CN110520493A - Self-stopping technology polishing composition and the method planarized for bulk oxide - Google Patents

Self-stopping technology polishing composition and the method planarized for bulk oxide Download PDF

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CN110520493A
CN110520493A CN201880025600.XA CN201880025600A CN110520493A CN 110520493 A CN110520493 A CN 110520493A CN 201880025600 A CN201880025600 A CN 201880025600A CN 110520493 A CN110520493 A CN 110520493A
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polishing composition
polishing
substrate
acid
agent
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CN110520493B (en
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A.W.海恩斯
张柱然
李常怡
林越
崔骥
S.布罗斯南
南哲祐
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CMC Materials LLC
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Jiabo Microelectronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/04—Aqueous dispersions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H01L21/31055—Planarisation of the insulating layers involving a dielectric removal step the removal being a chemical etching step, e.g. dry etching

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The present invention provides the chemical-mechanical polishing compositions comprising grinding agent, self-stopping technology agent, aqueous carrier and optionally cation type polymer, moreover, providing the method for being suitable for polishing substrate.

Description

Self-stopping technology polishing composition and the method planarized for bulk oxide
Background technique
In the manufacture of integrated circuit and other electronic devices, conduction, semiconductive and the dielectric deposition of multilayer are in base In plate surface or self-reference substrate surface removes.It is removed as the material of several layers is sequentially deposited on substrate and from the substrate, it should The uppermost surface of substrate may become nonplanar and require planarization.The planarization on surface or " polishing " on surface are wherein Material self-reference substrate surface is removed to form the process on substantial uniform flat surface.Planarization is suitable for removing departing from expectation Surfac topography and surface defect, such as, rough surface, agglomerated materials, crystal lattice damage, scratch and contaminated layer or material. Planarization applies also for providing the mistake of uniform outer surface by the metallization and processing that remove for filling feature and to succeeding layer grade It measures deposition materials and forms feature on substrate.
It is known for planarizing or polishing the composition and method of substrate surface in the art.Chemical-mechanical planarization Or chemically mechanical polishing (CMP) is the common technology for planarizing substrate.CMP is using referred to as CMP composition or more simply Referred to as the Chemical composition that of polishing composition (also referred to as polishing slurries) is selectively to remove material for self-reference substrate.It is typical Ground combines polishing by substrate surface is contacted with the polishing pad (such as polishing cloth or polishing disk) for being full of polishing composition Object is applied to substrate.Typically, by the chemical activity of polishing composition and/or it is suspended in polishing composition or is integrated to throwing The polishing of the mechanical activation of grinding agent in light pad (such as fixed abrasive polishing pad) and further assisting base plate.
Number with the integrated circuit on the size reduction of integrated circuit and chip increases, and the component for constituting circuit is necessary It is more closely placed together to meet the available confined space on typical chip.Being effectively isolated for ensuring most between circuit It is important for good semiconductor performance.For this purpose, by shallow trench be etched in semiconductor substrate and with insulating materials fill with every The active region (effect, active) from integrated circuit.More specifically, shallow trench isolation (STI) is wherein on a silicon substrate Form silicon-nitride layer, via etching or be lithographically formed shallow trench and dielectric layer to fill the process of groove.Due to this The depth for the groove that mode is formed changes, and typically, needs to deposit excessive dielectric material in substrate top to ensure to own Groove is filled up completely.The configuration of the underliing of dielectric material (such as Si oxide) and substrate (underlying) is consistent.
Therefore, after having put dielectric material, the surface of the dielectric material deposited is characterized in that by dielectric material The uneven combination of the elevated regions for the dielectric material that groove in material separates, the elevated regions and groove of dielectric material with underlie The corresponding elevated regions and trough aligned on surface.Substrate surface area including raised dielectric material and groove is referred to as substrate Patterning field, for example, be referred to as " patterning materials ", " patterned oxide " or " patterned dielectric matter (dielectric)".The patterning field is characterized in that " step height ", is the height phase of the elevated regions of dielectric material For the difference of groove height.
Typically, excessive dielectric material is removed by CMP method, this provides flat surfaces additionally for further Processing.During removing the material of elevated regions, a certain amount of material will be also removed from groove.The material from groove moves Except referred to as " trench erosion " or " groove loss ".Groove loss is to realize that patterning is situated between by initial step height is eliminated When the planarization of electric material from groove remove material amount (thickness, for example, with angstromFor unit).Groove loss is by initial Ditch slot thickness subtracts final ditch slot thickness to calculate.In line with expectations, it is far below from the rate that groove removes material from convex area The rate that domain removes.Therefore, with the material for removing elevated regions (remove the faster rate of material compared to from groove), figure Case dielectric medium becomes can be described as " code-pattern " region of processing substrate surface, such as " blanket dielectric " or " code-pattern oxygen The high planarization surface of compound ".
Polishing composition can be characterized according to its polishing speed (that is, removing rate) and its planarization efficiency.Polishing speed is Refer to self-reference substrate surface remove the rate of material and be often expressed as per time unit (such as per minute) length unit (thickness, For example, with angstromFor unit).To the different zones of substrate or different removal rates relevant with the different phase of polishing step It can be important in assessment method efficiency." pattern removal rate " is that the method and step phase of substantive step height is presented in substrate Between the rate of dielectric material is removed from the elevated regions of patterned dielectric layer." blanket covers object and removes rate " refers to terminate in polishing step When the rate of dielectric material is removed from planarization (that is, " code-pattern ") region of patterned dielectric layer, at this time step height by Reduce significantly (for example, substantially completely).Planarization efficiency is related to the step height compared with the quantity of material that self-reference substrate removes Reduce (that is, step height reduction is lost divided by groove).Particularly, polished surface (such as polishing pad) contacts the surface first " high point " and material must be removed to form flat surfaces.Cause to obtain flat surfaces in the case where less removal material Method be considered more more effective than the method for needing to remove more materials to realize flatness.
Typically for the dielectric polishing step in STI method, the removal rate speed limiting of Si oxide pattern material, And it is therefore desirable for the height of Si oxide pattern removes rate to improve device yield.However, if blanket covers object removal, rate is too fast, The excessive polishing of oxide in exposed groove leads to trench erosion and increased device defects.If reducing blanket covers object shifting Removal rates then can avoid excessive polishing and the loss of relevant groove.
Desirably, " self-stopping technology " behavior is presented in certain polishings application of CMP composition, so that having moved Except surface major part " high point " (i.e. elevated regions) when, remove rate reduce.In self-stopping technology polishing application, when significant When step height is present in substrate surface, it is effectively high to remove rate, and then, as surface effectively becomes plane, moves Removal rates reduce.In (such as STI method) multiple dielectric polishing steps, patterned dielectric material (such as dielectric layer) Remove the rate-limiting factor that rate is typically whole process.Therefore, it is desirable to which the high rate that removes of patterned dielectric material is to improve Yield.In addition, it is expected that in the good efficiencies of relatively low groove loss form.In addition, if realizing the dielectric after planarizing Matter removal rate is still high, then excessive polishing occurs, additional groove is caused to be lost.
The advantages of self-stopping technology slurry, covers object by reduced blanket and removes rate generation, generates wide endpoint window.It lifts Example for, self-stopping technology behavior allow polish have reduced dielectric film thickness substrate, allow the material of reduction amount be deposited on through The top of the lower layer of structuring.In addition, engine torque end point determination can be used for more effectively monitoring final configuration.It can be flat After smoothization, by the unnecessary removal for avoiding excessive polishing or dielectric medium, base is polished under the case where lower groove is lost Plate.
Currently, being based on cerium oxide/anionic polyelectrolyte system research and development goes out self-stopping technology CMP composition.Citing and Speech, U.S. Patent Application Publication 2008/0121839 are disclosed comprising inorganic abradant, polyacrylic acid/acid/maleic acid copolymers And the polishing composition of Gemini surface active agent.Korean Patent No. 10-1524624 discloses comprising cerium oxide, carboxylic acid and mixes Close the polishing composition (english abstract) of amine compounds.International Patent Application Publication the WO2006/115393rd discloses and includes The polishing composition of cerium oxide, hydroxycarboxylic acid and amino alcohol.However, as the structure of semiconductor devices becomes more sophisticated and especially As NAND technology becomes 3D from 2D, due to current self-stopping technology CMP composition is faced with using anionic polymer The limited step height as caused by the electrostatic repulsion between grinding agent and silicon oxide surface reduces the challenge of rate.
There is still a need for by applicable removal rate is provided and meanwhile also provide improvement planarization efficiency be used for chemical machinery throw The composition and method of light oxide containing silicon substrate.The present invention provides such polishing composition and methods.Of the invention this A little and other advantages and additional features of the invention will be apparent from description of the invention presented herein.
Summary of the invention
The present invention provides the chemical machine comprising grinding agent, self-stopping technology agent, aqueous carrier and optionally cationic compound Tool polishing composition, and the method suitable for polishing substrate using polishing composition of the present invention.
More specifically, it includes chemical-mechanical polishing compositions below: (a) grinding agent that the present invention, which provides,；(b) formula Q-B Self-stopping technology agent, wherein Q can be the hydrophobic group for being substituted or being unsubstituted or assign steric hindrance group, B be in conjunction with base Group, wherein conjugated group has structure: C (O)-X-OH or-C (O)-OH, and wherein X is C1-C2 alkyl；And (c) aqueous carrier, The pH of middle polishing composition is about 3 to about 9.
The present invention also provides include chemical-mechanical polishing compositions below: (a) including the grinding of cerium oxide (ceria) Agent；(b) self-stopping technology agent selected from the following: kojic acid (5- hydroxyl -2- (hydroxymethyl) -4H- pyrans -4- ketone), crotonic acid ((E) -2- Butenoic acid), tiglic acid ((2E) -2- methyl but-2-ene acid), valeric acid (valeric acid/pentanoic acid), 2- amylene Acid, maltol (3- hydroxy-2-methyl -4H- pyrans -4- ketone), benzoic acid, 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy benzenes first Acid, caffeic acid, ethylmaltol, potassium sorbate, sorbic acid and combinations thereof；And (c) aqueous carrier, the wherein pH of polishing composition It is about 3 to about 9.
The present invention also provides include chemical-mechanical polishing compositions below:
(a) comprising the grinding agent of cerium oxide (ceria)；
(b) self-stopping technology agent selected from the following:
Formula (I) compound:
Wherein R is selected from: hydrogen, alkyl, naphthenic base, aryl, Heterocyclylalkyl and heterocyclic aryl, and each of these person can be through taking In generation, is unsubstituted；
Formula (II) compound:
Wherein X1To X3It is each independently selected from N, O, S, sp2Hydridization carbon and CY1Y2, wherein Y1And Y2It is each independently selected from Hydrogen, hydroxyl, C1-C6Alkyl, halogen and combinations thereof, and Z1-Z3It is each independently selected from hydrogen, hydroxyl, C1-C6Alkyl and combinations thereof, Each of these person can be substituted or be unsubstituted；
Formula (III) compound:
Z-(C(X1X2)n)p-CO2M (III),
Wherein Z is selected from C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl and aryl (such as phenyl, benzyl, naphthalene, Azulene, anthracene, Pyrene etc.), X1And X2Independently selected from hydrogen, hydroxyl, amino and C1-C6Alkyl, and wherein, with the combined X of the carbon being connect1 And X2Sp can be formed2Hydridization carbon, n are 1 or 2, and p is 0 to 4, and M is selected from hydrogen and suitable counter ion (such as I race metal), wherein Each can be substituted or be unsubstituted；And combinations thereof；
Formula (IV) compound:
Wherein X, Y and Z are independently selected from H, O, S, NH and CH2, R1、R2And R3Independently selected from H, alkyl, alkenyl, alkynyl, Aryl, halogen (halo) and halogenated alkyl, and M is selected from hydrogen and suitable counter ion；
(c) optionally cation type polymer；And
(d) aqueous carrier,
Wherein the pH of polishing composition is about 3 to about 9.
The present invention further provides the methods of chemically mechanical polishing substrate, comprising: (i) provides substrate, and wherein substrate includes Patterned dielectric layer on substrate surface, wherein patterned dielectric layer includes the elevated regions of dielectric material (for example, relative to week Enclose the active region (effect, active) in the region (peri)), and wherein the initial step height of patterned dielectric layer describes oxidation The thickness range (for example, active (effect, active) thickness range relative to peripheral thickness range) of object；(ii) polishing is provided Pad；(iii) chemical-mechanical polishing compositions as described herein are provided；(iv) make substrate and polishing pad and chemically mechanical polishing Composition contact；And (v) it is located on substrate surface relative to the mobile polishing pad of substrate and chemical-mechanical polishing compositions with grinding Patterned dielectric layer at least part, to polish substrate.
Detailed description of the invention
The viewgraph of cross-section of Fig. 1 (not in scale) depicted example substrate is to illustrate active (effect, active) region, groove Region, step height and groove loss.
Fig. 2 is painted the polishing efficiency that polishing composition of the present invention changes with the spacing width and pattern density of substrate.
Specific embodiment
It includes chemical-mechanical polishing compositions below: (a) grinding agent that the present invention, which provides,；(b) the self-stopping technology agent of formula Q-B, Wherein Q can be the hydrophobic group for being substituted or being unsubstituted or the group for assigning steric hindrance, and B is conjugated group, wherein combining base Group has structure: C (O)-X-OH or-C (O)-OH, and wherein X is C1-C2 alkyl；And (c) aqueous carrier, wherein polishing composition PH be about 3 to about 9.
Polishing composition of the invention includes grinding agent.The grinding agent of polishing composition desirably is suitable for polishing substrate Non-metallic part is (for example, patterned dielectric material, blanket dielectric material, patterned oxide material, code-pattern oxide material Material etc.).Suitable grinding agent includes cerium oxide (ceria) (such as CeO2), zirconium oxide (zirconia) (such as ZrO2), silicon oxygen Compound (silica, silica) (such as SiO2) and combinations thereof.
In the preferred embodiment, grinding agent is selected from cerium oxide, zirconium oxide and combinations thereof.In another preferred embodiment In, grinding agent is cerium oxide.
