CN1906333A - Method and composition for polishing a substrate - Google Patents

Method and composition for polishing a substrate Download PDF

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Publication number
CN1906333A
CN1906333A CN 200480041087 CN200480041087A CN1906333A CN 1906333 A CN1906333 A CN 1906333A CN 200480041087 CN200480041087 CN 200480041087 CN 200480041087 A CN200480041087 A CN 200480041087A CN 1906333 A CN1906333 A CN 1906333A
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substrate
composition
phosphoric acid
sulfuric acid
electrode
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Chinese (zh)
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丰·Q·刘
斯坦·D·蔡
马丁·S·沃勒特
元·A·田
贾仁和
胡永崎
陈梁韵
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Applied Materials Inc
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Applied Materials Inc
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Abstract

Polishing compositions and methods for removing conductive materials from a substrate surface are provided. In one aspect, a composition is provided for removing at least a conductive material from a substrate surface including sulfuric acid or derivative, phosphoric acid or derivative, a first chelating agent including an organic salt, a pH adjusting agent to provide a pH between about 2 and about 10 and a solvent. The composition may further include a second chelating agent. The composition may be used in a single step or two step electrochemical mechanical planarization process. The polishing compositions and methods described herein improve the effective removal rate of materials from the substrate surface, such as tungsten, with a reduction in planarization type defects.

Description

The method and composition that is used for polished substrate
Technical field
The present invention relates to remove electro-conductive material compositions for use and method from substrate.
Background technology
The feature (feature) of making sub-half-micron and littler live width reliably is one of the super large-scale integration (VLSI) of semiconducter device of future generation and gordian technique of ultra large scale integrated circuit (ULSI).Yet along with advancing to the circuit engineering ultimate, the interconnect dimensions of dwindling in VLSI and the ULSI technology has proposed extra requirement to processing power.The reliable formation of interconnection is to the success of VLSI and ULSI, and all is important concerning the ongoing effort that the quality that improves single substrate and tube core and current densities are done.
Utilization sequentially deposited and removed material on substrate surface technology to be forming a plurality of feature structures within it, thereby forms multistage interconnected.Along with the deposition and the removal of material layer order, it is uneven that the upper space of substrate may become, and require to carry out before subsequent disposal planarization.Planarization or " polishing " are to remove material technology generally even to form, flat surfaces from substrate surface.The planarization material that removes excess deposition, remove surface topography and the surface imperfection do not expected, as surface irregularity, material clumps, lattice damage, scuffing and contaminated layer or material, thereby provide uniform surface for photoetching and other semiconductor technology subsequently.
Shown in Figure 1A and 1B, by utilize metallic surface that chemically reactive and mechanical activity carry out planarization to layer chemically machinery polished (CMP) inlays (damasceneinlay) to Damascus with high surface flatness particularly the planarization of carrying out on tungsten surface be difficulty very.Damascus is inlayed and is formed technology and can comprise feature structure in the etching interlayer dielectric (for example silicon oxide layer), also comprise in the feature structure sometimes and substrate surface on the blocking layer, and on blocking layer and substrate surface the thick-layer of deposits tungsten material.Usually cause the tungsten surface smooth inadequately in order to remove the excess tungsten on the substrate surface to the chemically machinery polished that the tungsten material carries out.And the chemical Mechanical Polishing Technique of removing the tungsten material fully often causes the pattern defective that can influence substrate subsequent processing, for example caves in and corrodes.
When the part on the embedded with metal surface of the interconnection that forms in the feature structure in the interlayer dielectric during by excessive polishing, promptly produce depression, forms one and a plurality of pits (can be described as recess and be recessed into).Referring to Figure 1A, by depositing for example material of tungsten (W) and tungstenalloy in Damascus opening that forms in the interlayer dielectric 10 (for example, silicon-dioxide), inlay in formation conductor wire 11 and Damascus of 12.Although also not shown, the blocking layer that is used for the suitable material (for example titanium and/or titanium nitride) of tungsten can be deposited between interlayer dielectric 10 and the embedded with metal 12.After the planarization, the part of embedded with metal can be measured (being called amount of recess) with D and be depressed.Depression is more prone to occur in the less feature structure of broad on the substrate surface or intensity.
Traditional planarization also causes corroding sometimes, shows as the excessive polishing to the layer of not wanting to remove (for example dielectric layer of metallicity structure periphery).Referring to Figure 1B, metal wire 21 and intensive array of metal lines 22 are embedded in the interlayer dielectric 20.Polishing metal line 22 can cause the loss of the dielectric medium 20 between the metal wire 22 or corrode E.Observe near the narrower and closeer feature structure that in substrate surface, forms to corrode and take place.Improvement to traditional tungsten CMP polishing technology has caused polishing velocity not reach requirement, and polish results was accepted in commercial being difficult to.
Therefore, need be used for removing electro-conductive material (for example excessive tungsten material) so that substrate formed pattern defective combination of minimum thing and method during planarization from substrate.
Summary of the invention
The invention provides the composition and the method that remove electro-conductive material by the electrochemical etching technology.In one aspect, provide to be used for removing the composition of tungsten material at least from substrate surface, said composition comprise about 0.2vol% to the sulfuric acid or derivatives thereof of about 5vol%, about 0.2vol% extremely about 5vol% phosphoric acid or derivatives thereof, about 0.1wt% extremely about 5wt% Citrate trianion, pH regulator agent and the solvent of about 3 to about 8 pH can be provided.
The invention provides the composition and the method that remove the tungsten material by the electrochemical etching technology.In one aspect, provide to be used for removing the composition of tungsten material at least from substrate surface, said composition comprise about 0.2vol% to the sulfuric acid or derivatives thereof of about 5vol%, about 0.2vol% to the phosphoric acid or derivatives thereof of about 5vol%, about 0.1wt% extremely the Citrate trianion of about 5wt%, about 0.5wt% extremely about 5wt% have one or more sequestrants that are selected from the functional group of amido, amide group and combination thereof.
In yet another aspect, described composition is used in the method for process substrate, and described method comprises: the substrate arrangement that will have the tungsten layer that forms on it is in the process unit that comprises first electrode and second electrode, and wherein the substrate and second electrode electrically contact; Between first electrode and substrate, provide polishing composition, wherein polishing composition comprise sulfuric acid and derivative, phosphoric acid and derivative thereof, contain organic salt first sequestrant, pH regulator agent and the solvent of about 2 to about 10 pH can be provided; Substrate is contacted with polished part; Between substrate and polished part, provide relative movement; Between first electrode and second electrode, apply bias voltage; Remove the tungsten material from the tungsten material layer.
In yet another aspect, described composition is used in the method for process substrate, and described method comprises: the substrate arrangement that will have the tungsten layer that forms on it is in the process unit that comprises first electrode and second electrode, and wherein the substrate and second electrode electrically contact; With the method polished substrate that may further comprise the steps to remove the first part of tungsten layer: first polishing composition is provided between first electrode and substrate, wherein polishing composition comprises sulfuric acid and derivative thereof, phosphoric acid and derivative thereof, first sequestrant that contains organic salt, have one and a plurality of amidos that are selected from, second sequestrant of the functional group of amide group and combination thereof, pH regulator agent and the solvent of about 6 to about 10 pH can be provided, substrate and polished part are contacted under first pressure between substrate and the polished part, first relative movement is provided between substrate and polished part, between first electrode and second electrode, applies first bias voltage; With the method polished substrate that may further comprise the steps to remove the second section of tungsten layer: between first electrode and substrate, provide the and polishing composition, wherein polishing composition comprise sulfuric acid and derivative, phosphoric acid and derivative thereof, contain organic salt first sequestrant, pH regulator agent and the solvent of about 2 to about 8 pH can be provided, substrate and polished part are contacted under second pressure between substrate and the polished part, second relative movement is provided between substrate and polished part, between first electrode and second electrode, applies second bias voltage.
Description of drawings
In order to obtain above-mentioned aspect of the present invention, and can carry out understood in detail, can the embodiments of the present invention of above concise and to the point description be done to describe more specifically by with reference to illustrational embodiment in the accompanying drawings to it.
But, it should be noted that the only for example clear exemplary embodiment of the present invention of accompanying drawing, therefore do not think to limit its scope, because the present invention can comprise the embodiment of other effects equivalent.
Figure 1A and 1B are respectively the synoptic diagram of explanation depression and erosion;
Fig. 2 is the orthographic plan of electrochemical machinery planarization systems;
Fig. 3 is the sectional view of the first electrochemical machinery planarization (ECMP) of Fig. 2 system a kind of embodiment of standing;
The fragmentary cross-sectional view that Fig. 4 A stands for the ECMP by two contact assemblies;
Fig. 4 B-C is the sectional view of other embodiments of contact assembly;
Fig. 4 D-E is the sectional view of bolt;
Fig. 5 A and 5B are the sectional view and the exploded view of a kind of embodiment of contact assembly;
Fig. 6 is a kind of embodiment of contact member;
Fig. 7 is the vertical cross section of the another kind of embodiment at ECMP station;
Fig. 8 A-8D is for carrying out the diagrammatic cross-section of glossing on substrate according to a kind of embodiment.
Embodiment
Generally speaking, the invention provides and be used for removing the composition and the method for tungsten material at least from substrate surface.Following reference is by the flatening process of electrochemical mechanical polishing (ECMP) technology from substrate surface removal tungsten material, and present invention is described.
Speech used herein and phrase should have meaning common and commonly used in this area understood by one of ordinary skill in the art, unless otherwise defined.Chemical rightenning should be broadly interpreted as and include but not limited to, utilizes chemically reactive that substrate surface is carried out planarization.Electropolishing should be broadly interpreted as and include but not limited to, the Applied Electrochemistry activity is carried out planarization to substrate.Electrochemical mechanical polishing (ECMP) should be broadly interpreted as and include but not limited to, Applied Electrochemistry activity, mechanical activity, chemically reactive to be removing material from substrate surface, thereby substrate is carried out planarization.
Anode dissolution should be broadly interpreted as and include but not limited to, directly or indirectly substrate is applied anodic bias, thereby removes electro-conductive material and it is entered the polishing composition on every side from substrate surface.Polishing composition should be broadly interpreted as and include but not limited to, generally comprises the material that is called electrolyte components, and ionic conductivity is provided in liquid medium thereby the composition of electroconductibility is provided.The amount of every kind of electrolyte components can recently be measured with volume percent or weight percent in the polishing composition.Volume percent is meant based on the volume of the desired liquid ingredient per-cent divided by all liquid cumulative volume in the whole composition.Per-cent based on weight percent is the per-cent of the weight of desired component divided by the gross weight of all liquid component in the whole composition.
Device
Fig. 2 is a kind of sectional view of embodiment with planarization systems 100 of the device that is used for the electrochemical treatment substrate.Example system 100 generally includes factor interface district (factory interface) 102, loads robot arm 104 and planarization module 106.Load that robot arm 104 is disposed near factor interface district 102 and the planarization module 106 so that translate substrate 122 betwixt.
Provide controller 108 so that the module of control and integrated system 100.Controller 108 comprises central processing unit (CPU) 110, storer 112 and supports circuit 114.Controller 108 is coupled (couple) so that for example planarization, cleaning and transfer process are controlled with each parts of system 100.
Factor interface district 102 generally includes cleaning module 116 and one or more wafer cassette 118.With interface area robot arm 120 translate substrate 122 between wafer cassette 118, cleaning module 116 and load module 124.The position of setting load module 124 is so that by clamper (for example holder fixed by vacuum and mechanical clamp (not shown)) translate substrate 122 between planarization module 106 and factor interface district 102.
