(19)
(11)EP 3 670 621 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
11.10.2023 Bulletin 2023/41

(21)Application number: 19173321.1

(22)Date of filing:  08.05.2019
(51)International Patent Classification (IPC): 
C09G 1/02(2006.01)
(52)Cooperative Patent Classification (CPC):
C09G 1/02

(54)

POLISHING COMPOSITIONS AND METHODS OF USING SAME

POLIERZUSAMMENSETZUNGEN UND VERFAHREN ZUR VERWENDUNG DAVON

COMPOSITIONS DE POLISSAGE ET LEURS PROCÉDÉS D'UTILISATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 19.12.2018 US 201862781648 P
18.03.2019 US 201916356669

(43)Date of publication of application:
24.06.2020 Bulletin 2020/26

(73)Proprietor: Fujifilm Electronic Materials U.S.A., Inc.
N. Kingstown, RI 02852 (US)

(72)Inventors:
  • TURNER, Eric
    Chandler, AZ 85248 (US)
  • MISHRA, Abhudaya
    Gilbert, AZ 85234 (US)
  • BALLESTEROS, Carl
    San Tan Valley, AZ 85143 (US)

(74)Representative: Fish & Richardson P.C. 
Highlight Business Towers Mies-van-der-Rohe-Straße 8
80807 München
80807 München (DE)


(56)References cited: : 
US-A1- 2006 068 589
US-A1- 2015 221 521
US-A1- 2011 230 048
US-A1- 2017 029 664
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    BACKGROUND



    [0001] The semiconductor industry is continually driven to improve chip performance by further miniaturization of devices through process and integration innovations. Chemical Mechanical Polishing/Planarization (CMP) is a powerful technology as it makes many complex integration schemes at the transistor level possible, thereby facilitating increased chip density.

    [0002] US 2011/230048 discloses an aqueous chemical mechanical polishing composition comprising a mixture of one or more surfactants chosen from an amine alkoxylate, an ammonium alkoxylate, or mixtures thereof, and colloidal silica particles having at least one cationic species, and the compositions having a pH ranging from 2 to 6. The CMP polishing compositions of examples have ratios for the TEOS/SiN removal rates that are significantly less then 3:1.

    SUMMARY



    [0003] Transistors are generally fabricated at the Front End of Line (FEOL) transistor fabrication step. The FEOL material stack typically includes a metal gate and multiple stacks of dielectric materials. Electrical isolation of the billions of active components in each integrated circuit is a goal in FEOL and may be achieved using a shallow trench isolation (STI) process. A portion of a STI process is shown in Figure 1 for demonstration purposes. As can be seen from Figure 1, prior to the STI CMP process, thermal silicon oxide and SiN can be deposited on top of silicon (e.g., a silicon wafer) (Fig. 1 (a)) and then etched out to create trenches/isolation and "active" non-trench areas (to form transistor containing areas) (Fig. 1 (b)). Thereafter, these trench/isolation areas can be filled by depositing (e.g., by using plasma-enhanced chemical vapor deposition (PECVD)) silicon oxide (e.g., TEOS) in the trenches such that the active non-trench areas can be isolated by the silicon oxide in the trenches (Fig. 1 (c)). Thereafter, the "overburden/extra" silicon oxide above the active non-trench areas can be selectively removed while keeping silicon oxide in the shallow trenches (Fig. 1(d)). The selective removal of the silicon oxide is achieved by a shallow trench isolation (STI) chemical mechanical polishing/planarization (CMP) process, where a CMP slurry composition (such as that described in this disclosure) having a high material removal rate (MRR) selectivity of silicon oxide to silicon nitride (e.g., SiN) is used to remove silicon oxide at a high rate, preferably without substantially removing silicon nitride (a stop-on layer). After the above STI CMP step, etching can be used to expose silicon to complete the isolation and prevent adjacent transistors formed in the active non-trench areas from coming into contact with each other and thereby prevent shorting of electrical circuits.

    [0004] The dielectric films prevalently used in STI are silicon nitride (e.g., SiN), silicon oxide (e.g., TEOS: tetra-ethyl ortho-silicate), poly-silicon (P-Si), silicon carbon nitride (e.g., SiCN), and low-k/ultra-low k dielectric films (e.g., SiCOH). With the introduction of high-k metal gate technology at 45nm and FinFET technology at 22 nm chip production, SiN, TEOS, SiCN and P-Si films are starting to be used more often and in a greater number of applications in FEOL. Additionally, in Back End of Line (BEOL), as the resistivity of conventional barrier materials (e.g., Ta/TaN or Ti/TiN) has been shown to not effectively scale down for advanced sub-10nm manufacturing nodes, these barrier materials can be replaced by dielectrics such as SiN, TEOS, SiCN, and P-Si for various BEOL material stacks. Thus, for both FEOL and BEOL, these dielectric films can be used as an etch stop layer, capping material, spacer material, additional liner, diffusion/passivation barrier, hard mask and/or stop-on layer.

    [0005] In general, dielectric films are being used much more generously in advanced semiconductor manufacturing. From a CMP perspective, most of these integrations incorporating dielectrics require polishing compositions (slurries) that can work/polish and/or stop on these films, such as slurries that can remove SiN but not remove (stop on) TEOS/P-Si or slurries that can remove TEOS/p-Si but not remove (stop on) SiN.

    [0006] The present disclosure relates to stable aqueous slurries that can selectively polish a wide variety of materials (e.g., oxides such as silicon oxides) while achieving very low polishing/removal rates on silicon nitride and associated silicon and nitrogen based films like SiCN (silicon carbo-nitride). For example, the polishing compositions can polish silicon oxide (e.g., SiO2) at a relatively high material removal rate (MRR) and stop on or polish at very low rates silicon nitride (e.g., SiN) or related films. For example, silicon oxides that can be removed by the polishing compositions described herein include silicon oxides selected from TEOS, thermal oxides (TOX) (e.g., caused by autoclave induced oxidation of bare silicon), silicon oxides formed by plasma enhanced PVD deposition (e.g., high density plasma or high aspect ratio plasma), silicon oxides formed by CVD deposition with post plasma surface cure, carbon doped silicon oxide (SiOC), and silicon oxides formed by liquid application of an oxide precursor followed by light or thermal induced curing. In some instances, the target film to be removed at high MRRs can be a metal or a metal oxide or a metal nitride rather than silicon oxide dielectrics. Common examples of metals, metal oxides and metal nitrides include copper, cobalt, ruthenium, aluminum, titanium, tungsten, and tantalum for metals, hafnium oxide, titanium oxide, aluminum oxide, zirconium oxide and tantalum oxide for metal oxides and nitrides of ruthenium, aluminum, titanium, tungsten, and tantalum. For such instances, the stop-on/low removal rate film can still be a silicon nitride film and thus the polishing compositions containing the nitride removal rate reducing agent from this disclosure can be utilized to achieve a desired selectivity.

    [0007] More particularly, the present disclosure relates to polishing compositions including an abrasive, a nitride removal rate reducing agent, an acid or base, water, and optionally, a dishing reducing agent (e.g., an anionic dishing agent). The pH of the polishing compositions described herein can be in the range of 2 to 6.5 or, more specifically, in the range of 2 to 4.5. The compositions of the present disclosure can also be diluted (e.g., at the point of use) to form a polishing composition without any deterioration in performance. This disclosure also discusses methods for polishing semiconductor substrates using the aforementioned polishing compositions.

    [0008] The present invention relates to a polishing composition, including at least one abrasive, at least one nitride removal rate reducing agent, an acid or a base, and water. The nitride removal rate reducing agent includes a hydrophobic portion containing a C12 to C40 hydrocarbon group; and a hydrophilic portion containing at least one group selected from the group consisting of a sulfinite group, a sulfate group, a carboxylate group, a phosphate group, and a phosphonate group; and wherein the hydrophobic portion and the hydrophilic portion are separated by zero to ten alkylene oxide groups. The polishing composition has a pH of 2 to 6.5.

    [0009] In one aspect, embodiments disclosed herein relate to a polishing composition including: at least one abrasive; at least one nitride removal rate reducing agent including a hydrophobic portion and a hydrophilic portion; an acid or a base; and water; wherein the polishing composition has a pH of about 2 to about 6.5; and the polishing composition has a ratio of a removal rate for a silicon oxide to a removal rate for a silicon nitride of at least about 3:1 during polishing a patterned wafer including at least silicon nitride patterns, in which the silicon nitride patterns are overlayed with at least silicon oxide (and optionally other materials such as metals or dielectrics).

    [0010] In another aspect, embodiments disclosed herein relate to a polishing composition including: at least one abrasive; at least one nitride removal rate reducing agent including a hydrophobic portion and a hydrophilic portion; an acid or a base; and water; wherein the polishing composition has a pH of about 2 to about 6.5; and wherein less than about 1000 angstroms of silicon oxide dishing occurs when polishing a patterned wafer including at least silicon nitride patterns overlayed with at least silicon oxide with the polishing composition, in which the polishing exposes the silicon nitride patterns on the patterned wafer.

