, with the little functional component of auxiliary filling.
Electroplating composition can comprise additive such as halide ions, for example muriate, bromide, iodide, their combination etc.In some embodiment of disclosed composition, muriate and some inhibitor additive (as polyethers) are united adding, and the amount of adding enough interacts and suppresses deposition or the increase overpotential of copper when constant voltage and is used for the given current density that applies.Known to those skilled in the art, the halid concentration of interpolation is typically by determining according to the selected operating parameters of specific hardware.In some embodiment of disclosed composition, halide concentration at about 10ppm to about 100ppm.For example, in the vitriolic composition of the copper that comprises about 50g/L and about 80g/L, can add the HCl of about 50ppm.In another embodiment, the HCl that in the vitriolic electroplating composition of the copper that comprises about 40g/L and about 100g/L, adds about 20ppm.Can add other suitable additives (it is known for those of ordinary skill in the art), be used for that auxiliary inhibitor reduces sedimentation rate and/or auxiliary accelerator increases sedimentation rate.
Polarization and the absorption on the substrate surface that inhibitor increases negative electrode usually deposit with the copper that suppresses or reduce at adsorption zone.The inhibitor that adds in the electroplating composition can comprise that binary polyethylene glycol groups inhibitor is as the inhibitor to make than the random copolymers or the segmented copolymer of blended oxyethane and propylene oxide for instance on a large scale.For example, can use from WestHaven, the CUBATH ViaForm inhibitor (DF75) that the Enthone of CT, Inc buy, or from Marlborough, the Shipley C-3100 inhibitor that the Shipley Company of MA buys.
The embodiment of electroplating composition can comprise the inhibitor of any adequate types and concentration.For example, can working concentration at the CUBATH ViaForm DF75 inhibitor of about 2ml/L to about 30ml/L, or also can use about 2 to about 10ml/L.In additional embodiments, can working concentration at the Shipley C-3100 inhibitor of about 5ml/L to about 25ml/L, or also can use about 10 to 20ml/L.In a special embodiment, in the vitriolic electroplating composition of the copper that contains the 50g/L that has an appointment and about 80g/L, used the CUBATH inhibitor of about 2ml/L.In another embodiment, in the vitriolic electroplating composition of the copper that comprises about 40g/L and about 100g/L, used about 17.5ml/L from Marlborough, the Shipley C-3100 inhibitor that the Shipley Company of MA buys.
Accelerator reduces the polarized action of negative electrode, and with inhibitor competitive adsorption site to quicken the growth of copper at adsorption zone.For example, the accelerator that uses in electroplating composition can comprise the compound of sulfur-bearing, as sodium polydithio-dipropyl sulfonate (SPS).The accelerator expanding of small molecules size is faster than inhibitor.For example, can use CUBATH ViaForm accelerator (DF74) or the Shipley B-3100 (buying) that buys from Enthone from Shipley.For example, the embodiment of electroplating composition can comprise accelerator such as CUBATH ViaForm DF74.Such accelerator can use about 2ml/L to about 30ml/L, any concentration from about 2 to 8ml/L.For example, in the vitriolic electroplating composition of the copper that contains the 50g/L that has an appointment and about 80g/L, use about 5mI/L.To excellent spreading rate such as the kind crystal layer of CVD are arranged, can use this accelerator of about 8ml/L.To the kind crystal layer (as the space, bottom) of bottom coating rate variance, can use DF74 or the similar accelerator of about 2ml/L.In another embodiment, in the vitriolic electroplating composition of the copper that comprises about 40g/L and about 100g/L, used the Shipley B-3100 accelerator (buying) of about 10ml/L from Shipley.
Inhibitor and accelerator accumulate in around the functional component densely, because inhibitor has stoped the growth of copper, plant the opening of the little protuberance branch closing function parts of crystal layer and produce breach in functional component.Therefore, suppress on landform functional component (topographical features) top therein be effectively most of and in functional component accelerator with respect to inhibitor account for leading active be useful especially with the electroplating composition that reaches growth from bottom to top.
These component concentrations can change, with at certain components and/or necessary operations condition optimizing.As known to persons of ordinary skill in the art, the proper concentration of additive in the electroplating composition (as halogenide, accelerator, inhibitor, optional leveling agent) can change according to selected especially method and/or the required specific condition of doing of instrument (as temperature, speed of rotation, flow rate, current density).
The acceleration that continues after filling functional component can cause the hypertrophy of copper on functional component, and produces protrusion of surface.Therefore, leveling agent can be added into the electroplating composition disclosed herein as CUBATHViaForm leveling agent DF97 or the Shipley U-3100 leveling agent of buying from Enthone (buying from Shipley).Other suitable leveling agents also can be used for being suppressed at the electric current of prominence to obtain the surface of level.The particular of electroplating composition comprises concentration from about 0.5ml/L to about 3ml/L or from about leveling agent of 1.0 to about 3.0ml/L.For example, in the vitriolic electroplating composition of the copper that comprises about 50g/L and about 80g/L, can use the DF79 leveling agent of about 2.5ml/L.In another embodiment, in the vitriolic electroplating composition of the copper that comprises about 40g/L and about 100g/L, can use the Shipley U-3100 leveling agent (buying) of about 2ml/L from Shipley company.