Planarization module 106 comprises that at least the first electrochemical machinery planarization (ECMP) stands 128, and it is disposed in the shell 188 of environment control.The example that can be suitable for planarization module 106 of the present invention comprises it being can be from the Applied Materials of Santa Clara, California, the MIRRA that Inc. obtains , MIRRA MESA TM, REFLEXION , REFLEXION LK and REFLEXION LK ECMP TMThe chemical mechanical planarization systems transformation obtains.Other planarization modules are applicable to the present invention after also can transforming, comprise planarization module that those use processing pad, planarization net (web) or its combinations and with rotatablely move, motion of translation or other planar motions make the planarization module of substrate with respect to the planarized surface motion.
In embodiment shown in Figure 2, planarization module 106 comprises the 130 and the 3rd ECMP station, the 128, the 2nd ECMP station, ECMP station 132.The main body removal that is deposited on the electro-conductive material on the substrate 122 is carried out on ECMP station 128 by the electrochemical dissolution process.Perhaps, first station 128 can be to be used to remove for example traditional chemical mechanical polishing platform of the electro-conductive material of tungsten, and second station 130 is ECMP stations described here.After on ECMP station 128, carrying out the material of main part removal, can on the 2nd ECMP station 130, remaining electro-conductive material be removed from substrate by multistep electrochemical machinery process, the part that multistep process wherein is set is with removing remaining electro-conductive material.Can remove process after carry out at different stations in main body, utilizing stands more than one ECMP carries out this multistep and removes process.Perhaps, main body and multistep electro-conductive material of carrying out on the single station of each in available first and second ECMP station 128,130 removed.All ECMP stations (for example 3 of module 106 stations among Fig. 2) can also be set handle conductive layer by two step removal processes.In a kind of embodiment of module 106, on first and second stations 128 and 130, to remove after the electro-conductive material, the 3rd station 132 is used to remove barrier material, for example titanium, titanium nitride, tantalum and tantalum nitride.Perhaps, the 3rd station 132 can be the traditional chemical mechanical polishing platform that is used to remove blocking material.
Exemplary planarization module 106 also comprise transfer station 136 and be positioned at the end face of device pedestal 140 or first on first rotating disk 134.In one embodiment, transfer station 136 comprises input buffering station 142, output buffered station 144, shifts robot arm 146 and loads cup assembly 148.Input buffering station 142 is by loading the substrate that robot arm 104 receives from factor interface district 102.Loading robot arm 104 also is used for substrate is back to factor interface district 102 from output buffered station 144.Transfer robot arm 146 is used at buffered station 142,144 and loads mobile substrate between the cup assembly 148.
In one embodiment, shift robot arm 146 and comprise two clamp assemblies (not shown), wherein each has the pneumatic clamping finger that can clamp substrate at edges of substrate.Shift robot arm and treated substrate from input buffering station 142 can be transferred to loading cup assembly 148 with pending substrate from loading when cup assembly 148 is transferred to output buffered station 144.In the U.S. Patent No. 6156124 (by reference it all being incorporated into this) of the Tobin that authorizes on December 5th, 2000 example that can be used for transfer station of the present invention has been described.
Rotating disk 134 is placed in the center of base 140.Rotating disk 134 generally includes a plurality of arms 150, and each arm supports a planarization assembly 152.Two of arm 150 are shown in broken lines in Fig. 2, so that the transfer station 136 at ECMP station 128 and planarized surface 126 are as seen.Rotating disk 134 can have index, so that a planarization assembly 152 can move between planarization station 128,130,132 and transfer station 136.In the U.S. Patent No. 5804507 (by reference it all being incorporated into this) that Perlov equals to authorize on September 8th, 1998 a kind of rotating disk of the present invention that can be used for has been described.
Each planarization station 128,130,132 adjacent position is arranged setting device 182 on base 140.Setting device 182 is periodically regulated and is arranged in station 128,130,132 smoothing material to keep uniform planarization results.
Fig. 3 shows the sectional view of a planarization assembly 152 on a kind of embodiment that is positioned at ECMP station 128.The second and the 3rd ECMP station 130,132 can be provided with similarly.A planarization assembly 152 generally includes the drive system 202 that is connected to planarization 204.Drive system 202 generally planarization 204 provide at least and rotatablely move.Planarization 204 also can be driven to 128 motions of ECMP station, thereby the substrate 122 that is clipped in the planarization 204 can be pressed on the planarized surface 126 at ECMP station 128 during processing.Controller 108 is coupled with drive system 202, provides signal to it, is used to control the speed of rotation and the direction of planarization 204.
In one embodiment, the planarization head can be Applied Materials, the TITAN HEAD that Inc. makes TMOr TITAN PROFILER TMThe wafer carriage.Usually, planarization 204 comprises housing 214 and clamp ring 224, and clamp ring 224 has a drop-center, and substrate 122 is clipped in wherein.Clamp ring 224 defines the substrate 122 that is positioned at planarization 204, prevents to add the slippage below planarization 204 of substrate in man-hour.The material of making clamp ring 224 can be for example poly-sulphur benzene (PPS), polyether-ether-ketone plastic materials such as (PEEK), or electro-conductive materials such as stainless steel, Cu, Au, Pd for example, or its certain combination.Can also apply electrical bias with the electric field of control during the ECMP to conduction clamp ring 224.Conduction or bias voltage clamp ring often reduce near the polishing velocity the edges of substrate.Also can use other planarization heads.
The one ECMP station 128 generally includes rotatable the assembly 230 that is positioned on the base 140.Platform assembly 230 is supported on the base 140 by bearing 238, so platform assembly 230 can be with respect to base 140 rotations.The zone of the base 140 that is limited by bearing 238 is open, and the pipeline that is provided for electricity, machinery, air, control signal and is connected exchange with platform assembly 230.
The traditional bearing, swivel joint and the slip ring that are referred to as rotary connector 276 are provided so that electricity, machinery, liquid, gas, control signal and be connected base 140 and universal stage assembly 230 between be coupled.Platform assembly 230 links to each other with the motor 232 that rotatablely moves is provided for it usually.Motor 232 is coupled with controller 108, provides the signal of the speed of rotation and the direction of supervisory control desk assembly 230 by it.
The top surface of platform assembly 230 supports the processing pad assembly 222 on it.Can the processing pad assembly be clamped on the platform assembly 230 by magneticattraction, vacuum, clamp, tackiness agent etc.
Pressurizing chamber (plenum) 206 is set to promote that electrolytic solution is evenly distributed to planarized surface 126 in the table apparatus 230.Form a plurality of passages (hereinafter more detailed description) in the platform assembly 230 so that provide to the pressurizing chamber 206 electrolytic solution evenly to flow through platform assembly 230 and contact with substrate 122 man-hour adding by electrolyte source 248.Different steps in processing can provide different electrolyte compositions.
Processing pad assembly 222 comprises electrode 292 and planarization part at least 290.Electrode 292 is made by for example electro-conductive materials such as stainless steel, copper, aluminium, gold and silver and tungsten usually.Electrode 292 can be impermeable electrolytic solution or permeable electrolytic solution or porous solid.At least one contact assembly 250 extends on processing pad assembly 222, and the substrate of just processing on processing pad assembly 222 is electrically connected with power supply 242.Electrode 292 also is connected with power supply 242, thereby sets up electromotive force between substrate and electrode 292.
Provide tolerance meter (not shown) to detect the tolerance indication of electrochemical process.The tolerance meter can be connected or be positioned between power supply 242 and at least one electrode 292 or the contact assembly 250.The tolerance meter also can be integrated on the power supply 242.In one embodiment, the tolerance meter is set and thinks that controller 108 provides the tolerance indication of processing, for example electric charge, electric current and/or voltage.Controller 108 can utilize this to measure original position to adjust machined parameters make endpoint detection or other operation stages more easy.
The window 246 that forms by pad assembly 222 and/or platform assembly 230 is provided, it is provided with so that be positioned at the tolerance indication that pad assembly 222 following transmitters 254 can be read polishing operation.For example, transmitter 704 can be eddy current sensor or interferometer etc.The tolerance that is offered controller 108 by transmitter 254 provides the information that original position is adjusted the detection in other stages in processing characteristics, end point determination or the electrochemical process that can be used to.In one embodiment, transmitter 254 is the interferometers that can produce collimated beam, during processing light beam towards and be radiated at a side of polished substrate 122.Interference between reflected signal indicates the thickness of the conductive layer of processed material.In the U.S. Patent No. 5893796 (by reference it all being incorporated into this) that Birang equals to authorize on April 13rd, 1999 a kind of transmitter of the present invention that can be used for has been described.
Be suitable for to comprise the planarized surface 126 of dielectric basically usually from the embodiment that substrate 122 is removed the processing pad assembly 222 of electro-conductive material.Be suitable for to comprise the planarized surface 126 of conduction basically usually from other embodiments that substrate 122 is removed the processing pad assembly 222 of electro-conductive material.Provide at least one contact assembly 250 so that substrate links to each other with power supply 242, thereby during processing, can make substrate produce bias voltage with respect to electrode 292.Form hole 210 by planarization layer 290 and electrode 292 and any element of being positioned at below the electrode, make electrolytic solution between substrate 112 and electrode 292, set up conductive path.
In one embodiment; The example that is suitable for processing pad assembly of the present invention after can transforming has been described among the U.S. Patent application No.10/455895 (by reference the two all being incorporated into this) that is entitled as " Conductive Planarizing Article ForElectrochemical Mechanical Planarizing " that the U.S. Patent application No.10/455941 that is entitled as " Conductive Planarizing Article ForElectrochemical Mechanical Planarizing " that the planarization part 290 of processing pad assembly 222 is dielectric mediums, for example urethane.2003 submitted at June 6 and on June 6th, 2003 submit to.
Fig. 4 A is that Fig. 5 A-5C is side-view, exploded view and the sectional view of a contact assembly 250 shown in Fig. 5 A by the fragmentary cross-sectional view at the ECMP station 128 of two contact assemblies 250.Platform assembly 230 comprises the contact assembly 250 that at least one is outstanding from it, and contact assembly 250 links to each other with power supply 242, and power supply 242 applies bias voltage to the surface of substrate 122 during processing.Contact assembly 250 can be connected to the part of platform assembly 230, processing pad assembly 222 or element independently.Though two contact assemblies 250 have been shown among Fig. 4 A, can use the contact assembly of any amount, and these contact assemblies can distribute in any way with respect to the medullary ray of platform assembly 230.
Contact assembly 250 is electrically connected with power supply 242 by platform assembly 230 usually, and each hole 368 by forming in processing pad assembly 222, can move at least in part.The position that can select contact assembly 250 is to form predetermined structure on platform assembly 230.For predefined technology, independent contact assembly 250 can be reorientated in different hole 368, and to not containing the hole of contact assembly, available block 392 shutoff or fill (shown in Fig. 4 D-E) with nozzle 394 can make electrolytic solution 206 flow to substrate from the pressurizing chamber during wherein with nozzle 394.Be suitable for contact assembly of the present invention after having described a kind of can the transformation among the U.S. Patent application No.10/445239 (by reference it all being incorporated into this) that Butterfield equals to submit on May 23rd, 2003.