    [0011] In yet another aspect, embodiments disclosed herein relate to a polishing composition including: at least one abrasive; at least one nitride removal rate reducing agent including a hydrophobic portion and a hydrophilic portion; an acid or a base; and water; wherein the polishing composition has a pH of about 2 to about 6.5; and wherein less than about 500 angstroms of silicon nitride erosion occurs when polishing a patterned wafer including at least silicon nitride patterns overlayed with at least silicon oxide with the polishing composition, in which the polishing exposes the silicon nitride patterns on the patterned wafer.

    [0012] In yet another aspect, embodiments disclosed herein relate to a method, including: applying a polishing composition described herein to a substrate having at least silicon nitride and at least silicon oxide on a surface of the substrate; and bringing a pad into contact with the surface of the substrate and moving the pad in relation to the substrate.

    [0013] The synergistic use of abrasive, the nitride RR reducing agent, and the optional dishing reducing agent in the same composition provides unique advantages not found in currently available slurries. Among others, these benefits include the following:
    1. 1. The compositions described herein can achieve very low silicon nitride (e.g., SiN) removal rates. Superior silicon nitride protection can be achieved through judicious selection and formulation/loading of the silicon nitride removal rate reducing agent. Furthermore, low silicon nitride removal rates are observed on both blanket wafers (i.e., wafers containing only silicon nitride film) and patterned wafers (i.e., wafers containing silicon nitride film and other films, for example TEOS, etched in a pattern) as demonstrated in this disclosure.
    2. 2. The very low silicon nitride removal rates enable obtaining minimal silicon nitride loss and thereby very low silicon nitride erosion post-polishing on patterned wafers.
    3. 3. The compositions can achieve low silicon oxide dishing/step-height. Dishing performance can be tuned with judicious selection and loading/concentration of the dishing reducing agent.
    4. 4. The compositions are compatible with a wide variety of abrasives. Through particle modification, the zeta potential of the abrasive can be tuned to further modulate removal rates on the target film. Anionic, cationic, and neutral abrasives are all capable of forming stable slurries with higher silicon oxide removal rates and comparably lower silicon nitride removal rates.
    5. 5. The compositions can form stable slurries with high purity colloidal silica as the abrasive. This allows for the creation of slurries with low trace metal counts and low large particle counts, resulting in reduced defects on the polished wafers, when compared with wafers polished with conventionally used ceria abrasives (which generally generates a large amount of defects on a polished wafer). In addition, the compositions described herein can overcome certain disadvantages of conventional silica-based STI CMP compositions, such as their high silicon nitride removal rates and low removal selectivity between silicon oxide and silicon nitride.
    6. 6. The compositions produce low nitride removal rates across a variety of polish conditions. For example, silicon nitride removal rates remain low on both hard polish pads (e.g., polyurethane based pads) and soft polish pads (e.g., poromeric and low shore D hardness value pads). Additionally, it has been observed that downforce and velocity do not appreciably affect silicon nitride removal rates, which is a good CMP attribute to have as the stop-on film behavior is non-prestonian. The fact that the compositions of the present disclosure exhibit little variation in removal rates as a function of pressure and velocity leads to very good topography and high yields post patterned wafer polishing. In the language of the field, compositions of the present disclosure lead to low values for silicon oxide dishing and step height along with low values of silicon nitride erosion/loss.


    [0014] The polishing compositions and concentrates discussed in this disclosure contrast with currently available contemporary slurries in providing performance sustenance on current generation integrated circuit substrates, whereas simultaneously displaying marked advantages for next generation substrates and integration schemes. The compositions of the present disclosure can successfully and efficiently remove a variety of metal and dielectric layers with very high selectivity over removing the silicon nitride layers. The compositions can be used for shallow trench isolation (STI) processes, self-aligned contact processes, or other processes where very low silicon nitride material removal rate is desired.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0015] 

    Fig. 1 is a schematic diagram of a process flow in a shallow trench isolation (STI) processes (including STI CMP) in semiconductor fabrication. Fig. 1(a) shows that thermal silicon oxide (TOX) and silicon nitride (SiN) are deposited on top of silicon (Si) prior to shallow trench isolation (STI) chemical mechanical planarization (CMP). This is followed by etch in order to create active areas. Fig. 1(b) shows trenches have been created leaving active areas of silicon covered by TOX and SiN. This is then filled with a dielectric - usually PE-CVD silicon oxide (SiO2). Fig. 1(c) shows that active areas are isolated by silica dielectric in the shallow trenches. To complete STI, SiO2 is selectively removed from active areas while keeping SiO2 within the shallow trenches. This can be done by STI CMP, the subject of this invention, wherein SiO2 is removed at high rates and SiN (stop-on layer) is not removed. Fig. 1(d) shows that etch can be used to remove SiN and expose silicon to complete the STI. The active areas of silicon will become transistors once gates, metal wiring and device fabrication is completed.

    Fig. 2 is a schematic diagram of a STI patterned wafer film stack prior to polishing.

    Fig. 3 is a wafer map depicting the overall defectivity after STI CMP using a silica based polishing composition according to the present disclosure.

    Fig. 4 is a wafer map depicting the overall defectivity after STI CMP using a commercial ceria abrasive containing composition.


    DETAILED DESCRIPTION OF THE DISCLOSURE



    [0016] The present disclosure relates to polishing compositions, and methods for polishing semiconductor substrates using the same. In some embodiments, this disclosure relates to selectively polishing silicon oxide surfaces over silicon nitride surfaces. The selective polishing of silicon oxide over silicon nitride is a critical process in semiconductor manufacturing and is commonly performed during the shallow trench isolation (STI) process. Conventionally, STI polishing compositions (slurries) utilize ceria abrasives to achieve the required polishing performance (e.g., selectivity) in the STI process because compositions that use silica abrasives have not performed adequately (e.g., high silicon nitride removal rates). However, ceria abrasives are known to give high rates of defectivity and scratches when used in polishing compositions due to their "inorganic hard" nature. Further, ceria-based polishing compositions exhibit a shorter shelf life (e.g., lower storage capability, lower useable time period, and earlier expiration date), a shorter pot life (e.g., activity after opening container and/or in a holding tank or distribution loop) than silica-based polishing compositions, and ceria has greater price volatility than silica. In addition, ceria includes a rare earth metal and is more expensive than silica. Compositions according to this disclosure allow for the use of silica abrasives, which are softer than ceria abrasives, for STI slurries. The silica containing polishing compositions can give very good selectivity in material removal rates (MRR) of silicon oxide (e.g., TEOS) over silicon nitride (e.g., SiN), while also providing polished wafer surfaces with a very low defectivity when compared to STI processes that utilize a ceria abrasive. Thus, the polishing compositions according to the present application are capable of increasing the device yield of the wafers when compared with conventional polishing compositions that utilize ceria abrasives.

    [0017] The polishing compositions described herein can include (a) an abrasive, (b) a nitride removal rate reducing agent, (c) an acid or base, (d) water, and optionally (e) a dishing reducing agent (e.g., an anionic dishing reducing agent). The polishing composition can have a pH of at least about 2 to at most about 6.5. The polishing compositions of the present disclosure can have a high selectivity for polishing dielectrics or metals over polishing silicon nitrides. The present disclosure also provides a method of using the polishing compositions to polish semiconductor substrates. Particularly, the present disclosure provides a method for polishing dielectrics or metals with high selectivity over silicon nitrides.

    [0018] In one or more embodiments, the at least one (e.g., two or three) abrasive is selected from cationic abrasives, substantially neutral abrasives, and anionic abrasives. In one or more embodiments, the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products thereof, coated abrasives, surface modified abrasives, and mixtures thereof. In some embodiments, the at least one abrasive does not include ceria.

    [0019] In one or more embodiments, the abrasive is a silica-based abrasive, such as one selected from the group consisting of colloidal silica, fumed silica, and mixtures thereof. In one or more embodiments, the abrasive has a surface modified with organic groups and/or non-siliceous inorganic groups. For example, the cationic abrasive can include terminal groups of formula (I):

            -Om-X-(CH2)n-Y (I),

    in which m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, or Zr; and Y is a cationic amino or thiol group. As another example, the anionic abrasive can include terminal groups of formula (I):

            -Om-X-(CH2)n-Y (I),

    in which m is an integer from 1 to 3; n is an integer from 1 to 10; X is Al, Si, Ti, or Zr; and Y is an acid group. In some embodiments, the at least one abrasive can be present in a polishing composition described herein in an amount of from at least about 0.05 wt% (e.g., at least about 0.1 wt%, at least about 0.5 wt%, at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, or at least about 5 wt%) to at most about 20 wt% (e.g., at most about 15 wt%, at most about 10 wt%, at most about 8 wt%, at most about 6 wt%, at most about 4 wt%, or at most about 2 wt%) based on the total weight of the composition.

    [0020] In one or more embodiments, the abrasive described herein can have a mean particle size of at least about 1 nm (e.g., at least about 5 nm, at least about 10 nm, at least about 20 nm, at least about 40 nm, at least about 50 nm, at least about 60 nm, at least about 80 nm, or at least about 100 nm) to at most about 1000 nm (e.g., at most about 800 nm, at most about 600 nm, at most about 500 nm, at most about 400 nm, or at most about 200 nm). As used herein, the mean particle size (MPS) is determined by dynamic light scattering techniques.

