CN101313388A - Friction reducing aid for cmp - Google Patents

Friction reducing aid for cmp Download PDF

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Publication number
CN101313388A
CN101313388A CNA2006800437962A CN200680043796A CN101313388A CN 101313388 A CN101313388 A CN 101313388A CN A2006800437962 A CNA2006800437962 A CN A2006800437962A CN 200680043796 A CN200680043796 A CN 200680043796A CN 101313388 A CN101313388 A CN 101313388A
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China
Prior art keywords
polishing
water
polishing system
substrate
grinding agent
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CNA2006800437962A
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Chinese (zh)
Inventor
凯文·J·莫根伯格
菲利普·W·卡特
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Cabot Corp
CMC Materials Inc
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Cabot Corp
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Publication of CN101313388A publication Critical patent/CN101313388A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/005—Control means for lapping machines or devices
    • B24B37/0056—Control means for lapping machines or devices taking regard of the pH-value of lapping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
    • B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The invention provides a chemical-mechanical polishing system for polishing a substrate comprising a polishing component, a water-soluble silicate compound, an oxidizing agent, and water, wherein the pH of the polishing system is about 8 to about 12. The invention further provides a method of chemically-mechanically polishing a substrate with the aforementioned polishing system. The polishing system provides for reduced friction during polishing of substrates.

Description

The friction reducing aid that is used for chemico-mechanical polishing
Technical field
The friction reducing aid (frction reducing aid) of the present invention about being used for chemico-mechanical polishing.
Background technology
Integrated circuit by among millions of substrates that are formed at silicon wafer for example or on active device form.These active devices are connected in the substrate and by the use multilayer interconnection with chemistry and physics mode and are connected to each other to form functional circuit.In one manufacturing approach, by traditional dry etching method with the dielectric substrate patterning to be formed for vertically reaching the hole and the groove of horizontal interconnect.Patterned then surface randomly covers with diffusion impervious layer and/or adhesion promoting layer, and then depositing metal layers is to fill these grooves and hole.Use chemico-mechanical polishing (CMP) to reduce the thickness of metal layer thickness and diffusion impervious layer and/or adhesion promoting layer then, the dielectric layer below exposing forms circuit devcie thus.
In chemico-mechanical polishing, the polishing component of polishing pad (polishing component) contacts to make substrate surface and polishing composition for example reach.Polishing composition (being also referred to as polishing slurries) contains the grinding-material in the aqueous solution usually, and by making the surface and contacting with the saturated polishing pad of polishing composition and polishing composition is applied to the surface.The chemical composition of polishing composition is considered to the surfacing reaction with the substrate that is polishing, the derivative of more soft, the easier wearing and tearing by surfacing being converted into described material, then the mechanism by grinding-material and/or polishing pad removes described derivative, perhaps by dissolving the surfacing that removes via mechanism separately.In some applications, grinding agent can be fixed on the surface of polishing pad.
In polishing processing, the frictional force that relative motion caused by substrate surface that polishing composition is arranged therebetween and pad interface can be via destroying circuit by abrasive grains and/or polishing pad scratch substrate, and via the layering of superficial layer, thereby cause the defective of the device that just on substrate, forming from substrate.In addition, polishing pad can cause filling up premature failure at the frictional heat at pad/slurry interface place.The strategy that reduces friction, for example surfactant being joined in the polishing composition, use the polishing pad that is made of softer material or reducing to be applied to power on substrate/polishing pad interface causes the speed that removes of the material that polishing to reduce usually, this can cause increase process time, therefore reduces output and increases total unit cost.
In addition, for reduce the electric capacity between the conductive layer on the microelectronic component and therefore increase frequency or the speed that device can operate, using have permittivity ratio normally used based on the low material of the dielectric material of silicon dioxide so that the electric insulation between the circuit-line to be provided.The example of advanced low-k materials generally includes organic polymer material, inorganic and organic porous dielectric material, reaches blend or compound organic and inorganic material (it can be porous or non-porous).These materials mechanically than soft based on the dielectric material of silicon dioxide and in the manufacture process of device easier being damaged.Very desirable is that advanced low-k materials is incorporated in the semiconductor structure, still can utilize the surface of conventional chemico-mechanical polishing (CMP) system polishing obtained device simultaneously in the semiconductor wafer course of processing.
Therefore, exist the such chemical-mechanical polishing compositions and the needs of system, it demonstrates the friction that reduces between substrate and the polishing component.These and other advantage of the present invention, and other inventive features will become distinct from the embodiment of the present invention that this paper provided.