Though the embodiment of the contact assembly 250 that describes below illustrates with bobbin type contact in Fig. 4 A, contact assembly 250 can also comprise having and is suitable for during processing substrate 122 being applied the conductive overlayer of electrical bias or the structure or the assembly of conductive surface.For example shown in Fig. 4 B, contact assembly 250 can comprise the mat structure 350 with upper strata 352, it at the middle and upper levels 352 by electro-conductive material or electrically conductive composite (promptly, material monolithic distribution conductive compositions or have the upper surface of forming by electro-conductive material) make, for example have the polymeric matrix 354 of the electrically conductive particles 356 that is scattered in wherein or have fabric of conductive coating etc.Mat structure 350 can comprise one or more holes 210, electrolytic solution is delivered to the upper surface of pad assembly by it.Other examples of suitable contact assembly have been described among the U.S. Provisional Patent Application No.60/516680 (by reference it all being incorporated into this) that Hu equals to submit on November 3rd, 2003.
In one embodiment, each contact assembly 250 comprises hollow housing 302, joint 304, ball 306, contact member 314 and clamp sleeve 316.Ball 306 has conductive outer surface and places housing 302 movably.Ball 306 can be placed in the first location and the second position at least, stretching out on the planarized surface 126 of first location ball 306 wherein to small part, and second position ball 306 is concordant with planarized surface 126 basically.Ball 306 also can move to the below of planarized surface 126 fully.Ball 306 is suitable for substrate 122 is electrically connected with power supply 242 usually.Shown in Fig. 3 C, a plurality of balls 306 that are used for the bias voltage substrate can be placed in single housing 358.
Power supply 242 provides positive electrical bias to ball 306 during being provided at processing usually.At the interval of planarization substrate, power supply 242 can be alternatively applies negative bias so that process chemical minimizes the corrosion of ball 306 to ball 306.
Be provided with shell 302 be provided for making electrolytic solution during processing from the source 248 passages that flow to substrate 122.Housing 302 is to be made by the dielectric substance compatible with process chemical.The bearing 326 that forms in the housing 302 prevents that ball 306 from passing first end 308 of housing 302.Bearing 326 can comprise one or more grooves that form therein alternatively so that liquid from outflow housing 302 between ball 306 and the bearing 326.Keeping liquid flow to cross ball 306 can make the trend of process chemical corrosion ball 306 minimize.
Contact member 314 connects clamp sleeve 316 and joint 304.Contact member 314 is provided in usually on whole substantially or whole ball positions in the housing 302 and is electrically connected with joint 304 and ball 306.In one embodiment, contact member 314 can be configured to form of springs.
Shown in Fig. 4 A-E and the 5A-C and in the embodiment that describes in detail of Fig. 6, contact member 314 comprises the circular base 324 with a plurality of tabs 344 that stretch out from it in the annular array mode.Tabs 344 is usually by elasticity that is suitable for using with process chemical and electro-conductive material manufacturing.In one embodiment, tabs 344 is by gold-plated beryllium copper manufacturing.
Referring to Fig. 4 A and Fig. 5 A-B, clamp sleeve 316 comprises the flared end 424 with the threaded post 426 of extending from it.Clamp sleeve 316 can be made by dielectric medium or electro-conductive material or its combination, in one embodiment, and by making with housing 302 identical materials.Flared end 424 keeps the tabs 344 and the medullary ray of contact assembly 250 to acutangulate, so that the tabs 344 of contact member 314 spreads all over the surface of ball 306, thereby prevent that tabs 344 is in assembling during contact assembly 250 and crooked in the moving process of ball 306, bonding and/or damage.
Ball 306 can be solid or hollow, and usually by the electro-conductive material manufacturing.For example, ball 306 can be by metal, conductive polymers or the polymeric material manufacturing of filling with electro-conductive material, for example metal, conductive carbon or graphite and other electro-conductive materials.Perhaps, ball 306 can be by the core manufacturing of the solid or hollow of coated with conductive material.This core can be nonconducting, and to small part coated with conductive coating.
Ball 306 drives towards planarized surface 126 by spring, buoyancy or fluid force usually.In embodiment shown in Figure 5, during processing, the fluid that flows through the passage that is formed by joint 304 and clamp sleeve 316 and platform assembly 230 from electrolyte source 248 promotes ball 306, and it is contacted with substrate.
Fig. 7 is the sectional view of a kind of embodiment at the 2nd ECMP station 130.The first and the 3rd ECMP station 128,132 can be provided with in a similar manner.The 2nd ECMP station 130 generally includes the platform 602 that supports whole conduction processing pad assembly 604.Platform 602 can be configured to above-mentioned assembly 230 similar, thereby by processing pad assembly 604 conveying electrolytes, perhaps, platform 602 can have the liquid conveying arm (not shown) that is adjacent, and is used for electrolyte supply to the planarized surface of processing pad assembly 604.Platform assembly 602 comprises that at least one tolerance meter or transmitter 254 (as shown in Figure 3) are so that endpoint detection.
In one embodiment, processing pad assembly 604 comprises the slotting pad 612 that is clipped between conductive pad 610 and the electrode 614.Conductive pad 610 conducts electricity on its top finished surface basically, and usually (promptly by electro-conductive material or electrically conductive composite, the overall distribution conductive compositions or comprise the material of forming planarized surface) make, for example electrically conductive particles disperses polymeric matrix wherein or has the fabric etc. of conductive coating.Conductive pad 610, slotting pad 612 and electrode 614 can be made into removable single component.The normally permeable or porous of processing pad assembly 604 is so that electrolytic solution can flow through between electrode 614 and conductive pad 310.In embodiment shown in Figure 7, processing pad assembly 604 have hole 622 so that electrolytic solution from wherein flowing through.In one embodiment, conductive pad 610 is made up of the electro-conductive material on the polymeric matrix on the electro-conductive fiber, for example, covers the tin particulate in the polymeric matrix on the copper polymer fabric.Conductive pad 610 also can be used for the contact assembly 250 in the embodiment shown in Figure 3.
Can between conductive pad 610 and subpad 612, arrange conductive foil 616 in addition.Paillon foil 616 links to each other with power supply 242, and the equally distributed voltage that is applied on whole conductive pad 610 by power supply 242 is provided.In the embodiment that does not comprise conductive foil 616, conductive pad 610 can for example directly link to each other with power supply 242 by the terminal that is integrated on the pad 610.And pad assembly 604 can comprise inserts pad 618, provides physical strength with paillon foil 616 for the conductive pad 610 of top.Describe to some extent in the U.S. Patent application 10/455941 and 10/455895 that the example of suitable pad assembly is introduced in front.
Polishing composition and technology
In one aspect, but for example polishing composition of the metal of tungsten of planarization is provided.Usually, polishing composition comprise one or more plant acidic group electrolyte systems, contain organic salt first sequestrant, pH regulator agent and the solvent of about 2 to about 10 pH can be provided.Polishing composition also can comprise and has one or more second sequestrants that are selected from the functional group of amido, amide group and combination thereof.One or more are planted the acidic group electrolyte system and preferably comprise two kinds of acidic group electrolyte systems, for example, and sulfate electrolyte system and phosphate electrolyte system.The embodiment of polishing composition can be used for polishing main body and/or residual materials.Polishing composition can comprise one or more alternatively and plant corrosion inhibitor or polishing strongthener, for example abrasive particles.Although this paper composition described herein is the composition of oxygen-free agent, the present invention also can use oxygenant as the polishing strongthener, and it can use with abrasive substance.Can think, remove for example effective removal speed of the material of tungsten from substrate surface when polishing composition as herein described has improved ECMP, and reduced the planarization type flaw and obtained more slick substrate surface.The embodiment of composition can be used for single step or two step glossings.
Although polishing composition is specially adapted to remove tungsten, can think that polishing composition also can remove other materials, for example aluminium, platinum, copper, titanium, titanium nitride, tantalum, tantalum nitride, cobalt, gold and silver, ruthenium and combination thereof.For example, can be used to improve the removal speed of Flatness and these electro-conductive materials of raising by contacting the mechanical mill that forms and/or apply the anode dissolution that electrical bias causes with conductive pad 203 and/or abrasive.
The sulfate electrolyte system comprises for example having sulfate radical (SO 4 2-) (sulfuric acid (H for example 2SO 4)) and/or its salt derivative (comprise for example monoammonium sulfate (NH 4HSO 4), ammonium sulfate, vitriolate of tartar, sulfuric acid tungsten or its combination) electrolytic solution and compound, wherein sulfuric acid is preferred.Salt derivative can comprise ammonium (NH 4 +) salt, sodium (Na +) salt, tetramethyl-ammonium (Me 4N -) salt, potassium (K +) salt or its combination, or the like.
The phosphate electrolyte system comprises for example having sulfate radical (PO 4 3-) electrolytic solution and the compound of (for example phosphoric acid) and/or its salt derivative, wherein salt derivative comprises for example phosphoric acid salt (M xH (3-x)PO 4) (x=1,2,3) (wherein M comprises ammonium (NH 4 +), sodium (Na +), tetramethyl-ammonium (Me 4N +) or potassium (K +) or its combination), phosphoric acid tungsten, primary ammonium phosphate ((NH 4) H 2PO 4), Secondary ammonium phosphate ((NH 4) 2HPO 4) and combination, wherein phosphoric acid is preferred.Perhaps, available acetoxyl electrolytic solution (comprising acetate and/or its salt derivative) or salicyl electrolytic solution (comprising Whitfield's ointment and/or its salt derivative) substitute the phosphate electrolyte system.Acidic group electrolyte system as herein described also can cushion composition, thereby keeps required pH level for process substrate.The present invention also can use known and unknown traditional electrolytic solution to form composition as herein described by technology as herein described.
Sulfate electrolyte system and phosphate electrolyte system can comprise about 0.1 to about 30 the weight percent (wt%) or the total composition solution of volume percent (vol%) respectively, thereby provide suitable electroconductibility for implementing technology as herein described.The concentration of used acid electrolyte is extremely about 5vol% of about 0.2vol% in the composition, and for example about 0.5vol% is to about 3vol%, and for example about 1vol% is to about 3vol%.The content of acid electrolyte in different polishing compositions can change.For example, in first composition, acid electrolyte can comprise about 1.5vol% to the sulfuric acid of about 3vol% and 2vol% extremely the phosphoric acid of about 3vol% be used to remove base metal, and in second composition, acid electrolyte can comprise about 1vol% to the sulfuric acid of about 2vol% and 1.5vol% extremely the phosphoric acid of about 2vol% be used to remove residual metal.The present invention comprises that also institute's sulfur acid and/or phosphoric acid concentration are less than second composition of first composition
Embodiment.
One aspect of the present invention or part are to plant sequestrant with one or more to combine with substrate surface to strengthen the electrochemistry dissolving agent process.In any embodiment as herein described, sequestrant can with the electro-conductive material ion for example tungsten ion combine, and improve the removal speed of metallic substance and/or improve polishing performance.Sequestrant also can be used to cushion polishing composition, thereby keeps required pH level for process substrate.
The sequestrant that one class is suitable comprises inorganic or organic acid salt.May other suitable inorganic acid salts be the salt of compound with functional group of one or more mixtures that are selected from carboxylate radical, dicarboxylic acid radical, tricarboxylic acid group, hydroxyl and carboxylate radical and combination thereof.With functional groups before, during or afterwards, metallic substance to be removed (for example tungsten) can be in any oxidation state.Functional group can be during processing combines with the metallic substance that forms on the substrate surface, and removes this metallic substance from substrate surface.