    [0021] In one or more embodiments, the at least one (e.g., two or three distinct) nitride removal rate reducing agent is a compound that includes a hydrophobic portion containing a C12 to C40 hydrocarbon group (e.g., containing an alkyl group and/or an alkenyl group); and a hydrophilic portion containing at least one group selected from the group consisting of a sulfinite group, a sulfate group, a carboxylate group, a phosphate group, and a phosphonate group. In one or more embodiments, the hydrophobic portion and the hydrophilic portion are separated by zero to ten (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or 9) alkylene oxide groups (e.g., -(CH2)nO- groups in which n can be 1, 2, 3, or 4). In one or more embodiments, the nitride removal rate reducing agent has zero alkylene oxide groups separating the hydrophobic portion and the hydrophilic portion. Without wishing to be bound by theory, it is believed that the presence of alkylene oxide groups within the nitride removal rate reducing agent may not be preferred in some embodiments as they may create slurry stability issues and increase silicon nitride removal rate.

    [0022] In one or more embodiments, the nitride removal rate reducing agent is included in a polishing composition described herein in an amount from at least about 0.1 ppm (e.g., at least about 0.5 ppm, at least about 1 ppm, at least about 5 ppm, at least about 10 ppm, at least about 25 ppm, at least about 50 ppm, at least about 75 ppm, or at least about 100 ppm) to at most about 1000 ppm (e.g., at most about 900 ppm, at most about 800 ppm, at most about 700 ppm, at most about 600 ppm, at most about 500 ppm, or at most about 250 ppm) based on the total weight of the composition.

    [0023] In one or more embodiments, the nitride removal rate reducing agent has a hydrophobic portion containing a hydrocarbon group that includes at least 12 carbon atoms (C12) (e.g., at least 14 carbon atoms (C14), at least 16 carbon atoms (C16), at least 18 carbon atoms (C18), at least 20 carbon atoms (C20), or at least 22 carbon atoms (C22)) and/or at most 40 carbon atoms (C34) (e.g., at most 38 carbon atoms (C38), at most 36 carbon atoms (C36), at most 34 carbon atoms (C34), at most 32 carbon atoms (C32), at most 30 carbon atoms (C30), at most 28 carbon atoms (C28), at most 26 carbon atoms (C26), at most 24 carbon atoms (C24), or at most 22 carbon atoms (C22)). The hydrocarbon groups mentioned herein refer to groups that contain only carbon and hydrogen atoms and can include both saturated groups (e.g., linear, branched, or cyclic alkyl groups) and unsaturated groups (e.g., linear, branched, or cyclic alkyenyl groups; linear, branched, or cyclic alkynyl groups; or aromatic groups (e.g., phenyl or naphthyl)). In one or more embodiments, the hydrophilic portion of the nitride removal rate reducing agent contains at least one group selected from a phosphate group and a phosphonate group. It is to be noted that the term "phosphonate group" is expressly intended to include phosphonic acid groups.

    [0024] In one or more embodiments, the nitride removal rate reducing agent is selected from the group consisting of lauryl phosphate, myristyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl sulfate, lacceryl phosphate, oleth-3-phosphate, and oleth-10-phosphate.

    [0025] In one or more embodiments, the polishing compositions described herein optionally further include at least one (e.g., two or three) dishing reducing agent (e.g., anionic dishing reducing agent). In one or more embodiments, the at least one dishing reducing agent is a compound including at least one group selected from the group consisting of hydroxy, sulfate, phosphonate, phosphate, sulfonate, amine, nitrate, nitrite, carboxylate, and carbonate groups. In one or more embodiments, the at least one dishing reducing agent is at least one selected from the group consisting of a polysaccharide and a substituted polysaccharide. In one or more embodiments, the at least one dishing reducing agent is at least one selected from the group consisting of carrageenan, xanthan gum, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methylcellulose, and carboxymethylcellulose. In one or more embodiments, the at least one nitride removal rate reducing agent and the at least one dishing reducing agent are chemically distinct from each other.

    [0026] In one or more embodiments, the dishing reducing agent is included in a polishing composition described herein in an amount from at least about 0.1 ppm (e.g., at least about 0.5 ppm, at least about 1 ppm, at least about 5 ppm, at least about 10 ppm, at least about 25 ppm, at least about 50 ppm, at least about 75 ppm, or at least about 100 ppm) to at most about 1000 ppm (e.g., at most about 900 ppm, at most about 800 ppm, at most about 700 ppm, at most about 600 ppm, or at most about 500 ppm) based on the total weight of the composition.

    [0027] In one or more embodiments, the acid is selected from the group consisting of formic acid, acetic acid, malonic acid, citric acid, propionic acid, malic acid, adipic acid, succinic acid, lactic acid, oxalic acid, hydroxyethylidene diphosphonic acid, 2-phosphono-1,2,4-butane tricarboxylic acid, aminotrimethylene phosphonic acid, hexamethylenediamine tetra(methylenephosphonic acid), bis(hexamethylene)triamine phosphonic acid, amino acetic acid, peracetic acid, potassium acetate, phenoxyacetic acid, glycine, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphonic acid, hydrochloric acid, periodic acid, and mixtures thereof.

    [0028] In one or more embodiments, the base is selected from the group consisting of potassium hydroxide, sodium hydroxide, cesium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, monoethanolamine, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, lithium hydroxide, imidazole, triazole, aminotriazole, tetrazole, benzotriazole, tolytriazole, pyrazole, isothiazole, and mixtures thereof.

    [0029] In one or more embodiments, the acid or base can be present in a polishing composition described herein in an amount of from at least about 0.01 wt% (e.g., at least about 0.05 wt%, at least about 0.1 wt%, at least about 0.5 wt%, or at least about 1 wt%) to at most about 10 wt% (e.g., at most about 8 wt%, at most about 6 wt%, at most about 5 wt%, at most about 4 wt%, or at most about 2 wt%) based on the total weight of the composition. For example, the acid or base can be added in an amount sufficient to adjust the pH of a polishing composition to the desired value.

    [0030] In one or more embodiments, the water can be present in a polishing composition described herein (e.g., as a liquid medium or carrier) in an amount of from at least about 50 wt% (e.g., at least about 55 wt%, at least about 60 wt%, at least about 65 wt%, at least about 70 wt%, or at least about 75 wt%) to at most about 99.9 wt% (e.g., at most about 99.5 wt%, at most about 99 wt%, at most about 97 wt%, at most about 95 wt%, or at most about 90 wt%) based on the total weight of the composition.

    [0031] In one or more embodiments, the polishing compositions described herein can have a pH of at least about 2 (e.g., at least about 2.5, at least about 3, at least about 3.5, or at least about 4) to at most about 6.5 (e.g., at most about 6, at most about 5.5, at most about 5, or at most about 4.5). Without wishing to be bound by theory, it is believed that a polishing composition having a pH above 6.5 may reduce the silicon oxide/silicon nitride removal rate selectivity and have stability issues.

    [0032] In one or more embodiments, the polishing described herein can be substantially free of one or more of certain ingredients, such as salts (e.g., halide salts), polymers (e.g., cationic or anionic polymers, or polymers other than a dishing reducing agent), surfactants (e.g., those other than a nitride removal rate reducing agent), plasticizers, oxidizing agents, corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), and/or certain abrasives (e.g., ceria abrasives or non-ionic abrasives). The halide salts that can be excluded from the polishing compositions include alkali metal halides (e.g., sodium halides or potassium halides) or ammonium halides (e.g., ammonium chloride), and can be chlorides, bromides, or iodides. As used herein, an ingredient that is "substantially free" from a polishing composition refers to an ingredient that is not intentionally added into the polishing composition. In some embodiments, the polishing compositions described herein can have at most about 1000 ppm (e.g., at most about 500 ppm, at most about 250 ppm, at most about 100 ppm, at most about 50 ppm, at most about 10 ppm, or at most about 1 ppm) of one or more of the above ingredients that are substantially free from the polishing compositions. In some embodiments, the polishing compositions described can be completely free of one or more the above ingredients.

    [0033] In one or more embodiments, the polishing compositions described herein have a ratio of a removal rate for silicon oxide (e.g., TEOS) to a removal rate for silicon nitride (i.e., a removal rate selectivity) of at least about 3:1, or at least about 4:1, or at least about 5:1, or at least about 10:1, or at least about 25:1, or at least about 50:1, or at least about 60:1, or at least about 75:1, or at least about 100:1, or at least about 150:1, or at least about 200:1, or at least about 250:1, or at least about 300:1, or at least about 500:1, or at least about 750:1, or at most about 1000:1, or at most about 5000:1. In one or more embodiments, the ratios described above can be applicable when measuring removal rates for polishing either blanket wafers or patterned wafers (i.e., wafers including at least silicon nitride patterns, in which the silicon nitride patters are overlayed with at least silicon oxide (and optionally with other materials such as metals and dielectrics)).

