CN102051128B - A kind of chemical mechanical polishing liquid - Google Patents

A kind of chemical mechanical polishing liquid Download PDF

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CN102051128B
CN102051128B CN200910198377.1A CN200910198377A CN102051128B CN 102051128 B CN102051128 B CN 102051128B CN 200910198377 A CN200910198377 A CN 200910198377A CN 102051128 B CN102051128 B CN 102051128B
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polishing fluid
polishing
silicon nitride
tbah
water surplus
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CN102051128A (en
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姚颖
宋伟红
孙展龙
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Anji microelectronic technology (Shanghai) Limited by Share Ltd
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Anji Microelectronics Shanghai Co Ltd
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Abstract

The invention discloses a kind of chemical mechanical polishing liquid, it is for polishing silicon nitride materials.This polishing fluid comprises abrasive grain, quaternary ammonium compound, a kind of silicon nitride polishing accelerator and water.This silicon nitride accelerator is selected from a kind of anion surfactant.Chemical mechanical polishing liquid of the present invention can remove silicon nitride material effectively, and provides silicon nitride material to the selectivity of the removal speed of silica material.

Description

A kind of chemical mechanical polishing liquid
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid.
Background technology
In integrated circuit fabrication, the standard of interconnection technique is in improve, along with the interconnection increase of the number of plies and reducing of technology feature size, also more and more higher to the requirement of silicon chip surface evenness, if there is no the ability of planarization, it is very limited for creating complicated and intensive structure on a semiconductor wafer, and cmp method CMP is exactly the most effective method that can realize whole silicon chip planarization.
CMP is exactly use a kind of mixture containing abrasive material and polishing pad polishing integrated circuit surface.In typical cmp method, substrate is directly contacted with rotating polishing pad, applies pressure with a loads at substrate back.During polishing, pad and operating desk rotate, the power simultaneously kept down at substrate back, is applied on pad by abrasive material and chemism solution (being commonly referred to polishing fluid or polishing slurries), this polishing fluid with just start to carry out polishing process at the film generation chemical reaction of polishing.
As the method for each element of isolation of semiconductor devices, shallow trench isolation is the semiconductor processing technology of extensive use from (STI) technique, wherein form silicon nitride layer on a silicon substrate, form shallow slot by etching or photoetching process, and dielectric layer is to fill this groove.Due to the change of the degree of depth of the groove that formed by this way or line, excessive dielectric material generally must be deposited to guarantee that safety fills all grooves in base top.
Generally remove excessive dielectric material to expose silicon nitride layer by CMP (Chemical Mechanical Polishing) process.When silicon nitride layer exposes, the substrate being exposed to the maximum area of chemical-mechanical polishing system comprises silicon nitride.Then silicon nitride must polished with obtain high-flatness and uniformly surface.Usually, the practice in past focuses on selectivity oxide cmp being had precedence over to silicon nitride polishing.Therefore, when silicon nitride layer exposes, total polishing speed declines, and silicon nitride layer is used as stop-layer.But, because oxide line width becomes more and more less in device generations, in some cases, expect to use and there is the optionally polishing system of silicon nitride to oxide cmp, to reduce the defect of the oxide line formed on the surface of the substrate.China applies for a patent polishing fluid disclosed in 200510116191.9 and utilizes a kind of acid additive be selected from hydrochloric acid, formic acid, acetic acid, oxalic acid, adipic acid and lactic acid to improve the removal speed of silicon nitride, removes the selectivity of speed to silica removal speed to improve silicon nitride.China applies for a patent 20078006548.5 and discloses the polishing fluid with the pH value of 1 to 6 for polish silicon nitride.It comprises grinding agent and acidic components (such as, the combination of malonic acid and amino carboxylic acid, stannate, uric acid, phenylacetic acid, or the combination of malonic acid, amino carboxylic acid and sulfate).This polishing fluid can obtain the removal speed of higher silicon nitride, obtain silicon nitride and remove speed removes speed selectivity to silica, China applies for a patent 200780026767.X and discloses a kind of polishing fluid, it contains cataloid, the at least one acidic components of the pKa of 1 to 4.5, and aqueous carrier, pH value is in the scope of 0.5 PH unit less of the pKa of these acidic components to 1.5 PH units larger than this pKa.This polishing fluid can obtain higher silicon nitride and remove speed and lower silica removal speed.In this kind of patent, be all utilize acidic components to improve the removal speed of silicon nitride.