Both cerium oxide abrasive and zirconium, oxide abrasive are well known in the field CMP and are commercially available.It is suitble to The example of cerium oxide abrasive include wet oxidation cerium, calcined oxide cerium and metal-doped cerium oxide etc..Suitable oxidation The example of zirconium grinding agent includes the zirconium oxide etc. of metal-doped zirconium oxide and nonmetal doping.In metal-doped zirconium oxide For the oxidation of doping cerium, calcium, magnesium or yttrium with the dopant element weight percent preferably in the range of 0.1-25% Zirconium.
Cerium oxide abrasive and preparation method thereof suitable for polishing composition of the present invention, which is described in, to be mentioned on March 5th, 2015 The U.S. Patent Application No. of entitled " the Polishing Composition Containing Ceria Abrasive " that hands over Entitled " the Methods that No. 14/639,564 (present U.S. Patent No. 9,505,952) and on July 12nd, 2016 submit The U.S. Patent Application No. 15/207 of and Compositions for Processing Dielectric Substrate ", In No. 973 (as No. 2017/0014969 disclosures of U.S. Patent Application Publication No.), side of the disclosure respectively applied to quote Formula is incorporated herein.
Preferred grinding agent is wet oxidation cerium particle.Based on size, composition, preparation method, particle diameter distribution or other Mechanically or physically characteristic, polishing composition may include the abrasive particles or a variety of different types of grinding agents of single type Grain.Cerium oxide abrasive particle can be made by various distinct methods.For example, cerium oxide abrasive particle can be for through precipitating Cerium oxide particle or cerium oxide particle through condensation-polymerized, including colloidal silica cerium particle.
Cerium oxide abrasive particle can be made by any suitable method.As example, cerium oxide abrasive particle can For the wet oxidation cerium particle according to made from following methods.Typically, it is the first step in synthesizing wet oxidation cerium particle Cerium oxide precursor is dissolved in the water.Cerium oxide precursor can be any suitable cerium oxide precursor and may include having any be suitble to Charge oxidation cerium salt, for example, Ce3+Or Ce4+.Suitable cerium oxide precursor include such as cerous nitrate III, cerous nitrate IV ammonium, Cerous carbonate III, cerous sulfate IV and cerium chloride III.Preferably, cerium oxide precursor is cerous nitrate III.
Typically, increase the pH of cerium oxide precursor solution to form amorphous Ce (OH)3.The pH of solution can increase to any suitable The pH of conjunction.For example, the pH of solution can increase to about 10 or higher pH, for example, about 10.5 or higher pH, about 11 or more High pH, or about 12 or higher pH.Typically, solution will have an about 14 or lower pH, for example, about 13.5 or lower pH, Or about 13 or lower pH.Any suitable alkali can be used to increase the pH of solution.Suitable alkali include such as KOH, NaOH, NH4OH and tetramethyl ammonium hydroxide.Organic base (such as ethanol amine and diethanol amine) is also to be suitble to.With pH increase and amorphous Ce(OH)3It is formed, solution will become white and muddy.
Cerium oxide precursor solution typically mixes several hours.For example, when solution can mix about 1 hour or longer Between, for example, about 2 hours or longer time, about 4 hours or longer time, about 6 hours or longer time, about 8 hours or longer when Between, about 12 hours or longer time, about 16 hours or longer time, about 20 hours or longer time or about 24 hours or longer Time.Typically, solution is mixed about 1 hour to about 24 hours, for example, about 2 hours, about 8 hours or about 12 hours.Work as mixing When completion, solution can be transferred in pressurizing vessel and be heated.
Cerium oxide precursor solution can be heated to any suitable temperature.For example, solution can be heated to about to 50 DEG C Or it is higher, for example, about 75 DEG C or higher, about 100 DEG C or higher, about 125 DEG C or higher, about 150 DEG C or higher, about 175 DEG C or more High or about 200 DEG C or higher temperature.Selectively, or in addition, solution can be heated to about to 500 DEG C or lower, for example, about 450 DEG C or lower, about 400 DEG C or lower, about 375 DEG C or lower, about 350 DEG C or lower, about 300 DEG C or lower, about 250 DEG C or Lower, about 225 DEG C or about 200 DEG C or lower temperature.Therefore, solution can be heated to by appointing the two to limit in aforementioned endpoint In the range of temperature.For example, solution can be heated to about to 50 DEG C to about 300 DEG C, for example, about 50 DEG C to about 275 DEG C, about 50 DEG C to about 250 DEG C, about 50 DEG C to about 200 DEG C, about 75 DEG C to about 300 DEG C, about 75 DEG C to about 250 DEG C, about 75 DEG C to about 200 DEG C, about 100 DEG C to about 300 DEG C, about 100 DEG C to about 250 DEG C or about 100 DEG C to about 225 DEG C of temperature.
Cerium oxide precursor solution typically heats several hours.For example, when solution can be heated about 1 hour or longer Between, for example, about 5 hours or longer time, about 10 hours or longer time, about 25 hours or longer time, about 50 hours or longer Time, about 75 hours or longer time, about 100 hours or longer time or about 110 hours or longer time.Selectively, or Solution in addition, about 200 hours or shorter time can be heated by person, for example, about 180 hours or shorter time, about 165 hours or more Short time, about 150 hours or shorter time, about 125 hours or shorter time, about 115 hours or shorter time are about 100 small When or shorter time.Therefore, solution can be heated by the period for appointing the two to limit in aforementioned endpoint.For example, it can incite somebody to action Solution heats about 1 hour to about 150 hours, for example, about 5 hours to about 130 hours, about 10 hours to about 120 hours, it is about 15 small Up to about 115 hours or about 25 hours to about 100 hours.
After heating, it may filter that cerium oxide precursor solution to isolate the cerium oxide particle through precipitating.It can be with excessive Water rinses sediment to remove unreacted cerium oxide precursor.The mixture of sediment and excessive water can be after each rinsing step Filtering is with removal of impurity.Once sufficiently rinsing, then cerium oxide particle can be dried for extra process (such as sintering), alternatively, oxygen Changing cerium particle can direct redisperse.
Optionally, simultaneously sintering oxidation cerium particle can be dried before redisperse.Term " sintering " and " calcining " are herein Be used interchangeably with refer to it is described below under conditions of heated oxide cerium particle.Its gained knot of sintering oxidation cerium particles effect Brilliant degree.In the case where being not intended to be bound to any particular theory, it is believed that sintering oxidation cerium particle and lasting extension at high temperature Period reduce the defects of lattice structure of particle.Any suitable method can be used to carry out sintering oxidation cerium particle.Make For example, can dry and then can sintering oxidation cerium particle at elevated temperatures.It can at room temperature or at elevated temperatures It is dried.Specifically, can be done at a temperature of about 20 DEG C to about 40 DEG C, for example, about 25 DEG C, about 30 DEG C or about 35 DEG C It is dry.Selectively, or in addition, can at about 80 DEG C to about 150 DEG C, for example, about 85 DEG C, about 100 DEG C, about 115 DEG C, about 125 DEG C or It is dried at about 140 DEG C of raised temperature.After cerium oxide particle has been dried, powder can be formed through milling.It can It is milled using any suitable milling material (such as zirconium oxide).
It can be in any suitable baking oven and in any suitable at a temperature of sintering oxidation cerium particle.It for example, can be About 200 DEG C or higher, for example, about 215 DEG C or higher, about 225 DEG C or higher, about 250 DEG C or higher, about 275 DEG C or higher, about Sintering oxidation cerium particle at 300 DEG C or higher, about 350 DEG C or higher or about 375 DEG C or higher temperature.Selectively, or In addition, can be at about 1000 DEG C or lower, for example, about 900 DEG C or lower, about 750 DEG C or lower, about 650 DEG C or lower, about 550 DEG C Or lower, about 500 DEG C or lower, sintering oxidation cerium particle at about 450 DEG C or lower or about 400 DEG C or lower temperature.Cause This, can be by the at a temperature of sintering oxidation cerium particle for appointing the two to limit in aforementioned endpoint.It for example, can be at about 200 DEG C extremely About 1000 DEG C, for example, about 250 DEG C to about 800 DEG C, about 300 DEG C to about 700 DEG C, about 325 DEG C to about 650 DEG C, about 350 DEG C to about 600 DEG C, about 350 DEG C to about 550 DEG C, about 400 DEG C to about 550 DEG C, about 450 DEG C to about 800 DEG C, about 500 DEG C to about 1000 DEG C or Sintering oxidation cerium particle at a temperature of about 500 DEG C to about 800 DEG C.
The sinterable any suitable time span of cerium oxide particle.For example, sinterable about 1 hour of cerium oxide particle or For more time, for example, about 2 hours or longer time, about 5 hours or longer time about 8 hours or longer time.It may be selected Ground, or in addition, sinterable about 20 hours of cerium oxide particle or shorter time, for example, about 18 hours or shorter time, about 15 small When or shorter time, about 12 hours or shorter time or about 10 hours or shorter time.Therefore, cerium oxide particle it is sinterable by The period for appointing the two to limit in aforementioned endpoint.For example, sinterable about 1 hour to about 20 hours of cerium oxide particle, example Such as from about 1 hour to about 15 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 20 hours or about 10 hours to about 20 hours.
Cerium oxide particle can also be sintered at various temperatures and continue the various time spans in range as described above. For example, sintering oxidation cerium particle, the partition type furnace it can make cerium oxide in partition type furnace (zone furnace, zone furnace) Particle is exposed to the various time spans of one or more constant temperatures.It, can be in about 200 DEG C to about 1000 DEG C of temperature as example It lower sintering oxidation cerium particle about 1 hour or longer time, and then, can difference in the range of about 200 DEG C to about 1000 DEG C At a temperature of be sintered about 1 hour or longer time.
Typically, it is redispersed in cerium oxide particle in suitable carrier (such as aqueous carrier, especially water).If sintering Cerium oxide particle, then sintering complete after redisperse cerium oxide particle.Any suitable method can be used to carry out redisperse oxidation Cerium particle.Typically, carry out redisperse cerium oxide by the pH for the mixture for using suitable acid to reduce cerium oxide particle and water Grain.As pH is reduced, the surface of cerium oxide particle generates cationic zeta potential.The cation zeta potential produces between cerium oxide particle Raw repulsive force, promotes cerium oxide particle redisperse.Any suitable acid can be used to reduce the pH of mixture.Suitable acid packet Include such as hydrochloric acid and nitric acid.High water soluble and with hydrophilic functional group group organic acid be also suitable.Suitable has Machine acid includes such as acetic acid.Acid (such as H with multivalent anions3PO4And H2SO4) usual and not preferred.The pH of mixture can It is reduced to any suitable pH.For example, the pH of mixture can be reduced to about 2 to about 5, for example, about 2.5, about 3, about 3.5, about 4 or about 4.5.Typically, the pH of mixture does not decrease below about 2.
Typically, it mills and is subdivided scattered cerium oxide particle to reduce its partial size.Preferably, it mills while redisperse Cerium oxide particle.Any suitable milling material (such as zirconium oxide) can be used to mill.Ultrasonic treatment or wet can also be used Throw sequence is milled.After milling, it may filter that cerium oxide particle to remove any remaining bulky grain.For example, may be used It the use of aperture is about 0.3 μm or bigger, for example, about 0.4 μm or bigger or about 0.5 μm or bigger of filter filtering cerium oxide Grain.
The median particle diameter of abrasive particles (such as cerium oxide abrasive particle) is preferably from about 40nm to about 100nm.Particle Partial size be surround particle smallest sphere diameter.Any suitable technology can be used to measure for the partial size of abrasive particles.It lifts For example, disc centrifuge is can be used in the partial size of abrasive particles, that is, measures by differential centrifugation sedimentation (DCS).Suitable disk Formula centrifuge particle size measuring instrument is purchased from such as CPS Instruments (Prairieville, La.), such as DC24000UHR type CPS disc centrifuge.Unless specified otherwise herein, it otherwise reports and claimed median particle diameter value herein It is to be measured based on disc centrifuge.
By means of example, the median particle diameter of abrasive particles (such as cerium oxide abrasive particle) can be about 40nm or more Greatly, for example, about 45nm or bigger, about 50nm or bigger, about 55nm or bigger, about 60nm or bigger, about 65nm or bigger, about 70nm or bigger, about 75nm or bigger or about 80nm or bigger.Selectively, or in addition, abrasive particles median particle diameter It can be about 100nm or smaller, for example, about 95nm or smaller, about 90nm or smaller, about 85nm or smaller, about 80nm or smaller, about 75nm or smaller, about 70nm or smaller or about 65nm or smaller.Therefore, the median particle diameter of abrasive particles can be by aforementioned end In the range of both times in point limits.For example, the median particle diameter of abrasive particles can be about 40nm to about 100nm, example Such as from about 40nm to about 80nm, about 40nm are to about 75nm, about 40nm to about 60nm, about 50nm to about 100nm, about 50nm to about 80nm, about 50nm are to about 75nm, about 50nm to about 70nm, about 60nm to about 100nm, about 60nm to about 80nm, about 60nm to about 85nm or about 65nm are to about 75nm.Preferably, the median particle diameter of abrasive particles is about 60nm to about 80nm, for example, intermediate value grain Diameter is about 65nm, median particle diameter is about 70nm or median particle diameter is about 75nm.
Chemical-mechanical polishing compositions may include the grinding agent of any suitable amount.If composition includes very few grinding agent, Composition may not be presented removes rate enough.In contrast, if polishing composition includes excessive grinding agent, composition may It presents departing from desired polishing efficiency, may not be cost-effective, and/or may deficient in stability.Therefore, grinding agent can be with About 5wt% or less, for example, about 4wt% or less, about 3wt% or less, about 2wt% or less or about 1wt% or less Concentration is present in polishing composition.Selectively, or in addition, grinding agent can about 0.001wt% or bigger, for example, about 0.005wt% or bigger, about 0.01wt% or bigger, about 0.05wt% or bigger, about 0.1wt% or bigger or about 0.5wt% Or bigger concentration is present in polishing composition.Therefore, grinding agent can be by the concentration for appointing the two to limit in aforementioned endpoint It is present in polishing composition.For example, grinding agent can about 0.001wt% to about 5wt%, for example, about 0.005wt% extremely The concentration of about 4wt%, about 0.01wt% to about 3wt%, about 0.05wt% to about 2wt% or about 0.1wt% to about 1wt% are deposited It is in polishing composition.