The service temperature of electroplating composition of the present invention can change between about 15 ℃ to about 30 ℃ or between about 22 ℃ to about 27 ℃.For example, found that about 25 ℃ service temperature is favourable to the vitriolic electroplating composition of the copper that contains the 50g/L that has an appointment and about 80g/L.
For example, at present by Kalispell, the Semitool of MT, Inc, San Jose, the Novellus Systems company of CA or Santa Clara, the fountain type electroplating reaction device that the Applied Materials of CA sells can use the electro-plating method of electroplating composition of the present invention.These instruments typical case has merged the electroplating reaction device that has as single anodic anode system, perhaps uses single dish shape anode or anode particle cage.
Yet the electroplating composition of Miao Shuing is specially adapted to United States Patent (USP) 6,497 herein, 801,6,569,297,6,565,729 and disclosed PCT application WO 00/61498 in the electro-plating method that carries out of the reactor of the multianode type described.United States Patent (USP) 6,497801,6,569,297,6,565,729 and PCT application WO 00/61498 be incorporated herein by reference.
Fig. 7 (a) has illustrated the part schematic cross sectional views of typical plating station 110.Strut member 140 comprises rotation motor 144 and the rotor 142 that is connected with rotation motor 144.Rotor 142 supporting contact assemblies 160.Rotor 142 can comprise base plate 145 and sealing member 141.Base plate 145 moves laterally to workpiece 101 (arrow T) between following two positions, touch first position (demonstration of Fig. 7 (a) solid line) at workpiece 101 rear portions and base plate 145 second position (demonstration of Fig. 7 (a) dotted line) away from workpiece 101 rear portions at base plate 145.
In operation, strut member 140 is supporting the workpiece that is positioned at reactor 130 and is handling the workpiece 101 of position (as workpiece planarization), makes that the plate surface of workpiece 101 engages Working liquids at least.By between the plate surface of workpiece 101 and one or more electrode (below figure 7 (b), providing more details) that is arranged in inner room 132, applying current potential, in Working liquids, set up electric field.For example, in one approach, at the electrode in the inner room 132, contact assembly 160 has deviation with negative potential, plated with conductive material to workpiece 101.In the one side of this method, at other electrodes, one of electrode (" illusory " electrode (thieving electrode)) also has deviation with negative potential, with the control consistence, thereby material is administered on the workpiece 101.
Fig. 7 (b) is the indicative icon of embodiment with reactor vessel 130 of a plurality of electrodes (comprising dummy electrode).Reactor 130 is included in the spiral helicine drainage channel 134 between inner room 132 and the mistress 131.The Working liquids that drainage channel 134 acceptance are overflowed from inner room 132, as the embodiment of electrod composition of the present invention, and the guiding Working liquids is towards liquid exit 135.Liquid passes the first import 136a and the second import 136b enters inner room 132.The first import 136a combines with first flow passage 137, and the part Working liquids in described first flow passage, the 137 guiding inner rooms 132 is to first flow guide 170.First flow guide 170 comprises hole 171, the central shaft 139 of described hole 171 directed flow direction of flow inner rooms 132.Then, fluid upwards flows to the machining functions parts that are filled from first flow guide 170.
The second import 136b can be connected with divider 189, and divider 189 guiding second liquid (for example identical or different embodiment of electroplating composition of the present invention) flow to a plurality of electrodes.Inner room 132 comprises four coaxal electrodes 180.Controller 183 functionally is connected to electrode 180a-d and goes up with control individually and be applied to electric current on each electrode, thus the corresponding conductive path between control electrode and workpiece functional component.
Electrode 180 is arranged in and forms a unit 176, forms a unit 176 and has and be spaced apart corresponding a plurality of pole compartments 177 (as compartment 177a-177d) that thing 178 separates.Divider 189 guiding second liquid enters in each compartment 177 via a plurality of corresponding dispenser grooves 179 (shown in dispenser grooves 179a-179d).Thereby second liquid flows through divider 189 forward, through electrode 180, and upwards arrives the workpiece functional component.Shown in effective electrode position 181a-181d, the effect that is formed unit 176 by the field on the electric field of electrode 180 generations is to make electrode 180 as the outlet that is positioned at each compartment 177.
First flow guide 170 forms from the first liquid-inlet 136a and makes progress and outward extending wall of container 138 towards the inboard (shown in broken lines among Fig. 7 (b)).Shielding 184 with hole 182 can be between electrode 180 and workpiece 101 functional components, with the interaction between the electric field in control workpiece functional component and fluxion and the reaction vessel 130.
In the reaction vessel 130 shown in Fig. 7 (b), each compartment 177 have one or more can be by liquid and bubble hole 174 (as, hole and/or seam).Therefore, the bubble that is trapped in each compartment 177 is overflowed up to leaving inner room 132 by 174 radially outwards of the hole in each compartment.Each compartment 177 can comprise interfacial film 175.Interfacial film 175 can comprise strainer or other element, and it is arranged as voids and other predetermined substance, transports the second flow direction workpiece functional component simultaneously.In another embodiment, interfacial film 175 comprises the ionic membrane of permission ionic current to the workpiece functional component, and stops or stop substantially the second flow direction functional component.As an alternative, second liquid flows through hole 174 via spirrillum drainage channel 134, and flows out inner room 132.First liquid can be collected in isolating drainage channel (not shown).In another embodiment, ionic membrane allows liquid and ion to pass through.