Summary of the invention
The invention provides a kind of chemical-mechanical polishing system that is used for polishing substrate, it comprises the polishing component that (a) is selected from polishing pad, grinding agent and combination thereof, and (b) water-soluble silicate compound presents in an amount at least sufficient to provide 0.1 weight % or more SiO 2, (c) oxidant of at least a portion of oxidase substrate reaches (d) water, and wherein the pH value of polishing system is 8 to 12.The present invention further provides a kind of method of chemical-mechanical polishing substrate, this method comprises: substrate is contacted with chemical-mechanical polishing system, this chemical-mechanical polishing system comprises: the polishing component that (a) is selected from polishing pad, grinding agent and combination thereof, (b) water-soluble silicate compound presents in an amount at least sufficient to provide 0.1 weight % or more SiO 2, (c) oxidant of at least a portion of oxidase substrate reaches (d) water; At least a portion that reaches the substrate that (ii) weares and teares is with polishing substrate, and wherein the pH value of polishing system is 8 to 12.
Description of drawings
Fig. 1 explanation is used to measure the method for the coefficient of friction of CMP (Chemical Mechanical Polishing) process.
Embodiment
The invention provides a kind of chemico-mechanical polishing (CMP) system, it comprises the polishing component, is enough to provide 0.1 weight % or more SiO 2Oxidant, and the water of at least a portion of water-soluble silicate compound, oxidase substrate of amount, wherein the pH value of this polishing system is 8 to 12.Water and any dissolving or be suspended in the polishing composition that wherein component forms chemical-mechanical polishing system.Unless otherwise noted, otherwise the amount of component described herein all based on the total weight of polishing composition (that is, water and any dissolving or be suspended in the weight of component wherein).
The polishing component is selected from polishing pad, grinding agent, reaches the combination of polishing pad and grinding agent.If there is grinding agent, then grinding agent can be any suitable form (for example abrasive grains).Grinding agent can be fixed on the polishing pad and/or it can be particulate form and suspends in water.Polishing pad can be any suitable polishing pad, and wherein many are as known in the art.
Grinding agent can be any suitable grinding agent, and for example grinding agent can be natural or syntheticly, and can comprise metal oxide, carbide, nitride, diamond dust etc.Grinding agent also can be polymer beads or the particle through applying.Grinding agent desirably comprises metal oxide.Preferably, this metal oxide is selected from aluminium oxide, ceria, silicon dioxide, zirconia, it forms product (coformed product) and combination thereof altogether.Abrasive grains has the particle mean size (for example average grain diameter) of 20nm to 500nm usually.Preferably, abrasive grains has the particle mean size of 30nm to 400nm (for example, 40nm to 300nm, or 50nm to 250nm, or 75nm to 200nm).
When grinding agent is suspended in water (, when grinding agent is the component of polishing composition), the grinding agent of any suitable amount can be present in the polishing composition.Usually, the grinding agent of 0.01 weight % or more (for example 0.05 weight % or more) can be present in the polishing composition.More specifically, 0.1 weight % or more grinding agent can be present in the polishing composition.The amount of grinding agent can not surpass 20 weight % usually in the polishing composition, more generally can not surpass 10 weight % (for example can not surpass 5 weight %).Preferably, the amount of grinding agent is 0.05 weight % to 2 weight % in the polishing composition, and 0.1 weight % to 1 weight % more preferably.
Polishing system can comprise any suitable polishing pad (for example polished surface).Suitable polishing pad comprises, for example, and braiding and non-woven polishing pad.Resilience when in addition, suitable polishing pad can comprise different densities, hardness, thickness, compressibility, compression and any suitable polymers of modulus of compressibility.Suitable polymers comprises, for example, polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbon, Merlon, polyester, polyacrylate, polyethers, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, its form altogether product, and composition thereof.
Polishing system comprises water-soluble silicate compound.This water-soluble silicate compound can be any suitable water-soluble silicate compound.Desirably, this water-soluble silicate compound is an alkali silicate.Preferably, this water-soluble silicate compound is selected from potassium silicate, sodium metasilicate, potassium metasilicate and sodium metasilicate.More preferably, this water-soluble silicate compound is a potassium silicate.
The water-soluble silicate compound that is suitable for use among the present invention can be silicate glass.The silicate glass high temperature by silica sand and suitable alkali metal compound (for example sodium carbonate or potash) usually merges and prepares.
Water-soluble silicate has formula M 2OmSiO 2NH 2O, wherein M is the alkali metal that is selected from sodium, potassium and lithium, and the m and the n that are called coefficient are respectively every mole of M 2The SiO of O 2And H 2The molal quantity of O.Coefficient m is SiO 2With M 2The mol ratio of O.SiO 2With M 2The weight ratio of O also is generally used for describing the composition of water-soluble alkali metal silicates.Coefficient m can be any suitable positive nonzero number (for example 1 or bigger), is generally 1 to 4, be more typically 2 to 4 (for example, 2.8 to 3.9, or 3 to 3.6).