    [0034] In one or more embodiments, at most about 1000 angstroms, at most about 500 angstroms, or at most about 375 angstroms, or at most about 250 angstroms, or at most about 200 angstroms, or at most about 100 angstroms, or at most about 50 angstroms, and/or at least about 0 angstrom of silicon oxide (e.g., TEOS) dishing occurs when polishing a patterned wafer (which can include at least silicon nitride patterns overlayed with at least silicon oxide) with the polishing composition (e.g., until the polishing exposes the silicon nitride patterns on the patterned wafer). In one or more embodiments, at most about 500 angstroms, or at most about 400 angstroms, or at most about 300 angstroms, or at most about 250 angstroms, at most about 200 angstroms, at most about 100 angstroms, or at most about 75 angstroms, or at most about 65 angstroms, or at most about 50 angstroms, or at most about 32 angstroms and/or at least about 0 angstrom of silicon nitride erosion occurs when polishing a patterned wafer (which can include at least silicon nitride patterns overlayed with at least silicon oxide) with the polishing composition (e.g., until the polishing exposes the silicon nitride patters on the patterned wafer).

    [0035] In one or more embodiments, the planarization efficiency (i.e., the change in silicon oxide step height divided by the amount of silicon oxide removed during the polish, multiplied by 100) is at least about 14% (e.g., at least about 20%, at least about 30%, at least about 38%, at least about 40%, at least about 46%, at least about 50%, at least about 60%, at least about 70%, or at least about 74%) and at most about 100% (e.g., at most about 99.9%, at most about 99%, at most about 95%, at most about 90%, at most about 80%, at most about 70%, and at most about 60%) when polishing a patterned wafer using a polishing composition according to the present disclosure. In one or more embodiments, the total defect counts on a patterned wafer having a diameter of 12 inches (i.e., about 300 mm) is at most 175 (e.g., at most 170, at most 160, at most 150, at most 125, at most 100, at most 75, at most 50, at most 25, at most 10, or at most 5) when polishing the patterned wafer using a polishing composition according to the present disclosure (e.g., a composition including a silica abrasive and the nitride removal rate reducing agent). As described herein, the defects counted are those at least about 90 nm in size.

    [0036] In one or more embodiments, this disclosure features a method of polishing that can include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least silicon nitride and silicon oxide on a surface of the substrate; and bringing a pad into contact with the surface of the substrate and moving the pad in relation to the substrate. In some embodiments, when the substrate includes at least silicon nitride patterns overlayed with at least silicon oxide (e.g., silicon oxide in the presence of other materials such as silicon based dielectrics (e.g., silicon carbide, etc.), metals, metal oxides and nitrides, etc.), the above method can remove at least a portion of the silicon oxide (e.g., the silicon oxide on active, non-trench areas) to expose silicon nitride. It is to be noted that the terms "silicon nitride" and "silicon oxide" described herein are expressly intended to include both un-doped and doped versions of silicon nitride and/or silicon oxide. For example, in one or more embodiments, the silicon nitride and silicon oxide can, independently, be doped with at least one dopant selected from carbon, nitrogen (for silicon oxide), oxygen, hydrogen, or any other known dopants for silicon nitride or silicon oxide. Some examples of silicon oxide film types include TEOS (Tetra-ethyl orthosilicate), SiOC, SiOCN, SiOCH, SiOH and SiON, to name a few. Some examples of silicon nitride film types include SiN (pure silicon nitride), SiCN, SiCNH, and SiNH, to name a few.

    [0037] In some embodiments, the method that uses a polishing composition described herein can further include one or more additional steps to produce a semiconductor device from the substrate treated by the polishing composition. For example, the method can include one or more of the following steps prior to the polishing method described above: (1) depositing silicon oxide (e.g., thermal silicon oxide) on a substrate (e.g., a silicon wafer) to form a silicon oxide layer, (2) depositing silicon nitride on the silicon oxide layer to form a silicon nitride layer, (3) etching the substrate to form trenches and non-trench areas, and (4) depositing silicon oxide to the etched substrate to fill the trenches with silicon oxide. As another example, the method can include at least one additional step after the polishing method described above, such as etching the substrate (e.g., to remove silicon nitride and silicon oxide) to expose silicon and/or silicon oxide or other heterogeneous films on the wafer substrate.

    Examples



    [0038] Examples are provided to further illustrate the capabilities of the polishing compositions and methods of the present disclosure. The provided examples are not intended and should not be construed to limit the scope of the present disclosure. Any percentages listed are by weight (wt%) unless otherwise specified. The nitride removal rate reducing agents described in the examples were obtained a variety of suppliers and may, in some instances, include minor amounts of similar compounds having carbon chain lengths smaller or larger than what is specified in the tables below. The carbon chain length specified in the tables identifies the majority component of the nitride removal rate reducing agent.

    Example 1: Demonstration of nitride stop



    [0039] In this example, polishing compositions used in samples 1A-1F primarily included: 3 w/w% neutral colloidal silica abrasive, malonic acid as a pH adjuster, a nitride removal rate reducing agent (if present), and water as a liquid carrier. The pH of the polishing compositions was 2.3. An Applied Materials Mirra CMP polisher was used with a downforce of 2 psi and a flow rate of 175 mL/min to polish on a Dow VP6000 pad 200 mm silicon oxide (TEOS) and silicon nitride (SiN) blanket wafers.
    Table 1. TEOS and SiN removal rates vs. nitride removal rate reducing surfactant species
    SampleNitride Removal Rate Reducing AgentEO GroupsTEOS RR [Å/min]SiN RR [Å/min]TEOS RR/ SiN RR
    Control None 0 982 121 8
    1A stearyl phosphate 0 816 2 408
    1B n-Octadecylphosphonate 0 868 1 868
    1C Oleyl phosphate 0 965 4 241
    1D Octadecyl sulfate 0 854 1 854
    1E Oleth-3 phosphate 3 790 10 79
    1F Oleth-10 phosphate 10 629 7 90
    "EO" refers to ethylene oxide. "RR" refers to removal rate.


    [0040] The results in Table 1 showed that the control polishing composition (which did not include a nitride removal rate reducing agent) had a removal rate selectivity between silicon oxide and silicon nitride of 8, which is too low for most applications requiring low silicon nitride rates. However, with the addition of a nitride removal rate reducing agent, the silicon nitride removal rates of the polishing compositions dropped to as low as 1 Å/min and the removal rate selectivity climbed to as high as 868.

    Example 2: Demonstration of pH range and different abrasive surface charge



    [0041] In this example, polishing compositions used in samples 2A-2I included: 3 w/w% colloidal silica abrasive, an organic acid as a pH adjuster, n-octadecylphosphonic acid, and water as a liquid carrier. n-Octadecylphosphonic acid is representative of the class of nitride removal rate reducing agent described herein. Furthermore, in this example, the colloidal silica charge was varied by using neutral, cationic, and anionic silica, as shown in Table 2. The pH of the polishing compositions was varied from about 2.25 to about 4.25. An Applied Materials Mirra CMP polisher was used with a downforce of 2 psi and a flow rate of 175 mL/min on a Dow VP6000 pad to polish 200 mm silicon oxide (TEOS) and silicon nitride blanket wafers.
    Table 2. TEOS and SiN removal rates vs. pH with three types of Silica
    SampleAbrasiven-octadecylphosphonic acid relative concentrationpHTEOS RR [Å/min]SiN RR [Å/min]TEOS TEOS RR/ SiN RR SiN RR
    2A Neutral Silica x 2.25 925 3 308
    2B   x 2.75 1186 2 593
    2C   x 3.50 921 3 307
    2D   x 4.25 587 9 65
    2E Cationic Silica 2x 2.75 389 2 194
    2F   2x 3.50 458 2 229
    2G   2x 4.25 815 2 407
    2H Anionic Silica 2x 2.25 47 27 2
    2I   2x 3.25 44 13 3


    [0042] As shown in Table 2, the nitride removal rate reducing agent was capable of controlling silicon nitride removal rates with neutral, cationic, and anionic silica from a pH range of about 2.25 to about 4.25. The robust nitride rate reduction of the above system irrespective of the surface charge of the silica abrasive is surprising. For example, it is commonly thought that cationic abrasives would have poor compatibility with anionic nitride removal rate reducing agent. In contrast, in this system the slurry remained stable and the nitride removal rate reducing agent remained active.

    [0043] Conventionally, silicon nitride removal rates when using anionic abrasives are generally very high (~400 Å/min) and difficult to control. Significantly, the nitride removal rate reducing agents described herein were capable of significantly reducing silicon nitride removal rates. This type of system may be useful when low TEOS and silicon nitride removal rates are desired with high removal rates on a film that is polished well by anionic abrasives (e.g., a silicon carbide film).

    Example 3: Demonstration of the effect of chain length and head type of a nitride removal rate reducing agent



    [0044] In this example, polishing compositions used in samples 3A-3L included: 3 w/w% colloidal silica abrasive, malonic acid as a pH adjuster, a nitride removal rate reducing agent shown in Table 3, and water as a liquid carrier. The pH of the polishing compositions was 2.25. Specifically, the nitride removal rate reducing agents used in samples 3A-3L included the head type and hydrophobe described In Table 3 without any alkylene oxide group. In addition, the nitride removal rate reducing agents used in samples 3I, 3J, and 3K included a mixture of surfactants, in which lauryl/myristyl phosphate, stearyl phosphate, and lacceryl phosphate are respectively the predominate components.