Typically, polishing composition does not include a large amount of metal (such as copper, silver, the tungsten for being suitable for polishing on substrate surface Deng) grinding agent.For example, polishing composition does not include a large amount of special metal for being suitable for polished metal surface typically Oxide (such as aluminium oxide).Typically, with the total weight of the grinding agent in polishing composition, polishing composition includes to be less than The grinding agent for being different from cerium oxide abrasive and zirconium, oxide abrasive of 0.1wt%.For example, polishing composition may include 0.05wt% or less is different from the grinding agent of cerium oxide abrasive and zirconium, oxide abrasive, alternatively, 0.01wt% or less The grinding agent for being different from cerium oxide abrasive and zirconium, oxide abrasive.More specifically, polishing composition may include 0.05wt% or less is different from the metal oxide of cerium oxide and zirconium oxide, alternatively, 0.01wt% or less is different from The metal oxide of cerium oxide and zirconium oxide.
In line with expectations, grinding agent is suspended in polishing composition, more specifically, is suspended in the aqueous of polishing composition In carrier.More specifically, when grinding agent includes particle, abrasive particles are suspended in polishing composition in line with expectations, And abrasive particles are preferably Colloidal stability.Term colloid refers to suspension of the abrasive particles in aqueous carrier.Colloidal state Stability refers to the maintenance of suspension over time.In the context of the present invention, if when abrasive particles are placed in In 100ml graduated cylinder and allow to stand with not stirring 2 hours time, the granule density ([B], with g/ in the bottom 50ml of graduated cylinder ML meter) with the difference between the granule density ([T], in terms of g/mL) in the top 50ml of graduated cylinder divided by abrasive composition When particle initial concentration ([C], in terms of g/mL) is less than or equal to 0.5 (that is, { [B]-[T] }/[C]≤0.5), then it is assumed that grinding agent Particle is Colloidal stability.In line with expectations, the value of [B]-[T]/[C] is less than or equal to 0.3 and preferably lower than or equal to 0.1.
Polishing composition of the present invention includes self-stopping technology agent.Self-stopping technology agent is for the relatively high pattern removal rate of promotion and relatively Low blanket, which covers, promotes to remove rate transition from high pattern into relatively low blanket when object removes rate and planarization during polishing Cover the compound that object removes rate.In the case where being not intended to be bound to any particular theory, it is believed that connection is served as in self-stopping technology agent To grinding agent (for example, to cerium oxide or to zirconium oxide) to provide steric hindrance by between grinding agent and hydrophilic oxide surface To promote the ligand of self-stopping technology behavior.Any suitable technology, such as isothermal drop can be used in self-stopping technology agent and the combination of grinding agent Thermal method (ITC) is quantified to assess.
In the case where being not intended to be bound to any particular theory, it is believed that self-stopping technology agent promotes to tetraethoxysilane (TEOS) nonlinear response to lower pressure (DF) on blanket dielectric material.During polishing, patterned dielectric material It is subjected to higher than effective lower pressure of the lower pressure (DF) of blanket dielectric material, this is because contact is only dispersed in patterned dielectric On some parts that material is contacted with pad.The higher effective DF for being applied to TEOS patterned dielectric material generates TEOS and removes rate It is about"high" remove rate (such as pattern removal rate) polishing condition, wherein lower effective DF Generating TEOS and removing rate is aboutOr " stopping " polishing condition of lower (such as blanket covers object and removes rate). Difference between " high " state and " stopping " state typically it will be evident that so that for given DF, observes the shifting of "high" Removal rates or " stopping " removing rate.Therefore it is believed that " stopping even if being in applied DF as what is measured with blanket wafers Only " when state, self-stopping technology agent also can be realized the removal rate (i.e. pattern removal rate) of "high" in line with expectations.
Further, it should also be noted that mechanism depends not only on DF, this is because the trench oxide on patterned dielectric material It removes rate and covers object removal rate higher than blanket, even if having than in blanket wafers smaller effective DF in the trench.Citing For, in some polishings application, the concentration of self-stopping technology agent works in the effect observed, this is because in low concentration Under, self-stopping technology agent may act as rate booster (for example, observing that "high" removes rate), and observe automatic stop at higher concentrations Only behavior (for example, observing that " stopping " removing rate).Therefore, some rate boosters can have double action.By means of reality Example, when polishing composition includes pyridine carboxylic acid (the picolinic acid) of low concentration, pyridine carboxylic acid may act as rate increasing Strong agent.However, pyridine carboxylic acid may act as self-stopping technology agent when polishing composition includes the pyridine carboxylic acid of higher concentration.Typically, Pyridine carboxylic acid serves as rate enhancing in the case where concentration is less than about 1000ppm (for example, about 500ppm, about 250ppm etc.) by weight Agent.
In certain embodiments of the present invention, self-stopping technology agent has formula Q-B, and wherein Q is substituted or is unsubstituted Hydrophobic group or the group for assigning steric hindrance, and B is conjugated group, such as-C (O)-C-OH ,-C (O)-C-C-OH or-C (O)- OH.For example, in some embodiments, it includes grinding agent, the self-stopping technology agent of formula Q-B, cationic that the present invention, which provides, The polishing composition of object and aqueous carrier (such as water) is closed, wherein the pH of polishing composition is that about 3 to about 9 (for example, about 6.5 to about 8.5)。
In certain embodiments of the present invention, self-stopping technology agent has formula Q-B, and wherein Q is substituted or is unsubstituted Hydrophobic group or the group for assigning steric hindrance, and B is conjugated group, wherein conjugated group has structure :-C (O)-X-OH or-C (O)-OH.Wherein X is C1-C2 alkyl.When self-stopping technology agent is formula Q-B compound as described herein, Q can be suitble to be any Hydrophobic group or assign steric hindrance any suitable group.Suitable hydrophobic group include saturation and it is unsaturated dredge Aqueous group.Hydrophobic group can be straight chain or branching, and may include alkyl, naphthenic base and the ring structure of straight chain or branching, Including aromatics, heterocycle and fused ring system.
In embodiments, Q be selected from alkyl, naphthenic base, aromatic group, heterocycle, heteroaromatic base, and combinations thereof.
Q can be alkyl.Suitable alkyl includes the straight chain or branching, saturation or insatiable hunger for example with 1 to 30 carbon atom With the alkyl that is substituted or is unsubstituted (for example, C1-C30Alkyl, C1-C24Alkyl, Cl-C18Alkyl, C1-C12Alkyl or even C1-C6Alkyl), such as at least one carbon atom (i.e. methyl), at least two carbon atom (such as ethyl, vinyl), at least 3 A carbon atom (such as propyl, isopropyl, acrylic etc.), at least four carbon atom (butyl, isobutyl group, sec-butyl, butane etc.), At least five carbon atom (amyl, isopentyl, sec-amyl, neopentyl etc.), at least six carbon atom (hexyl etc.), at least seven carbon are former Son, at least eight carbon atom, at least nine carbon atom, at least ten carbon atom, at least 11 carbon atoms, at least 12 carbon atoms, At least 13 carbon atoms, at least 14 carbon atoms, at least 15 carbon atoms, at least 16 carbon atoms, at least 17 carbon atoms, extremely Few 18 carbon atoms, at least 19 carbon atoms, at least 20 carbon atoms, at least 25 carbon atoms or at least 30 carbon atoms.
The group being substituted refers to the group that the hydrogen of wherein one or more and bond with carbon is replaced by non-hydrogen atom.It is illustrative Substituent group include such as hydroxyl, ketone group, ester, amide, halogen (such as fluorine, chlorine, bromine and iodine), amino (primary, secondary, uncle and/or season Amino), and combinations thereof.
Q can be naphthenic base.Suitable naphthenic base includes saturation for example with 3 to 20 carbon atoms or unsaturation, through taking Generation or the naphthenic base being unsubstituted (such as C3-C20Cyclic group).For example, suitable naphthenic base includes cyclopropyl, ring fourth Base, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl and combinations thereof.In addition, suitable unsaturated ring alkyl includes for example Cyclobutane, cyclopentene, cyclohexene and combinations thereof.
Q can be aromatic group.Suitable aromatic group includes such as being substituted or being unsubstituted with 1 to 20 carbon atom Aromatic group.For example, suitable aromatic group include phenyl, benzyl, naphthalene, Azulene, anthracene, pyrene, and combinations thereof.
Q can be heteroaromatic base." hetero atom " is defined herein as any atom in addition to carbon and hydrogen atom.Suitable contains Heteroatomic functional group include for example hydroxyl, carboxylic acid group, ester group, ketone group, amino (such as primary, secondary and tertiary amino), acylamino-, Imino group, mercaptan ester group, thioether group, itrile group, nitro, halogen group and combinations thereof.
Suitable heterocycle includes such as ring containing 1 to 20 carbon atom and containing nitrogen, oxygen, sulphur, phosphorus, boron and combinations thereof Hydrocarbon compound.Heterocyclic compound can be saturated and it is unsaturated, be substituted or be unsubstituted.Heterocyclic compound refers to one Or multiple parts as ring system and by comprising hetero atom (such as N, O, S, P or B) 5-, 6- or 7- member ring chemical combination Object.Illustrative heterocyclic compound includes such as triazole, aminotriazole(ATA), 3- amino -1,2,4- triazole, 3- amino -1,2,4- three Azoles -5- carboxylic acid, 3- amino -5- sulfydryl -1,2,4- triazole, 4- amino -5- diazanyl -1,2,4- triazole -3- mercaptan, thiazole, 2- ammonia Base -5- methylthiazol, 2- amino -4- thiazolyl acetic acid, heterocyclic N-oxides, 2 hydroxy pyrimidine-N- oxide, 4- methyl morpholine - N- oxide and pyridine carboxylic acid N- oxide etc..Other illustrative heterocyclic compounds include such as pyranone compounds, pyridine Compound (including position isomer and stereoisomer), Pyrrolizidine, δ -2- pyrrolin, imidazolidine (imidazolidine), δ - 2- imidazoline, δ -3- pyrazoline, pyrazolidine (pyrazolidine), piperidines, piperazine, morpholine, quinuclidine, indoline, iso-indoles Quinoline, benzodihydropyran (chroman), isochroman, and combinations thereof.
Suitable heteroaromatic base includes such as pyridine, thiophene, furans, pyrroles, 2H- pyrroles, imidazoles, pyrazoles, differentAzoles, furan Our (furazan), isothiazole, pyrans (2H), pyrazine, pyrimidine, pyridazine, isobenzofuran, indolizine, indoles, 3H- indoles, 1H- Indazole, purine, iso-indoles, 4aH- carbazole, carbazole, B-carboline, 2H- chromene, 4H- quinolizine, isoquinolin, quinoline, quinoxaline, 1,8- naphthyridines, phthalazines, quinazoline, cinnolines, pteridine, xanthene, phenoThiophene, phenthazine, azophenlyene, pah pyridine (perimidine), 1,7- Phenanthroline (phenantrholine), phenanthridines, acridine, and combinations thereof.
In some embodiments, Q replaces through one or more substituent groups.Suitable substituent group may include such as this paper institute Any suitable compound/radical of description.For example, suitable substituent group include alkyl, naphthenic base, aryl, heterocycle, Heteroaromatic base and combinations thereof.
In some embodiments, Q is unsubstituted.In other embodiments, Q is the group for assigning steric hindrance.Citing and Speech, Q may not be in particular hydrophobic, but the chemistry that can will occur in relevant molecule with smaller Q group originally for prevention The large volume component of reaction or interaction.Without limitation, the example of the self-stopping technology agent with such Q group will be malt Phenol, ethylmaltol and kojic acid.
In some embodiments, conjugated group B is selected from carboxylic acid group, hydroxamic acid base, azanol base, hydroxyl, ketone group, sulfuric acid Foundation group, phosphate groups, and combinations thereof.
In some embodiments, self-stopping technology agent Q-B is selected from kojic acid, maltol, ethylmaltol, propyl maltol, different Hydroximic acid, benzene hydroxamic acid, salicylhydroxamic acid, benzoic acid, 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy-benzoic acid, coffee Coffee acid, sorbic acid and combinations thereof.
In addition, the salt of the self-stopping technology agent of preparation Q-B is also applied for polishing composition of the present invention.
In some embodiments, self-stopping technology agent is selected from kojic acid, maltol, ethylmaltol, propyl maltol, cautious each Acid, root of Dahurain angelica acid, benzoic acid, 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy-benzoic acid, caffeic acid, sorbic acid, potassium sorbate and its Combination.
In some embodiments, the self-stopping technology agent of preparation Q-B is selected from formula (I) compound, formula (II) compound, formula (III) compound, formula (IV) compound and combinations thereof.
Formula (I) compound has a structure that
Wherein R is selected from: hydrogen, alkyl, naphthenic base, aryl, Heterocyclylalkyl and heterocyclic aryl, and each of these person can be through taking In generation, is unsubstituted.
Formula (II) compound has a structure that
Wherein X1To X3It is each independently selected from N, O, S, sp2Hydridization carbon and CY1Y2, wherein Y1And Y2It is each independently selected from Hydrogen, hydroxyl, C1-C6Alkyl, halogen and combinations thereof, and Z1To Z3It is each independently selected from hydrogen, hydroxyl, C1-C6Alkyl and combinations thereof, Each of these person can be substituted or be unsubstituted.
Formula (III) compound has a structure that
Z-(C(X1X2)n)p-CO2M (III),
Wherein Z is selected from N, C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl and aryl (such as phenyl, benzyl, naphthalene, Azulene, Anthracene, pyrene etc.), X1And X2Independently selected from hydrogen, hydroxyl, amino and C1-C6Alkyl, C1-C6Alkenyl；And wherein, with the carbon that is connect Combined X1And X2Sp can be formed2Hydridization carbon, n are 1 or 2, and p is 0 to 4, and M be selected from hydrogen and suitable counter ion (such as I race metal), each of these person can be substituted or be unsubstituted.