In a preferred embodiment, this water-soluble silicate compound is for having general formula K 2OmSiO 2Potassium silicate, Coefficient m (for example, SiO wherein 2With K 2The mol ratio of O) is positive nonzero number.Potassium silicate can have any suitable coefficient.Desirably, this coefficient is 1 or bigger.Preferably, this coefficient is 2.8 to 3.9.More preferably, this coefficient is 3 to 3.6.
Water-soluble silicate compound is present in the aqueous solution in the polishing composition.A kind of method that water-soluble silicate compound is provided is that the water-soluble silicate compound with solid form is dissolved in the water so that solution to be provided.Perhaps, can dilute the concentrated solution of water-soluble silicate compound to obtain the desired concn of water-soluble silicate compound in the solution.The commercially available acquisition of the potassium silicate of each grade and sodium silicate aqueous solution, wherein said solution is by the concrete coefficient of employed silicate and the SiO of solution in its preparation 2Weight percent is K when 2O or Na 2The O percentage by weight characterizes.Zaclon, Inc. (Cleveland, OH) and PQCorporation (Valley Forge PA) is two key vendors of the solid form and the solution of potassium silicate and sodium metasilicate.
Also can obtain potassium silicate aqueous solution, wherein make silicon dioxide (SiO for example by the hydrothermal solution method 2) source and potassium hydroxide aqueous solution react under temperature that raises and/or pressure condition.The example that is used to produce the suitable hydrothermal solution method of potassium silicate aqueous solution is disclosed in United States Patent (USP) 5,084, in 262 and 5,238,668.
The polishing composition of polishing system can comprise the water-soluble silicate compound of any suitable amount.Usually, the content that is present in the water-soluble silicate compound in the polishing composition be expressed as in water and be dissolved in any component wherein total weight by SiO that this water-soluble silicate compound was provided 2Percentage by weight.Should understand formula " SiO 2" represent that for a kind of form it allows to calculate the amount of employed water-soluble silicate compound in polishing composition, and no matter its source (for example, the aqueous solution of the water-soluble silicate compound of various compositions as described herein or solid form).Usually, this polishing composition comprises sufficient water-soluble silicate compound so that 0.1 weight % or more (for example, 0.25 weight % or more, 0.5 weight % or more, 1 weight % or more, 1.5 weight % or more or 2 weight % or more than 2) SiO to be provided 2Polishing composition preferably comprise sufficient water-soluble silicate compound with provide 8 weight % or still less (for example, 6 weight % still less or 4 weight % still less or even 3 weight % or still less) SiO 2Polishing composition most preferably comprises 0.25 weight % to 5 weight % (for example, 0.5 weight % to 4 weight %, or 1 weight % to 3 weight %) SiO 2
The polishing composition of polishing system comprises the oxidant of at least a portion of oxidase substrate.Any suitable oxidant all can be used for the present invention.Suitable oxidant comprises inorganic and organic compound (per-compound), bromate, nitrate, chlorate, chromate, iodate, molysite and mantoquita (for example, nitrate, sulfate, edta salt and citrate), rare-earth oxide and transition metal oxide (for example osmium tetroxide), the potassium ferricyanide, potassium bichromate, acid iodide, quinone etc. crossed.Cross compound (as defined) for containing at least one peroxy (compound O-O-) or contain the compound of the element that is in its highest oxidation state by Hawley ' s Condensed Chemical Dictionary.The examples for compounds that contains at least one peroxy includes, but is not limited to hydrogen peroxide and adduct thereof, for example, and perhydrit and percarbonate (ester); Organic peroxide, for example, benzoyl peroxide, Peracetic acid and di-t-butyl peroxide; Single persulfate (monopersulfate, SO 5 2-), two persulfates (dipersulfate) (S 2O 8 2-) and sodium peroxide.The examples for compounds that contains the element that is in its highest oxidation state includes, but is not limited to periodic acid, periodates, perbromic acid, perbromate, crosses chloric acid, perchlorate, perboric acid, perborate and permanganate.Preferably, this oxidant is selected from complex salt (hydrogen peroxymonosulfate sulfate), molybdate, ferric nitrate, nitrate, quinone and the combination thereof of hydrogen peroxide, iodate, permanganate, persulfate (persulfate), peroxidating monosulfate and sulfate.More preferably, this oxidant is Potassiumiodate or hydrogen peroxide.