At shallow trench isolation from (STI) technique, the STI polishing fluid of current use has the removal speed to silica material faster (compared with silicon nitride material) usually.Therefore, when silicon nitride layer exposes, total polishing speed declines, and silicon nitride layer is used as stop-layer.But, because oxide line width becomes more and more less in device generations, in some cases, expect to use and there is the optionally polishing fluid of silicon nitride material to silica material polishing, to reduce the defect of the oxide line formed on the surface of the substrate.
Summary of the invention
The object of this invention is to provide and a kind ofly there is relatively high silicon nitride remove speed, the removal speed Selection radio of silicon nitride and silica can be regulated to meet the polishing requirement of technique, reduce the chemical mechanical polishing liquid of the defect of the oxide line formed on the surface of the substrate.
Polishing fluid of the present invention comprises: abrasive grain, quaternary ammonium compound, silicon nitride polishing accelerator and water.Wherein, silicon nitride polishing accelerator is anionic surfactant, such as DBSA, neopelex, sodium methylene bis-naphthalene sulfonate, alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salt, PAPE, glycerine polyoxypropylene ether phosphate triethanolamine salt, acrylic acid-2-acrylamide-2-methylpro panesulfonic acid copolymer, polyacrylic acid and PAMA etc.
In the present invention, polyacrylic molecular weight is 2000 ~ 5000, and the molecular weight of PAMA is 5,000,000 ~ 12,000,000.
In the present invention, the content of surfactant is mass percent: 0.001 ~ 0.2%, is preferably mass percent: 0.005 ~ 0.1%.
In the present invention, abrasive grains is silicon dioxide, alundum (Al2O3), ceria or the silica dioxide granule mixing aluminium.Abrasive grains particle diameter is 20 ~ 150nm, and content is mass percent: 1 ~ 20%.
In the present invention, quaternary ammonium compound is Tetramethylammonium hydroxide and/or TBAH, and content is mass percent: 0.01 ~ 0.2%.
In the present invention, the pH of polishing fluid is 2 ~ 7, is preferably 2 ~ 4.
Good effect of the present invention is: effectively remove silicon nitride material; There is provided silicon nitride material to the selectivity of the removal speed of silica material; Reduce the defect of the oxide line formed on the surface of the substrate.
Accompanying drawing explanation
Fig. 1 is that the consumption of alkyl phosphate diethanolamine salt in effect example 2 is to Si 3n 4scheme with the removal RATES of TEOS;
Fig. 2 is that the consumption of alkyl phosphate diethanolamine salt in effect example 2 is to Si 3n 4with the removal speed Selection radio figure of TEOS;
Fig. 3 is that the different PH of polishing fluid in effect example 3 is to Si 3n 4scheme with the removal RATES of TEOS;
Fig. 4 be in effect example 4 abrasive concentration to Si 3n 4scheme with the removal RATES of TEOS.
Embodiment
Set forth the present invention further below by specific embodiment, therefore do not limit the present invention among described scope of embodiments.
By listed formula, by simple for each composition Homogeneous phase mixing, surplus is water, adopts potassium hydroxide, ammoniacal liquor and nitric acid to be adjusted to suitable pH value afterwards, can obtain each embodiment polishing fluid.
Effect example 1
Contrast polishing fluid 1 ' abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 2 ' abrasive silica (150nm) 4%, TMAH 0.2%, water surplus, pH=3;
Polishing fluid 1 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 2 abrasive silica (100nm) 4%, TBAH 0.05%, PAPE 0.02%, water surplus, pH=3;
Polishing fluid 3 abrasive silica (100nm) 4%, TBAH 0.05%, DBSA 0.02%, water surplus, pH=3;
Polishing fluid 4 abrasive silica (100nm) 4%, TBAH 0.05%, acrylic acid-2-acrylamide-2-methylpro panesulfonic acid copolymer 0.02%, water surplus, pH=3;
Polishing fluid 5 abrasive silica (100nm) 4%, TBAH 0.05%, polyacrylic acid (molecular weight 3000) 0.02%, water surplus, pH=3;
Polishing fluid 6 abrasive silica (100nm) 4%, TBAH 0.05%, PAMA (molecular weight 8,000,000) 0.02%, water surplus, pH=3;
Polishing fluid 7 abrasive silica (100nm) 4%, TBAH 0.05%, sodium methylene bis-naphthalene sulfonate 0.02%, water surplus, pH=3;
Polishing fluid 8 abrasive silica (100nm) 4%, TBAH 0.05%, polyacrylic acid (molecular weight 2000) 0.02%, water surplus, pH=3;
Polishing fluid 9 abrasive silica (100nm) 4%, TBAH 0.05%, polyacrylic acid (molecular weight 5000) 0.02%, water surplus, pH=3;
Polishing fluid 10 abrasive silica (100nm) 4%, TBAH 0.05%, PAMA (molecular weight 5,000,000) 0.02%, water surplus, pH=3;
Polishing fluid 11 abrasive silica (100nm) 4%, TBAH 0.05%, PAMA (molecular weight 1,200 ten thousand) 0.02%, water surplus, pH=3;
Polishing fluid 12 abrasive silica (150nm) 4%, TMAH 0.05%, neopelex 0.02%, water surplus, pH=3;
Polishing fluid 13 abrasive silica (150nm) 4%, TMAH 0.05%, alkyl phosphate triethanolamine salt 0.15%, water surplus, pH=3;
Polishing fluid 14 abrasive silica (150nm) 4%, TMAH 0.05%, glycerine polyoxypropylene ether phosphate triethanolamine salt 0.2%, water surplus, pH=3;
Polishing fluid 15 alundum (Al2O3) abrasive material (20nm) 5%, DBSA 0.15%, TBAH 0.15%, water surplus, pH=3;
Polishing fluid 16 Ceria abrasive (150nm) 1%, di-2-ethylhexylphosphine oxide how sodium sulfonate 0.02%, Tetramethylammonium hydroxide 0.01%%, water surplus, pH=4;
Polishing fluid 17 mixes aluminium abrasive silica (45nm) 3%, polyacrylic acid (molecular weight 5000) 0.2%, Tetramethylammonium hydroxide 0.1%, water surplus, pH=3;
Polishing fluid 18 silicon dioxide (80nm) 6%, alkyl phosphate diethanolamine salt 0.05%, TBAH 0.02%, water surplus, pH=2.