Formula (IV) compound has a structure that
Wherein X, Y and Z are independently selected from H, O, S, NH and CH2, R1、R2And R3Independently selected from H, alkyl, alkenyl, alkynyl, Aryl, halogen and halogenated alkyl, and M is selected from hydrogen and suitable counter ion.
Polishing composition may include the self-stopping technology agent (such as formula Q-B compound) of any suitable amount.If composition included Few self-stopping technology agent, then suitable self-stopping technology behavior can not be presented in composition.In contrast, if polishing composition includes excessive Self-stopping technology agent, then composition can be presented departing from desired polishing efficiency, can not be cost-effective, and/or may lack stabilization Property.Therefore, polishing composition can include about 2wt% or lower, for example, about 1wt% or lower, about 0.5wt% or lower, about 0.1wt% or lower or about 0.01wt% or lower self-stopping technology agent.Selectively, or in addition, polishing composition may include About 0.0001wt% or higher, for example, about 0.0005wt% or higher, about 0.001wt% or higher, about 0.005wt% or more High, about 0.01wt% or higher or about 0.05wt% or higher self-stopping technology agent.Therefore, polishing composition may include concentration by preceding State the self-stopping technology agent for appointing the two to limit in endpoint.For example, self-stopping technology agent can about 0.0001wt% to about 2wt%, example Such as from about 0.0005wt% to about 1wt%, about 0.001wt% are to about 0.5wt%, about 0.005wt% to about 0.1wt% or about The concentration of 0.01wt% to about 0.05wt% are present in polishing composition.
In some embodiments, polishing composition of the present invention include about 0.5wt% or lower (for example, about 5,000ppm or It is lower) self-stopping technology agent.In some embodiments, polishing composition includes about 2,500ppm (0.25wt%) or lower, example Such as from about 2,000ppm or lower, about 1,500ppm or lower, about 1,000ppm or lower or about 500ppm or lower self-stopping technology Agent.
In some embodiments, polishing composition of the present invention includes and combines with smooth agent (i.e. cationic compound) Self-stopping technology agent, also known as configuration control agent.In the case where being not intended to be bound to any particular theory, it is believed that due to sun from Subtype compound is typically by oxide removal rate is reduced in conjunction with negatively charged oxide surface, therefore, sun from Subtype compound serves as smooth agent to improve the configuration of polished substrate.Polishing condition of the cationic compound in higher pH Under (for example, with about 6.5 to about 8.5 pH, with about 7.0 to 8.5 pH) also improve self-stopping technology composition planarization Efficiency.
Cationic compound can be for comprising being selected from quaternary amine, cationic polyvinyl alcohol, cationic cellulose and combinations thereof The polymer of monomer.Therefore, cation type polymer may include quaternary amine, cationic polyvinyl alcohol, cationic cellulose and its group It closes.
Suitable quaternary amine monomer includes such as vinyl imidazole, methacryloxyethyl trimethyl-ammonium halide, two Allyl dimethyl base ammonium halide and combinations thereof.Therefore, suitable cation type polymer includes quaternary amine for example selected from the following: poly- (vinyl imidazole)；Poly- (methacryloxyethyl trimethyl ammonium) halide, such as poly- (methacryloxyethyl Trimethyl ammonium) chloride (poly- MADQUAT)；Poly- (diallyl dimethyl ammonium) halide, such as poly- (diallydimethyl Ammonium) chloride (poly- DADMAC)；Poly- [bis- bis- [3- (dimethylamino) propyl] ureas of (2- chloroethyl) ether-alternating -1,3-] are (i.e. poly- Quaternary ammonium salt -2)；Copolymer (the i.e. polyquaternary amine of vinyl pyrrolidone and quaternized dimethylamine ethyl ester Salt -11)；The copolymer (i.e. polyquaternium -16) of vinyl pyrrolidone and quatemized vinylimidazol；Vinyl acyl in oneself The terpolymer (i.e. polyquaternium -46) of amine, vinyl pyrrolidone and quatemized vinylimidazol；And 3- methyl-1- Vinyl imidazole methylsulfate-n-vinyl pyrrolidone copolymer (i.e. polyquaternium -44).In addition, be suitble to sun from Subtype polymer includes the cation type polymer for personal nursing, such asSupreme、 Hold、UltraCare、FC 370、FC 550、FC 552、Excellence and combinations thereof.Any combination for the cation type polymer being mentioned above can be used.
In embodiments, cation type polymer is quaternary amine, and cation type polymer is poly- (methacryloxy Ethyl trimethyl ammonium) halide, such as poly- MADQUAT.
In embodiments, cation type polymer is quaternary amine, and cation type polymer is poly- (vinyl imidazole).
Cation type polymer can be any suitable cationic polyvinyl alcohol or cationic cellulose.Preferably, sun from Subtype polymer is cationic polyvinyl alcohol.For example, cationic polyvinyl alcohol can be Nippon Gosei GOHSEFIMER K210TMPolyvinyl alcohol product.
When it is present, cation type polymer (i.e. quaternary amine, cationic polyvinyl alcohol, cationic cellulose or combinations thereof, always Meter) it can be present in polishing composition with any suitable concentration.Typically, cation type polymer is with about 1ppm to about 500ppm, for example, about 1ppm are to about 475ppm, about 1ppm to about 450ppm, about 1ppm to about 425ppm, about 1ppm to about 400ppm, about 1ppm to about 375ppm, about 1ppm to about 350ppm, about 1ppm to about 325ppm, about 1ppm to about 300ppm, about 1ppm to about 275ppm, about 1ppm are to about 250ppm, about 1ppm to about 225ppm, about 1ppm to about 200ppm, about 1ppm to about 175ppm, about 1ppm to about 150ppm, about 1ppm to about 125ppm, about 1ppm to about 100ppm, about 1ppm to about 75ppm, about 1ppm to about 50ppm, about 1ppm are to about 40ppm, about 1ppm to about 25ppm, about 5ppm to about 225ppm, about 5ppm to about 100ppm, about 5ppm to about 50ppm, about 10ppm to about 215ppm, about 10ppm to about 100ppm, about 15ppm to about 200ppm, The concentration of about 25ppm to about 175ppm, about 25ppm to about 100ppm or about 30ppm to about 150ppm are present in polishing composition In.Unless otherwise stated, otherwise herein the total weight of listed ppm concentration reflection component and polishing composition based on weight The ratio of amount.
When cation type polymer is poly- (vinyl imidazole), cation type polymer is preferably with about 1ppm to about The concentration of 10ppm, for example, about 2ppm, about 5ppm, about 6ppm, about 7ppm, about 8ppm or about 9ppm are present in polishing composition. It is highly preferred that cation type polymer is preferably with about 1ppm to about when cation type polymer is poly- (vinyl imidazole) The concentration of 5ppm, for example, about 2ppm, about 3ppm or about 4ppm are present in polishing composition.
Polishing composition is optionally including additive selected from the following: carboxylic acid monomer, sulfonated monomer or phosphorated monomer With the anionic copolymer of acrylate, polyvinylpyrrolidone or polyvinyl alcohol (for example, 2- hydroxyethyl methacrylic acid with The copolymer of methacrylic acid)；Non-ionic polyalcohol, wherein non-ionic polyalcohol is polyvinylpyrrolidone or poly- second two Alcohol；Silane, wherein silane is amino silane, ureido silane or glycidyl silane；Be functionalized pyridine N- oxide (such as Pyridine carboxylic acid N- oxide)；Starch；Cyclodextrin (such as alpha-cyclodextrin or beta-cyclodextrin)；And combinations thereof.
When additive is non-ionic polyalcohol and when the non-ionic polyalcohol is polyvinylpyrrolidone, poly- second Alkene pyrrolidone can have any suitable molecular weight.For example, the molecular weight of polyvinylpyrrolidone can be about 10, 000g/mol to about 1,000,000g/mol, for example, about 20,000g/mol, about 30,000g/mol, about 40,000g/mol, about 50,000g/mol or about 60,000g/mol.When additive is non-ionic polyalcohol and when the non-ionic polyalcohol is poly- When ethylene glycol, polyethylene glycol can have any suitable molecular weight.For example, the molecular weight of polyethylene glycol can be about 200g/ Mol to about 200,000g/mol, for example, about 8000g/mol or about 100,000g/mol.
When additive is silane, silane can be any suitable amino silane, ureido silane or glycidyl silane. For example, silane can be 3- TSL 8330,3- aminopropyl silane triol, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- TSL 8330 triol, (N, N)-dimethyl - 3- TSL 8330, N- phenyl -3- TSL 8330, ureidopropyltriethoxysilane or 3- Glycidylpropyl dimethylethoxysilane.
Preferably, when polishing composition includes additive, additive is selected from 2- hydroxyethyl methacrylic acid and methyl-prop The copolymer of olefin(e) acid, polyvinylpyrrolidone, aminopropyl silane triol, pyridine carboxylic acid N- oxide, starch, alpha-cyclodextrin, Beta-cyclodextrin, and combinations thereof.
Additive is (that is, carboxylic acid monomer, sulfonated monomer or phosphorated monomer and acrylate, polyvinylpyrrolidone or poly- The anionic copolymer of vinyl alcohol；Silane；It is functionalized the N- oxide of pyridine；Starch；Cyclodextrin；Or combinations thereof, amount to) it can It is present in chemical-mechanical polishing compositions with any suitable concentration.Preferably, additive is with about 1ppm to about 500ppm, example Such as from about 5ppm to about 400ppm, about 10ppm to about 400ppm, about 15ppm to about 400ppm, about 20ppm to about 400ppm, about 25ppm to about 400ppm, about 10ppm are to about 300ppm, about 10ppm to about 250ppm, about 30ppm to about 350ppm, about 30ppm Concentration to about 275ppm, about 50ppm to about 350ppm or about 100ppm to about 300ppm is present in polishing composition.More Preferably, additive is with about 1ppm to about 300ppm, for example, about 1ppm to about 275ppm, about 1ppm to about 250ppm, about 1ppm To about 100ppm, about 1ppm to about 50ppm, about 10ppm to about 250ppm, about 10ppm to about 100ppm or about 35ppm to about The concentration of 250ppm is present in polishing composition.
In addition to one or more of additive described herein is (that is, carboxylic acid monomer, sulfonated monomer or phosphorated monomer With the anionic copolymer of acrylate, polyvinylpyrrolidone or polyvinyl alcohol；Non-ionic polyalcohol；Silane；Function Change the N- oxide of pyridine；Starch；And one or more of cyclodextrin) other than, polishing composition optionally also may include as Cation type polymer described herein.Selectively, polishing composition may include not having additive as described above One or more of (that is, do not have carboxylic acid monomer, sulfonated monomer or phosphorated monomer and acrylate, polyvinylpyrrolidine The anionic copolymer of ketone or polyvinyl alcohol；Non-ionic polyalcohol；Silane；It is functionalized the N- oxide of pyridine；Starch；And One or more of cyclodextrin) cation type polymer.
Polishing composition includes aqueous carrier.Aqueous carrier includes water (such as deionized water) and can contain one or more Organic solvent miscible with water.The example of workable organic solvent includes: alcohol, such as acrylic alcohol, isopropanol, ethyl alcohol, 1- propyl alcohol, methanol, 1- hexanol and fellow；Aldehyde, such as acetaldehyde and fellow；Ketone, such as acetone, diacetone alcohol, methyl ethyl ketone and Fellow；Ester, such as Ethyl formate, propyl formate, ethyl acetate, methyl acetate, methyl lactate, butyl lactate, ethyl lactate And fellow；Ether, including sulfoxide, such as dimethyl sulfoxide (DMSO), tetrahydrofuran, twoAlkane, diethylene glycol dimethyl ether and class Like person；Amide, such as n,N-Dimethylformamide, methylimidazole alkanone, N-Methyl pyrrolidone and fellow；Polyalcohol and Its derivative, such as ethylene glycol, glycerine, diethylene glycol, diethylene glycol monomethyl ether and fellow；And nitrogenous organic compound Object, such as acetonitrile, amylamine, isopropylamine, imidazoles, dimethylamine and fellow.Preferably, aqueous carrier is only water, that is, there is no have Solvent.
The pH of polishing composition of the present invention is about 3 to about 9.Typically, the pH of polishing composition is about 3 or bigger.In addition, The pH of polishing composition is typically about 9 or lower.For example, the pH of polishing composition can be about 3.5 to about 9, for example, about 4 To about 9, about 4.5 to about 9, about 5 to about 9, about 5.5 to about 9, about 6 to about 9, about 6.5 to about 9, about 7 to about 9, about 7.5 to about 9, About 8 to about 9 or about 8.5 to about 9.Selectively, the pH of polishing composition can be about 3 to about 8.5, for example, about 3 to about 8, about 3 To about 7.5, about 3 to about 7, about 3 to about 6.5, about 3 to about 6, about 3 to about 5.5, about 3 to about 5, about 3 to about 4.5, about 3 to about 4, Or about 3 to about 3.5.Therefore, the pH of polishing composition can be by appointing the two to limit in aforementioned endpoint.
Preferably, the pH of polishing composition is about 3 to about 5 or about 7.0 to about 8.5.For example, in preferred embodiment In, polishing composition includes the self-stopping technology agent and aqueous carrier of grinding agent, formula Q-B as described herein, wherein polishing combination The pH of object is about 3 to about 5.
In another preferred embodiment, polishing composition includes the self-stopping technology of grinding agent, formula Q-B as described herein Agent, cation type polymer and aqueous carrier, wherein the pH of polishing composition is about 7.0 to about 9.0.In some preferred implementation sides In formula, polishing composition of the present invention includes grinding agent, the self-stopping technology agent of formula as described herein (I), cation type polymer And aqueous carrier, wherein the pH of polishing composition is about 7.0 to about 9.0.