    [0045] An Applied Materials Mirra CMP polisher was used with a downforce of 2 psi and a flow rate of 175 mL/min on a Dow VP6000 pad to polish 200 mm silicon oxide (TEOS) and silicon nitride blanket wafers.
    Table 3. TEOS and SiN removal rates vs. the head group and hydrophobe of the nitride removal rate reducing agent
    SampleHead TypeHydrophobeTEOS RR [Å/min]SiN RR [Å/min]TEOS RR/SiN RR SiN RR
    3A Phosphonate n-hexyl 953 157 6
    3B Phosphonate n-octyl 906 138 7
    3C Phosphonate n-decyl 895 146 6
    3D Phosphonate n-dodecyl 940 3 313
    3E Phosphonate n-tetradecyl 919 3 306
    3F Phosphonate n-hexadecyl 855 2 427
    3G Phosphonate n-octadecyl 811 2 405
    3H Phosphate Hexyl (C6) 946 139 7
    3I Phosphate Lauryl/Myristyl (C12/C14) 925 4 231
    3J Phosphate Stearyl (C18) 835 3 279
    3K Phosphate Behenyl (C22) 828 2 414
    3L Phosphate Laceryl (C32) 898 23 39


    [0046] As shown in Table 3, the size of the hydrophobe in the nitride removal rate reducing agent plays an important role in determining the efficacy of the rate reduction of silicon nitride. Table 3 shows that, among the agents tested, a chain length of 12 or greater performs best for an effective nitride stop under the tested conditions. A carbon chain length of 12 or greater (see samples 3D, 3E, 3F, 3G, 3I, 3J, 3K, and 3L in Table 3) in the nitride removal rate reducing agent ensures low SiN RR (typically < 5 A/min) and generates high selectivity ratio for TEOS: SiN RR (> 250) for blanket films. Thus, such polishing compositions are ideally suited for STI CMP processes where a high selectivity ratio of silicon oxide to silicon nitride is desired.

    Example 4: Demonstration of downforce effects



    [0047] In this example, polishing compositions used in samples 4A-4C included: 3 w/w% colloidal silica abrasive, an organic acid as a pH adjuster, n-octadecylphosphonic acid, and water as a liquid carrier. The pH of the polishing compositions was between 2 and 6.5. An Applied Materials Mirra CMP polisher was used with a downforce of 2, 3, and 4 psi and a flow rate of 175 mL/min on a Dow IC1010 pad to polish 200 mm high density plasma (HDP) silicon oxide, tetraethyl orthosilicate oxide (TEOS), borophosphosilicate glass (BPSG), and silicon nitride coated wafers.
    Table 4. HDP, TEOS, BPSG, and SiN removal rates vs. downforce
    SamplePressure [psi]HDP RR [Å/min]TEOS RR [Å/min]BPSG RR [Å/min]SiN RR [Å/min]
    4A 2 1147 1835 4971 4
    4B 3 1506 2324 6675 2
    4C 4 1752 3140 8173 1


    [0048] As shown in Table 4, silicon oxide films (HDP, TEOS, and BPSG) exhibited Prestonian behavior while silicon nitride removal rates exhibited non-Prestonian behavior and remained well controlled regardless of the downforce applied. In CMP language, Prestonian behavior of removal rates implies that the polishing rates increase linearly with increase in polishing pressure and/or angular velocity/rpm (revolutions per minute) of the polisher. For the high rate target film, a Prestonian behavior is desirable (silicon oxide films herein). A non-Prestonian behavior implies that the polishing rates do not change appreciably with change in pressure or velocity. Non-Prestonian behavior is somewhat desirable for the stop on film (SiN herein). As seen in Table 4, the removal rates of silicon oxide films increase linearly/Prestonianly with increase in downforce (e.g., TEOS RR increases from 1835 to 2324 to 3140 A/min with increase in downforce from 2 to 3 to 4 psi pressure). Conversely, SiN (stop on film) removal rates do not change appreciably with increase in pressure (i.e., SiN RR fluctuates from 4 to 2 to 1 A/min with increase in downforce from 2 to 3 to 4 psi pressure). In addition, this example proves that the polishing compositions have similar behavior on silicon oxide family of films as defined earlier. To further clarify, in Table 4, we depict three examples of silicon oxide films: HDP, TEOS & BPSG. The polishing compositions of this disclosure work very effectively in giving high material removal rates on all the different types of silicon oxide films. Equivalent experiments using examples of different kinds of silicon nitride films (SiN, SiCN, etc.) showed similar slurry stopping behavior as those achieved on the SiN films depicted in Table 4. Only the SiN film rates are depicted in Table 4 for simplicity.

    Example 5: Demonstration of pad effect



    [0049] In this example, polishing compositions used in samples 5A-5C included: 3 w/w% colloidal silica abrasive, an organic acid as a pH adjuster, a nitride removal rate reducing agent, and water as a liquid carrier. The pH of the polishing compositions was between 2 and 6.5. An Applied Materials Mirra CMP polisher was used with a downforce of 2 psi and a flow rate of 175 mL/min on a Dow VP6000 or Fujibo H800 pad to polish 200 mm tetraethyl orthosilicate oxide (TEOS) and silicon nitride (SiN) blanket wafers.
    Table 5. TEOS and SiN removal rates vs. pad and nitride removal rate reducing agent
    SamplePadNitride Removal Rate Reducing AgentTEOS RR [Å/min]SiN RR [Å/min]TEOS RR/ SiN RR
    5A Dow VP6000 stearyl phosphate 745 2 373
    5B   n-octadecyl phosphonate 756 1 756
    5C   Oleyl phosphate 835 3 278
    5A Fujibo H800 stearyl phosphate 951 8 119
    5B   n-octadecyl phosphonate 942 2 471
    5C   Oleyl phosphate 970 61 16


    [0050] As shown in Table 5, the nitride removal rate reducing agent had an effect on silicon nitride protection. On the Dow VP6000 pad, which has a medium hardness, all samples (5A-5C) provided effective nitride protection as demonstrated by low SiN removal rates and high TEOS/SiN removal rate selectivity. However, on the Fujibo H800 pad, which is a soft pad, only samples containing nitride removal rate reducing agents with long-chain saturated hydrophobes (5A, 5B) provided an effective nitride stop. Thus, this example demonstrates that the polishing compositions of this disclosure work effectively on all kinds of polishing pads. Further, this example suggests the trend that nitride protection is increased when the nitride removal rate reducing agent includes longer hydrophobes, is more saturated, and/or is more hydrophobic.

    Example 6: Demonstration of dishing reduction



    [0051] In this example, polishing compositions used in samples 6A-6D included: 3 w/w% colloidal silica abrasive, an organic acid as a pH adjuster, n-octadecylphosphonic acid, anionic dishing reducing polymer (if present), and water as a liquid carrier. The pH of the polishing compositions was 3.0. An Applied Materials Mirra CMP polisher was used with a downforce of 2 psi and a flow rate of 175 mL/min on a Dow VP6000 pad to polish 200 mm STI 1 silicon oxide/silicon nitride patterned wafer. The wafers were end pointed by laser measurement after about 50 seconds and a 20 second over-polish.
    Table 6. Effect of anionic dishing reducing polymer on oxide dishing
    SampleAnionic dishing reducing polymerDishing [Å] 5 µm features | 50% denseDishing [Å] 20 µm features | 50% dense
    6A - 1194 1223
    6B Carrageenan 96 180
    6C Xanthan gum 37 1068
    6D Carboxymethylcellulose 172 900


    [0052] As shown in Table 6, the addition of anionic dishing reducing polymer is effective in controlling oxide dishing, particularly on small features. Sample 6A included no dishing reducing agent, whereas samples 6B, 6C & 6D included three different types of dishing reducing agents. As can be seen from Table 6, the silicon oxide dishing values on both 5 µm and 20 µm features are much less for samples 6B, 6C and 6D when compared to sample 6A.

    Example 7: Demonstration of concentrates



    [0053] In this example, polishing compositions used in samples 7A-7C included concentrates corresponding to a point of use formulation of: 3 w/w% neutral colloidal silica abrasive, an organic acid and/or potassium hydroxide as a pH adjuster, n-octadecylphosphonic acid, and water as a liquid carrier. The single pot solution contained all the components needed to polish, while the two-part system contained all components except for the organic acid. Mean particle size (MPS) is a reliable indicator of slurry stability. In unstable systems, particles agglomerated over time, causing measurable MPS growth. MPS was measured on a Malvern tool using dynamic light scatter technique. Slurries were stored in an oven set to 60°C and measured every 7 days. As per the Arrhenius relationship for accelerated aging tests, the full test run of 21 days corresponds to roughly one year of room temperature aging. In other words, if the slurry is kept at 60°C for 21 days and the MPS of the silica does not grow appreciably, it can be certified that the slurry has a real time shelf-life/expiration date of one year.
    Table 7. Accelerated aging (60°C) of slurry concentrates
    SampleTypepHMPS [nm] Day 0MPS [nm] Day 7MPS [nm] Day 14MPS [nm] Day 21
    7A 2x single pot 2.2 68 69 69 69
    7B 2x single pot 3.0 65 65 66 66
    7C 5x two-part 9.5 72 73 73 74


    [0054] As shown in Table 7, all formulations are stable through the full test run. Stability in the acidic region for neutral silica is typically difficult to achieve. The single pot solutions were stable from pH of about 2 to about 6.5 at a 2x concentration (select data shown in Table 7) and at other concentration levels (e.g., 3x, 4x, and up to 10x concentrations) (not shown). In the two-part solution (7C), all components, with the exception of the acid, could be concentrated to a much greater degree and remained stable (up to 10x also remains stable). At point of use, the acid and water would be added to reconstitute the slurry before running it on a polishing tool.