One or more aforesaid reactor assemblies can become one in machining tool easily, and this machining tool can be implemented several different methods on workpiece such as semiconductor microactuator electronic workpiece.A kind of above-mentioned processing tool is from Kalispell, the electroplating device that the Semitool Inc. of MT. buys.Fig. 9 (a) and Fig. 9 (b) illustrate such striking up partnership.
The system of Fig. 9 (a) comprises a plurality of processing stations 210.These processing stations comprise one or more flushings/drying station and one or more plating station.(other suitable submergence-chemical process instruments can use jointly with electroplating composition.) system comprises the hot-work station, as at 215 places, it comprises the thermal reactor of a suitable Rapid Thermal processing (RTP) at least.
Use one or more being arranged as to be used between processing station 210 and RTP station 215, shifting workpiece along centrode 225 linearly moving automatic control transfer organizations 220.One or more stations 210 also can be in conjunction with the structure that is suitable for carrying out the original position flushing.All processing stations and automatic control control transfer organization can be arranged in the cabinet that is full of filtered barotropic gas, have therefore limited the airborne contaminants that may reduce microelectronic workpiece processing validity.
Fig. 9 (b) illustrates another representational machining tool, wherein can use electroplating composition of the present invention.Machining tool shown in Fig. 9 (b) comprises the RTP station 235 that is arranged in the part 230 that has a thermal reactor at least, and described thermal reactor can be integral with tool equipment.Different with the machining tool of Fig. 9 (a), at least one thermal reactor is used by the automatic controls 240 of special use.Special-purpose automatic controls 240 receives the workpiece of transferring to it by automatic control transfer device 220.Transfer can be undertaken by intermediary framework door/zone 245.After this manner, the reactor part 230 of wholesomely separating machining tool from other parts of instrument is possible.In addition, use such structure, annealing station can realize with the separate modular in the existing work box of upgrading through connecting.
Electroplating composition of the present invention can with any use in the countless versions workpiece metallizing working method, be used for constituting the interconnection and the through hole of workpiece.For example, Fig. 8 (a)-8 (d) illustrates several possible electrochemical deposition of metal metallization processes flow processs, and electroplating composition wherein disclosed by the invention can be used to constitute interconnection, through hole or other such functional components.
Illustrate typical Damascus technics flow process at Fig. 8 (a).In this damascene process, at first equip metal seed layer and form blocking layer/bonding coat of arranging on the insulation layer of groove (or other device function parts) therein for workpiece.In Metal plating step subsequently, plant crystal layer and be used for guide current.Usually planting crystal layer is the metal level as thin as a wafer that can use the coating of one of several method.For example, can use physical vapor deposition or chemical vapour desposition method to produce the thick metal seed layer of about 500 .Kind of crystal layer can also by copper, gold, nickel, palladium and most of or all other metal form.Kind of crystal layer forms on the surface that the groove that exists or other workpiece functional component curl up, and they dent in the dielectric substrate.
In some method, before using electroplating composition of the present invention, carried out (in Fig. 8 (a), not showing) electrochemistry (electroless or electrolytic) and planted the crystal layer reparation or strengthen step.Especially, make kind of a crystal layer be suitable for subsequent metal deposition if desired, plant crystal layer and can be repaired, perhaps in independent deposition step, strengthen kind of crystal layer so that " reinforcement " kind crystal layer to be provided by deposition additional metal on already present kind of crystal layer as thin excessively kind crystal layer.Institute on the sidewall of all the depression functional components basically that distribute in workpiece has a few, and the thickness of the kind crystal layer of reinforcement typically equals at lip-deep nominal kind of crystal layer thickness of outer workpiece layout or greater than 10%.For example planting the crystal layer strengthening process can be as United States Patent (USP) 6,290,833 and 6,565,729 disclosed carrying out, and these patents are incorporated herein by reference.After having carried out kind crystal layer strengthening process, can be rinse step subsequently.
Continuation is with reference to figure 8 (a), on kind of crystal layer with tectal form copper electroplating layer.Tectal plating degree is for constituting superimposed layer, so that the copper layer of filling the groove (or other device function parts) that is used to form connecting wiring to be provided.Then, the copper layer randomly typically washes also (randomly) drying in DI water.If wash/drying, then according to the plating tool that uses, flushing/drying can or take place in independent chamber in galvanized chamber takes place.
Subsequently, by workpiece transfer is removed excessive copper to the demoulding unit, excessive copper is removed in etching as the oblique angle.In using the ad hoc approach of electroplating composition disclosed herein, to use as United States Patent (USP) 6,413,436 disclosed methods are optionally removed excessive copper from the periphery as the machined surface of the back side of workpiece and/or workpiece, and these patents are incorporated herein by reference.Can wash the workpiece of oblique angle etching and backside cleaning then.Backside cleaning and DI flushing primitively can be carried out simultaneously.