Polishing composition may include pH adjusting agent and pH buffer.PH adjusting agent can be any suitable pH adjusting agent.It lifts For example, pH adjusting agent can be alkylamine, hydramine, hydroxide quaternary amine, ammonia or combinations thereof.Specifically, pH adjusting agent can be three Ethanol amine (TEA), tetramethylammonium hydroxide (TMAH or TMA-OH) or tetraethylammonium hydroxide (TEAH or TEA-OH).In some implementations In mode, pH adjusting agent is triethanolamine.
PH adjusting agent can be present in polishing composition with any suitable concentration.In line with expectations, pH adjusting agent is with foot To reach and/or maintain the polishing composition pH within the scope of pH described in this paper, for example, be enough to maintain about 3 to about 9 pH, It is enough to maintain the pH of about 3 to about 5 or is enough to maintain the concentration of the pH of about 7.0 to about 8.5 to be present in polishing composition.
Polishing composition contains any suitable buffer.For example, suitable buffer may include phosphate, sulphur Hydrochlorate, acetate, malonate, oxalates, borate, ammonium salt, azoles and fellow.In some embodiments, buffer is 1H- benzotriazole.
Polishing composition contains the buffer (if present) of any suitable amount.For example, buffer can be about 0.0001wt% or higher, for example, about 0.0005wt% or higher, about 0.001wt% or higher, about 0.005wt% or higher, About 0.01wt% or higher or about 0.1wt% or higher concentration are present in polishing composition.Selectively, or in addition, Buffer can about 2wt% or lower, for example, about 1.8wt% or lower, about 1.6wt% or lower, about 1.4wt% or lower, About 1.2wt% or lower or about 1wt% or lower concentration are present in polishing composition.Therefore, buffer can be by aforementioned The concentration for appointing the two to limit in endpoint is present in polishing composition.For example, buffer can about 0.0001wt% extremely About 2wt%, for example, about 0.005wt% are to about 1.8wt%, about 0.01wt% to about 1.6wt% or about 0.1wt% to about 1wt% Concentration be present in polishing composition.
Polishing composition optionally further includes one or more other additional components.Illustrative additional component includes Rate booster, regulator, antisludging agent, dispersing agent etc..Rate booster is by the high complex of formation in line with expectations (such as silicon compound of pentacoordinate or hexa-coordinate) activates the organic carboxyl acid of polishing particles or substrate.Suitable rate booster packet Include such as pyridine carboxylic acid and 4-HBA.Polishing composition may include surfactant and/or rheology control agent, including viscous Spend reinforcing agent and coagulant (such as polymer-type rheology control agent, such as urethane polymer), dispersing agent, biocide (such as KATHONTM) and fellow LX.Suitable surfactant includes such as cationic surface active agent, anionic Surfactant, anionic polyelectrolyte, nonionic surface active agent, amphoteric surfactant, fluorinated surfactant, Its mixture and fellow.By means of example, additional component may include Brij S20 (polyethylene glycol octadecyl ether) Ji Juyi Glycol (such as PEG8000).
Polishing composition can be prepared by any suitable technology, many of these technologies are known to those skilled in the art 's.Polishing composition can be prepared with batch processes or continuation method.In general, polishing composition can be by group in any order Component herein is closed to prepare.Term " component " as used herein includes individual ingredient (such as grinding agent, self-stopping technology Agent, cationic compound etc.) and any group of each ingredient (such as grinding agent, self-stopping technology agent, cationic compound etc.) It closes.
For example, self-stopping technology agent can be added in aqueous carrier (such as water) with concentration desirably.Then may be used It adjusts (as needed) pH and grinding agent can be added in mixture with concentration desirably to form polishing composition.Polishing Composition can be prepared before the use, wherein will before use (such as using in about 1 minute first, or using it is preceding about In 1 hour, or using in about 7 days first) one or more components are added in polishing composition.Also it can be grasped by polishing Component is mixed at substrate surface to prepare polishing composition during work.
Polishing composition also can provide to be intended to diluted dense with suitable aqueous carrier (especially water) before the use Contracting object.In such an embodiment, polishing composition concentrate may include grinding agent, self-stopping technology agent, cation type polymer (if present) and aqueous carrier, amount make when diluting concentrate with suitable quantity of water, and each component of polishing composition will be with above It is present in polishing composition for the amount in proper range cited by each component.In addition, such as those of ordinary skill in the art It will be understood that, concentrate contains the water for the appropriate component being present in final polishing composition to ensure other components at least portion Divide or is fully dissolved in concentrate.
Although polishing composition for a long time or can be prepared even soon before the use before the use, polishing composition It can be generated by the component for mixing polishing composition at using position or near it.As used herein, term " uses position Set " refer to such position, at this location, polishing composition is applied to substrate surface (such as polishing pad or substrate surface Itself).When polishing composition will be using being blended to produce using position, the component of polishing composition is respectively stored in two Or more in storage device.
In order to mix component contained in storage device to generate polishing composition using at position or near it, store up Cryopreservation device typically be equipped with from each storage device guide to polishing composition using at position (such as platform, polishing pad or Substrate surface) one or more flowlines.Term " flowline ", which means to flow to from individual storage container, wherein to be stored up The path using position for the component deposited.One or more flowlines can be respectively directed directly to using position, alternatively, making In the case of more than one flowline, in flowline it is two or more can in any position place be merged into guidance extremely Use the single flowline of position.In addition, one or more flowline (such as individual flowline or combined flowing Pipeline) any one of can reach component using before position first guidance to one or more of the other device (for example, pump Send device, measuring equipment, mixing arrangement etc.).
The component of polishing composition can be independently delivered to using position (for example, component is delivered to substrate surface, it The mixed component during polishing processing procedure afterwards), alternatively, and then component can combine before being delivered to using position.If component is It was combined before reaching using position less than 10 seconds, preferably combined before reaching using position less than 5 seconds, more preferably reach It combined, or is even combined with while component is delivered to using position (for example, component is being divided less than 1 second using before position Combined at orchestration), then component is " and then before being delivered to using position " combination.If component is in the 5m using position It is interior, it is combined such as in the 1m using position or even in the 10cm using position (such as in the 1cm using position), then Component is also " and then before being delivered to using position " combination.
When reaching using two or more in the component for combining polishing composition before position, component can flow It combines in dynamic pipeline and is delivered in the case where not using mixing arrangement using position.Selectively, one in flowline Person or more persons are directed in mixing arrangement to promote the two or more combination in component.Any suitable mix can be used It attaches together and sets.For example, mixing arrangement can be the two or more nozzle flowed through or spout (such as high pressure nozzle in component Or spout).Selectively, mixing arrangement can be container-type mixing device, and it includes one or more entrances, by the entrance Two or more components of polishing composition are introduced in mixer；And at least one outlet, make to mix via the outlet The group of conjunction separates mixer directly or via other components (such as via one or more flowlines) of equipment to deliver To using position.In addition, mixing arrangement may include more than one chamber, each chamber have at least one entrance and at least one go out Mouthful, two of them or more component combines in each chamber.If mixing arrangement preferably comprises using container-type mixing device Mixed organization is further to promote the combination of component.Mixed organization is usually as known in the art and including blender, blending Device, agitator, vane-type baffle, gas sparger systems, vibrator etc..
The present invention also provides the sides for using invention as described herein CMP composition to polish substrate with carrying out chemical machinery Method.In embodiments, the present invention provides the method for chemically mechanical polishing substrate, comprising: (i) provides substrate, wherein substrate packet Containing the patterned dielectric layer being located on substrate surface, wherein patterned dielectric layer includes the elevated regions and dielectric material of dielectric material Trench region, and wherein the initial step height of patterned dielectric layer is the height and dielectric material of the elevated regions of dielectric material Difference between the height of trench region；(ii) polishing pad is provided；(iii) chemically mechanical polishing combination described herein is provided Object；(iv) contact substrate with polishing pad and chemical-mechanical polishing compositions；And (v) relative to the mobile polishing pad of substrate and chemistry Mechanical polishing composition is at least part of the patterned dielectric layer on grinding base plate surface, to polish substrate.
More specifically, the present invention provides the method for chemically mechanical polishing substrate, comprising: (i) provides substrate, wherein substrate Comprising the patterned dielectric layer being located on substrate surface, wherein patterned dielectric layer includes the elevated regions and dielectric material of dielectric material Trench region, and wherein the initial step height of patterned dielectric layer be dielectric material elevated regions height and dielectric material Trench region height between difference；(ii) polishing pad is provided；(iii) chemical-mechanical polishing compositions are provided, it includes (a) grinding agent；(b) the self-stopping technology agent of formula Q-B, wherein Q is the hydrophobic group for being substituted or being unsubstituted or imparting steric hindrance Group, B are conjugated group, and wherein conjugated group has structure C (O)-X-OH or-C (O)-OH, and wherein X is C1-C2 alkyl；(c) Aqueous carrier；(d) optionally cation type polymer, wherein the pH of polishing composition is about 3 to about 9；(iv) make substrate and throw Light pad and chemical-mechanical polishing compositions contact；And (v) relative to the mobile polishing pad of substrate and chemical-mechanical polishing compositions With at least part of the patterned dielectric layer on grinding base plate surface, to polish substrate.
The present invention also provides the methods of chemically mechanical polishing substrate, comprising: (i) provides substrate, and wherein substrate includes and is located at Patterned dielectric layer on substrate surface, wherein patterned dielectric layer includes the elevated regions of dielectric material and the trench area of dielectric material Domain, and wherein the initial step height of patterned dielectric layer is the height of the elevated regions of dielectric material and the trench area of dielectric material Difference between the height in domain；(ii) polishing pad is provided；(iii) chemical-mechanical polishing compositions are provided, include oxygen it includes (a) Change the grinding agent of cerium；(b) self-stopping technology agent selected from the following: kojic acid, maltol, caffeic acid, crotonic acid, tiglic acid, 2- penetenoic acid, 2- hydroxy niacin, ethylmaltol, potassium sorbate, sorbic acid, Deferiprone, valeric acid and combinations thereof；And (c) aqueous carrier, wherein The pH of polishing composition is about 3 to about 9；(iv) contact substrate with polishing pad and chemical-mechanical polishing compositions；And it is (v) opposite In the mobile polishing pad of substrate and chemical-mechanical polishing compositions at least part of the patterned dielectric layer on grinding base plate surface, To polish substrate.
The present invention also provides the methods of chemically mechanical polishing substrate, comprising: (i) provides substrate, and wherein substrate includes and is located at Patterned dielectric layer on substrate surface, wherein patterned dielectric layer includes the elevated regions of dielectric material and the trench area of dielectric material Domain, and wherein the initial step height of patterned dielectric layer is the height of the elevated regions of dielectric material and the trench area of dielectric material Difference between the height in domain；(ii) polishing pad is provided；(iii) chemical-mechanical polishing compositions are provided, it includes (a) grindings Agent；(b) it is selected from the self-stopping technology agent of formula (I) compound
Wherein R is selected from: hydrogen, alkyl, naphthenic base, aryl, Heterocyclylalkyl and heterocyclic aryl, and each of these person can be through taking In generation, is unsubstituted；(c) aqueous carrier；(d) cation type polymer, wherein the pH of polishing composition is about 7 to about 9；(iv) Contact substrate with polishing pad and chemical-mechanical polishing compositions；And it (v) is thrown relative to the mobile polishing pad of substrate and chemical machinery Light composition is at least part of the patterned dielectric layer on grinding base plate surface, to polish substrate.
The present invention also provides the methods of chemically mechanical polishing substrate, comprising: (i) provides substrate, and wherein substrate includes and is located at Patterned dielectric layer on substrate surface, wherein patterned dielectric layer includes the elevated regions of dielectric material and the trench area of dielectric material Domain, and wherein the initial step height of patterned dielectric layer is the height of the elevated regions of dielectric material and the trench area of dielectric material Difference between the height in domain；(ii) polishing pad is provided；(iii) chemical-mechanical polishing compositions are provided, it includes (a) grindings Agent；(b) the self-stopping technology agent of formula (II), (III) or (IV) compound are selected from, wherein
Wherein X1To X3It is each independently selected from N, O, S, sp2Hydridization carbon and CY1Y2, wherein Y1And Y2It is each independently selected from Hydrogen, hydroxyl, C1-C6Alkyl, halogen and combinations thereof, and Z1To Z3It is each independently selected from hydrogen, hydroxyl, C1-C6Alkyl and combinations thereof, Each of these person can be substituted or be unsubstituted.
Z-(C(X1X2)n)p-CO2M (III),
Wherein Z is selected from N, C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl and aryl (such as phenyl, benzyl, naphthalene, Azulene, Anthracene, pyrene etc.), X1And X2Independently selected from hydrogen, hydroxyl, amino and C1-C6Alkyl, C1-C6Alkenyl, and wherein, with the carbon being connect Combined X1And X2Sp can be formed2Hydridization carbon, n are 1 or 2, and p is 0 to 4, and M be selected from hydrogen and suitable counter ion (such as I race metal), each of these person can be substituted or be unsubstituted,
Wherein X, Y and Z are independently selected from H, O, S, NH and CH2, R1、R2And R3Independently selected from H, alkyl, alkenyl, alkynyl, Aryl, halogen and halogenated alkyl, and M is selected from hydrogen and suitable counter ion；(c) aqueous carrier, wherein the pH of polishing composition be About 3 to about 9；(iv) contact substrate with polishing pad and chemical-mechanical polishing compositions；And (v) relative to the mobile polishing pad of substrate And chemical-mechanical polishing compositions are at least part of the patterned dielectric layer on grinding base plate surface, to polish substrate.