    Example 8: Demonstration of patterned wafer removal rate selectivity



    [0055] In this example, polishing compositions used in samples 8A, 8B, and 8C, which contained a colloidal silica abrasive and a nitride removal rate reducing agent shown in Tables 1, 3 and 5, were used to polish 200 mm STI patterned wafers wherein patterned silicon nitride is filled with high density silicon oxide as shown in Figure 2. The pattern in the silicon nitride was such that a wide array of line space, square, checker, and mesh arrays of varying pitch and densities were arranged across the entire wafer face.

    [0056] Polishing occurred on an Applied Materials 200 mm Mirra polishing tool, which was equipped with a DowDupont VP6000 pad, 3M A165 CIP1 conditioning disk, and employing a 2 PSI wafer back pressure. Polishing times were varied based upon in-situ endpoint detection by both motor torque and red laser (650nm) absorbance. During polish, features within both of the endpoint signals can be observed indicating removal of silicon oxide in the active lines of the film stack and the exposure of the underlying silicon nitride. Patterned silicon oxide removal rate was calculated based upon the amount of material removed prior to the exposure of silicon nitride divided by polish time. Conversely, the patterned silicon nitride removal rates are calculated upon the amount of material removed divided by the time after it has been exposed to the polishing composition. Upon completion of the polishing, the wafers were cleaned via 200 mm OnTrack post CMP cleaning tool (from Lam Research company) using Fujifilm Wako 8901 post-CMP cleaning chemistry. Film thickness measurements (e.g., to determine removal rates) of all wafers were measured using a KLA Tencor F5X ellipsometer.
    Table 8. Patterned wafer removal rates and selectivity on various line space arrays
    SampleArray Active Line Width (µm)Array Pitch (µm)Array Pattern Density (%)Silicon Oxide Removal Rate (Å/min)Silicon Nitride Removal Rate (Å/min)Selectivity
    8A 5 50 10 1301 15 86.7
      45 50 90 749 8 93.6
      0.18 0.36 50 1330 7 190.0
      0.50 1.00 50 1072 10 107.2
      100 200 50 1920 18.0 106.6
    8B 100 200 50 1710 31.8 53.8
    8C 0.05 0.5 10 1043 238 4.3


    [0057] From the data presented in Table 8, the high selectivities between silicon oxide and silicon nitride material removal rates previously observed on blanket wafers are also observed on patterned wafers containing both silicon oxide (top) and silicon nitride (bottom). As can be seen in Table 8, for sample 8A, silicon oxide to silicon nitride selectivity varies from 86 all the way to 190 depending on pattern size, density and pitch. For sample 8B, silicon oxide to silicon nitride selectivity is 54 whereas for sample 8C, the selectivity is 4. Table 8 solely provides representative examples of performance on patterned wafers. In our in-house experiments selectivity ratios have been observed to vary from 3 (which is considered satisfactory for patterned wafers) all the way to about 1000 on patterned test wafers depending on film complexity. Moreover, the selectivities of the polishing compositions containing the nitride removal rate reducing agent presented herein exceed the selectivity of many legacy, industry standard, commercially available, ceria based, STI polishing compositions presented in prior art.

    Example 9: Demonstration of patterned wafer dishing and erosion



    [0058] In this example, patterned wafers similar to the ones used in example 8 were measured in a Park Systems AFM tool in order to quantify silicon oxide dishing/step-heights and silicon nitride erosion/loss at endpoint. Polishing compositions used in samples 9A and 9B contained a nitride removal rate reducing agent shown in Tables 1, 3 and 5, and were used to polish patterned wafers whose stack is depicted in Fig. 2. The silicon oxide dishing/step-height and silicon nitride erosion/loss results are shown in Table 9. Planarization efficiency (PE) is reported in percentage and is equal to the change in silicon oxide step height divided by the amount of oxide removed during polish then multiplied by one hundred (to convert to percentage).
    Table 9. Patterned Wafer Dishing and Erosion
    SampleArray Active Line WidthArray Pitch (µm)Array Pattern Density (%)Oxide Dishing (Å)Silicon Nitride Erosion (Å)Planarization Efficiency(%)
    9A 5 50 10 40 74 46
      45 50 90 157 10 38
      0.18 0.36 50 48 70 14
      0.50 1.00 50 35.6 60 17
      100 200 50 245 30 74
    9B 100 200 50 375 34 72


    [0059] As can be seen in Table 9, the silicon oxide dishing and the silicon nitride erosion are very small. Typically, for dishing and erosion, very low numbers are preferred. The dishing and erosion numbers are representative of the flatness of the final topography post CMP polishing of the patterned wafers. So, a low value (in Å) of these numbers is desirable as these numbers measure the separation in the peaks and valleys of the films on the wafers that contain multiple film types in a patterned wafer. The lower the number, the less separation that exists between the peaks and troughs, implying flatter the wafer surface, which is the overall goal of the CMP process step in semiconductor fabrication. Ideally, a zero dishing and erosion value is preferred (implying completely flat wafer surface). Conventionally, however, these numbers are generally in the hundreds or thousands of Å values' on actual device/product patterned wafers. Thus, the data shown in Table 9 indicate that the polishing compositions provide a unique/extraordinary performance in delivering very low dishing and erosion values and hence very good topography of patterned wafers. As can be seen in Table 9, the silicon oxide dishing can be as low as 35 Å and as high as 375 Å. The SiN erosion is much better than the dishing as the erosion numbers are as low as 30 Å and as high as 74 Å. Again, these are representative examples and we have seen these dishing and erosion numbers as high as 1000 Å and as low as 1 Å in our experiments, which are still satisfactory for the purpose of this invention and are acceptable to semiconductor manufacturers.

    [0060] For planarization efficiency (PE), the higher the number, the better the result. Ideally, a PE of 100% is desired as that value means that the whole wafer has been planarized and is flat, i.e., there is no step height between the peaks and valleys. From the data in Table 9, it can be seen that the PE varies from a low value of 14% all the way to 74%. Thus, these polishing compositions give good planarization efficiency on patterned wafers.

    [0061] Again, the data presented in table 9 show that the polishing compositions presented herein exceed the oxide dishing, silicon nitride erosion and planarization efficiency of state-of-the-art, commercially available, ceria based, STI polishing compositions.

    Example 10: Demonstration of patterned wafer defectivity after polishing



    [0062] In this example, defectivity of patterned wafers similar to the ones used in examples 8 and 9 was measured in a KLA-AIT XUV defect counter tool by using a commercial ceria based STI formulation and composition 8A described in Example 8 (which is a silica based polishing composition containing the nitride removal rate reducing agent). The wafer map for a wafer polished by using composition 8A is presented in Fig. 3. The wafer map for a wafer polished by using the commercial ceria-based STI polishing composition is presented Fig. 4.

    [0063] As demonstrated by Fig. 4, the ceria-based formulation was prone to heavy arc scratching with many defects spread throughout the wafer (the total defect count was greater than 10,000) - due to the relative hardness and size of the abrasive. Closer inspection of the defects showed that there are lots of macro and micro scratches accompanied by many residues, many of which may be considered overall device killing defects. However, Fig. 3 shows that polishing composition 8A, containing high purity colloidal silica as the abrasive, has far less scratching than the ceria based composition (Fig. 4). Indeed, the silica polishing composition shows near-to "defect-free" and a clean surface. The total defect count is approximately 175 for defects at least 90 nm in size. Defects are key to final device yield, and the production of sellable chips. In the patterned wafer shown in Fig. 4, suppose there are 1000 dies (each square) per patterned wafer. Each of the dies that has a defect may turn out to not be sellable if the defect is a device killer defect. Thus, as the ceria-based polishing composition shows a high amount of defects, its yield of the sellable chips per wafer would be lower. Conversely, for the polishing compositions of this disclosure, the defects are significantly less and thus the yield of sellable chips per wafer is significantly higher.

    [0064] Thus, the low defectivity obtained by using the polishing compositions of this disclosure is very attractive to semiconductor companies as that increases the top line and bottom line of their revenues. From a technical perspective, the ceria abrasives are inorganic in nature (e.g., cerium lanthanide metal based oxide) and are generally hard and larger in size than silica abrasives, so they are prone to give a large amount of scratching and defects on wafer surfaces. Conversely, the colloidal silica abrasives are organic in nature (silicon non-metal based oxide and in colloidal dispersion form) and are generally soft and therefore do not generate scratching or defects during polishing.