Each step in plating, flushing and the etching step can carry out in same chamber or in independent chamber.Subsequently to annealing through etched workpiece.Before annealing, can use as DI water flushing workpiece.Can use any suitable method that workpiece is annealed.For example, use as United States Patent (USP) 6,508,920 disclosed methods, can with traditional smelting furnace method or be lower than under 100 ℃ the temperature or even under ambient room temperature annealing workpiece, these patents are incorporated herein by reference.Then, for example can surpass the required copper of device function parts to remove excess deposition by chemical machinery ground polishing workpiece.
Shown in Fig. 8 (b), use the optionally method of electroplating composition of the present invention can comprise precleaning or pre-wetted step before the copper facing, with the limiting surface flaw and remove wherein waste material.Shown in Fig. 8 (b), precleaning or pre-wetted step, copper facing, backside cleaning and/or oblique angle etching and DI rinse step can carry out in plating tool.Annealing and CMP step can be proceeded outside plating tool then.
In the method for another possible suitable use electroplating composition of the present invention, kind crystal layer reparation or reinforcement step can be carried out prior to copper facing (Fig. 8 c).Plant crystal layer reparation step and can comprise second kind of crystal layer of electrochemical deposition, follow and wash by DI.The deposition of second kind of crystal layer can be undertaken by any suitable method, as above-mentioned method.Shown in Fig. 8 (c), plant crystal layer reparation, copper facing, backside cleaning and/or oblique angle etching and DI rinse step and can in plating tool, carry out.Annealing and CMP step can be proceeded outside plating tool then.
Shown in Fig. 8 (d), in the method for another selectable use electroplating composition of the present invention, copper facing, backside cleaning/oblique angle etching, DI flushing and annealing steps can carry out in plating tool.CMP can carry out outside plating tool then.
As above discussed, can in any plating tool in many use different workpieces metallization process methods, be used electroplating composition of the present invention.In addition, many machined parameters can be used to use the method for metallising of electroplating composition discussed here.The machined parameters that uses depends on functional component to be filled, the instrument of use and other the variable known to those skilled in the art.Elucidated hereinafter a possible method, only as representational example.
In the wiring and/or through hole (according to discussed above method one of or any other suitable method) process of copper electroless plating on device function parts such as the workpiece, the acid electroplating composition can corrode (etching) thin kind crystal layer and cause producing the space.Thereby workpiece filling deviation for example, when workpiece is immersed among the embodiment of electroplating composition disclosed by the invention, can apply voltage from about 0.1V to about 1.0V at workpiece surface.For example, have been found that the about 0.4V or the bigger filling deviation that are used for the 200mm workpiece produce the filling of tight functional component.Electroplate in order further to strengthen, for example, in order to electroplate the copper deposition of 1.0 μ m on the wafer of 200mm, wafer can be submerged in the electroplating composition to about 200rpm rotation with about 40rpm.During plating, wafer rotates to 150rpm with about 10rpm.The exemplary embodiment of electro-plating method is that wafer rotates with about 75rpm when submergence, and when electroplating with at about 75rpm 1.0amp, lasting 5 seconds, 40rpm at 1.0amp, continue 25 seconds, 40rpm is the essential time of remaining deposition desired thickness in 4.5amp, lasting time.As is known to the person skilled in the art, the time cycle of speed of rotation, deviation and utilization is depended on the plating tool of use and the device that will form and deciding.
Electroplate in order further to strengthen, for example, in order to electroplate the copper deposition of 0.85 μ m on the wafer of 200mm, wafer is submerged in the electroplate liquid to about 200rpm rotation with about 40rpm.Wafer rotates to about 150rpm with about 10rpm during plating.Electro-plating method exemplary is embodied as example to rotate with about 75rpm when the submergence, and when electroplating with about 75rpm at 1.0amp, continue 5 seconds, 40rpm was 1.0amp, lasting 5 seconds, 40rpm is at 2.0amp, continue 39 seconds, and 60rpm at 8.22amp up to reaching required thickness.
Perhaps, and use specified current density further describing possible plating enhancement method, on the wafer of the 200mm of the copper kind crystal layer of 400 that have an appointment, can deposit the copper deposit of 1 μ m.Wafer can be with about 150rpm rotation.Current density can be from about 2mAmps/cm
2To about 70mAmps/cm
2Perhaps, in the time period that obtains desired thickness, current density can be from about 3mAmps/cm
2To about 25mAmps/cm
2Certainly, the current density of utilizing in electroplating process can be different, typically but not proprietary beginning and finish in higher current density from low current density.
The representational embodiment of electroplating composition of the present invention is as shown in table 1.
Table 1
Constituent concentration g/L
H
2SO
4 80
Accelerator (DF74) 5.0
Inhibitor (DF75) 2.0
Leveling agent (DF79) 2.5
* halogen concentration is represented with ppm
With suitable current density (illustrating), shown in illustrated result among Fig. 2 (e), 3 (d), 4 (d)-4 (f) and 5 (B), in the embodiment of electroplating composition, obtained seamless filling as top.