The present invention also provides the methods of chemically mechanical polishing substrate, comprising: (i) provides substrate, and wherein substrate includes and is located at Patterned dielectric layer on substrate surface, wherein patterned dielectric layer includes the elevated regions of dielectric material and the trench area of dielectric material Domain, and wherein the initial step height of patterned dielectric layer is the height of the elevated regions of dielectric material and the trench area of dielectric material Difference between the height in domain；(ii) polishing pad is provided；(iii) chemical-mechanical polishing compositions are provided, include oxygen it includes (a) Change the grinding agent of cerium；(b) selected from hydroxamic acid (such as acetyl group hydroxamic acid, benzene hydroxamic acid, salicylhydroxamic acid and its Combination) self-stopping technology agent；(c) cation type polymer；And (d) aqueous carrier, wherein the pH of polishing composition is about 7 to about 9； (iv) contact substrate with polishing pad and chemical-mechanical polishing compositions；And (v) relative to the mobile polishing pad of substrate and chemical machine Tool polishing composition is at least part of the patterned dielectric layer on grinding base plate surface, to polish substrate.
Polishing composition of the invention is suitable for polishing any suitable substrate.The polishing composition is especially suitable for polishing Substrate comprising silicon oxide layer.Suitable substrate includes but is not limited to flat-panel monitor, integrated circuit, memory or Hard Magnetic Disk, metal, semiconductor, interlayer dielectric (ILD) device, MEMS (MEMS), 3D NAND device, ferroelectric and magnetic head. The polishing composition is particularly well-suited for planarizing or polishing the substrate for being subjected to shallow trench isolation (STI) processing.In accordance with the phase Hope ground, substrate includes the surface containing dielectric medium (such as oxide containing silicon), especially with the table in patterned dielectric material region Face, the patterned dielectric material region include the raised dielectric regions separated by the trench region of dielectric material.Substrate can be into one Step includes at least one other layer, such as insulating layer.Insulating layer can be metal oxide, porous metal oxide, glass, organic Polymer, fluorinated organic polymer or any other suitable high or low κ insulating layer.Insulating layer may include Si oxide, silicon nitrogen Compound or combinations thereof, substantially by Si oxide, silicon nitride or combinations thereof, alternatively, by Si oxide, silicon nitride or A combination thereof composition.Silicon oxide layer may include any suitable Si oxide, be substantially made of any suitable Si oxide, Or be made of any suitable Si oxide, many is as known in the art.For example, silicon oxide layer can wrap Containing tetraethoxysilane (TEOS), high-density plasma (HDP) oxide, boron-phosphorosilicate glass (BPSG), high aspect ratio processing procedure (HARP) oxide, spin-on dielectric matter (SOD) oxide, chemical vapor deposition (CVD) oxide, plasma-enhanced original Tetraethyl orthosilicate (PETEOS), thermal oxide or undoped silicate glass.Substrate can further include metal layer.Gold Category may include any suitable metal, substantially be made of any suitable metal or be made of any suitable metal, It is middle many for as known in the art, such as copper, tantalum, tungsten, titanium, platinum, ruthenium, iridium, aluminium, nickel or combinations thereof.
According to the present invention, polishing composition described herein can be used planarized by any suitable technology or Polish substrate.Polishing method of the invention is particularly suitable for being used in combination with chemically mechanical polishing (CMP) equipment.Typically, should CMP tool includes: platform, is in movement when in use and has the speed generated by track, linear or circular motion；It throws Light pad, it is with contact with platform and mobile with platform during exercise；And carrier, fixing is to by contact and relative to polishing pad The substrate that surface is mobile and polishes.The polishing of substrate is by by substrate, with polishing composition of the invention and typically polishing pad is connect Touching put and then at least part on polishing composition and typically polishing pad grinding base plate surface (such as Si oxide or One or more of baseplate material described herein) it is carried out with polishing substrate.According to the present invention, any be suitble to can be used Polishing condition polish substrate.
Can be used chemical-mechanical polishing compositions planarized together with any suitable polishing pad (for example, polished surface) or Polish substrate.Suitable polishing pad includes such as braiding and non-woven polishing pad.In addition, suitable polishing pad may include having Different densities, hardness, thickness, compressibility, compression rebound ability and compression modulus any suitable polymer.Suitable is poly- Close object include for example polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbons, polycarbonate, polyester, polyacrylate, polyethers, Polyethylene, polyamide, polyurethanes, polystyrene, polypropylene, its form product and its mixture altogether.
Although self-stopping technology behavior is presented in the present composition and method, CMP tool can further include polishing in situ eventually Detection system is put, many in the composition and method is as known in the art.For anti-from workpiece surface by analyzing The light penetrated or other radiation are as known in the art come the technology for checking and monitoring polishing process.Such method is described in example Such as U.S. Patent No. 5,196,353, U.S. Patent No. 5,433,651, U.S. Patent No. 5,609,511, United States Patent (USP) No. 5,643,046, U.S. Patent No. 5,658,183, U.S. Patent No. 5,730,642, U.S. Patent No. 5,838,447 Number, U.S. Patent No. 5,872,633, U.S. Patent No. 5,893,796, U.S. Patent No. 5,949,927 and the U.S. it is special In benefit the 5,964,643rd.In line with expectations, make about the inspection or monitoring of the progress of the polishing process of the workpiece polished It must can determine polishing end point, that is, determine when terminate the polishing process for specific workpiece.
For the substrate of any kind of device, substrate surface may include that be placed in it further include surface texture or configuration The layer of the continuous and structuring (non-flat forms, non-smooth) of the dielectric material of the top of lower layer.The structuring of dielectric material surface, Non-planar regions are referred to as " patterned dielectric matter ".It is generated by the dielectric material for being placed in the top of the uneven texture of lower layer To fill the groove or hole that are present in lower layer.Being filled up completely and being sufficiently covered in order to ensure all grooves or hole etc. The top on the surface of the lower layer containing groove or hole etc., with excessive amount deposition of dielectric materials.Dielectric material by with lower layer Uneven configuration is consistent, and generates the deposited continuous dielectric surface for being characterized in that the elevated regions separated by groove.Convex area Domain will be the position of active (effect, active) polishing and material removal, it is intended that the position of most of dielectric material is removed from it. Patterned dielectric material is further characterized in that so-called " step height ", for relative to the dielectric material at adjacent trenches The height of the dielectric material of the elevated regions of height.
Polishing composition of the present invention is particularly well-suited in planarizing or polishing being subjected to shallow-trench isolation (STI) or similarity Thus the substrate of reason makes dielectric medium be covered in the top of the lower layer of structuring to generate the region of patterned dielectric material.For It is subjected to the substrate of shallow trench isolation, typical step height can be in the range of about 1,000 angstrom to about 7,000 angstroms.
The certain embodiments of described polishing composition are also applied for planarizing or polish as the 3D in processing The substrate of NAND flash memory device.In such substrate, lower layer is by including groove, hole or having high aspect ratio (such as at least The aspect ratio of 10:1,30:1,60:1 or 80:1) the semiconductor layers of other structures be made.Have when by dielectric material covering When the surface of the structure of such high aspect ratio, high step height will be presented in resulting patterned dielectric matter, such as substantially Greater than about 7,000 angstrom, it is greater than about 10,000 angstrom, greater than about 20,000 angstrom, greater than about 30,000 angstrom or greater than about 40,000 Angstrom or higher step height.
The dielectric material of any one of device described herein may include any suitable dielectric material, substantially It is made of any suitable dielectric material, or is made of any suitable dielectric material, many of these is well known, including Various forms of Si oxides and dielectric material based on Si oxide.For example, the dielectric material including Si oxide or Dielectric layer based on Si oxide may include any one or more of the following, by any of the following or More person's compositions, or be substantially made of any one or more of the following: tetraethoxysilane (TEOS), high density Plasma (HDP) oxide, phosphorosilicate glass (PSG), boron-phosphorosilicate glass (BPSG), high aspect ratio processing procedure (HARP) oxide, Spin-on dielectric matter (SOD) oxide, chemical vapor deposition (CVD) oxide, plasma-enhanced tetraethyl orthosilicate (PETEOS), thermal oxide or undoped silicate glass.In the past, be ready for needing to patterned dielectric matter into Some examples of the substrate of row planarization, below active (effect, the active) polishing area of patterned dielectric material It include silicon-nitride layer (such as " silicon nitride top cover " or " lining (liner) ") at position, for example, being located at structuring semiconductor " top cover " of the top on surface platform (land) of layer.Silicon nitride is designed to make dielectric material when reaching silicon-nitride layer Polishing and removal at the active region (effect, active) stop.Silicon-nitride layer be used for be intended to reduce groove loss and The mode of recess in final configuration suspends the removal of (halt) material in polishing step.However, the step is manufacturing process Increase great amount of cost and still possible not exclusively pre- anti-depression.
According to the method for the present invention, substrate may include being intended at end position positioned at dielectric medium polishing and removing step Silicon nitride lining.In other embodiments, substrate does not need and optionally and preferably do not include being placed in from active Silicon nitride " lining " or " top cover " at the end position for the step of region (effect, active) removes dielectric medium.
In line with expectations, it planarizes and polishing patterned dielectric material is to reduce elevated regions (having elemental height) With the initial step height between groove (with initial trench thickness).In order to effectively and efficiently realize the planarization, The method of the present invention has the high removal rate of the elevated regions of (active (effect, active)) patterned dielectric material, and, ditch The substantially lower removal rate of the dielectric material of slot.Most preferably, self-stopping technology behavior is also presented in the method for the present invention.
During CMP planarization or planarization, dielectric material is removed with small amount from elevated regions and from groove.In the polishing phase Between, the height of elevated regions is reduced to finally substantial horizontal with the height of groove.For example, this can refer to step height Degree decreases below 1,000 angstrom, be, for example, less than 900 angstroms, less than 500 angstroms, less than 300 angstroms or less than 250 angstroms.Elevated regions height Reduction remove the patterns of the elevated regions between groove, effectively remove pattern and convert pattern to planarization dielectric medium Region, that is, " blanket dielectric " or " code-pattern oxide ", it is intended that the region of substantially planarization of dielectric material.
Depending on the substrate just polished, the initial step height measured before starting CMP processing step can be at least 1, 000 angstrom, for example, at least 2,000 angstrom or at least 5,000 angstrom, and can be substantially bigger, all such as larger than 7,000 angstrom, for example, at least 10, 000 angstrom, at least 20,000 angstroms, at least 30,000 angstroms or at least 40,000 angstroms.After polishing, step height reduces and groove is thick Degree reduces.
Fig. 1, which describes, has initial step height (h0) and initial trench thickness (t0) exemplary substrate.The material of step height Expect be mainly dielectric medium, the material of the silicon oxide-containing (silica) of such as TEOS, BPSG or other amorphous.3D NAND dielectric Committed step in matter (and other blocky (bulk) oxide removals) processing is to reduce step height (h1) (such as be reduced to small In aboutOr it decreases below about) and there is the smallest groove (t is lost0-t1).Good planarization is imitated For rate, it is necessary to reach final step height without the loss of significant groove.This needs polishing composition (to make active With on active) (i.e. raised) region than in trench region with higher removal rate.Additionally, it is preferred that polishing composition The behavior of " self-stopping technology " or " stopping in the plane " will be generated, to allow not cause the more effective final polishing of excessive polishing. In line with expectations, polishing composition of the present invention has high compared with the removal rate on the dielectric material that blanket covers (substantially smooth) Pattern much removes rate (the removal rate at the active region (effect, active)).
The removal rate of dielectric material at active (effect, active) region is referred to as patterning materials (such as pattern Change oxide) removal rate or " pattern removal rate " or " active (effect, active) removes rate ".Use such as this paper institute The pattern that the method and polishing composition of description are reached, which removes rate, to be any suitable rate, and for any given It, will be largely depending on the size of elevated regions (such as spacing and width) for processing procedure and substrate.According to preferred side Method, the removal rate of patterned dielectric material can be at least about 2,000 angstrom min, preferably at least about 4,000 angstrom min, such as At least about 5,000 angstrom mins, at least about 6,000 angstrom mins, at least about 10,000 angstrom mins, at least about 14,000 angstrom mins Or at least about 15,000 angstrom mins.
It can be, for example, less than 3 minutes, less than 2 points by CMP pattern Processing dielectric medium less than 5 minutes according to preferred method Clock or time less than 1 minute and will be patterned into dielectric medium and be processed into planarization surface.This can be for patterned dielectric material The substrate of material and realize, the patterned dielectric material include at least 7,000 angstrom, for example, at least 10,000 angstrom, at least 20,000 angstrom, At least 30,000 angstroms or at least 40,000 angstroms of step height.Realizing the step reduced (by polishing) less than 1,000 angstroms Highly (i.e. " residue " step height) when, it is believed that the surface is effectively planarized.Therefore, polishing composition of the present invention and method It can provide less than 1,000 angstrom, be, for example, less than 900 angstroms, less than 500 angstroms, the remaining step height less than 300 angstroms or less than 250 angstroms.
In addition, according to the preferred polishing method for using polishing composition as described herein, relative to without just like this The polishing composition of self-stopping technology agent described in text (such as formula Q-B compound) can reduce groove loss and can improve planarization Efficiency.Groove loss refers to the ditch slot thickness (t before CMP processing0) with ditch slot thickness (t after the cmp processing1) between Difference, that is, groove loss be equal to t0-t1(for given processing time or result) (Fig. 1).Preferably, will be polished to it is flat Occur during change groove waste (such as by less than 1,000 angstrom, be, for example, less than 900 angstroms, less than 500 angstroms, less than 300 angstroms Or " residue " the step height definition less than 250 angstroms) or can be by making such as this for the groove waste of given processing time quantum Self-stopping technology agent described in text is present in polishing composition as described herein and reduces.Therefore, throwing described herein The loss of groove caused by light method is substantially less than (for example, at least lack 10%) using same treatment condition and device with similar But the polishing composition (such as polishing composition without formula Q-B compound) without self-stopping technology agent as described herein polishes The loss of groove caused by the substrate of same type.In line with expectations, the method for polishing substrate of the invention, which provides, is less than about 2, 000 angstrom (for example, less than about 1,500 angstroms, be less than about 1,000 angstroms, be less than about 500 angstroms or be less than about 250 angstroms) groove loss.