    [0065] People skilled in the art have not been able to develop a silica based STI polishing composition with satisfactory removal selectivity of silicon oxide over silicon nitride. As disclosed herein, the present inventors have found a synergistic combination of silica and silicon nitride removal rate reducing agents that can supply to the industry, a silica based STI polishing composition. In addition, the invention described in this disclosure can be applied to abrasives other than silica (such as alumina, titania, etc.).


    Claims

    1. A polishing composition comprising:

    at least one abrasive;

    at least one nitride removal rate reducing agent comprising:

    a hydrophobic portion comprising a C12 to C40 hydrocarbon group; and

    a hydrophilic portion comprising at least one group selected from the group consisting of a sulfinite group, a sulfate group, a carboxylate group, a phosphate group, and a phosphonate group; and

    wherein the hydrophobic portion and the hydrophilic portion are separated by zero to ten alkylene oxide groups;

    an acid or a base; and

    water;

    wherein the polishing composition has a pH of 2 to 6.5.


     
    2. The polishing composition of claim 1, further comprising:

    at least one dishing reducing agent;

    wherein the at least one dishing reducing agent is a compound comprising at least one group selected from the group consisting of hydroxyl, sulfate, phosphonate, phosphate, sulfonate, amine, nitrate, nitrite, carboxylate, and carbonate groups.


     
    3. The polishing composition of claim 1, wherein the at least one dishing reducing agent is at least one selected from the group consisting of a polysaccharide and a substituted polysaccharide.
     
    4. The polishing composition of claim 1, wherein the at least one dishing reducing agent comprises carrageenan, xanthan gum, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methylcellulose, or carboxymethylcellulose.
     
    5. The polishing composition of claim 1, wherein the hydrophobic portion comprises a C12 to C32 hydrocarbon group, optionally wherein the hydrophobic portion comprises a C16 to C22 hydrocarbon group.
     
    6. The polishing composition of claim 1, wherein the hydrophilic portion comprises a phosphate group or a phosphonate group.
     
    7. The polishing composition of claim 1, wherein the at least one nitride removal rate reducing agent is selected from the group consisting of lauryl phosphate, myristyl phosphate, stearyl phosphate, octadecylphosphonic acid, oleyl phosphate, behenyl phosphate, octadecyl sulfate, lacceryl phosphate, oleth-3-phosphate, and oleth-10-phosphate.
     
    8. The polishing composition of claim 1, wherein the at least one nitride removal rate reducing agent has zero alkylene oxide group separating the hydrophobic portion and the hydrophilic portion.
     
    9. The polishing composition of claim 2, wherein the at least one nitride removal rate reducing agent and the at least one dishing reducing agent are chemically distinct from each other.
     
    10. The polishing composition of claim 1, wherein the polishing composition has a ratio of a removal rate for a silicon oxide to a removal rate for a silicon nitride of at least 3:1, optionally wherein the polishing composition has a ratio of a removal rate for a silicon oxide to a removal rate for a silicon nitride of at least 100:1.
     
    11. The polishing composition of claim 1, wherein the at least one abrasive is selected from the group consisting of cationic abrasives, substantially neutral abrasives, and anionic abrasives, or wherein the at least one abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products thereof, coated abrasives, surface modified abrasives, and mixtures thereof.
     
    12. The composition of claim 1, wherein the acid is selected from the group consisting of formic acid, acetic acid, malonic acid, citric acid, propionic acid, malic acid, adipic acid, succinic acid, lactic acid, oxalic acid, hydroxyethylidene diphosphonic acid, 2-phosphono-1,2,4-butane tricarboxylic acid, aminotrimethylene phosphonic acid, hexamethylenediamine tetra(methylenephosphonic acid), bis(hexamethylene)triamine phosphonic acid, amino acetic acid, peracetic acid, potassium acetate, phenoxyacetic acid, glycine, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, phenylalanine, proline, glutamine, aspartic acid, glutamic acid, arginine, lysine, tyrosine, benzoic acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphonic acid, hydrochloric acid, periodic acid, and mixtures thereof.
     
    13. The composition of claim 1, wherein the base is selected from the group consisting of potassium hydroxide, sodium hydroxide, cesium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, monoethanolamine, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, lithium hydroxide, imidazole, triazole, aminotriazole, tetrazole, benzotriazole, tolytriazole, pyrazole, isothiazole, and mixtures thereof.
     
    14. A method, comprising:

    applying the polishing composition of claim 1 to a substrate having at least a silicon nitride and at least a silicon oxide on a surface of the substrate;

    bringing a pad into contact with the surface of the substrate and moving the pad in relation to the substrate; and

    optionally forming a semiconductor device from the substrate.


     
    15. The method of claim 14, wherein at least one of the silicon nitride and silicon oxide is doped with at least one dopant selected from the group consisting of carbon, nitrogen, oxygen, and hydrogen.
     


    Ansprüche

    1. Polierzusammensetzung, umfassend:

    wenigstens einen Abrasivstoff;

    wenigstens ein Nitridentfernungsrate-verringerndes Mittel, umfassend:

    einen hydrophoben Teil, der eine C12- bis C40-Kohlenwasserstoffgruppe umfasst; und

    einen hydrophilen Teil, der wenigstens eine Gruppe ausgewählt aus der Gruppe bestehend aus einer Sulfinitgruppe, einer Sulfatgruppe, einer Carboxylatgruppe, einer Phosphatgruppe und einer Phosphonatgruppe umfasst; und

    wobei der hydrophobe Teil und der hydrophile Teil durch null bis zehn Alkylenoxidgruppen getrennt sind;

    eine Säure oder eine Base; und

    Wasser;

    wobei die Polierzusammensetzung einen pH-Wert von 2 bis 6,5 aufweist.


     
    2. Polierzusammensetzung gemäß Anspruch 1, ferner umfassend:

    wenigstens ein Muldenbildung-verringerndes Mittel;

    wobei das wenigstens eine Muldenbildung-verringernde Mittel eine Verbindung ist, die wenigstens eine Gruppe ausgewählt aus der Gruppe bestehend aus Hydroxy-, Sulfat-, Phosphonat-, Phosphat-, Sulfonat-, Amin-, Nitrat-, Nitrit-, Carboxylat- und Carbonatgruppen umfasst.


     
    3. Polierzusammensetzung gemäß Anspruch 1, wobei das wenigstens eine Muldenbildung-verringernde Mittel wenigstens eines ausgewählt aus der Gruppe bestehend aus einem Polysaccharid und einem substituierten Polysaccharid ist.
     
    4. Polierzusammensetzung gemäß Anspruch 1, wobei das wenigstens eine Muldenbildung-verringernde Mittel Carrageenan, Xanthangummi, Hydroxypropylcellulose, Methylcellulose, Ethylcellulose, Hydroxypropylmethylcellulose oder Carboxymthylcellulose umfasst.
     
    5. Polierzusammensetzung gemäß Anspruch 1, wobei der hydrophobe Teil eine C12- bis C32-Kohlenwasserstoffgruppe umfasst, wobei der hydrophobe Teil gegebenenfalls eine C16- bis C22-Kohlenwasserstoffgruppe umfasst.
     
    6. Polierzusammensetzung gemäß Anspruch 1, wobei der hydrophile Teil eine Phosphatgruppe oder eine Phosphonatgruppe umfasst.
     
    7. Polierzusammensetzung gemäß Anspruch 1, wobei das wenigstens eine Nitridentfernungsrate-verringernde Mittel ausgewählt ist aus der Gruppe bestehend aus Laurylphosphat, Myristylphosphat, Stearylphosphat, Octadecylphosphonsäure, Oleylphosphat, Behenylphosphat, Octadecylphosphat, Laccerylphosphat, Oleth-3-phosphat und Oleth-10-phosphat.
     
    8. Polierzusammensetzung gemäß Anspruch 1, wobei das wenigstens eine Nitridentfernungsrate-verringernde Mittel null Alkylenoxidgruppen aufweist, die den hydrophoben Teil und den hydrophilen Teil trennen.
     
    9. Polierzusammensetzung gemäß Anspruch 2, wobei das wenigstens eine Nitridentfernungsrate-verringernde Mittel und das wenigstens eine Muldenbildung-verringernde Mittel chemisch voneinander verschieden sind.
     
    10. Polierzusammensetzung gemäß Anspruch 1, wobei die Polierzusammensetzung ein Verhältnis einer Entfernungsrate für ein Siliciumoxid zu einer Entfernungsrate für ein Siliciumnitrid von wenigstens 3:1 aufweist, wobei die Polierzusammensetzung gegebenenfalls ein Verhältnis einer Entfernungsrate für ein Siliciumoxid zu einer Entfernungsrate für ein Siliciumnitrid von wenigstens 100:1 aufweist.
     