When oxidant was salt, this oxidant can have any suitable cation.Suitable cationic limiting examples comprises potassium, ammonium etc.
When oxidant was quinone, this oxidant can be any suitable quinone.The limiting examples of suitable quinone comprises benzoquinones, naphthoquinones and anthraquinone.Quinone can be replaced by any suitable substituents or substituent combination in any available position.Preferred substituted is included in the group of giving quinone dissolubility or emulsibility in the water of polishing composition.Suitable substituents includes, but is not limited to hydroxyl, amino, alkyl monosubstituted amino, dialkyl amido, sulfonic acid, carboxyl, phosphonic acids, its salt and combination thereof.In execution mode, quinone is replaced by at least one hydroxyl.In other embodiments, quinone is replaced by at least one acid substituting group or its salt.Preferably, this at least one acid substituting group is selected from sulfonic acid, carboxyl and phosphonic acids.More preferably, this at least one acid substituting group is sulfonic acid (SO 3H).Should understand acid substituting group and can form salt, and have acid substituent quinone in this and can be used as acid, salt and exist, perhaps replace or can be used as part salt (for example single salt of disulfonic acid) existence when polysubstituted when two.Have acid substituent quinone can sour form or salt form provide to be used for polishing composition of the present invention.Preferred anthraquinone is selected from anthraquinone-2,6-disulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1,8-disulfonic acid, anthraquinone-1,5-disulfonic acid, acid blue 45, its salt and combination thereof.Preferred benzoquinones comprises 1,4-benzoquinones and 2,5-dihydroxy-1,4-benzoquinones.Preferred naphthoquinones comprises 1,2-naphthoquinones-4-sulfonic acid and salt thereof.
The concentration of the oxidant in the polishing composition of polishing system desirably is 1mM or bigger (for example, 2mM or bigger, or 3mM or bigger, or 5mM or bigger).The concentration of oxidant is preferably 1M or littler (for example, 0.5M or littler, or 0.25M or littler, or 0.1M or littler) in the polishing composition.The desired concn of oxidant can obtain by any suitable method, for example by using in water and dissolving in the preparation of polishing composition or being suspended in the oxidant of 0.05 weight % to 20 weight % of the weight of any component wherein.
Polishing system have a pH value of 8 to 12.Preferably, the pH value of polishing system is 8 to 11, more preferably 9 to 11.The pH value of polishing system can and/or be kept by any suitable method acquisition.More specifically, polishing system can further comprise pH value conditioning agent, pH value buffer or its combination.The aqueous solution that obtain by dissolve silicates glass (for example alkali silicate) or the water-soluble silicate compound by the preparation of hydrothermal solution method has 11 or bigger strong basicity pH value, and its salt by highly basic and weak acid is formed.If need, then can come the M of the strong alkali solution of acidifying water-soluble silicate compound by the acid of adding capacity with the existing abundance that neutralizes 2O is obtaining required pH value, thus the pH value of regulating polishing system.PH value conditioning agent can be any suitable pH value and regulates compound.For example, pH value conditioning agent can be enough strong to produce any suitable acid of required final pH value.The embodiment of suitable acid comprises nitric acid, acetate, phosphoric acid etc.If need, then can increase the pH value by adding highly basic.The example of highly basic comprises potassium hydroxide, ammonium hydroxide and tetraalkylammonium hydroxide (for example tetramethyl ammonium hydroxide).
PH value buffer can be any suitable reducing, for example, and phosphate, acetate, borate, ammonium salt etc.When using buffer to regulate the pH value of polishing system, the buffer that should understand abundance adds in the polishing system with the sufficient M that neutralizes 2O, thus required pH value is provided.Polishing system can comprise the pH value conditioning agent and/or the pH value buffer of any suitable amount, as long as such amount is enough to obtain and/or maintain the pH value of the polishing system in the listed scope of this paper.
The pH value that can regulate polishing system in any suitable time.For example, can in the polishing composition that water-soluble silicate compound is added to polishing system as described herein, regulate the pH value in the back.Also the water-soluble silicate compound of aequum can be added in the polishing composition, wherein this polishing composition comprises the pH value conditioning agent and/or the pH value buffer of capacity, makes water-soluble silicate compound and polishing composition are being mixed fully the required pH value of back acquisition.In other embodiments, in the pH value of using point (point-of-use) surface of substrate (for example) to regulate polishing system.