It can reflect lower groove loss with planarization efficiency, planarization efficiency refers to step height reductionDivided by ditch Slot lossPreferred method according to the present invention, can be by being present in self-stopping technology agent as described herein such as this paper institute Improve planarization efficiency in the polishing composition of description.Therefore, planarization caused by polishing method described herein is imitated Rate is substantially higher than that (for example, at least high 10%) is used similar but without as described herein using same treatment condition and device Produced by the substrate of polishing composition (such as polishing composition without formula Q-B compound) the polishing same type of self-stopping technology agent Planarization efficiency.In line with expectations, the method that the present invention polishes substrate provides at least about 2.0, preferably at least about 3.0, such as At least about 3.5 planarization efficiency.
Self-stopping technology behavior can also be presented in preferred method, it is intended that dielectric material (is less than from blanket dielectric material in arrival When 1,000 angstroms, step height less than 900 angstroms, less than 500 angstroms, less than 300 angstroms or less than 200 angstroms) removal rate (" blanket Cover object and remove rate ") it is substantially less than the removal rate of patterned dielectric material.Think, if the removal speed of blanket dielectric material Rate is less than about 1,000 angstrom min, then self-stopping technology behavior occurs.Therefore, in the preferred embodiment, the method for the present invention provides small In about 1,000 angstrom min, for example, less than about 800 angstrom mins, less than about 500 angstrom mins, less than about 300 angstrom mins or be less than The blanket dielectric material removal rate of about 200 angstrom mins.
By other measurements, self-stopping technology behavior can be by by the removal rate of blanket dielectric material and patterned dielectric material The removal rate of material is compared to measure.Blanket covers the good automatic stop of low-ratio instruction that object removes rate and pattern removes rate Only behavior.Therefore, in the preferred embodiment, the removal speed of the removal rate of blanket dielectric material and patterned dielectric material The ratio of rate is less than about 1, for example, less than about 0.5, is less than about 0.3 or less than about 0.1.Therefore, caused by polishing method of the present invention Blanket cover object and remove rate and pattern and remove the ratio of rate and be substantially less than (for example, at least few about 10%) and use same treatment The similar but polishing composition without self-stopping technology agent as described herein of condition and device (such as without formula Q-B compound Polishing composition) polishing same type substrate caused by blanket cover object remove rate and pattern removal rate ratio.
In embodiments, the present invention provides such method, and wherein patterned dielectric layer includes at least about 1,000 angstrom just Beginning step height, wherein this method include during polishing by initial step height decrease below about 900 angstroms it is flat to generate Change dielectric medium, and the removal rate for wherein planarizing dielectric medium is less than about 1,000 angstrom min.
In embodiments, the present invention provides such method, including removing dielectric material from patterned dielectric layer surface At least about 10,000 angstroms of elevated regions.
In embodiments, the present invention provides such method, the removal rate of the elevated regions of dielectric material with The ratio of the removal rate of the trench region of dielectric material is greater than about 5, preferably greater than about 10, greater than about 15 or greater than about 20.
In embodiments, the present invention provides such method, and the removal rate of the elevated regions of dielectric material is big In about 1000 angstrom mins.Therefore, in the preferred embodiment, the removal rate of the elevated regions of dielectric material is greater than about 2,000 Angstrom min, is greater than about 4, and 000 angstrom min, greater than about 5,000 angstrom min, greater than about 6,000 angstrom min are greater than about 10,000 angstrom mins or greater than about 15,000 angstrom mins.
In embodiments, the present invention provides such method, and wherein patterned dielectric layer includes to be selected from Si oxide, tetrem The dielectric material of oxysilane, phosphorosilicate glass, boron-phosphorosilicate glass and combinations thereof.
Embodiment
(1) provide in embodiment (1) includes chemical-mechanical polishing compositions below: (a) grinding agent；(b) formula Q-B Self-stopping technology agent, wherein Q be the hydrophobic group for being substituted or being unsubstituted or assign steric hindrance group, B is conjugated group, Wherein conjugated group have structure :-C (O)-X-OH or-C (O)-OH, wherein X be C1-C2 alkyl (such as formula (II), (III) and (IV) any compound)；And (c) aqueous carrier, wherein the pH of polishing composition is about 3 to about 9.
(2) polishing composition such as embodiment (1) is provided in the embodiment (2), wherein grinding agent be selected from cerium oxide, Zirconium oxide and combinations thereof.
(3) polishing composition such as embodiment (2) is provided in embodiment (3), wherein grinding agent is cerium oxide.
(4) polishing composition such as embodiment (1) to any one of (3) is provided in embodiment (4), wherein grinding Agent is present in polishing composition with the concentration of about 0.001wt% to about 5wt%.
(5) it is provided in embodiment (5) such as embodiment (1) to the polishing composition of any one of (4), wherein Q choosing From alkyl, naphthenic base, aromatic group, heterocycle, heteroaromatic base and combinations thereof.
(6) polishing composition such as embodiment (5) is provided in the embodiment (6), wherein Q pass through selected from hydroxyl, alkyl, One or more groups of halogen, amido or any combination thereof replace.
(7) polishing composition such as embodiment (1) is provided in embodiment (7), wherein Q-B is selected from maltol, song Acid, crotonic acid, tiglic acid, 2- penetenoic acid, valeric acid, benzoic acid, 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy-benzoic acid, coffee Acid, ethylmaltol, potassium sorbate, sorbic acid and combinations thereof.
(8) it provides in embodiment (8) such as embodiment (1) to the polishing composition of any one of (7), wherein automatic stop Only agent is present in polishing composition with about 0.5wt% or lower concentration.
(9) polishing composition such as embodiment (1) to any one of (8) is provided in embodiment (9), further Include cation type polymer.
(10) polishing composition such as embodiment (9) is provided in embodiment (10), wherein cation type polymer Monomer comprising being selected from quaternary amine, cationic polyvinyl alcohol, cationic cellulose and combinations thereof.
(11) polishing composition such as embodiment (10) is provided in embodiment (11), wherein cation type polymer Comprising quaternary amine monomer, and wherein, quaternary amine monomer is selected from vinyl imidazole, methacryloxyethyl trimethyl-ammonium halide, two Allyl dimethyl base ammonium halide and combinations thereof.
(12) polishing composition such as embodiment (9) is provided in embodiment (12), wherein cation type polymer Selected from poly- (vinyl imidazole), poly- (methacryloxyethyl trimethyl ammonium) chloride, poly- (diallydimethyl Ammonium) chloride, polyquaternium -2 and combinations thereof.
(13) polishing composition such as (1) to any one of (12) in embodiment is provided in embodiment (13), The pH of middle polishing composition is about 6.5 to about 8.5.
(14) polishing composition such as embodiment (1) to any one of (12) is provided in embodiment (14), wherein The pH of polishing composition is about 3 to about 5.
(15) polishing composition such as embodiment (1) to any one of (14) is provided in embodiment (15), into One step includes rate booster and/or pH buffer.
(16) providing in embodiment (16) includes chemical-mechanical polishing compositions below: (a) comprising cerium oxide Grinding agent；(b) self-stopping technology agent selected from the following: kojic acid, crotonic acid, tiglic acid, valeric acid, 2- penetenoic acid, maltol, benzoic acid, 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy-benzoic acid, caffeic acid, ethylmaltol, potassium sorbate, sorbic acid and combinations thereof； And (c) aqueous carrier, wherein the pH of polishing composition is about 3 to about 9.
(7) polishing composition such as embodiment (16) is provided in embodiment (17), wherein the pH of polishing composition It is about 3 to about 5.
(18) polishing composition such as embodiment (16) is provided in embodiment (18), further includes planarization Agent, the smooth agent include selected from poly- (vinyl imidazole), poly- (methacryloxyethyl trimethyl ammonium) chloride, gather The cation type polymer of (diallyl dimethyl ammonium) chloride, polyquaternium -2 and combinations thereof.
(19) polishing composition such as embodiment (18) is provided in embodiment (19), wherein the pH of polishing composition It is about 6.5 to about 8.5.
(20) providing in embodiment (20) includes chemical-mechanical polishing compositions below:
(a) comprising the grinding agent of cerium oxide；
(b) it is selected from the self-stopping technology agent of formula (I) compound:
Wherein R is selected from: hydrogen, alkyl, naphthenic base, aryl, Heterocyclylalkyl and heterocyclic aryl, and each of these person can be through taking In generation, is unsubstituted；
(c) cationic compound selected from the following: aluminium salt, methacrylic acid 2- (dimethylamino) ethyl ester, two allyls Base dimethyl ammonium, poly- (vinyl imidazole), poly- (methacryloxyethyl trimethyl ammonium) halide, poly- (diallyl Dimethyl ammonium) halide, polyquaternium -2, polyquaternium -11, polyquaternium -16, polyquaternium -46, polyquaternium -44, Luviquat Supreme、Luviquat Hold、Luviquat UltraCare、Luviquat FC 370、Luviquat FC 550, Luviquat FC 552, Luviquat Excellence and combinations thereof；And
(d) aqueous carrier,
Wherein the pH of polishing composition is about 7 to about 9.
(21) polishing composition such as embodiment (20) is provided in embodiment (21), wherein the pH of polishing composition It is about 7 to about 9.
(22) method of chemically mechanical polishing substrate is provided in embodiment (22), comprising: (i) provides substrate, wherein Substrate includes the patterned dielectric layer being located on substrate surface, and wherein patterned dielectric layer includes the elevated regions and dielectric of dielectric material The trench region of material, and wherein the initial step height of patterned dielectric layer is the height and dielectric of the elevated regions of dielectric material Difference between the height of the trench region of material；(ii) polishing pad is provided；(iii) it provides if embodiment (1) is into (21) The chemical-mechanical polishing compositions of any one；(iv) contact substrate with polishing pad and chemical-mechanical polishing compositions；And (v) phase Polishing pad mobile for substrate and chemical-mechanical polishing compositions are at least one of the patterned dielectric layer on grinding base plate surface Point, to polish substrate.
(23) polishing method such as embodiment (22) is provided in embodiment (23), wherein patterned dielectric layer includes extremely Few about 1,000 angstrom of initial step height, wherein this method includes decreasing below initial step height about during polishing 900 angstroms planarize dielectric medium to generate, and the removal rate for wherein planarizing dielectric medium is less than about 1,000 angstrom min.
(24) polishing method such as embodiment (22) or embodiment (23) is provided in embodiment (24), wherein should Method includes at least about 10,000 angstroms from the elevated regions of patterned dielectric layer surface removal dielectric material.
(25) it provides in embodiment (25) such as the polishing method of embodiment (22) to any one of (24), intermediary The ratio of the removal rate of the trench region of the removal rate and dielectric material of the elevated regions of electric material is greater than about 5.
(26) it provides in embodiment (26) such as the polishing method of embodiment (22) to any one of (25), intermediary The removal rate of the elevated regions of electric material is greater than about 1,000 angstrom mins.
(27) polishing method such as embodiment (22) to any one of (26) is provided in embodiment (27), wherein scheming Case dielectric layer includes the dielectric material selected from Si oxide, tetraethoxysilane, phosphorosilicate glass, boron-phosphorosilicate glass and combinations thereof.
Embodiment
Following embodiment further illustrates the present invention, but should not be construed in any way as limiting its range certainly.
Use following abbreviation in embodiment: PEG8000 refers to that molecular weight is the polyethylene glycol of 8,000g/mol； PMADQUAT refers to poly- MADQUAT；SHA refers to salicylhydroxamic acid；BHA refers to benzene hydroxamic acid；BTA refers to 1H- benzo Triazole；TEA refers to triethanolamine；POU refers to using position；RR refers to removal rate；AA refers to the active area (effect, active) Domain；TA refers to trench region；BW refers to TEOS blanket wafers；And SH refers to step height.
Embodiment 1
The embodiment illustrates the self-stopping technology agent optionally combined with cationic compound to the polishing composition comprising it In polishing efficiency influence.
With 14 kinds of polishing composition (i.e. polishing composition 1A-1N) polishing patterned substrates.Polishing composition 1A-1N by By by abrasive composition C1 and C2 (being described in the following table 1) and additive formulation F1-F15 (being described in the following table 2) by body Product meter is mixed with the ratio of 7:3 to prepare.
Abrasive composition C1 and C2 contain cerium oxide abrasive, pyridine carboxylic acid and water, as illustrated in table 1.HC60 And HC30 cerium oxide abrasive is purchased from Rhodia.H-30 cerium oxide abrasive is to be described in earlier application (US publication Wet oxidation cerium in application 2016/0257855).Abrasive composition C1 and C2 respectively have 4.2 pH.
Table 1: abrasive composition
Additive formulation F4-F15 contains cationic compound (pMADQUAT), self-stopping technology agent (SHA or BHA) and adds Add agent (BTA), as illustrated in table 2.Adjust each of additive formulation F3-F15's using triethanolamine (TEA) pH.Additive formulation F1 and F2 are without alkali and pH is 4.2.
Table 2: additive formulation
It will be about comprising being initially covered in step heightPatterned silicon substrate on pattern density be 50% 250 μm of TEOS features (aboutThick feature) individual patterned sample (coupon) substrate (coming From SKW Associates, the square cutout with 40mm on each side of the SKW 7-2 chip of Inc.) with 200mm IC1010 is used on the POLI-300 (G&P Tech.Inc.) of CMP platformTMPad (Rohm and Haas Electronic Materials it) is polished 60 seconds under pressure at 20.68kPa (3psi), wherein platform speed and head speed are respectively 120rpm And 110rpm.The overall flow rate rate of polishing composition is 200mL/min.As a result it is set forth in table 3.
Table 3: the influence of cationic compound and pH to polishing efficiency
Result as illustrated in from table 3 is apparent, includes the grinding agent formulation with self-stopping technology agent (hydroxamic acid) The polishing composition 1A and 1B with acid pH (pH4.2) show in line with expectations it is active in the range of about 3 to 6 The region (effect, active) removes the ratio removed with trench region.Therefore, polishing composition 1A and 1B make in line with expectations Patterning materials planarize while retaining " self-stopping technology " composition of trench material.
Polishing composition 1I comprising both self-stopping technology agent and cationic compound present about 8.6 it is active (effect, Active) region removes the ratio removed with trench region and at 6.1 pHActive (effect, active) area Domain removes.Therefore, polishing composition 1I is also " self-stopping technology " group for planarizing patterning materials while retaining trench material Close object.