    11. Polierzusammensetzung gemäß Anspruch 1, wobei der wenigstens eine Abrasivstoff ausgewählt ist aus der Gruppe bestehend aus kationischen Abrasivstoffen, im Wesentlichen neutralen Abrasivstoffen und anionischen Abrasivstoffen, oder wobei der wenigstens eine Abrasivstoff ausgewählt ist aus der Gruppe bestehend aus Aluminiumoxid, Siliciumdioxid, Titandioxid, Cerdioxid, Zirkoniumdioxid, gemeinsam gebildeten Produkten davon, überzogenen Abrasivstoffen, oberflächenmodifizierten Abrasivstoffen und Gemischen davon.
     
    12. Polierzusammensetzung gemäß Anspruch 1, wobei die Säure ausgewählt ist aus der Gruppe bestehend aus Ameisensäure, Essigsäure, Malonsäure, Citronensäure, Propionsäure, Apfelsäure, Adipinsäure, Bernsteinsäure, Milchsäure, Oxalsäure, Hydroxyethylidendiphosphonsäure, 2-Phosphono-1,2,4-butantricarbonsäure, Aminotrimethylenphosphonsäure, Hexamethylendiamintetra(methylenphosphonsäure), Bis(hexamethylen)triaminphosphonsäure, Aminoessigsäure, Peressigsäure, Kaliumacetat, Phenoxyessigsäure, Glycin, Bicin, Diglycolsäure, Glyerinsäure, Tricin, Alanin, Histidin, Valin, Phenylalanin, Prolin, Glutamin, Asparaginsäure, Glutaminsäure, Arginin, Lysin, Tyrosin, Benzoesäure, Salpetersäure, Schwefelsäure, schwefliger Säure, Phosphorsäure, Phosphonsäure, Salzsäure, Periodsäure und Gemischen davon.
     
    13. Polierzusammensetzung gemäß Anspruch 1, wobei die Base ausgewählt ist aus der Gruppe bestehend aus Kaliumhydroxid, Natriumhydroxid, Cäsiumhydroxid, Ammoniumhydroxid, Triethanolamin, Diethanolamin, Monoethanolamin, Tetrabutylammoniumhydroxid, Tetramethylammoniumhydroxid, Lithiumhydroxid, Imidazol, Triazol, Aminotriazol, Tetrazol, Benzotriazol, Tolytriazol, Pyrazol, Isothiazol und Gemischen davon.
     
    14. Verfahren, umfassend:

    Aufbringen der Polierzusammensetzung gemäß Anspruch 1 auf ein Substrat, das wenigstens ein Siliciumnitrid und wenigstens ein Siliciumoxid auf einer Oberfläche des Substrats aufweist;

    Inkontaktbringen eines Kissens mit der Oberfläche des Substrats und Bewegen des Kissens relativ zu dem Substrat; und

    gegebenenfalls Bilden einer Halbleitervorrichtung aus dem Substrat.


     
    15. Verfahren gemäß Anspruch 14, wobei wenigstens eines von dem Siliciumnitrid und dem Siliciumoxid mit wenigstens einem Dotierstoff ausgewählt aus der Gruppe bestehend aus Kohlenstoff, Stickstoff, Sauerstoff und Wasserstoff dotiert ist.
     


    Revendications

    1. Composition de polissage comprenant :

    au moins un abrasif ;

    au moins un agent de réduction de la vitesse d'élimination de nitrure comprenant :

    une partie hydrophobe comprenant un groupe hydrocarboné en C12 à C40 ; et

    une partie hydrophile comprenant au moins un groupe choisi dans le groupe constitué par un groupe sulfinite, un groupe sulfate, un groupe carboxylate, un groupe phosphate, et un groupe phosphonate ; et

    la partie hydrophobe et la partie hydrophile étant séparées par zéro à dix groupes oxyde d'alkylène ;

    un acide ou une base ; et

    de l'eau ;

    la composition de polissage ayant un pH de 2 à 6,5.


     
    2. Composition de polissage selon la revendication 1, comprenant en outre :

    au moins un agent de réduction d'emboutissage ;

    l'au moins un agent de réduction d'emboutissage étant un composé comprenant au moins un groupe choisi dans le groupe constitué par des groupes hydroxyle, sulfate, phosphonate, phosphate, sulfonate, amine, nitrate, nitrite, carboxylate et carbonate.


     
    3. Composition de polissage selon la revendication 1, l'au moins un agent de réduction d'emboutissage étant au moins l'un choisi dans le groupe constitué par un polysaccharide et un polysaccharide substitué.
     
    4. Composition de polissage selon la revendication 1, l'au moins un agent de réduction d'emboutissage comprenant un carraghénane, une gomme xanthane, une hydroxypropylcellulose, une méthylcellulose, une éthylcellulose, une hydroxypropylméthylcellulose, ou une carboxyméthylcellulose.
     
    5. Composition de polissage selon la revendication 1, la partie hydrophobe comprenant un groupe hydrocarboné en C12 à C32, éventuellement la partie hydrophobe comprenant un groupe hydrocarboné en C16 à C22.
     
    6. Composition de polissage selon la revendication 1, la partie hydrophile comprenant un groupe phosphate ou un groupe phosphonate.
     
    7. Composition de polissage selon la revendication 1, l'au moins un agent de réduction de la vitesse d'élimination de nitrure étant choisi dans le groupe constitué par le phosphate de lauryle, le phosphate de myristyle, le phosphate de stéaryle, l'acide octadécylphosphonique, le phosphate d'oléyle, le phosphate de béhényle, le sulfate d'octadécyle, le phosphate de laccéryle, l'oleth-3-phosphate, et l'oleth-10-phosphate.
     
    8. Composition de polissage selon la revendication 1, l'au moins un agent de réduction de la vitesse d'élimination de nitrure ayant zéro groupe oxyde d'alkylène séparant la partie hydrophobe et la partie hydrophile.
     
    9. Composition de polissage selon la revendication 2, l'au moins un agent de réduction de la vitesse d'élimination de nitrure et l'au moins un agent de réduction d'emboutissage étant chimiquement distincts l'un de l'autre.
     
    10. Composition de polissage selon la revendication 1, la composition de polissage ayant un rapport d'une vitesse d'élimination pour un oxyde de silicium sur une vitesse d'élimination pour un nitrure de silicium d'au moins 3 : 1, éventuellement la composition de polissage ayant un rapport d'une vitesse d'élimination pour un oxyde de silicium sur une vitesse d'élimination pour un nitrure de silicium d'au moins 100 : 1.
     
    11. Composition de polissage selon la revendication 1, l'au moins un abrasif étant choisi dans le groupe constitué par des abrasifs cationiques, des abrasifs sensiblement neutres, et des abrasifs anioniques, ou l'au moins un abrasif étant choisi dans le groupe constitué par l'alumine, la silice, l'oxyde de titane, l'oxyde de cérium, la zircone, des produits coformés correspondants, des abrasifs revêtus, des abrasifs modifiés en surface, et des mélanges correspondants.
     
    12. Composition selon la revendication 1, l'acide étant choisi dans le groupe constitué par l'acide formique, l'acide acétique, l'acide malonique, l'acide citrique, l'acide propionique, l'acide malique, l'acide adipique, l'acide succinique, l'acide lactique, l'acide oxalique, l'acide hydroxyéthylidène diphosphonique, l'acide 2-phosphono-1,2,4-butane tricarboxylique, l'acide aminotriméthylène phosphonique, l'acide hexaméthylènediamine tétra(méthylènephosphonique), l'acide bis(hexaméthylène)triamine phosphonique, l'acide amino acétique, l'acide peracétique, l'acétate de potassium, l'acide phénoxyacétique, la glycine, la bicine, l'acide diglycolique, l'acide glycérique, la tricine, l'alanine, l'histidine, la valine, la phénylalanine, la proline, la glutamine, l'acide aspartique, l'acide glutamique, l'arginine, la lysine, la tyrosine, l'acide benzoïque, l'acide nitrique, l'acide sulfurique, l'acide sulfureux, l'acide phosphorique, l'acide phosphonique, l'acide chlorhydrique, l'acide périodique, et des mélanges correspondants.
     
    13. Composition selon la revendication 1, la base étant choisie dans le groupe constitué par l'hydroxyde de potassium, l'hydroxyde de sodium, l'hydroxyde de césium, l'hydroxyde d'ammonium, la triéthanolamine, la diéthanolamine, la monoéthanolamine, l'hydroxyde de tétrabutylammonium, l'hydroxyde de tétraméthylammonium, l'hydroxyde de lithium, l'imidazole, le triazole, l'aminotriazole, le tétrazole, le benzotriazole, le tolytriazole, le pyrazole, l'isothiazole, et des mélanges correspondants.
     
    14. Procédé, comprenant :

    l'application de la composition de polissage selon la revendication 1 sur un substrat ayant au moins un nitrure de silicium et au moins un oxyde de silicium sur une surface du substrat ;

    la mise en contact d'un tampon avec la surface du substrat et le déplacement du tampon par rapport au substrat ; et

    éventuellement la formation d'un dispositif semiconducteur à partir du substrat.


     
    15. Procédé selon la revendication 14, au moins l'un parmi le nitrure de silicium et l'oxyde de silicium étant dopé avec au moins un dopant choisi dans le groupe constitué par le carbone, l'azote, l'oxygène et l'hydrogène.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description