Polishing system randomly comprises corrosion inhibitor (being film forming agent).Corrosion inhibitor can be any suitable corrosion inhibitor of any parts that are used for substrate.Preferably, corrosion inhibitor is a copper corrosion inhibitor.For purposes of the present invention, corrosion inhibitor is any compound of the formation that promotes passivation layer (that is, dissolving suppresses layer) at least a portion at polished surface just or the mixture of compound.Useful corrosion inhibitor comprises, for example, and nitrogen-containing heterocycle compound.Corrosion inhibitor desirably comprises one or more 5 yuan or 6 yuan of heterocycles and contains azo-cycle.Preferred corrosion inhibitor comprises 1,2,3-triazoles, 1,2,4-triazole, BTA, benzimidazole, benzothiazole and derivative thereof, for example, it is through hydroxyl, amino, imino group, carboxyl, sulfydryl, nitro, urea, thiocarbamide or alkyl-substituted derivatives.Most preferably, this corrosion inhibitor is selected from BTA, 1,2,3-triazoles, 1,2, the 4-triazole, and composition thereof.Polishing system of the present invention can comprise the corrosion inhibitor of any suitable amount.Usually, the polishing composition of polishing system comprises the corrosion inhibitor of 0.005 weight % to 1 weight % (for example, 0.01 weight % to 0.5 weight %, or 0.02 weight % to 0.2 weight %).
Polishing system randomly further comprises one or more other additive.Such additive comprises any suitable surfactant and/or rheology control agent.Suitable surfactant comprises, for example, and cationic surfactant, anion surfactant, anionic polyelectrolyte, nonionic surface active agent, amphoteric surfactant, fluorinated surfactant, its mixture etc.
Polishing system randomly further comprises defoamer.This defoamer can be any suitable defoamer.Suitable defoamer includes, but is not limited to based on silicon and based on the defoamer of acetylenic glycols.The amount of the defoamer that exists in the polishing composition of polishing system is generally 40ppm to 140ppm.
Polishing system randomly further comprises biocide.This biocide can be any suitable biocide, for example OIT biocide.The amount that is used in the biocide in the polishing system is generally 1ppm to 500ppm, and is preferably 10ppm to 200ppm.
The polishing composition of polishing system can be by the preparation of any suitable technique, and wherein many are well known by persons skilled in the art.Polishing composition can intermittence or continuation method preparation.Usually, this polishing composition can be by preparing its component with any sequential combination.Term as used herein " component " comprises any combination of independent composition (for example, grinding agent, water-soluble silicate compound etc.) and composition (for example, grinding agent, water-soluble silicate compound, oxidant etc.).
The polishing composition of polishing system also can be used as concentrate and provides, and this concentrate is intended to before use with an amount of water dilution.In such execution mode, the polishing composition concentrate can comprise grinding agent, water-soluble silicate compound, oxidant and water, its amount makes that each component of polishing composition will be present in the polishing composition the described amount in proper range of each component with above after diluting concentrate with an amount of water.For example, grinding agent, water-soluble silicate compound and oxidant can respectively think above to 2 times of the described concentration of each component (for example, 3 times, 4 times or 5 times) amount be present in the concentrate, make and (for example work as with isopyknic water, use 2 times of isopyknic water, 3 times of isopyknic water or 4 times of isopyknic water respectively) dilution is during concentrate, and each component can be present in the polishing composition with the amount in the above scope listed to each component.In addition, should understand as those of ordinary skills, this concentrate can contain the water that is present in the appropriate fraction in the final polishing composition, is dissolved in this concentrate at least in part or fully to guarantee water-soluble silicate compound, oxidant and other suitable additive.
Being used for any component of the present invention can provide at the mixture of water or the form of solution.Two or more components desirably store separately and mix subsequently to form the polishing composition of polishing system then.In this, preparation polishing composition (for example, all components being mixed), it is suitable being sent to substrate surface then.Prepare polishing composition at substrate surface, by sending the component from the polishing composition of two or more separate sources, to converge on substrate surface (for example use point) also be suitable to these components of polishing composition thus.In either case, before polishing processing or the component that in polishing processing, all can change polishing composition be sent to substrate surface flow velocity (promptly, the conveying capacity of the specific components of polishing composition), make polishing system the polishing characteristic for example polishing speed change.
Polishing composition can be used as the single packaging system that comprises water-soluble silicate compound, oxidant and water and provides.Perhaps, water-soluble silicate compound and water can be provided in first container, and oxidant can dried forms or be provided in second container as solution or dispersion in water.Can be with optional component, for example grinding agent, surfactant and/or corrosion inhibitor place first and/or second container, or in the 3rd container.In addition, the component in first or second container can be dried forms, and the component in the corresponding container can be water-borne dispersions or solution form simultaneously.In addition, the component in first or second container has different pH values, perhaps have similar or even the pH value that equates be suitable.If optional component for example grinding agent is a solid, then it can dried forms or provides as the mixture in water.Desirably, other component of oxidant and polishing composition provides respectively, and by for example final user with other component of itself and polishing composition soon before use (for example, 1 week or shorter time, 1 day before use or shorter time, 1 hour before use or shorter time, 10 minutes before use or shorter time or 1 minute before use or shorter time) before use merge.In the ken that is combined in those of ordinary skills of the component of other two containers or three or more containers, polishing composition.