Polishing composition 1C-1H and 1J-1N comprising both self-stopping technology agent and cationic compound are presented about 5.76: The active region (effect, active) in the range of 1 to about 50:1 removes the ratio removed with trench region and 7.6 to 8.8 PH under aboutTo aboutActive (effect, active) region remove.Therefore, polishing composition 1C-1H and 1J-1N is to planarize patterning materials while retaining trench material " self-stopping technology " composition.
Embodiment 2
The embodiment illustrates the self-stopping technology agent optionally combined with cationic compound to the polishing composition comprising it In polishing efficiency influence.
With three kinds of polishing composition (i.e. polishing composition 2A-2C) polishing patterned substrates.Using described in embodiment 1 Abrasive composition and additive formulation (7:3 by volume) prepare polishing composition 2B and 2C.Composition 2A (comparison) Only contain grinding agent formulation C2.
What it is obtained from Silyb Inc. is about comprising being initially covered in the step height with a variety of width and density Patterned silicon substrate on TEOS (aboutThick feature) individual patterned substrate have The AP-300 of 300mm CMP platformTMIC1010 is used on (CTS Co., Ltd.)TMPad polishes repeatedly under pressure under 3psi, In, platform speed and head speed are respectively 93rpm and 87rpm.The overall flow rate rate of polishing composition is 250mL/min.
Table 4: the description of polishing composition 2A-2C
Polishing composition Grinding agent and compositions of additives (7:3) pH(POU) Polishing time (second)
2A (comparison) C2 4.2 35
2B (present invention) C2:F2 4.2 35 and 45
2C (present invention) C2:F12 7.7 30,60 and 90
It is before polishing and surplus depending on the spacing of the result as embodiment 2 and pattern density after polishing Remaining active (effect, active) thickness is graphically present in Fig. 2.
The result such as presented from Fig. 2 is apparent, containing grinding agent, benzene hydroxamic acid and poly- MADQUAT 7.7 pH (POU) low pattern density dependence is presented with the increase of polishing time in the polishing composition 2C of the present invention under, moreover, when with Polishing composition 2A and 2B are compared, and have (the polishing composition 2C polishing 90 of uniform configuration when stopping occurring above substrate Second).
Additional polishing Potency data is set forth in table 5 and Fig. 2.Data in table 5 are described above chip with polishing time And remaining active (effect, the active) thickness become, it includes 900 μm of TEOS features (50% pattern densities).
Table 5: the remaining Si oxide become with polishing time
It is such as apparent from table 5 and result illustrated in fig. 2, polishing composition 2C initially on patterning materials present compared with Low polishing speed, but compared with comparison (polishing composition 2A and 2B), rate above chip reduce with step height and Equably decline.The embodiment further illustrates, compared with compareing polishing composition, at the pH in about 7.0 to about 8.5 ranges Using the automatic stop prepared at position with self-stopping technology agent (such as hydroxamic acid) and cationic compound (such as pMADQUAT) Only property polishing composition is directed to polishing speed variation in the topographical variations (pattern density dependence) above substrate and chip (WIWNU) advantage.
Embodiment 3
The embodiment illustrates the pH range and self-stopping technology agent of the invention optionally combined with cationic compound to throwing The influence of light transmittance efficiency.
With 14 kinds of (i.e. polishing composition 3A-3N) polishing patterned substrates of the polishing composition as described in the following table 7 and The silicon substrate covered through TEOS.By by additive formulation described in abrasive composition (being described in Table 1) and table 6 It is mixed by volume with the ratio of 7:3 to prepare polishing composition.
Additive formulation G1-G5 is free of cationic compound, and formulation G6-G14 contains cationic compound (i.e. pMADQUAT or Luviquat Supreme).All formulations contain self-stopping technology agent and volume as illustrated in table 6 Outer component.
Table 6: additive formulation
Patterned chip is obtained from Silyb Inc., and includes initially to be covered in step height aboutThrough scheming 900 μm of TEOS features that pattern density on the silicon substrate of case is 50% are (aboutThick feature).TEOS blanket covers Formula chip is obtained from WRS material.Use MIRRATMPolishing tool (Applied Materials, Inc.) polishing test chip, for Patterned wafers and blanket wafers polish 60 seconds and 90 seconds respectively.Using pressure and difference under 3psi on 200mm platform For 93rpm and 87rpm platform speed and head speed come usingE6088(Cabot Microelectronics Corporation) polishing pad.Total slurry flow rate is 150mL/min.As a result it is set forth in table 7 In.
Table 7: the influence of additive and POU pH to polishing efficiency
Result as illustrated in from table 7 is apparent, all to combine comprising grinding agent formulation with the polishing of self-stopping technology agent The high step height removal rate and the low oxide removal rate in blanket wafers for pattern is presented in object. This shows to planarize with patterned wafers, and the significant rate that removes occurs on patterned wafers and declines.Step height removes Rate and oxide blanket cover object and remove the ratio of rate according to the type and POU pH and cationic compound of self-stopping technology agent And it is scheduled in the range of about 4 to 24.
By all references cited herein (including publications, patent applications and patents) hereby by reference to drawing Enter, with reference to degree as each bibliography individually and is specifically described to be incorporated by reference into and quilt herein It fully illustrates the same.
Term " one (kind) is used (especially in the range of following claims) in description the scope of the present invention (a, an) " and " (being somebody's turn to do, the) " are to be interpreted as covering odd number and plural number with " at least one (kind) " and similar indicant The two, unless in addition illustrating or being apparently contradicted in the context herein.Term " at least one (kind) "+one or more project The use of list (for example, " at least one of A and B (kind) ") should be interpreted that the item meant selected from listed project Two or more any combination (A and B) in mesh (A or B) or the project listed, unless other explanation herein Or it is apparently contradicted in the context.Term "comprising", " having ", " comprising " and " containing " are to be interpreted as open-ended term (that is, meaning Taste " including, but are not limited to "), unless otherwise stated.Enumerating for numberical range herein is merely intended to fall as independent refer to The shorthand method of each independent values in the range unless in addition illustrating herein, and introduces each only in the description Vertical value is individually enumerated the same herein just as it.All methods described herein can be with any suitable suitable Sequence carries out, unless in addition illustrating or being apparently contradicted in the context herein.Any and all embodiments provided herein, Or the use of exemplary language (e.g., " such as ") is only used to that the present invention is better described, rather than the scope of the present invention is subject to Limitation, unless otherwise stated.There is no language that should be interpreted that the element by any undesired protection is indicated as being pair in this specification Necessary to practice of the invention.
There is described herein the preferred embodiment of the present invention, including known to the present inventor it is for carrying out the present invention most Preference pattern.After reading the above description, the modification of those preferred embodiments can become those of ordinary skill in the art It is apparent.The present inventor wishes that those of skill in the art use such modification in due course, and the present inventor is intended to that the present invention is allowed to use It is practiced different from mode specifically described herein.Therefore, the present invention includes such as being invested by applicable law is permitted All modifications and equivalents of theme described in this claims.In addition, above-mentioned element is all possible with its Any combination of modification is covered by the present invention, unless in addition illustrating herein or being apparently contradicted in the context on the contrary.

Claims (20)

1. chemical-mechanical polishing compositions include:
(a) it is selected from the grinding agent of cerium oxide, zirconium oxide and combinations thereof,
(b) self-stopping technology agent selected from the following:
Formula (II) compound
Wherein X1To X3It is each independently selected from N, O, S, sp2Hydridization carbon and CY1Y2, wherein Y1And Y2It is each independently selected from hydrogen, hydroxyl Base, C1-C6Alkyl, halogen and combinations thereof, and Z1-Z3It is each independently selected from hydrogen, hydroxyl, C1-C6Alkyl and combinations thereof, it is therein Each can be substituted or be unsubstituted；
Formula (III) compound:
Z-(C(X1X2)n)p-CO2M (III),
Wherein Z is selected from N, C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl and aryl (such as phenyl, benzyl, naphthalene, Azulene, anthracene, pyrene Deng), X1And X2Independently selected from hydrogen, hydroxyl, amino and C1-C6Alkyl, C1-C6Alkenyl, and wherein, it is incorporated in the carbon being connect X together1And X2Sp can be formed2Hydridization carbon, n are 1 or 2, and p is 0 to 4, and M is selected from hydrogen and suitable counter ion (such as I race gold Belong to), each of these person can be substituted or be unsubstituted；And combinations thereof；
Formula (IV) compound:
Wherein X, Y and Z are independently selected from H, O, S, NH and CH2, R1、R2And R3Independently selected from H, alkyl, alkenyl, alkynyl, aryl, Halogen and halogenated alkyl, and M is selected from hydrogen and suitable counter ion, and
(c) aqueous carrier,
Wherein the pH of the polishing composition is about 3 to about 9.
2. the polishing composition of claim 1, wherein the polishing composition further includes rate booster.
3. the polishing composition of claim 1, wherein the grinding agent is present in this with the concentration of about 0.001wt% to about 5wt% In polishing composition.
4. the polishing composition of claim 1, wherein the self-stopping technology agent be selected from maltol, ethylmaltol, kojic acid, benzoic acid, It is 3,4- dihydroxy-benzoic acid, 3,5- dihydroxy-benzoic acid, caffeic acid, ethylmaltol, sorbic acid, butyric acid, valeric acid, caproic acid, cautious Each acid, root of Dahurain angelica acid, crotonic acid, sorbic acid, Deferiprone, 2- hydroxy niacin, 2- penetenoic acid, 3- penetenoic acid, other saturations and insatiable hunger The alkyl carboxylic acid of sum, they salt, and combinations thereof.
5. the polishing composition of claim 1, wherein the self-stopping technology agent is present in the polishing with about 1wt% or lower concentration In composition.
6. the polishing composition of claim 1 further includes the sun selected from polymer, oligomer, small molecule, salt and combinations thereof Ionic compound.
7. the polishing composition of claim 6, wherein the cationic compound is comprising being selected from quaternary amine, cationic polyvinyl The polymer or oligomer of the monomer of alcohol, cationic cellulose and combinations thereof.
8. the polishing composition of claim 7, wherein the cationic compound is the polymer comprising quaternary amine monomer or oligomeric Object, and wherein, which is selected from vinyl imidazole, methacryloxyethyl trimethyl-ammonium halide, diallyl Dimethy lammonium chloride and combinations thereof.
9. the polishing composition of claim 6, wherein the cationic compound be cationic oligomer selected from the following or Cation type polymer: methacrylic acid 2- (dimethylamino) ethyl ester, diallyl dimethyl ammonium, poly- (vinyl imidazole ), poly- (methacryloxyethyl trimethyl ammonium) halide, poly- (diallyl dimethyl ammonium) halide, polyquaternium- 2, polyquaternium -11, polyquaternium -16, polyquaternium -46, polyquaternium -44, Luviquat Supreme, Luviquat Hold、Luviquat UltraCare、Luviquat FC 370、Luviquat FC 550、Luviquat FC 552、 Luviquat Excellence, and combinations thereof.
10. the polishing composition of claim 1, wherein the pH of the polishing composition is about 6.0 to about 8.5.
11. the polishing composition of claim 1, wherein the pH of the polishing composition is about 3 to about 5.
12. chemical-mechanical polishing compositions include:
(a) it is selected from the grinding agent of cerium oxide, zirconium oxide and combinations thereof,
(b) it is selected from the self-stopping technology agent of formula (I) compound:
Wherein R is selected from: hydrogen, alkyl, naphthenic base, aryl, Heterocyclylalkyl and heterocyclic aryl, each of these person can be substituted or It is unsubstituted；
(c) cation type polymer,
(d) aqueous carrier,
Wherein the pH of the polishing composition is about 7 to about 9.
13. the polishing composition of claim 12, wherein it is different that the self-stopping technology agent is selected from hydroxamic acid, acetyl group hydroxamic acid, benzene Hydroximic acid, salicylhydroxamic acid and combinations thereof.
14. the polishing composition of claim 12, wherein the cation type polymer is selected from methacrylic acid 2- (dimethylamino Base) ethyl ester, diallyl dimethyl ammonium, poly- (vinyl imidazole), poly- (methacryloxyethyl trimethyl ammonium) halogenation Object, poly- (diallyl dimethyl ammonium) chloride, polyquaternium -2, polyquaternium -11, polyquaternium -16, polyquaternium -46, Polyquaternium -44, Luviquat Supreme, Luviquat Hold, Luviquat UltraCare, Luviquat FC 370, Luviquat FC 550, Luviquat FC 552, Luviquat Excellence, and combinations thereof.
15. the polishing composition of claim 12, wherein the polishing composition further includes rate booster.
16. the polishing composition of claim 12, wherein the self-stopping technology agent is present in the throwing with about 1wt% or lower concentration In light composition.
17. the polishing composition of claim 12, wherein the grinding agent is cerium oxide.
18. the polishing composition of claim 12, wherein the grinding agent is present in the concentration of about 0.001wt% to about 5wt% In the polishing composition.
19. the method for chemically-mechanicapolish polishing substrate, comprising:
(i) substrate is provided, wherein the substrate includes the patterned dielectric layer on the surface of the substrate,
(ii) polishing pad is provided,
(iii) chemical-mechanical polishing compositions of claim 1 are provided,
(iv) substrate is contacted with the polishing pad and the chemical-mechanical polishing compositions, and
(v) it is located on the substrate surface relative to the mobile polishing pad of the substrate and the chemical-mechanical polishing compositions with grinding At least part of the patterned dielectric layer, to polish the substrate.
20. the method for chemically-mechanicapolish polishing substrate, comprising:
(i) substrate is provided, wherein the substrate includes the patterned dielectric layer on the surface of the substrate,
(ii) polishing pad is provided,
(iii) chemical-mechanical polishing compositions of claim 12 are provided,
(iv) substrate is contacted with the polishing pad and the chemical-mechanical polishing compositions, and
(v) it is located on the substrate surface relative to the mobile polishing pad of the substrate and the chemical-mechanical polishing compositions with grinding At least part of the patterned dielectric layer, to polish the substrate.
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