The example of suitable inorganic or organic acid salt comprises organic acid ammonium salt and sylvite, for example ammonium oxalate, ammonium citrate, Succinic acid ammonium salt, monobasic Tripotassium Citrate, binary Tripotassium Citrate, ternary Tripotassium Citrate, soluble tartrate, ammonium tartrate, potassium succinate, potassium oxalate, and combination.The example of suitable acid that is used to form the salt of the sequestrant with one or more carboxylate radicals comprises citric acid, tartrate, succsinic acid, oxalic acid, acetate, hexanodioic acid, butyric acid, capric acid, caproic acid, sad, pentanedioic acid, oxyacetic acid, formic acid, fumaric acid, lactic acid, lauric acid, oxysuccinic acid, toxilic acid, propanedioic acid, tetradecanoic acid, palm (plamitic) acid, phthalandione, propionic acid, pyruvic acid, stearic acid, valeric acid, and combination.
Polishing composition can comprise one or more and plant inorganic or organic salt, its concentration be composition volume or weight about 0.1% to about 15%, for example, about 0.2% to about 5% (volume or weight), for example about 1% to about 3% (volume or weight).For example, in polishing composition, can use about 0.5% ammonium citrate to about 2% (weight).
Perhaps, can use in the composition and have one or more second sequestrants that are selected from the functional group of amido, amide group, hydroxyl and combination thereof.Preferred functional group is selected from the group of being made up of amido, amide group, hydroxyl and combination thereof, and does not have for example acidic functionality of carboxylate radical, dicarboxylic acid radical, tricarboxylic acid group and combination thereof.Polishing composition can comprise one or more kinds and have one or more sequestrants that are selected from the functional group of amido, amide group, hydroxyl and combination thereof, its concentration is about 0.1% to about 5% (volume or weight), preferred about 1% to about 3% (volume or weight), for example about 2% (volume or weight).For example, available about 2vol% to the quadrol of about 3vol% as sequestrant.Other examples of suitable sequestrant comprise the compound with one or more amine or amide functional group, for example quadrol and derivative thereof (comprising diethylenetriamine), hexanediamine, amino acid, ethylenediamine tetraacetic acid (EDTA), methylformamide, or its combination.
Solution can comprise one or more and plant pH regulator agent to obtain about 2 to about 10 pH.In different compound methods, the amount of pH regulator agent can change and change along with other component concentrations, yet in general, contained one or more of complete soln are planted the pH regulator agent up to about 70wt%, but preferably about 0.2wt% is to about 25wt%.Under given concentration, different compounds can provide different pH levels, for example, composition can comprise about 0.1wt% to the alkali of about 10wt% (for example potassium hydroxide, sodium hydroxide, ammonium hydroxide, Tetramethylammonium hydroxide (TMAH) or its make up) so that required pH level to be provided.One or more plant the pH regulator agent can be selected from a class organic acid, for example component (comprising phosphoric acid, ammonium phosphate, potassiumphosphate and combination thereof) of carboxylic acid (for example acetate, citric acid, oxalic acid), phosphorous acid group, or its combination.Also can use the mineral acid that comprises hydrochloric acid, sulfuric acid and phosphoric acid in the polishing composition.
Usually, the amount of pH regulator agent can depend on the required pH scope that is used for the different components of forming of having of various glossings and changes in the polishing composition.For example, in main body tungsten glossing, the amount that can regulate the pH regulator agent is to provide about 6 to about 10 pH.In one embodiment, main body tungsten is removed composition and is had about 7 to about 9 neutrality or alkaline pH, and for example, pH is greater than 7 and be less than or equal to the basic solution of 9 (for example about 8 to about 9).
In residual tungsten glossing Ah embodiment, the amount that can regulate the pH regulator agent is to provide about 2 to about 8 pH level.In one embodiment, residual tungsten is removed composition and is had about 6 to about 7 neutrality or acid pH, for example, has greater than 6 and less than the acid pH of 7 (for example about 6.4 to about 6.8).
Composition as herein described can comprise about 1vol% to the sulfuric acid of about 5vol%, about 1vol% to the phosphoric acid of about 5vol%, about 1wt% to the ammonium citrate of about 5wt%, about 0.5wt% extremely about 5wt% quadrol, pH regulator agent and the deionized water of about 6 to about 10 pH can be provided, for example comprise about 1vol% extremely about 3vol% sulfuric acid, about 1vol% extremely about 3vol% phosphoric acid, about 1wt% extremely about 3wt% ammonium citrate, about 1wt% extremely about 3wt% quadrol, potassium hydroxide and the deionized water of about 7 to about 9 pH can be provided.The another kind of embodiment of composition can comprise about 0.2vol% to the sulfuric acid of about 5vol%, about 0.2vol% extremely about 5vol% phosphoric acid, about 0.1wt% extremely about 5wt% ammonium citrate, about 2 to the pH of about 8 (for example about 3 to about 8) pH regulator agent and deionized water can be provided.The another kind of embodiment of composition can comprise about 0.5vol% to the sulfuric acid of about 2vol%, about 0.5vol% extremely about 2vol% phosphoric acid, about 0.5wt% extremely about 2wt% ammonium citrate, potassium hydroxide and the deionized water of about 6 to about 7 pH can be provided.
In any embodiment as herein described, polishing composition as herein described is preferably the composition of oxygen-free agent, for example, and the composition of oxygen-free agent and oxygenizement agent.The example of oxygenant and oxygenizement agent includes but not limited to, hydrogen peroxide, ammonium persulphate, Potassium Iodate, potassium permanganate and cerium compound comprise cerous nitrate, cerium ammonium nitrate, bromate, oxymuriate, chromic salt, acid iodide, or the like.
Perhaps, polishing composition can comprise oxidant compound.The example of suitable oxidant compound except above listed can also be nitrate compound, comprise iron nitrate, nitric acid and saltpetre.In the another kind of embodiment of composition as herein described, available nitroxyl electrolyte system replaces sulfate electrolytic solution, and wherein the nitroxyl electrolyte system for example is to have nitrate radical (NO 3 1-) electrolytic solution and compound, nitric acid (HNO for example 3) and/or its salt derivative (comprise iron nitrate (Fe (NO 3) 3).
In any embodiment as herein described, (for example can add the etching inhibitor, corrosion inhibitor), reduce the oxidation or the corrosion of metallic surface by chemistry or electrical way, for example by forming material layer so that substrate surface minimize with the chemical interaction of electrolytic solution on every side.The electrochemistry that the material layer that forms by inhibitor can suppress or reduce on the substrate surface flows, thus restriction electrochemical deposition and/or dissolving.
The etching inhibitor of tungsten has suppressed solid-state tungsten and has changed into the soluble tungsten compound, and makes composition tungsten be changed into the softish oxide film that can evenly be removed by wearing and tearing simultaneously.The suitable etching inhibitor that is used for tungsten comprises the compound with nitrogenous functional group, for example nitrogen heterocyclic ring, alkyl phosphate ion, aminoalkyl group, amino acid.The etching inhibitor comprises corrosion inhibitor, for example the compound of nitrogen heterocyclic ring functional group, for example 2,2-ethyl-3, quinoxaline, acetyl pyrrole, pyridazine, Histidine, pyrazine, benzoglyoxaline and composition thereof.
Term used herein " alkyl phosphate ion " is meant to have the nitrogenous compound that can generate the functional group of alkyl phosphate ion in the aqueous solution.The level of the alkyl phosphate ion that generates in the aqueous solution that comprises the compound with nitrogen-containing functional group is the function of pH value of solution and selected one or more compounds.Corrosion inhibitor with nitrogen-containing functional group can generate the alkyl phosphate ion functional group of amount of suppression at pH in less than 9.0 the aqueous solution, the example of this corrosion inhibitor comprises, isostearylethylimididonium, cetyltrimethylammonium hydroxide, alkaterge E (2-17 thiazolinyls-4-ethyl-2-azoles quinoline-4-methyl alcohol), aliquat 336 (tri-n-octyl methyl ammonium chloride), nuospet 101 (4, the 4-dimethyl oxazolidine), TBAH, lauryl amine, Tetramethylammonium hydroxide, its derivative and composition thereof.
Available aminoalkyl corrosion inhibitor comprises for example aminopropyl silanol, aminopropyl siloxanes, lauryl amine and composition thereof, and synthetic and natural amino acid comprises for example Methionin, tyrosine, glutamine, L-glutamic acid, glycine, Gelucystine and glycine.
The etching inhibitor that contains alkyl phosphate ion functional group that preferably is used for tungsten is OSI Specialties, the SILQUEST A-1106 silane that Inc. makes.The mixture that SILQUEST A-1106 silane is made up of the aminopropyl silanol of the aminopropyl siloxanes of the water of about 60wt%, about 30wt% and about 10wt%.Aminopropyl siloxanes and each leisure of aminopropyl silanol form the corresponding alkyl phosphate ion of amount of suppression down less than about 7 pH.Most preferred aminoalkyl corrosion inhibitor is glycine (Padil).
The example of the suitable etching inhibitor that is used for tungsten comprises halogen derivative (for example Trimethyllaurylammonium bromide), imines (for example polymine), carboxylic acid derivative (for example lime acetate), silicoorganic compound (for example two (sulfydryl propyl group) dimethoxy silane) and the polyacrylic ester (for example polymethacrylate) of alkyl phosphate ion.
The amount of the etching inhibitor that is used for tungsten that exists in the composition of the present invention should be about 0.001w% to about 2.0wt%, and preferably about 0.005w% is to about 1.0wt%, and most preferably from about 0.01w% is to about 0.10wt%.
The etching inhibitor that is used for tungsten is effective at pH up to about 9.0 composition.The pH of composition of the present invention is preferably less than about 7, most preferably less than about 6.5.
Other inhibitor can comprise about 0.001wt% to about 5.0wt% by an organic compound that forms with a plurality of azoles bases (azole group).General preferable range is between about 0.2wt% and about 0.4wt%.Example with organic compound of azoles base comprises benzotriazole, sulfydryl benzotriazole, 5-methyl-benzotriazole and combination thereof.Other suitable corrosion inhibitors are included as the membrane-forming agent of ring compound, for example imidazoles, benzoglyoxaline, triazole and combination thereof.Derivative with benzotriazole, imidazoles, benzoglyoxaline and triazole of hydroxyl, amino, imino-, carboxyl, sulfydryl, nitro and alkyl substituent also can be used as corrosion inhibitor.Other corrosion inhibitors comprise urea and thiocarbamide etc.
Perhaps, polymerization retarder, nonrestrictive for example polyoxyethylene alkyl aryl base ether phosphate or nonyl phenol ethoxyquin ammonium sulfate can be used to substitute and contain the corrosion inhibitor of azoles or therewith use, its consumption be composition volume or weight about 0.002% and about 1.0% between.
Although above-mentioned polishing composition oxygen-free agent (non-oxidation agent) and/or abrasive particles (abrasive-free), but polishing composition can comprise one or more plants surface finish strongthener and/or the speed of removal strongthener, these materials can comprise abrasive particles, one or more plant oxygenant, and combination.Can use one or more to plant tensio-active agent in the polishing composition accelerates the dissolving of material (for example by product that generates during metal and metal ion or the processing) or improves the possibility of abrasive particles caking in solubleness, the reduction polishing composition, the decomposition that improves chemical stability and reduce the polishing composition component.Suitable oxygenant and abrasive are described in the pending trial U.S. Patent application No.10/378097 that submitted on February 26th, 2004 to some extent, and by reference that it is consistent with claim of the present invention and disclosure part is incorporated into this.