For purpose relatively, under same additive the same terms, detected the electroplating composition of prior art in same concentration.Shown in Fig. 4 (a)-4 (c), obtain the functional component in space.Especially, the electroplating composition of prior art that contains the composition (for example, the sulfuric acid of the copper of 50g/L and 10g/L) of the combination of conventional high density copper and lower concentration acid produces the through hole that visible void is arranged.Existing at Fig. 4 (a)-4 (c) to the relatively demonstration of result shown in 4 (d)-4 (f), have the electroplating composition (Fig. 4 (a)-4 (c)) of the high density copper/lower concentration acid of technology to cause being formed with the interconnection in obvious space, black patches can be seen in the following fragrant zone that interconnects under Photomicrograph.Shown in Fig. 4 (d), although use electroplating composition of the present invention an embodiment interconnection be filled in the interconnection channel completely filled before be interrupted, but can see in the Photomicrograph of 4 (d) that interconnection is forming but do not having tangible space-obviously the be better than improvement of traditional electroplating composition.In addition, although the interconnection of using the embodiment of electroplating composition to form shown in Fig. 4 (f) has shown some spaces, but in the microphotograph of Fig. 4 (c), can see, the void ratio that produces in the interconnection that forms with the electroplating composition of high density copper/lower concentration acid of using aforementioned techniques, the number in the space in the interconnection and size are significantly still less and littler.
For further comparison, the electroplating composition (that is the mixture of traditional lower concentration copper/high concentrated acid) that uses same additive to detect another prior art under the same conditions causes the groove of the seam gaps illustrated just like Fig. 5 (a).Especially, the electroplating composition that contains the vitriolic prior art of the copper of 20g/L and 180g/L has produced seam gaps in metallized groove.Compare, the embodiment of electrochemistry electroplating composition of the present invention particularly contains the composition of the Cu of the sulfuric acid of 80g/L and 50g/L, has given birth to the tight functional component (shown in Fig. 5 (b) produces) in the onesize groove.
Embodiment 2 and comparative data
Another embodiment of electroplating composition of the present invention is as shown in table 2.
Table 2
Constituent concentration g/L
Cu 40
H
2SO
4 100
Accelerator (B-3100) 10.0
Inhibitor (C-3100) 17.5
Leveling agent (U-3100) 3.0
HCl 20*
* the concentration of halogen is represented with ppm.
Use suitable current density, illustrate as mentioned, illustrate as Fig. 6 (b), the tight that uses the embodiment of electroplating composition of the present invention to obtain through hole is filled.
For purpose relatively, with the embodiment 2 identical electroplating compositions that use same additive to detect prior art under the same conditions.Can see that in Fig. 6 (a) through hole that uses prior art compositions can obtain the space is filled.Especially, shown in Fig. 6 (a), compared traditional high concentrated acid and lower concentration copper are arranged combination (for example, the electroplating composition of the prior art sulfuric acid of 20g/LCu and 180g/L) has produced the through hole that visible void is arranged, simultaneously shown in Fig. 6 (b), the embodiment of electroplating composition of the present invention has shown surprising excellent results, has obtained void-free through hole and has filled.
Embodiment 3
As Fig. 2 (a) to shown in 2 (e), measured width at about 0.12 to about 0.15 μ m copper semiconductor interconnect groove in interconnection half eminence, use the different embodiments of electroplating composition to fill, wherein copper concentration difference and acid concentration be at about 80g/L, and compared different prior art combinations.Especially, to shown in 2 (c), utilize the electroplating composition of the prior art of the copper comprise 20g/L and 80g/L acid to fill interconnection channel as Fig. 2 (a).Photomicrograph at these figure can see that the composition of the lower concentration copper/high concentrated acid of prior art causes having the device in obvious space.Yet, compare, as Fig. 2 (b) with (d), the space that has the electroplating composition of the present invention near copper dissolution ultimate copper and acid concentration to cause forming relative low number.Especially, shown in Fig. 2 (b) and 2 (d), utilization comprises the copper of 35g/L and the electroplating composition filling interconnection channel of 80g/L acid has produced excellent results.
Embodiment 4
The result who makes form as Fig. 2 (f) has listed the embodiment of the electroplating composition of the certain number that detects, and wherein copper concentration progressively increases and acid concentration keeps low relatively.Copper concentration has provided the result of surprising excellence once more with respect to the increase (opposite with conventional wisdom) of low acid concentration.
Especially, it is constant that additive concentration and halide concentration keep, and acid and copper concentration change between the 50g/l to 150g/l and 20g/l at 10g/l respectively.After the plating, be cut open, and check the existence in space through galvanized wafer.To each embodiment of the electroplating composition that detects, fill functional components for five that have detected each size in three sizes (0.12,0.15,0.20 μ m).Fill above five functional component number and keep the score by size.It is 5 that the best of each size is kept the score.The input of this data has produced the lever diagram statistical analysis software instrument drawn as Fig. 2 (f) (as, JMP statistical analysis software program) then.As Fig. 2 (f) as seen, the electroplating composition of copper concentration high relatively relative with acid concentration low (be the embodiment of electroplating composition of the present invention, wherein copper concentration is near solubility limit) has produced statistical improvement significantly to the top-down filling capacity of functional component.