Though the component of the polishing composition of polishing system can be before use or even combination well soon before use, can use point or use near the component of the merging polishing composition point.As used herein, term " use point " is meant polishing composition and the contacted point of substrate surface.When using point to merge the component of polishing composition, the component of polishing composition is stored in respectively in two or more storage facilitiess.
In order to use point or to use near the component of mixing the polishing composition that is contained in the storage facilities point, storage facilities provides one or more usually and leads to the fluid line (flow line) of the use point (for example, workbench (platen) or substrate surface) of polishing composition from each storage facilities.Term " fluid line " is meant the path of the fluid of the use point from independent reservoir vessel to the component that wherein stores.Described one or more fluid line can directly lead to the use point separately, and perhaps, under situation about using more than a fluid line, two or more fluid lines can be merged into the single fluid line that uses point that leads at any point.In addition, any described one or more fluid line (for example, the independent fluid line or the fluid line of merging) all can before the use point that arrives component, at first lead to one or more miscellaneous equipments (for example, pumping equipment, measuring equipment, mixing apparatus etc.).
The component of polishing composition can be sent to independently uses point (for example, in polishing processing, these components are sent to substrate surface, these components are mixed at substrate surface), and perhaps these components can be sent to the merging not long ago of use point.If these components arrive to use point merge in preceding 10 seconds, preferably arrive use point merge in preceding 5 seconds, more preferably arrive use point to merge in preceding 1 second or even merging is (for example when component is sent to use, these components merge in distributor), then these components " being sent to the use point not long ago " merge.If these components are within the 5m that uses point, for example, within the 1m that uses point or even using that (for example, within the 1cm that uses point) merges within the 10cm of point, then these components also are that " using point not long ago being sent to " merges.
When two or more components of the polishing composition of polishing system arrive when merging before using point, these components can merge and be sent to use and not use mixing apparatus in fluid line.Perhaps, one or more fluid line can lead in the mixing apparatus to promote the merging of two or more components.Can use any suitable mixing apparatus.For example, this mixing apparatus can be two or more components through its nozzle that flows through or spout (for example high pressure nozzle or spout).Perhaps, this mixing apparatus can be the container type mixing apparatus that comprises one or more inlets and at least one outlet, wherein two or more components of polishing composition are introduced blender via described inlet, and the component through mixing is left blender by this at least one outlet and directly or via other element (for example, via one or more fluid line) that installs is sent to the use point.In addition, mixing apparatus can comprise the chamber more than, and each chamber has at least one inlet and at least one outlet, and wherein two or more components merge in each chamber.If use the container type mixing apparatus, then this mixing apparatus preferably comprises the merging of mixing machinery device (mixing mechanism) with further promotion component.The mixing machinery device is widely known by the people in the art, and comprises blender, blender, agitator, vane-type baffle (paddled baffle), gas distributor (gas sparger) system, vibrator etc.
The present invention further provides a kind of method of using polishing system polishing substrate as herein described.The method of described polishing substrate comprises: substrate is contacted with aforementioned polishing system, and (ii) wear and tear or at least a portion of removing substrate with polishing substrate.
Particularly, the inventive method may further comprise the steps: (i) make substrate and comprise the polishing component, be enough to provide 0.1 weight % or more SiO 2Oxidant, and the chemical-mechanical polishing system contact of water of at least a portion of water-soluble silicate compound, oxidase substrate of amount, wherein the pH value of this polishing system is 8 to 12, at least a portion that reaches the substrate that (ii) weares and teares is with polishing substrate.
According to the present invention, substrate can polish with polishing system as herein described by any suitable technique.Method of the present invention especially is fit to use with chemico-mechanical polishing (CMP) device.Usually, this device comprises the polishing pad that is in the motion and moves with workbench when having by the workbench of track, linearity or the speed that circular motion caused, with the workbench contact and when being in motion in, reaches and fixedly treat by contacting with the surface of polishing pad and with respect to moving and the clamper (carrier) of the substrate that polishes on the surface of polishing pad when using.The polishing of substrate is carried out by the following method: substrate is placed to polishing system of the present invention contacts, and polishing pad is moved with respect to substrate, other component that polishing system is arranged therebetween is with wearing and tearing and remove the part of substrate, with at least a portion of polishing substrate.