Polishing material: blank Si 3n 4wafer, polishing condition: 4psi, polishing disk rotating speed 70rpm, polishing pad PPG, polishing fluid flow velocity 200ml/min, Logitech LP50 Polisher.Experimental result is as shown in table 1:
The different anion surfactant of table 1 is to Si 3n 4remove the impact of speed
Result is as shown in table 1: polishing fluid of the present invention effectively can remove Si 3n 4.The anion surfactant wherein added can improve Si significantly 3n 4removal speed, especially, the interpolation of DBSA makes Si 3n 4removal speed reach
Effect example 2
Contrast polishing fluid 19 ' abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=3;
Polishing fluid 19 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.001%, water surplus, pH=3;
Polishing fluid 20 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.005%, water surplus, pH=3;
Polishing fluid 21 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.01%, water surplus, pH=3;
Polishing fluid 22 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 23 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.03%, water surplus, pH=3;
Polishing fluid 24 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.05%, water surplus, pH=3;
Polishing fluid 25 abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.1%, water surplus, pH=3;
Polishing material: blank Si 3n 4wafer, blank TEOS wafer; Polishing condition: 4psi, polishing disk rotating speed 70rpm, polishing pad PPG, polishing fluid flow velocity 200ml/min, Logitech LP50 Polisher.Experimental result is as shown in table 2, Fig. 1 and Fig. 2:
Table 2 alkyl phosphate diethanolamine salt consumption is to Si 3n 4the impact of speed is removed with TEOS
Result is as shown in Table 2 and Figure 1: after adding anion surfactant in polishing fluid of the present invention, can improve Si significantly 3n 4removal speed and suppress the removal speed of TEOS.Along with the increase of anionic surfactant dose, polishing fluid of the present invention is to Si 3n 4polishing facilitation first strengthen gradually, weaken gradually after reaching particular value.Illustrate and only have when the consumption of anion surfactant is a particular value, could to Si 3n 4removal speed have facilitation.Otherwise excessive anion surfactant can suppress Si on the contrary 3n 4polishing, even reduce Si 3n 4removal speed.As shown in table 2 and Fig. 2, Si can be regulated by regulating the concentration of anion surfactant 3n 4with the Selection radio of the removal speed of TEOS, along with the increase of anionic surfactant dose, Si 3n 4also increase gradually with the Selection radio of the removal speed of TEOS.
Effect example 3
Contrast polishing fluid 26 ' (1) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=2;
Contrast polishing fluid 26 ' (2) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 26 ' (3) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 26 ' (4) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=5;
Contrast polishing fluid 26 ' (5) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=7;
Polishing fluid 26 (1) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=2;
Polishing fluid 26 (2) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 26 (2) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=4;
Polishing fluid 26 (3) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=5;
Polishing fluid 26 (4) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=7;
Polishing material: blank Si 3n 4wafer, polishing condition: 4psi, polishing disk rotating speed 70rpm, polishing pad PPG, polishing fluid flow velocity 200ml/min, Logitech LP50 Polisher.
Result is as shown in Figure 3: when the pH of polishing fluid is 2 ~ 4, and relative to the polishing fluid not containing anion surfactant, the polishing fluid containing anion surfactant of the present invention significantly can increase Si 3n 4polishing speed.
Effect example 4
Contrast polishing fluid 27 ' (1) abrasive silica (100nm) 1%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (2) abrasive silica (100nm) 2%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (3) abrasive silica (100nm) 4%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (4) abrasive silica (100nm) 8%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (5) abrasive silica (100nm) 10%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (6) abrasive silica (100nm) 15%, TBAH 0.05%, water surplus, pH=3;
Contrast polishing fluid 27 ' (7) abrasive silica (100nm) 20%, TBAH 0.05%, water surplus, pH=3;
Polishing fluid 27 (1) abrasive silica (100nm) 1%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (2) abrasive silica (100nm) 2%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (3) abrasive silica (100nm) 4%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (4) abrasive silica (100nm) 8%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (5) abrasive silica (100nm) 10%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (6) abrasive silica (100nm) 15%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing fluid 27 (7) abrasive silica (100nm) 20%, TBAH 0.05%, alkyl phosphate diethanolamine salt 0.02%, water surplus, pH=3;
Polishing material: blank Si 3n 4wafer, polishing condition: 4psi, polishing disk rotating speed 70rpm, polishing pad PPG, polishing fluid flow velocity 200ml/min, Logitech LP50 Polisher.
As shown in Figure 4, when the concentration of abrasive silica is between 1% ~ 20%, relative to the polishing fluid not containing anion surfactant, the polishing fluid containing anion surfactant of the present invention significantly can increase Si to result 3n 4polishing speed.