Embodiment 5 and comparative data
Shown in Fig. 3 (a)-3 (d), use the sulfuric acid concentration difference and copper concentration (is respectively 20g/LCu and 80 and 150g/L acid as 20g/L or 50g/L in Fig. 3 (a)-3 (b), in Fig. 3 (c)-3 (d), be respectively 50g/LCu and 10 and 80g/L acid) filled copper semiconductor interconnect groove, the width of measuring in interconnection half eminence is about 0.15 μ m.Shown in Fig. 3 (a), use comprises the copper of 20g/L and the electroplating composition of 80g/L acid has been filled interconnection channel.
For purpose relatively, shown in Fig. 3 (b), utilize the composition that comprises the copper of 20g/L and the vitriolic electroplating composition of 150g/L-the be similar to high concentrated acid/lower concentration copper of typical routine-filled interconnection channel.Obtained excellent result with this composition again.
For the purpose of further haggling over, shown in Fig. 3 (c), utilization contains the copper of 50g/L and the vitriolic electroplating composition of 10g/L has been filled interconnection channel.The result is shown in Fig. 3 (c).(result shown in Fig. 3 (d) has shown the excellent results that obtains with the electroplating composition of the present invention in the foregoing description 1.)
Embodiment 6
Prove further that as result in Fig. 3 (f) form the increase acid concentration increases copper concentration simultaneously, and extremely or near its solubility limit filling provides statistics to improve significantly to functional component.Detected the embodiment of many electroplating compositions, wherein acid concentration progressively increases and keeps high relatively one near its solubility limit for specific acid concentration copper concentration.
Especially, the maintenance of additive concentration and halide concentration is constant and sour changes from 10g/L to 150g/L and from 20g/L to 50g/L respectively with copper concentration.After plating, be cut open and detect the existence in space through galvanized wafer.To each embodiment of the electroplating composition that detects, fill functional components for five that have test in three sizes (0.12,0.15,0.20 μ m) each.The functional component number exceeds five keep the score by size.It is 5 that the best of each size is kept the score.The input of this data produces the lever diagram statistical analysis software instrument that Fig. 3 (f) draw (as, JMP statistical analysis software program) then.As Fig. 3 (f) as seen, copper concentration or produced statistics near the electroplating composition of its solubility limit at the top-down filling capacity of functional component and improved significantly.
Although electroplating composition of the present invention and method are described with reference to multiple embodiments and embodiment, it should be understood that invention is not limited to these embodiments and embodiment.On the contrary, the present invention's meaning is to comprise all can be included in the defined spirit and scope of claim interior modification, Res fungibiles and Equivalent.
Claims (69)
1. water base electroplating composition comprises:
About 35 to about 60g/L copper;
About 65 to 150g/L sulfuric acid;
The glycol-based inhibitor.
2. the composition of claim 1, wherein the concentration of glycol-based inhibitor is about 2 to about 30ml/L.
3. the composition of claim 1 further comprises concentration and is about 2 to about 30ml/L copper and deposits accelerator.
4. the composition of claim 1 further comprises about 10 to about 100ppm halide ions.
5. the composition of claim 4 further comprises about 30 to about 60ppm HCl.
6. electroplating composition comprises:
About 35 to about 60g/L copper;
About 65 to about 150g/L sulfuric acid; With
About 2 to about 130ml/L copper sedimentation inhibitor;
Wherein the remainder of composition is a water.
7. the composition of claim 6 further comprises the copper deposition accelerator that concentration about 2 arrives about 30ml/L.
8. the composition of claim 6, wherein the copper sedimentation inhibitor is random copolymers or segmented copolymer.
9. the composition of claim 6, wherein the copper sedimentation inhibitor is electroless copper bath viaform inhibitor or shipley C-3100 inhibitor.
10. the composition of claim 6, wherein the copper sedimentation inhibitor is a glycol-based.
11. the composition of claim 6 further comprises copper deposition accelerator.
12. the composition of claim 11, wherein copper deposition accelerator is electroless copper bath viaform accelerator or shipley B-3100 accelerator.
13. the composition of claim 11, wherein copper deposition accelerator is SPS.
14. the composition of claim 6 further comprises about 10 to about 100ppm HCl.
15. the water-based electroplating composition comprises:
About 35 to about 60g/L copper;
About 65 to about 150g/L sulfuric acid;
About 2 to about 30g/L copper deposition accelerator;
About 2 to about 30g/L copper sedimentation inhibitor; With
About 40 to about 60ppm hydrogenchloride.
16. the composition of claim 15, wherein the copper sedimentation inhibitor is a glycol-based.
17. the composition of claim 15, wherein copper deposition accelerator is the compound of sulfur-bearing.
18. the composition of claim 1 further comprises the HCl of about 50ppm.
19. electroplating composition comprises:
About 45 to about 55g/L copper;
About 75 to about 120g/L sulfuric acid;
The copper sedimentation inhibitor; With
Copper deposition accelerator.
20. the composition of claim 19, wherein the concentration of glycol-based inhibitor is about 2 to about 10ml/L.