Perhaps, polishing composition also can comprise inhibitor, toughener, levelling agent, brightening agent, stablizer and stripping agent, to improve the validity of polishing composition in the polished substrate surface.For example, some additive can reduce the ionization speed of atoms metal, thereby suppresses dissolution process, and other additives can provide bright and clean, bright substrate surface.The concentration of the additive that exists in the polishing composition can be up to about 15% (weight or meausurement), and can change based on desired polish results.
The example of other additives more fully is described among the U.S. Patent application No.10/141459 that submitted on May 7th, 2002 in the polishing composition, and by reference that it is consistent with claim of the present invention and disclosure part is contained in this.
In shortage or surplus in the above-mentioned polishing composition is a solvent, for example polar solvent (comprising water), preferably deionized water.Other solvents can comprise for example organic solvent (for example alcohol or glycol), can use with water in some embodiments.The amount of useable solvents is come various component concentrations in the control combination thing.For example, electrolytic solution can be concentrated into 3 times of concentration as herein described, before using on the processing station as herein described, with solvent spissated electrolytic solution is diluted then.
Usually, ECMP solution has much larger than the electroconductibility of traditional C MP solution.The specific conductivity of ECMP solution is about 10 milli siemenss (mS) or bigger, and the specific conductivity of traditional C MP solution is about 3mS to about 5mS.The speed that the electroconductibility remarkably influenced ECMP technology of ECMP solution is carried out, ie in solution electroconductibility is strong more, and material removal rate is fast more.For removing material of main part, the specific conductivity of ECMP solution is about 10mS or bigger, preferably at about 40mS to the scope of about 80mS, for example, about 50mS is about 70mS extremely, for example about 60mS is about 64mS extremely.For residual materials, the specific conductivity of ECMP solution is about 10mS or bigger, preferably at about 30mS to the scope of about 60mS, for example, about 40mS is about 55mS extremely, for example about 49mS.
Find that the substrate smooth finish that has improvement with the substrate of composition processing as herein described (comprises the surface imperfection (as pit) of minimizing, the erosion that reduces (removing the dielectric substance of metallicity structure periphery) and the Flatness that scratches and improve.Can further specify composition as herein described by following embodiment.
Electrochemical machinery processing
The electrochemical mechanical polishing technology of utilizing chemically reactive, mechanical activity and electroactive combination to remove tungsten material and planarization substrate surface can followingly be carried out.The tungsten material comprises tungsten, tungsten nitride, tungsten silicon nitride etc.Although following technology is described at tungsten, the present invention can also remove other materials except removing tungsten, comprise aluminium, platinum, titanium, titanium nitride, tantalum, tantalum nitride, brill, gold and silver, ruthenium and combination thereof.
Can carry out the removal of excess tungsten in one and a plurality of procedure of processings, for example, single tungsten removes step or main body tungsten is removed step and residual tungsten removal step.Material of main part this by generalized definition be deposited on the substrate, it measures greater than any material that is enough to fully be filled in the feature structure that forms on the substrate surface.Residual materials is any material remaining after one or more main bodys or remaining glossing step by generalized definition.Usually, main body remove during an ECMP technology, removed conductive layer at least about 50%, preferably at least about 70%, more preferably at least about 80%, for example at least about 90%.The remaining removal removed if not all during the 2nd ECMP technology, also is most remaining electro-conductive material on the blocking layer, with the plug (plug) that stays filling.
Main body is removed ECMP technology and can be carried out on first polishing block, remaining remove ECMP technology can with first second identical or different polishing block on carry out.In another embodiment, the remaining ECMP technology of removing can be carried out on first platform that carries out main body removal technology.Can on other independent platform, remove blocking material, in the device for example shown in Figure 2 the 3rd.For example, said apparatus according to technology described here can comprise three platforms of removing the tungsten material, for example remove first of material of main part, remove second of residual materials and remove the 3rd of blocking material, wherein main body removal and remaining the removal are ECMP technology, stop that removing is CMP technology or another ECMP technology.In another embodiment, use three ECMP platforms to remove material of main part, residual materials and blocking material.
Fig. 8 A-8D is the diagrammatic cross-section of the glossing that carries out according to a kind of embodiment of planarization substrate surface described here on substrate.Shown in Fig. 8 A, an ECMP technology can be used to remove main body tungsten material from substrate surface, shown in Fig. 8 B-8C, removes the residual tungsten material with the 2nd ECMP technology then.Fig. 8 D shows the subsequent technique that is used to produce structure, for example stops to remove and buffering.It is fast that the one ECMP technology is removed the speed of tungsten layer, and the 2nd ECMP arts demand is accurately removed remaining tungsten material, forms smooth substrate surface and make the pit of surface features and corrode minimizing or minimum.
Fig. 8 A is a kind of diagrammatic cross-section of embodiment that is used to remove the first electrochemical mechanical polishing technology of main body tungsten material.Substrate is placed in susceptor, for example contains the basin or the platform of first electrode.Substrate 800 has the dielectric layer 810 with narrow feature structure 820 and quant's sign structure 830 patternings.Has blocking material 840 (for example, titanium and/or titanium nitride) on feature structure 820 and the feature structure 830, afterwards filled conductive material 860 (for example, tungsten).The depositional texture of excess material comprises the high overload 870 (being also referred to as slope or peak) that is formed on the narrow feature structure 820 and is formed on minimum overload 880 (being also referred to as paddy) on the quant's sign structure 830.
Provide polishing composition 850 as herein described to substrate surface.Can polishing composition be provided to substrate surface with the flow velocity of about 100 to about 400mL/min (for example about 300mL/min).Be used for main body remove the example of the polishing composition of step comprise about 1vol% to the sulfuric acid of about 5vol%, about 1vol% extremely about 5vol% phosphoric acid, about 1wt% extremely about 5wt% ammonium citrate, about 0.5wt% extremely about 5wt% quadrol, pH regulator agent and the deionized water of about 6 to about 10 pH can be provided.Another example of polishing composition comprise the ammonium citrate of the phosphoric acid of the sulfuric acid of about 2vol%, about 2vol%, about 2wt%, about 2wt% quadrol, potassium hydroxide and the deionized water of about 8.4 to about 8.9 pH can be provided.The specific conductivity of composition be about 60 to about 64 the milli siemenss (mS).The alkaline pH that main body polishing composition as herein described has the strong etching reagent of vitriolic for example and more can dissolve tungsten is so that removal speed is greater than remaining polishing composition as herein described.
Then, the polished part that links to each other with the polished part assembly that contains second electrode contacts and/or is electrically connected with substrate physics by conductive polishing spare.Substrate surface and polished part are less than about 2 pounds of/square inch (lb/in 2Or psi) contact down of pressure (13.8kPa).The operation pressure that carries out the removal of electro-conductive material 860 can be at about 1psi (6.9kPa) or lower, for example about 0.01psi (69Pa) is to about 1psi (6.9kPa), for example about 0.1psi (0.7kPa) extremely about 0.8psi (5.5kPa) or about 0.1psi (0.7kPa) extremely less than about 0.5psi (3.4kPa).In the one side of this technology, use about 0.3psi (2.1kPa) or lower pressure.
Here used polish pressure has reduced deleterious shearing force of the substrate that contains low k dielectric and frictional force or has made it reach minimum.Be reduced or minimized power can reduce or minimize because the defective of the distortion that causes of polishing and feature structure forms.Find that in addition lower shearing force and frictional force reduce or minimized the formation of the pattern defective (for example pit of the erosion of dielectric substance and electro-conductive material material) during polishing and reduced leafing.Contact between substrate and the conductive polishing spare also makes by it being connected with power supply when the polished part contact substrate that formation electrically contacts between power supply and the substrate.
Between substrate surface and conductive pad assembly 222, provide relative movement.Rotate the conductive pad assembly 222 that is positioned on the platform with about 7rpm to the platform speed of rotation of about 50rpm (for example, about 28rpm), be arranged in the substrate of bracket head with about 7rpm to the bracket head speed of rotation rotation of about 70rpm (for example, about 37rpm).When polished part contacted with substrate, the rotation of platform and bracket head had reduced shearing force and frictional force respectively.Bracket head speed of rotation and platform speed of rotation all can be about 7rpm extremely approximately less than 40rpm.In one aspect of the invention, can carry out the technology of this paper under greater than the condition of platform speed of rotation to remove the tungsten material in the bracket head speed of rotation, the ratio of bracket head speed of rotation and platform speed of rotation was greater than about 1: 1, for example the bracket head speed of rotation is about 1.5: 1 to 12: 1 with the ratio of platform speed of rotation, for example about 1.5: 1 to 3: 1.
Between two electrodes, apply bias voltage by power supply 224.Bias voltage can reach substrate 208 from the electrode conductive pad and/or the polished part assembly 222.This process also can be carried out to about 60 ℃ temperature at about 20 ℃.
Usually at the highest about 100mA/cm 2Current density under provide bias voltage (being about 40 amperes) with the processing diameter substrate of the most about 300mm corresponding to the electric current that applies.For example, the substrate of diameter 200mm can have about 0.01mA/cm 2To about 50mA/cm 2Current density, this is about 0.01A about 20A extremely corresponding to the electric current that is applied.The present invention also can apply and monitor bias voltage in the mode of volt, ampere and watt.For example, in one embodiment, the power that power supply applies is that about 0W to 100W, voltage are extremely about 10V of about 0V, and electric current is that about 0.01A is between about 10A.In one embodiment, when being applied to main body polishing composition as herein described on the substrate, apply the voltage of about 2.5V to about 4.5V (for example about 3V).Substrate is exposed to the tungsten that polishing composition and the power enough main bodys of time in applying are removed overload on it usually.
According to the customer need of removing material from substrate surface, can change the power of bias voltage and apply.For example, observed and increased the increase that the power apply causes anode dissolution.Bias voltage also can apply by the electricimpulse modulation technique.Pulse modulation technique can change, but generally includes following circulation: apply constant current density or voltage in first period, do not apply current density or voltage or apply constant reverse current density or voltage in second period then.Repeat the one or more circulations of this process then, these circulations can have different power levels and time length.Power level, time length (" connection " circulation) and inactivity (" disconnections " circulates) and round-robin frequency can be adjusted based on the degree of removal speed, material to be removed and glossing.For example, observe the increase power level and increased the time length that applies power, can increase anode dissolution.
In a pulsed modulation process of electrochemical mechanical polishing, the pulsed modulation process comprise power apply the phase " connection " afterwards then inactivity apply the on/off power technology of phase " disconnection ".The on/off circulation can repeat one or many in glossing." connection " phase makes the electro-conductive material of exposure be removed from substrate surface, " disconnection " phase make the by product (as metal ion) of polishing composition component and " connection " phase diffuse to the surface and with the electro-conductive material complexing.In the pulse modulation technique process, metal ion is considered to move and interact with corrosion inhibitor and/or sequestrant by attaching to the passivation layer that is not subjected to the mechanical disturbance zone.Therefore, this process makes in " connection " phase and is not passivated the electrochemical active regions that layer covers and obtains etching, passivation layer is shaped again in some zone and removes other regional excess material in " disconnection " phase of pulse modulation technique then.Thereby the setting pulse modulation technique can be controlled speed and the amount of removing material from substrate surface.
Each " connection "/" disconnection " phase can be between about 1 second and about 60 seconds, for example between about 2 seconds and about 25 seconds, and it is considered herein that and uses " connection " and " disconnection " phase of pulsed technique can be longer or shorter than period described here.In an embodiment of pulse modulation technique, the anode dissolution power that applies is between each round-robin about 16% and about 66%.