Claims (11)

1. a chemical mechanical polishing liquid, it comprises: abrasive grain, quaternary ammonium compound, silicon nitride polishing accelerator and water, wherein said silicon nitride polishing accelerator is anionic surfactant, described anionic surfactant is selected from DBSA, neopelex, sodium methylene bis-naphthalene sulfonate, alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salt, PAPE, glycerine polyoxypropylene ether phosphate triethanolamine salt, one or more of acrylic acid-2-acrylamide-2-methylpro panesulfonic acid copolymer and PAMA.
2. polishing fluid as claimed in claim 1, is characterized in that: the molecular weight of described PAMA is 5,000,000 ~ 1,200 ten thousand.
3. polishing fluid as claimed in claim 1, is characterized in that: the content of described anionic surfactant is mass percent: 0.001 ~ 0.2%.
4. polishing fluid as claimed in claim 3, is characterized in that: the content of described anionic surfactant is mass percent: 0.005 ~ 0.1%.
5. polishing fluid as claimed in claim 1, is characterized in that: described abrasive grains be selected from silicon dioxide, alundum (Al2O3), ceria and mix in the silica dioxide granule of aluminium one or more.
6. polishing fluid as claimed in claim 1, is characterized in that: the particle diameter of described abrasive grains is 20 ~ 150nm.
7. polishing fluid as claimed in claim 6, is characterized in that: the content of described abrasive grains is mass percent: 1 ~ 20%.
8. polishing fluid as claimed in claim 1, is characterized in that: described quaternary ammonium compound is Tetramethylammonium hydroxide and/or TBAH.
9. polishing fluid as claimed in claim 8, is characterized in that: the content of described quaternary ammonium compound is mass percent: 0.01 ~ 0.2%.
10. polishing fluid as claimed in claim 1, is characterized in that: the pH of described polishing fluid is 2 ~ 7.
11. polishing fluids as claimed in claim 10, is characterized in that: the pH of described polishing fluid is 2 ~ 4.
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Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
CN102533116B (en) * 2010-12-10 2015-06-17 安集微电子（上海）有限公司 Chemical mechanical polishing solution
CN102559058B (en) * 2010-12-21 2015-05-27 安集微电子（上海）有限公司 Chemical-mechanical polishing liquid
CN103173127B (en) * 2011-12-23 2016-11-23 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid for the planarization of silicon through-hole blocking layer
CN103509468B (en) * 2012-06-21 2017-08-11 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid planarized for silicon hole
CN103834305B (en) * 2012-11-22 2017-08-29 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid
CN105802509B (en) * 2014-12-29 2018-10-26 安集微电子（上海）有限公司 A kind of application of composition in barrier polishing
CN108117840B (en) * 2016-11-29 2021-09-21 安集微电子科技（上海）股份有限公司 Silicon nitride chemical mechanical polishing solution
CN108117838B (en) * 2016-11-29 2021-09-17 安集微电子科技（上海）股份有限公司 Silicon nitride chemical mechanical polishing solution
CN111378375B (en) * 2018-12-28 2022-05-13 安集微电子科技（上海）股份有限公司 Chemical mechanical polishing solution

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101016440A (en) * 2006-02-08 2007-08-15 罗门哈斯电子材料Cmp控股股份有限公司 Multi-component barrier polishing solution

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016440A (en) * 2006-02-08 2007-08-15 罗门哈斯电子材料Cmp控股股份有限公司 Multi-component barrier polishing solution

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