This substrate can be any suitable substrate that can polish by method of the present invention.This substrate (for example can comprise metal, copper, tantalum, aluminium, titanium, molybdenum etc.), metal alloy (for example, stainless steel, cobalt-chromium etc.), semiconductor (for example, gallium nitride, GaAs etc.), the pottery (for example, carborundum), polymer (for example, Merlon), optical material (for example, sapphire, zinc sulphide, zinc selenide etc.), diamond and insulating material.
This substrate can comprise any suitable microelectronic substrate (for example, integrated circuit, metal, ILD layer, semiconductor, film, MEMS, magnetic head), and can further comprise any suitable insulation, metal or metal alloy layer (for example, metal conducting layer).Preferably, this metal level comprises tantalum.More preferably, this substrate further comprises the metal level of cupric.This insulating barrier can be metal oxide, porous metal oxide, glass, organic polymer, fluoridizes organic polymer or any other suitable high or low k insulating barrier.It is 3.5 or lower dielectric material that this insulating barrier preferably comprises dielectric constant.
The example of low-k (promptly low k dielectric) material include, but is not limited to flourine deped silicon dioxide, for example carbon doped silicon dioxide (CDO) through organically-modified silex glass, fluorocarbons, and for example fluoridize or without the organic material of Parylene of fluoridizing and polyimides.Low k dielectric can be porous or non-porous.The example of porous low dielectric material is porous silica structure, low temperature depositing silicon-carbon film, the low temperature depositing Si-O-C film of porous hydrogen silsesquioxane (hydrosilsequioxane) or porous methyl silsesquioxane, for example aeroge and the porous silica that is doped with methyl.Preferably, this insulating barrier is through organically-modified silex glass or carbon doped silicon dioxide.
Advantageously, polishing system of the present invention allows to reduce the coefficient of friction relevant with the chemico-mechanical polishing of substrate, keeps acceptable polishing speed simultaneously.
Desirably, the CMP device further comprises the original position polishing endpoint detection system, many being well known in the art wherein.Be well known in the art from the light of the surface reflection of substrate or the technology that other radiation detected and monitored polishing process by analysis.Desirably, the detection or the monitoring of the process of the polishing process of the substrate that polishing made it possible to determine polishing end point, promptly determine when particular substrate is stopped polishing process.
Littler embodiment progress explanation the present invention limits category of the present invention by any way but should not be construed as certainly.
Embodiment
This embodiment proof is using the inventive method polishing to comprise reducing of observed coefficient of friction in the substrate of tantalum.
The similar substrate that comprises the 250nm tantalum layer with different polishing composition (polishing composition A and B) polishing.Each polishing composition A and B all contain ceria that the pH value is 11 0.5 weight % in water and the Potassiumiodate of 0.20 weight %.Polishing composition B further contains the potassium silicate of 3 weight %.
This substrate uses polyurethane polishing pad to use following burnishing parameters polishing 60 seconds on Logitech Model CDP polishing machine: substrate is 13.8kPa (2psi) with respect to the downforce of polishing pad, rotating speed of table is 66rpm, the clamper rotating speed is 70rpm, the polishing composition flow velocity is 160mL/min, and uses polyurethane polishing pad.After the polishing, use resistivity measurements to measure and remove speed.
Relation between displacement by clamper axle in the polishing operation process and the power that produced by the friction between polishing pad and the substrate is determined coefficient of friction.With reference to figure 1, the clamper axle (30) that will be electrically connected to the contiguous polishing machine of non-contact capacitive displacement transducer (10) (40) of recording equipment (20) is placed, and has gap (50) therebetween.The displacement of the caused clamper axle of power F (60) that is caused by the frictional force that produces in the polishing process of substrate causes the change of the output voltage of transducer.Obtain calibration curve by the measuring transducer output voltage as the function that is applied to the known force of clamper axle in direction perpendicular to the central shaft of clamper axle.Use the average output voltage in 60 seconds polishing times to determine the polishing experiments process, to be applied to the mean force F of clamper axle from calibration curve aFrom equation μ=F a/ P is by power F aAnd substrate (80) calculates coefficientoffriction with respect to the downforce (70) of polishing pad P (90).These the results are shown in the following table.
Table: potassium silicate removes the influence of speed to coefficient of friction and tantalum
Figure A20068004379600161
Can find out that as the result from list in this table it is about 20% to exist the potassium silicate of 3 weight % to cause comprising in polishing composition of the present invention to observe in the polishing of substrate of tantalum layer coefficient of friction to reduce, tantalum removes speed and only reduces about 12% simultaneously.Therefore, the result of this embodiment proof can realize that friction reduces by polishing composition of the present invention and method.