21. the composition of claim 19, the copper that further comprises concentration about 2 to about 8ml/L deposits accelerator.
22. the composition of claim 19 further comprises about 10 to about 100ppm halide ions.
23. the composition of claim 19 further comprises about 30 to about 60ppm HCl.
24. the composition of claim 21, wherein copper deposition accelerator is the compound of sulfur-bearing.
25. the composition of claim 19 further comprises leveling agent.
26. electroplating composition comprises:
Copper and vitriolic aqueous mixture are that the ratio of copper and the acid of unit is about 0.4 to about 0.8 with grams per liter solution wherein;
The copper sedimentation inhibitor; And
Copper deposition accelerator.
27. the composition of claim 26, wherein the copper sedimentation inhibitor is random copolymers or segmented copolymer.
28. the composition of claim 26, wherein the copper sedimentation inhibitor is electroless copper bath viaform inhibitor or shipley C-3100 inhibitor.
29. the composition of claim 26, wherein the copper sedimentation inhibitor is a glycol-based.
30. the composition of claim 26, the copper that further comprises concentration about 2 to about 30ml/L deposits accelerator.
31. the composition of claim 26, wherein copper deposition accelerator is electroless copper bath viaform accelerator or shipley B-3100 accelerator.
32. the composition of claim 26, wherein copper deposition accelerator is SPS.
33. the composition of claim 26 further comprises about 10 to about 100ppm HCl.
34. electroplating composition comprises:
Copper and vitriolic aqueous mixture are that the ratio of copper and the acid of unit is about 0.3 to about 0.8 with grams per liter solution wherein;
The copper sedimentation inhibitor;
Copper deposition accelerator;
Wherein only using the electroplating composition deposited copper on workpiece that contains copper and vitriolic mixture, in described electroplating composition is that the ratio of copper and the acid of unit is about 0.3 to about 0.8 with g/L.
35. electroplating composition comprises:
Copper and vitriolic aqueous mixture, wherein when vitriolic concentration be about 65 to about 150g/L the time, the concentration of copper is in about 60% to about 90% of its solubility limit in the composition;
The copper sedimentation inhibitor; With
Copper deposition accelerator.
36. the composition of claim 35, wherein the concentration of copper sedimentation inhibitor is about 2 to about 30ml/L.
37. the composition of claim 35, the copper that further comprises concentration about 2 to about 30gml/L deposits accelerator.
38. the composition of claim 36 further comprises about 10 to about 100ppm halogenation ion.
39. the composition of claim 36 further comprises about 30 to about 60ppm HCl.
40. the composition of claim 36, wherein the concentration of copper sedimentation inhibitor is about 2 to about 10ml/L.
41. the composition of claim 36, the copper that further comprises concentration about 2 to about 8ml/L deposits accelerator.
42. the composition of claim 36, wherein copper deposition accelerator is the compound of sulfur-bearing.
43. the composition of claim 36, wherein the copper sedimentation inhibitor is a glycol-based.
44. electroplating composition comprises:
The copper of about 40g/L;
The sulfuric acid of about 100g/L;
The copper sedimentation inhibitor; With
Copper deposition accelerator.
45. the composition of claim 44, wherein the concentration of copper sedimentation inhibitor is about 2 to about 30ml/L.
46. the composition of claim 44, the copper that further comprises concentration about 2 to about 30ml/L deposits accelerator.
47. the composition of claim 44 further comprises about 10 to about 100ppm halide ions.
48. the composition of claim 44 further comprises about 30 to about 60ppm HCl.
49. the composition of claim 44, wherein the concentration of copper sedimentation inhibitor is about 2 to about 10ml/L.
50. the composition of claim 44, the copper that further comprises concentration about 2 to about 8ml/L deposits accelerator.
51. the composition of claim 44, wherein copper deposition accelerator is the compound of sulfur-bearing.
52. the composition of claim 44, wherein the copper sedimentation inhibitor is a glycol-based.
53. the water-based electroplating composition comprises:
The copper of about 50g/L;
The sulfuric acid of about 80g/L;
About 2 to about 10ml/L copper sedimentation inhibitor; With
About 2 to about 8ml/L copper deposition accelerator.
54. the composition of claim 53 further comprises about 10 to about 100ppm halide ions.
55. the electro-plating method of workpiece comprises:
Workpiece is provided, and this workpiece has a plurality of device function parts that contain kind of crystal layer, and wherein a plurality of device function parts will metallize;
Use comprises about 35 copper, about 65 that arrive about 60g/L and arrives the sulfuric acid of about 150g/L and electroplating composition deposited copper in a plurality of device function parts of glycol-based inhibitor.
56. the method for claim 55 further comprises kind of the brilliant step of strengthening.
57. the method for claim 55 further is included in flushing and dry workpiece in the course of processing, wherein flushing and/or drying take place in carrying out the sedimentary chamber of copper.
58. the method for claim 55 further comprises selective etch sedimentary copper on workpiece.
59. the method for claim 55 further is included on the workpiece cleaning workpiece back side behind the deposited copper.
60. the method for claim 55 further is included in and is lower than annealing workpiece under about 100 ℃ temperature.