The non-limitative example that on/off round-robin pulse modulation technique is arranged that is used for the electrochemical mechanical polishing material described here comprises: applied power (" connection ") about 5 seconds to about 10 seconds, do not apply power (" disconnection ") then about 2 seconds to about 25 seconds; Apply about 10 seconds of power and do not apply power 5 seconds, or apply power 10 seconds and do not apply power 2 seconds, or apply power 5 seconds and do not apply power 25 seconds, so that desired polish results to be provided.To each selected process, repeat this circulation on demand.An example of pulsed modulation process is described in the U.S. Patent No. 6379223 of common transfer, by reference wherein consistent with claim of the present invention and disclosure part is contained in this.The other example of pulsed modulation process is described among the pending trial U.S. Provisional Patent Application No.10/611805 that is entitled as " Effective Method To Improve Surface Finish In Electrochemically AssistedChemical Mechanical Polishing " that submitted on June 30th, 2003, by reference wherein consistent with claim of the present invention and disclosure part is contained in this.
Can realize removing speed by method described here up to the electro-conductive material of about 15000 /min.Usually, high removal speed is desired, but owing to will make process consistency reach maximum and other processing parameters (for example, the reaction kinetics of anode and negative electrode), generally dissolution rate is controlled at about 100 /min to about 15000 /min.In one embodiment of the invention, under the situation of main body tungsten material thickness less than 5000  to be removed, can apply voltage (or electric current) so that about 100 /min to be provided the removal speed to about 5000 /min, for example about 2000 /min is to about 5000 /min.The removal speed of residual materials is less than the removal speed of material of main part, by technology described here, can remove residual materials to the speed of about 1500 /min with about 400 /min.
The 2nd ECMP process speed is more slowly to prevent that excess metal from remove forming the pattern defective, for example being called shown in Figure 1A the cave in pit of D or the erosion E shown in recess and Figure 1B.Therefore, most conductive layer 860 is removed during an ECMP technology with fast speeds, and its speed is greater than residue or the remaining removal speed of conductive layer 860 during the 2nd ECMP technology.Two step ECMP technologies have improved total treatment capacity of process substrate, and have obtained zero defect or defective smooth surface seldom simultaneously.
Fig. 8 B shows after the main body of an ECMP technology is removed, the 2nd ECMP polishing step after the electro-conductive material 860 of (for example 90%) is removed at least about 50%.After an ECMP technology, electro-conductive material 860 still may comprise high overload 870 (peak) and/or minimum overload 880 (paddy), but its dimension scale reduces.Yet electro-conductive material 860 also may quite smooth (not shown) on the entire substrate surface.
Provide second polishing composition that residual materials is removed that is used for as herein described to substrate surface.Can polishing composition be provided to substrate surface with the flow velocity of about 100 to about 400mL/min (for example about 300mL/min).Be used for the remaining example of removing the polishing composition of step comprise about 0.2vol% to the sulfuric acid of about 5vol%, about 0.2vol% extremely about 5vol% phosphoric acid, about 0.1wt% extremely about 5wt% ammonium citrate, about 0.5wt% extremely about 5wt% quadrol, pH regulator agent and the deionized water of about 3 to about 8 pH can be provided, for example comprise the phosphoric acid of the sulfuric acid of about 1vol%, about 1.5vol%, about 0.5wt% ammonium citrate, potassium hydroxide and the deionized water of about 6.4 to about 6.8 pH can be provided.The remaining specific conductivity of removing composition is about 49 milli siemenss (mS).
Remaining polishing composition described here is considered to form poly-tungsten layer (polytungsten) 890 on the tungsten material surface that exposes.Poly-tungsten layer is to form by the chemical interaction between the tungsten material of ammonium citrate and phosphoric acid and exposure.Poly-tungsten layer is more stable than tungsten material, and removal speed is less than the tungsten material.Poly-tungsten layer also can be isolated and/or electrical isolation with the materials chemistry on the substrate surface.Think that also the acid pH that increases polishing composition can promote poly-tungsten material to form on substrate surface.Remove composition with the main body that has more alkalescence and compare, use to have more the remaining polishing composition of tart.Under the processing condition and polishing composition of described main body glossing, also may form poly-tungsten layer.
The thickness and the density of poly-tungsten layer can be indicated chemical reaction degree and/or anode dissolution amount.For example, find that compare with passivation layer thin and that density is less, thicker or closeer poly-tungsten layer makes anode dissolution less.With this, by pH, phosphoric acid and/or the sequestrant of control combination thing, may command is removed the removal speed and the removal amount of material from substrate surface.Compare the removal speed that reduces has reduced or has minimized the formation of the pattern defective (for example pit of the erosion of dielectric substance and electro-conductive material material) during the polishing and reduced leafing with the main body polishing composition.
Above-mentioned remaining mechanical mill of removing in the technology is less than about 2 pounds of/square inch (lb/in 2Or psi) carries out under polishing pad (13.8kPa) and the pressure between the substrate.The operation pressure of removing electro-conductive material 860 can be at about 1psi (6.9kPa) or lower, and for example about 0.01psi (69Pa) is to about 1psi (6.9kPa), and for example about 0.1psi (0.7kPa) is to about 0.8psi (5.5kPa).In the one side of this technology, use about 0.3psi (2.1kPa) or lower pressure.Contact between substrate and the conductive polishing spare also makes by it being connected with power supply when the polished part contact substrate that formation electrically contacts between power supply and the substrate.
Between substrate surface and conductive pad assembly 222, provide relative movement.Rotate the conductive pad assembly 222 that is positioned on the platform with about 7rpm to the speed of rotation of about 50rpm (for example, about 28rpm), be arranged in the substrate of bracket head with about 7rpm to the speed of rotation rotation of about 70rpm (for example, about 37rpm).When polished part contacted with substrate, the speed of rotation of platform and bracket head had reduced shearing force and frictional force respectively.
Removed the poly-tungsten layer 890 of isolating or suppress anodic dissolution current by the mechanical mill of conductive polishing spare, so that compare with minimum overload region, the high overload district preferentially is removed, and contact minimum or discontiguous zone with conductive pad assembly 222 because poly-tungsten layer 890 is retained in.The removal speed of the electro-conductive material 860 that is covered by poly-tungsten layer 890 is less than the removal speed of the electro-conductive material that does not have poly-tungsten layer 890.Equally, the removal speed of the excess material on narrow feature structure 820 and area 850 is greater than the removal speed of the excess material of still being gathered tungsten layer 890 coverings on quant's sign structure 830.
Between two electrodes, apply bias voltage by power supply 224.Bias voltage can reach substrate 208 from the electrode conductive pad and/or the polished part assembly 222.Apply bias voltage in above-mentioned mode at the main body glossing, the power level that this bias voltage adopts usually is less than or equal to the power level of main body glossing.For example, remove technology for remnants, the voltage that power applies is that about 1.8V is to about 2.5V, for example 2V.Substrate is exposed to polishing composition and the power time in applying usually and enough removes at least a portion or all of the material of the desired removal on it.This process also can be carried out to about 60 ℃ temperature at about 20 ℃.
Referring to Fig. 8 C, remove most of (if not all) conductive layer 860 to expose blocking layer 840 and conductive trench 865 by second (remnants) ECMP technology that comprises the 2nd ECMP polishing composition as herein described.Conductive trench 865 is formed by remaining electro-conductive material 860.Can polish the smooth substrate surface that contains conductive trench 875 to provide to electro-conductive material and the barrier material of any remnants by the 3rd polishing step then, shown in Fig. 8 D.The 3rd glossing can be the 3rd ECMP technology or CMP technology.The example of blocking material glossing is disclosed among the U.S. Patent application No.10/193810 (U.S. Patent Publication No. 20030013306) that is entitled as " Dual Reduced Agents For Barrier Removal In ChemicalMechanical Polishing " that submitted on July 11st, 2002, and by reference that it is consistent with claim of the present invention and disclosure part is contained in this.Another example of blocking material glossing is disclosed among the U.S. Patent application No.60/572183 that submitted on May 17th, 2004, and by reference that it is consistent with claim of the present invention and disclosure part is contained in this.
After electro-conductive material and blocking material removal procedure of processing, (buff) substrate of can polishing is so that surface imperfection is minimum.Polishing can be carried out under for example about 2psi or littler low polish pressure with soft polished part, this soft polished part is positioned under the Shore D hardness standard that the American Society forTesting and Materials (ASTM) of philadelphia, pa describes and measure in general headquarters, and its hardness is about 40 or lower.
Alternatively, can behind each glossing, apply cleaning liquor, thereby remove particulate matter and waste material, and make the defective that forms on the sedimentary metal residues and substrate surface on the polished part minimum from glossing to substrate.The example of suitable cleaning liquor is can be from the Applied Materials of Santa Clara, California, the ELECTRA CLEAN that Inc. buys TM
At last, can polish the back cleaning procedure to substrate, to reduce formed defective during polishing or substrate processing.Such technology can make oxidation or other defective do not expected in the copper feature structure that forms on the substrate surface reach minimum.The example of this polishing back cleaning procedure is that application can be from the Applied Materials of Santa Clara, California, the ELECTRA CLEAN that Inc. buys TM
Observe, the substrate that is flattened by method described here has presented the pattern defective (for example pit and erosion) of minimizing, resistates, the Flatness of raising and the substrate smooth finish of raising that reduces.
Provide the example of following indefiniteness for further describing embodiments of the present invention.Yet these examples and not exclusively also non-ly are intended to limit the scope of the invention.
Polishing composition embodiment
Below be provided for polishing the example of the polishing composition of main body tungsten material and residual tungsten material.Main body tungsten polishing composition can comprise:
Example #1
The sulfuric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.4 to about 8.9 pH can be provided; With
Deionized water.
Example #2
The sulfuric acid of about 4vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #3
The sulfuric acid of about 1.5vol%;
The phosphoric acid of about 2.5vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #4
The sulfuric acid of about 1vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #5
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.4 to about 8.9 pH can be provided; With
Deionized water.
Example #6
The sulfuric acid of about 2vol%;
The Whitfield's ointment of about 2vol%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #7
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The potassium hydroxide of about 8.7 pH can be provided; With
Deionized water.
Example #8
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.7 pH can be provided; With
Deionized water.
Example #9
The sulfuric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #10
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #11
The phosphoric acid of about 4vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #12
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.4 to about 8.9 pH can be provided; With
Deionized water.
Example #13
The nitric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.4 to about 8.9 pH can be provided; With
Deionized water.
Example #14
The nitric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.5 pH can be provided; With
Deionized water.
Example #15
The nitric acid of about 4vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
Example #16
The sulfuric acid of about 1.5vol%;
The phosphoric acid of about 2.5vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.5 pH can be provided; With
Deionized water.
The residual tungsten polishing composition can comprise:
Example #1
The sulfuric acid of about 1vol%;
The ammonium citrate of about 1wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
Example #2
The sulfuric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The ammonium citrate of about 0.5wt%;
Can provide greater than 6 and less than the potassium hydroxide of 7 pH; With
Deionized water.
Example #3
The phosphoric acid of about 4vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
Example #4
The sulfuric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The Whitfield's ointment of about 1wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
Example #5
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 0.5wt%;
Can provide greater than 6 and less than the potassium hydroxide of 7 pH; With
Deionized water.
Example #6
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
Example #7
The sulfuric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.4 to about 6.8 pH can be provided; With
Deionized water.
Example #8
The nitric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.4 to about 6.8 pH can be provided; With
Deionized water.