Claims (33)

1. chemical-mechanical polishing system that is used for polishing substrate, it comprises:
(a) the polishing component that is selected from polishing pad, grinding agent and makes up,
(b) water-soluble silicate compound presents in an amount at least sufficient to provide 0.1 weight % or more SiO 2,
(c) oxidant of at least a portion of oxidase substrate, and
(d) water,
Wherein the pH value of this polishing system is 8 to 12.
2. the polishing system of claim 1, wherein this water-soluble silicate compound is selected from potassium silicate, sodium metasilicate, potassium metasilicate and sodium metasilicate.
3. the polishing system of claim 2, wherein this water-soluble silicate compound is a potassium silicate.
4. the polishing system of claim 3, wherein this potassium silicate is to be enough to provide 0.25 weight % or more SiO 2Amount exist.
5. the polishing system of claim 3, the wherein SiO of this potassium silicate 2: K 2The O mol ratio is 2.8 to 3.9.
6. the polishing system of claim 5, the wherein SiO of this potassium silicate 2: K 2The O mol ratio is 3 to 3.6.
7. the polishing system of claim 1, wherein this oxidant is selected from complex salt (hydrogenperoxymonosulfate sulfate), molybdate, ferric nitrate, nitrate, quinone and the combination thereof of hydrogen peroxide, iodate, permanganate, persulfate, peroxidating monosulfate and sulfate.
8. the polishing system of claim 1, wherein this polishing system further comprises grinding agent, and wherein this grinding agent suspends in water.
9. the polishing system of claim 8, wherein this grinding agent is selected from aluminium oxide, ceria, silicon dioxide, zirconia and combination thereof.
10. the polishing system of claim 1, wherein this polishing system comprises polishing pad and grinding agent, and wherein this grinding agent is fixed on this polishing pad.
11. the polishing system of claim 1, wherein this water-soluble silicate compound exists with 0.5 weight % or bigger amount.
12. the polishing system of claim 1, wherein this pH value is 9 to 11.
13. the method that substrate is carried out chemico-mechanical polishing, this method comprises:
(i) substrate is contacted with chemical-mechanical polishing system, this chemical-mechanical polishing system comprises:
(a) the polishing component that is selected from polishing pad, grinding agent and makes up,
(b) water-soluble silicate compound presents in an amount at least sufficient to provide 0.1 weight % or more SiO 2,
(c) oxidant of at least a portion of oxidase substrate, and
(d) water, and
(ii) wear and tear at least a portion of this substrate polishing this substrate,
Wherein the pH value of this polishing system is 8 to 12.
14. the method for claim 13, wherein this water-soluble silicate compound is selected from potassium silicate, sodium metasilicate, potassium metasilicate and sodium metasilicate.
15. the method for claim 14, wherein this water-soluble silicate compound is a potassium silicate.
16. the method for claim 15, wherein this potassium silicate is to be enough to provide 0.25 weight % or more SiO 2Amount exist.
17. the method for claim 15, the wherein SiO of this potassium silicate 2: K 2The O mol ratio is 2.8 to 3.9.
18. the method for claim 17, the wherein SiO of this potassium silicate 2: K 2The O mol ratio is 3 to 3.6.
19. the method for claim 13, wherein this oxidant is selected from complex salt, molybdate, ferric nitrate, nitrate, quinone and the combination thereof of hydrogen peroxide, iodate, permanganate, persulfate, peroxidating monosulfate and sulfate.
20. the method for claim 13, wherein this polishing system further comprises grinding agent, and wherein this grinding agent suspends in water.
21. the method for claim 20, wherein this grinding agent is selected from aluminium oxide, ceria, silicon dioxide, zirconia and combination thereof.
22. the method for claim 13, wherein this polishing system comprises polishing pad and grinding agent, and wherein this grinding agent is fixed on this polishing pad.
23. the method for claim 13, wherein this water-soluble silicate compound exists with 0.5 weight % or bigger amount.
24. the method for claim 13, wherein this pH value is 9 to 11.
25. the method for claim 13, wherein this substrate comprises metal level.
26. the method for claim 25, wherein this metal level comprises tantalum.
27. the method for claim 26, wherein this metal level further comprises copper.
28. the method for claim 13, wherein to comprise dielectric constant be 3.5 or lower dielectric layer to this substrate.
29. the method for claim 28, wherein this dielectric layer is through organically-modified silex glass.
30. the method for claim 28, wherein this dielectric layer is a carbon doped silicon dioxide.
31. the method for claim 28, wherein this substrate further comprises metal level.
32. the method for claim 31, wherein this metal level comprises tantalum.
33. the method for claim 32, wherein this metal level further comprises copper.
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