61. the method for claim 55 further is included in deposited copper precleaning workpiece before, wherein the precleaning of workpiece is carried out in carrying out sedimentary identical plating tool.
62. the method for claim 55, wherein electroplating composition comprises about 35 and arrives the copper sedimentation inhibitor of about 30g/L to the copper of about 60g/L, about 65 to about 150g/L sulfuric acid and about 2.
63. the electro-plating method of workpiece comprises:
Workpiece is provided, and this workpiece has a plurality of device function parts that contain kind of crystal layer, and wherein a plurality of device function parts will metallize;
Use contains have an appointment 35 to about 60g/L copper, about 65 to about 150g/L sulfuric acid, about 2 to about 30g/L copper deposition accelerator, about 2 to about 30g/L copper sedimentation inhibitor and the about 40 electroplating composition deposited coppers in a plurality of device function parts to about 60ppm hydrogenchloride.
64. the method for claim 63, wherein to comprise wherein be that the ratio of copper and acid of unit is about 0.4 to about 0.8 copper and vitriolic mixture, copper sedimentation inhibitor and copper deposition accelerator with g/L to electroplating composition.
65. the method for claim 63, wherein to comprise wherein be that the ratio of copper and acid of unit is about copper of 0.3 to 0.8 and vitriolic mixture, copper sedimentation inhibitor and copper deposition accelerator with g/L to electroplating composition, and wherein only use wherein with g/L to the copper of unit and vitriolic than being about 0.3 to about 0.8 copper and electroplating composition deposited copper on workpiece of vitriolic mixture.
66. apply the method for metallization interconnect structure, comprising:
The workpiece that is formed with metal seed layer on it by first deposition method is provided;
In first liquid chamber of reactor, use deposition method by electrochemical deposition additional metal reparation kind crystal layer on kind of crystal layer, so that the kind crystal layer of reinforcement to be provided, described deposition method comprises electroplates energy to the indoor a plurality of concentric anode supply of arranging at the different positions place with respect to workpiece of first liquid-flow; And
Use comprises electroplating composition electro-deposition of metal on the kind crystal layer that process is strengthened of about copper of 35 to about 60g/L, about sulfuric acid of 65 to about 150g/L and glycol-based inhibitor.
67. the electroplating composition of claim 66, wherein electroplating composition comprises about 35 and arrives the copper sedimentation inhibitor of about 30g/L to the copper of about 60g/L, about 65 to about 150g/L sulfuric acid and about 2.
68. apply the method for metallization interconnect structure, comprising:
The workpiece that has been formed with metal seed layer on it is provided;
Use deposition method by electrochemical deposition additional metal reparation kind crystal layer on kind of crystal layer in first liquid chamber of reactor, so that the kind crystal layer of reinforcement to be provided, described deposition method comprises that energy is electroplated in indoor a plurality of electrode supplies to first liquid-flow;
In the process of repairing kind of crystal layer, control to the electric energy supply of at least two electrodes independently; And
In the sedimentation rate of method for electrodeposition substantially greater than adopting electroplating composition to repair under the condition of sedimentation rate of the brilliant method therefor of metal kind, copper electrowinning on through the kind crystal layer of strengthening, described electroplating composition comprise wherein being that the ratio of copper and acid of unit is that about 0.4 to about 0.8 copper and vitriolic mixture, copper sedimentation inhibitor and copper deposit accelerator with g/L.
69. the method for claim 68, wherein to comprise wherein be that copper and the vitriolic of unit is than the copper and the vitriolic mixture that are about 0.3 to about 0.8 with g/L to electroplating composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/688,420 US20050081744A1 (en) | 2003-10-16 | 2003-10-16 | Electroplating compositions and methods for electroplating |
| US10/688,420 | 2003-10-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1867703A true CN1867703A (en) | 2006-11-22 |
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|---|---|---|---|
| CN200480029839.2A Pending CN1867703A (en) | 2003-10-16 | 2004-10-08 | Electroplating compositions and methods for electroplating |
Country Status (6)
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| US (1) | US20050081744A1 (en) |
| EP (1) | EP1680535A4 (en) |
| JP (1) | JP2007508461A (en) |
| CN (1) | CN1867703A (en) |
| TW (1) | TW200516176A (en) |
| WO (1) | WO2005040459A2 (en) |
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| CN107326407B (en) * | 2017-07-25 | 2018-11-16 | 上海新阳半导体材料股份有限公司 | Leveling agent, the metal plating compositions containing it and preparation method, application |
| CN107858728A (en) * | 2017-12-20 | 2018-03-30 | 武汉新芯集成电路制造有限公司 | TSV electro-plating methods |
| CN107858728B (en) * | 2017-12-20 | 2019-08-23 | 武汉新芯集成电路制造有限公司 | TSV electro-plating method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005040459A2 (en) | 2005-05-06 |
| EP1680535A2 (en) | 2006-07-19 |
| WO2005040459A3 (en) | 2006-01-12 |
| JP2007508461A (en) | 2007-04-05 |
| TW200516176A (en) | 2005-05-16 |
| EP1680535A4 (en) | 2008-05-07 |
| US20050081744A1 (en) | 2005-04-21 |
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