Example #9
The nitric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 0.5wt%;
Can provide about 6 to potassium hydroxide less than 7 pH; With
Deionized water.
Example #10
The sulfuric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.5 pH can be provided; With
Deionized water.
Glossing embodiment
Example 1
At the Applied Materials from Santa Clara, California, the REFLEXION that Inc. buys In the improvement unit in the system, be that the plating tungsten substrate of 300mm polishes and planarization to diameter with following polishing composition.The substrate of about 4000  of surperficial tungsten layer thickness is placed in the device on the bracket head, and this device has first that arranges first polished part on it.Speed with about 250mL/min is supplied to first polishing composition on this platform, and first polishing composition comprises:
About 2vol% is to the sulfuric acid of about 3vol%;
About 2vol% is to the phosphoric acid of about 4vol%;
About 2wt% is to the ammonium citrate of about 2.8wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
In this technology, substrate contacts with first contact pressure of first polished part with about 0.3psi, and first speed of rotation is about 20rpm, and the speed of rotation of first bracket head is about 39rpm, and first bias voltage that applies is about 2.9 volts.Substrate is polished and checks.Tungsten layer thickness reduces to about 1000 .
Substrate-transfer is had on second platform of second polished part on it.Speed with about 300mL/min is supplied to second polishing composition on this platform, and second polishing composition comprises:
About 1vol% is to the sulfuric acid of about 2vol%;
About 1.5vol% is to the phosphoric acid of about 2.5vol%;
The ammonium citrate of about 0.5wt%;
The quadrol of about 2wt%;
Can provide greater than 6 and less than the potassium hydroxide of 7 pH; With
Deionized water.
In this technology, substrate contacts with second contact pressure of second polished part with about 0.3psi, and second speed of rotation is about 14rpm, and the speed of rotation of second bracket head is about 29rpm, and second bias voltage that applies is about 2.4 volts.Substrate is polished and checks.The original excessive tungsten layer of substrate surface is removed and stays blocking layer and tungsten groove.
Example 2
At the Applied Materials from Santa Clara, California, the REFLEXION that Inc. buys In the improvement unit in the system, be that the plating tungsten substrate of 300mm polishes and planarization to diameter with following polishing composition.The substrate of about 4000  of surperficial tungsten layer thickness is placed in the device on the bracket head, and this device has first that arranges first polished part on it.Speed with about 250mL/min is supplied to first polishing composition on this platform, and first polishing composition comprises:
The sulfuric acid of about 3vol%;
The phosphoric acid of about 4vol%;
The ammonium citrate of about 2.8wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
In this technology, substrate contacts with first contact pressure of first polished part with about 0.3psi, and first speed of rotation is about 20rpm, and the speed of rotation of first bracket head is about 39rpm, and first bias voltage that applies is about 2.9 volts.Substrate is polished and checks.Tungsten layer thickness reduces to about 1000 .
Substrate-transfer is had on second platform of second polished part on it.Speed with about 300mL/min is supplied to second polishing composition on this platform, and second polishing composition comprises:
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2.5vol%;
The ammonium citrate of about 0.5wt%;
Can provide greater than 6 and less than the potassium hydroxide of 7 pH; With
Deionized water.
In this technology, substrate contacts with second contact pressure of second polished part with about 0.3psi, and second speed of rotation is about 14rpm, and the speed of rotation of second bracket head is about 29rpm, and second bias voltage that applies is about 2.4 volts.Substrate is polished and checks.The original excessive tungsten layer of substrate surface is removed and stays blocking layer and tungsten groove.
Example 3
At the Applied Materials from Santa Clara, California, the REFLEXION that Inc. buys In the improvement unit in the system, be that the plating tungsten substrate of 300mm polishes and planarization to diameter with following polishing composition.The substrate of about 4000  of surperficial tungsten layer thickness is placed in the device on the bracket head, and this device has first that arranges first polished part on it.Speed with about 250mL/min is supplied to first polishing composition on this platform, and first polishing composition comprises:
The sulfuric acid of about 2.5vol%;
The phosphoric acid of about 3vol%;
The ammonium citrate of about 2.4wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
In this technology, substrate contacts with first contact pressure of first polished part with about 0.3psi, and first speed of rotation is about 20rpm, and the speed of rotation of first bracket head is about 39rpm, and first bias voltage that applies is about 2.9 volts.Substrate is polished and checks.Tungsten layer thickness reduces to about 1000 .
Substrate-transfer is had on second platform of second polished part on it.Speed with about 300mL/min is supplied to second polishing composition on this platform, and second polishing composition comprises:
The sulfuric acid of about 1.5vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.4 to about 6.8 pH can be provided; With
Deionized water.
In this technology, substrate contacts with second contact pressure of second polished part with about 0.3psi, and second speed of rotation is about 14rpm, and the speed of rotation of second bracket head is about 29rpm, and second bias voltage that applies is about 2.4 volts.Substrate is polished and checks.The original excessive tungsten layer of substrate surface is removed and stays blocking layer and tungsten groove.
Example 4
At the Applied Materials from Santa Clara, California, the REFLEXION that Inc. buys In the improvement unit in the system, be that the plating tungsten substrate of 300mm polishes and planarization to diameter with following polishing composition.The substrate of about 4000  of surperficial tungsten layer thickness is placed in the device on the bracket head, and this device has first that arranges first polished part on it.Speed with about 250mL/min is supplied to first polishing composition on this platform, and first polishing composition comprises:
The sulfuric acid of about 3vol%;
The phosphoric acid of about 3vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8 to about 9 pH can be provided; With
Deionized water.
In this technology, substrate contacts with first contact pressure of first polished part with about 0.3psi, and first speed of rotation is about 20rpm, and the speed of rotation of first bracket head is about 39rpm, and first bias voltage that applies is about 2.9 volts.Substrate is polished and checks.Tungsten layer thickness reduces to about 1000 .
Substrate-transfer is had on second platform of second polished part on it.Speed with about 300mL/min is supplied to second polishing composition on this platform, and second polishing composition comprises:
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.4 to about 6.8 pH can be provided; With
Deionized water.
In this technology, substrate contacts with second contact pressure of second polished part with about 0.3psi, and second speed of rotation is about 14rpm, and the speed of rotation of second bracket head is about 29rpm, and second bias voltage that applies is about 2.4 volts.Substrate is polished and checks.The original excessive tungsten layer of substrate surface is removed and stays blocking layer and tungsten groove.
Example 5
At the Applied Materials from Santa Clara, California, the REFLEXION that Inc. buys In the improvement unit in the system, be that the plating tungsten substrate of 300mm polishes and planarization to diameter with following polishing composition.The substrate of about 4000  of surperficial tungsten layer thickness is placed in the device on the bracket head, and this device has first that arranges first polished part on it.Speed with about 250mL/min is supplied to first polishing composition on this platform, and first polishing composition comprises:
The sulfuric acid of about 2vol%;
The phosphoric acid of about 2vol%;
The ammonium citrate of about 2wt%;
The quadrol of about 2wt%;
The potassium hydroxide of about 8.4 to about 8.9 pH can be provided; With
Deionized water.
In this technology, substrate contacts with first contact pressure of first polished part with about 0.3psi, and first speed of rotation is about 20rpm, and the speed of rotation of first bracket head is about 39rpm, and first bias voltage that applies is about 2.9 volts.Substrate is polished and checks.Tungsten layer thickness reduces to about 1000 .
Substrate-transfer is had on second platform of second polished part on it.Speed with about 300mL/min is supplied to second polishing composition on this platform, and second polishing composition comprises:
The sulfuric acid of about 1vol%;
The phosphoric acid of about 1.5vol%;
The ammonium citrate of about 0.5wt%;
The potassium hydroxide of about 6.4 to about 6.8 pH can be provided; With
Deionized water.
In this technology, substrate contacts with second contact pressure of second polished part with about 0.3psi, and second speed of rotation is about 14rpm, and the speed of rotation of second bracket head is about 29rpm, and second bias voltage that applies is about 2.4 volts.Substrate is polished and checks.The original excessive tungsten layer of substrate surface is removed and stays blocking layer and tungsten groove.
Although previous section relates to embodiments of the present invention, under the situation that does not break away from base region of the present invention, can design other or additional embodiments of the present invention, and scope of the present invention is determined by claims.

Claims (44)

1. be used for removing the composition of tungsten material at least, comprise from substrate surface:
About 0.2vol% is to the sulfuric acid or derivatives thereof of about 5vol%;
About 0.2vol% is to the phosphoric acid or derivatives thereof of about 5vol%;
About 0.1wt% is to the Citrate trianion of about 5wt%;
The pH regulator agent of about 3 to about 8 pH can be provided; With
Solvent.
2. composition as claimed in claim 1, wherein said Citrate trianion comprises ammonium citrate, and described pH regulator agent comprises potassium hydroxide and combination thereof.
3. composition as claimed in claim 1, wherein said composition comprises:
About 0.5vol% is to the sulfuric acid of about 2vo1%;
About 0.5vol% is to the phosphoric acid of about 2vol%;
About 0.5wt% is to the ammonium citrate of about 2wt%;
The pH regulator agent of about 6 to about 7 pH can be provided; With
Solvent.
4. be used for removing the composition of tungsten material at least, comprise from substrate surface:
About 0.2vol% is to the sulfuric acid or derivatives thereof of about 5vol%;
About 0.2vol% is to the phosphoric acid or derivatives thereof of about 5vol%;
About 0.1wt% is to the Citrate trianion of about 5wt%;
About 0.5wt% is to one or more sequestrants that are selected from the functional group of amido, amide group and combination thereof that have of about 5wt%;
The pH regulator agent of about 6 to about 10 pH can be provided; With
Solvent.
5. composition as claimed in claim 4, wherein said sequestrant are selected from by quadrol, diethylenetriamine, its derivative and the group formed thereof.
6. composition as claimed in claim 4, wherein said composition comprises:
About 1vol% is to the sulfuric acid of about 5vol%;
About 1vol% is to the phosphoric acid of about 5vol%;
About 1wt% is to the ammonium citrate of about 5wt%;
About 0.5wt% is to the quadrol of about 5wt%;
The potassium hydroxide of about 6 to about 10 pH can be provided; With
Deionized water.
7. composition as claimed in claim 6, wherein said composition comprises:
About 1vol% is to the sulfuric acid of about 3vol%;
About 1vol% is to the phosphoric acid of about 3vol%;
About 1wt% is to the ammonium citrate of about 3wt%;
About 1wt% is to the quadrol of about 3wt%;
The potassium hydroxide of about 7 to about 9 pH can be provided; With
Deionized water.
8. composition as claimed in claim 4, wherein said composition also comprises the etching inhibitor.
9. the method for process substrate comprises:
The substrate that will have the tungsten layer that forms on it places the process unit that comprises first electrode and second electrode, and wherein said substrate and described second electrode electrically contact;
Provide polishing composition between described first electrode and described substrate, wherein said polishing composition comprises:
The sulfuric acid or derivatives thereof;
The phosphoric acid or derivatives thereof;
First sequestrant that contains organic salt;
The pH regulator agent of about 2 to about 10 pH can be provided; With
Solvent;
Described substrate is contacted with polished part;
Between described substrate and described polished part, provide relative movement;
Between described first electrode and described second electrode, apply bias voltage; With
Remove the tungsten material from described tungsten material layer.
10. method as claimed in claim 9, the wherein said step that described substrate is contacted with polished part are included in and apply about 1psi or littler pressure between described substrate and the described polished part.
11. method as claimed in claim 9, wherein said polishing composition are to provide to the flow velocity of about 400mL/min with about 100mL/min.
12. method as claimed in claim 9, the wherein said step that relative movement is provided comprise with about 7rpm to about 50rpm rotate described polished part and with about 7rpm extremely about 70rpm rotate described substrate.
13. method as claimed in claim 9, the wherein said step that applies bias voltage be included in apply between described first and second electrodes about 1.8 volts to about 4.5 volts bias voltage.
14. method as claimed in claim 9, wherein said organic salt are selected from by ammonium citrate, Tripotassium Citrate, its derivative and the group formed thereof, the pH regulator agent is selected from the group of being made up of potassium hydroxide, ammonium hydroxide and combination thereof.
15. method as claimed in claim 9, wherein said polishing composition comprises:
About 0.2vol% is to the described sulfuric acid or derivatives thereof of about 5vol%;
About 0.2vol% is to the described phosphoric acid or derivatives thereof of about 5vol%;
About 0.1wt% is to first sequestrant that contains organic salt of about 5wt%;
The pH regulator agent of about 2 to about 8 pH can be provided; With
Solvent.
16. as the method for claim 15, wherein:
Described sulfuric acid or derivatives thereof comprises sulfuric acid;
Described phosphoric acid or derivatives thereof comprises phosphoric acid;
Described first sequestrant comprises ammonium citrate;
Described pH regulator agent comprises potassium hydroxide; And
Deionized water.
17. as the method for claim 15, wherein said polishing composition comprises:
About 0.5vol% is to the sulfuric acid of about 2vol%;
About 0.5vol% is to the phosphoric acid of about 2vol%;
About 0.5wt% is to the ammonium citrate of about 2wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
18. method as claimed in claim 9 also comprises and has one or more second sequestrants that are selected from the functional group of amido, amide group and combination thereof.
19. as the method for claim 18, wherein said second sequestrant is selected from by quadrol, diethylenetriamine, its derivative and the group formed thereof.
20. as the method for claim 18, wherein said polishing composition comprises:
About 1vol% is to the described sulfuric acid or derivatives thereof of about 5vol%;
About 1vol% is to the described phosphoric acid or derivatives thereof of about 5vol%;
About 1wt% is to first sequestrant of about 5wt%;
About 0.5wt% is to second sequestrant of about 5wt%;
The pH regulator agent of about 6 to about 10 pH can be provided; With
Solvent.
21. as the method for claim 20, wherein:
Described sulfuric acid or derivatives thereof comprises sulfuric acid;
Described phosphoric acid or derivatives thereof comprises phosphoric acid;
Described first sequestrant comprises ammonium citrate;
Described second sequestrant comprises quadrol
Described pH regulator agent comprises potassium hydroxide; And
Deionized water.
22. as the method for claim 20, wherein said polishing composition comprises:
About 1vol% is to the sulfuric acid of about 3vol%;
About 1vol% is to the phosphoric acid of about 3vol%;
About 1wt% is to the ammonium citrate of about 3wt%;
About 1wt% is to the quadrol of about 3wt%;
The potassium hydroxide of about 7 to about 9 pH can be provided; With
Deionized water.
23. method as claimed in claim 9, wherein said composition also comprises the etching inhibitor.
24. the method for process substrate comprises:
The substrate that will have the tungsten layer that forms on it places the process unit that comprises first electrode and second electrode, and wherein said substrate and described second electrode electrically contact;
Polish described substrate to remove the first part of described tungsten layer by following technology:
Provide first polishing composition between described first electrode and described substrate, wherein said first polishing composition comprises:
The sulfuric acid or derivatives thereof;
The phosphoric acid or derivatives thereof;
First sequestrant that contains organic salt;
Have one or more second sequestrants that are selected from the functional group of amido, amide group and combination thereof;
The pH regulator agent of about 6 to about 10 pH can be provided; With
Solvent;
Described substrate and polished part are contacted under first pressure between described substrate and the described polished part;
Between described substrate and described polished part, provide first relative movement; And
Between described first electrode and described second electrode, apply first bias voltage; With
Polish described substrate to remove the second section of described tungsten layer by following technology:
Provide second polishing composition between described first electrode and described substrate, wherein said second polishing composition comprises:
The sulfuric acid or derivatives thereof;
The phosphoric acid or derivatives thereof;
First sequestrant that contains organic salt;
The pH regulator agent of about 2 to about 8 pH can be provided; With
Solvent;
Described substrate and polished part are contacted under second pressure between described substrate and the described polished part;
Between described substrate and described polished part, provide second relative movement; And
Between described first electrode and described second electrode, apply second bias voltage;
25. as the method for claim 24, wherein said first and second pressure comprise about 1psi or littler pressure.
26. as the method for claim 24, wherein said first and second polishing compositions are to provide to the flow velocity of about 400mL/min with about 100mL/min.
27. as the method for claim 24, the wherein said step that described first and second relative movement are provided comprise with about 7rpm to about 50rpm rotate described polished part and with about 7rpm extremely about 70rpm rotate described substrate.
28. as the method for claim 24, wherein described first bias voltage between described first and second electrodes is about 2.5 volts to about 4.5 volts, described second bias voltage between described first and second electrodes is about 1.8 volts to about 2.5 volts.
29. as the method for claim 24, wherein said organic salt is selected from by ammonium citrate, Tripotassium Citrate, its derivative and the group formed thereof, the pH regulator agent is selected from the group of being made up of potassium hydroxide, ammonium hydroxide and combination thereof.
30. as the method for claim 24, wherein said first composition comprises:
About 1vol% is to the sulfuric acid of about 5vol%;
About 1vol% is to the phosphoric acid of about 5vol%;
About 1wt% is to the ammonium citrate of about 5wt%;
About 0.5wt% is to the quadrol of about 5wt%;
The pH regulator agent of about 6 to about 10 pH can be provided; With
Deionized water.
31. as the method for claim 24, wherein said first composition comprises:
About 1vol% is to the sulfuric acid of about 3vol%;
About 1vol% is to the phosphoric acid of about 3vol%;
About 1wt% is to the ammonium citrate of about 3wt%;
About 1wt% is to the quadrol of about 3wt%;
The potassium hydroxide of about 7 to about 9 pH can be provided; With
Deionized water.
32. as the method for claim 24, wherein said second composition comprises:
About 0.2vol% is to the sulfuric acid of about 5vol%;
About 0.2vol% is to the phosphoric acid of about 5vol%;
About 0.1wt% is to the ammonium citrate of about 5wt%;
The pH regulator agent of about 2 to about 8 pH can be provided; With
Deionized water.
33. as the method for claim 24, wherein said second composition comprises:
About 0.5vol% is to the sulfuric acid of about 2vol%;
About 0.5vol% is to the phosphoric acid of about 2vol%;
About 0.5wt% is to the ammonium citrate of about 2wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
34. as the method for claim 24, wherein said first composition also comprises the etching inhibitor.
35. as the method for claim 24, wherein said second composition also comprises the etching inhibitor.
36. the method for process substrate comprises:
The substrate that will have the tungsten material layer that forms on it places the process unit that comprises first electrode and second electrode, and wherein said substrate and described second electrode electrically contact;
Provide polishing composition between described first electrode and described substrate, wherein said polishing composition comprises:
The sulfuric acid or derivatives thereof;
The phosphoric acid or derivatives thereof;
First sequestrant that contains organic salt;
The pH regulator agent of about 3 to about 8 pH can be provided; With
Solvent;
On described substrate surface, form poly-tungsten layer;
Described substrate and polished part are contacted under the contact pressure between described substrate and the described polished part;
Between described substrate and described polished part, provide relative movement; And
Between described first electrode and described second electrode, apply bias voltage.
37. as the method for claim 36, wherein to remove described poly-tungsten layer than removing the slower removal speed of described tungsten material.
38. as the method for claim 36, wherein said contact pressure is that about 0.01psi is to about 1psi.
39. as the method for claim 36, wherein said polishing composition is to provide to the flow velocity of about 400mL/min with about 100mL/min.
40. as the method for claim 36, the wherein said step that relative movement is provided comprise with about 7rpm to about 50rpm rotate described polished part and with about 7rpm extremely about 70rpm rotate described substrate.
41. as the method for claim 36, wherein the described bias voltage between described first and second electrodes is about 1.8 volts to about 2.5 volts.
42. as the method for claim 36, wherein said composition comprises:
About 0.2vol% is to the sulfuric acid of about 5vol%;
About 0.2vol% is to the phosphoric acid of about 5vol%;
About 0.1wt% is to the ammonium citrate of about 5wt%;
The pH regulator agent of about 3 to about 8 pH can be provided; With
Deionized water.
43. as the method for claim 36, wherein said composition comprises:
About 0.5vol% is to the sulfuric acid of about 2vol%;
About 0.5vol% is to the phosphoric acid of about 2vol%;
About 0.5wt% is to the ammonium citrate of about 2wt%;
The potassium hydroxide of about 6 to about 7 pH can be provided; With
Deionized water.
44. as the method for claim 36, wherein said composition also comprises the etching inhibitor.
CN 200480041087 2004-01-29 2004-12-27 Method and composition for polishing a substrate Pending CN1906333A (en)

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US10/948,958 2004-09-24

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Cited By (6)

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CN101801579B (en) * 2007-09-14 2014-09-03 易趋宏挤压研磨有限公司 Device and method for electrochemical treatment
CN106104757A (en) * 2014-03-19 2016-11-09 应用材料公司 Electrochemistry electro-plating method
CN109401631A (en) * 2017-08-17 2019-03-01 弗萨姆材料美国有限责任公司 Chemical Mechanical Planarization (CMP) compositions and methods for copper and through-silicon via (TSV) applications
CN111138083A (en) * 2019-12-17 2020-05-12 河南豫科光学科技股份有限公司 Preparation process of anti-skid glass substrate
CN113399766A (en) * 2021-06-02 2021-09-17 贵州大学 Electrolyte for high-speed steel roll material electrolytic grinding and electrolyte supply system
CN113661276A (en) * 2019-04-09 2021-11-16 3Dm生物医学私人有限公司 Electropolishing method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801579B (en) * 2007-09-14 2014-09-03 易趋宏挤压研磨有限公司 Device and method for electrochemical treatment
CN106104757A (en) * 2014-03-19 2016-11-09 应用材料公司 Electrochemistry electro-plating method
CN112899735A (en) * 2014-03-19 2021-06-04 应用材料公司 Electrochemical plating method
CN112899735B (en) * 2014-03-19 2022-05-31 应用材料公司 Electrochemical plating method
CN109401631A (en) * 2017-08-17 2019-03-01 弗萨姆材料美国有限责任公司 Chemical Mechanical Planarization (CMP) compositions and methods for copper and through-silicon via (TSV) applications
CN113661276A (en) * 2019-04-09 2021-11-16 3Dm生物医学私人有限公司 Electropolishing method
US11873572B2 (en) 2019-04-09 2024-01-16 3DM Biomedical Pty Ltd Electropolishing method
CN111138083A (en) * 2019-12-17 2020-05-12 河南豫科光学科技股份有限公司 Preparation process of anti-skid glass substrate
CN113399766A (en) * 2021-06-02 2021-09-17 贵州大学 Electrolyte for high-speed steel roll material electrolytic grinding and electrolyte supply system
CN113399766B (en) * 2021-06-02 2022-06-14 贵州大学 Test method of electrolyte for high-speed steel roll material electrolytic grinding

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