CN104650739A - Chemical-mechanical polishing solution for polishing silica substrates - Google Patents

Chemical-mechanical polishing solution for polishing silica substrates Download PDF

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Publication number
CN104650739A
CN104650739A CN201310596299.7A CN201310596299A CN104650739A CN 104650739 A CN104650739 A CN 104650739A CN 201310596299 A CN201310596299 A CN 201310596299A CN 104650739 A CN104650739 A CN 104650739A
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China
Prior art keywords
polishing
mechanical polishing
silicon
chemical mechanical
chemical
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CN201310596299.7A
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Chinese (zh)
Inventor
陈宝明
荆建芬
邱腾飞
蔡鑫元
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Anji Microelectronics Shanghai Co Ltd
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Anji Microelectronics Shanghai Co Ltd
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Priority to CN201310596299.7A priority Critical patent/CN104650739A/en
Publication of CN104650739A publication Critical patent/CN104650739A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The invention relates to a chemical-mechanical polishing solution for polishing silica substrates. The chemical-mechanical polishing solution includes metal ions and grinding particles, and the pH value of the chemical-mechanical polishing solution is not greater than 7. The metal ions can improve the silica dielectric material removal rate of the silica grinding particles.

Description

A kind of chemical mechanical polishing liquid for polishing silicon dioxide base material
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid containing silicon-dioxide base material for polishing, under proposing a kind of acidic conditions, improve the scheme of silicon-dioxide clearance.
Background technology
In the manufacturing processed of unicircuit, Silicon Wafer substrate often constructs thousands of structural unit, these structural units form functional circuitry and components and parts further by multiple layer metal interconnection.In multilevel metal interconnection structure, fill the silicon-dioxide of silicon-dioxide or other elements that adulterate between plain conductor as interlayer dielectric (ILD).Along with the development of integrated circuit metal interconnection technique and the increase of the wiring number of plies, chemically machinery polished (CMP) has been widely used in the flattening surface in chip manufacturing proces.The chip surface of these planarizations contributes to the production of multilevel integration, and prevents from dielectric layer being coated in the distortion that uneven surface causes.
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 operator's console rotate, the power simultaneously kept down at substrate back, is applied on pad by abrasive material and chemically reactive 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.
Silicon-dioxide, as dielectric materials conventional in unicircuit, all can relate to the removal of silicon dioxide dielectric layers in a lot of glossing.As in interlevel oxide dielectric polish process, polishing slurries is mainly used in removing oxide dielectric layer and planarization; When shallow groove isolation layer polishing, polishing fluid is mainly used in removing and planarization oxide dielectric layer stop on silicon nitride; In barrier polishing, polishing fluid needs to remove silicon-dioxide, copper and copper barrier layer; In silicon through hole (TSV) technique, the formation of through hole also needs to remove unnecessary silicon-dioxide with polishing fluid.In these glossings, all require that the removal speed of higher oxide dielectric layer is to ensure production capacity.
Oxide dielectric material comprises film thermal zinc oxide-silicon dioxide (thin thermal oxide), high-density plasma silicon-dioxide (high density plasma oxide), boron phosphatization silex glass (borophosphosilicate glass), tetraethoxy silicon-dioxide (PETEOS) and carbon-doped silicon oxide (carbon doped oxide) etc.Remove speed to reach higher oxide material, the consumption usually by improving abrasive grains reaches, and do the cost that can improve polishing fluid like this, and the increase of abrasive grains consumption is unfavorable for concentrating.Existent technique CN1637101A proposes in polishing fluid, add basic cpd and corrodes glass substrate surface or etch, thus carries out chemical rightenning to glass substrate surface, improves stock removal rate.It is consistent that its shear action silicon-dioxide base material known with us is easily removed at basic ph.But a lot of polishing fluid needs to use in acid condition, and effective chemical process can not improve the removal speed of silicon-dioxide in acid condition at present.The present invention proposes to significantly improve under condition of acidic pH and relate to earth silicon material and remove rate option.
Polish abrasive for silica dielectric materials polishing slurries is mainly cerium dioxide and silicon-dioxide, but cerium oxide abrasives easy scratch surface in polishing process.The surface imperfection that silicon-dioxide produces in polishing process is less, therefore a large amount of silicon-dioxide that uses is as abrasive grains.
The present invention aims to provide a kind of technical scheme of improvement, can improve the removal speed of Silica abrasive particle to silica dielectric materials.
Summary of the invention
The present invention discloses a kind of technical scheme, adopts metal ion, improves Silica abrasive particle to the removal speed of silica dielectric materials.
An aspect of of the present present invention is to provide a kind of chemical mechanical polishing liquid, and it contains abrasive grains.Wherein abrasive grains is Silica abrasive particle.Content is 0.5 ~ 30wt%, is preferably 3 ~ 15wt%; Particle diameter is 20 ~ 200nm, is preferably 20 ~ 120nm.
Its this polishing fluid is at least containing 1 metal ion species, and wherein metal ion is Na +, K +, Rb +, Cs +, Mg2 +, Ca 2+, Sr 2+, Ba 2+, Al 3+, Cu 2+, Fe 2+, Zn 2+, Cr 3+, Ni 2+, Ti 4+, Mn 4+deng one or more.Be preferably K +, Al 3+, Mg 2+, Cu 2+, Ca 2+.
Meanwhile, because generally speaking above-mentioned metal ion is add in polishing fluid with the form of ionic compound, therefore this polishing fluid also can contain negatively charged ion, and negatively charged ion is selected from sulfate radical, nitrate radical, carbonate, hydroxide radical, bromide anion, iodide ion etc.The content of this ionic compound is 0.01 ~ 5wt%, is preferably 0.05 ~ 1wt%.
The pH of described polishing fluid is less than 7, is preferably 2 ~ 5.
Positive progressive effect of the present invention is:
1: by adding metal ion, effectively can improve the removal speed of Silica abrasive particle to silica dielectric materials.
2., under the silicon-dioxide required removes speed, add the consumption that metal ion can reduce abrasive grains, reduce costs.Be conducive to preparing concentrated product.
Embodiment
Set forth advantage of the present invention further below by specific embodiment, but protection scope of the present invention is not only confined to following embodiment.
Each polishing fluid in following examples, at least containing (a) abrasive grains and (b) metal ion, the simple Homogeneous phase mixing of each composition, surplus is water.Adopt potassium hydroxide and nitric acid to be adjusted to suitable pH afterwards, each embodiment polishing fluid can be obtained.
Embodiment 1
Colloidal sol type silicon-dioxide containing 6% mass content in this example, particle diameter is the potassium ion (being provided by potassium hydroxide) containing different concns in 90nm, 1A ~ 1E, and all the other are water.PH is adjusted to 3 by nitric acid.Polishing condition: polishing machine platform: Logitech LP50, polishing pad is IC1010pad, and downward pressure is 3.0psi, and rotating speed is polishing disk/rubbing head=70/90rpm, and polishing fluid flow velocity is 50ml/min, and polishing time is 1min.
Composition KOH content (%) SiO 2RR(A/min) Ratio
1A / 318 1
1B 0.1 679 2.1
1C 0.2 809 2.5
1D 0.4 905 2.8
1E 0.8 963 3.0
In table, polishing fluid 1A is control sample, and 1B ~ 1E increases (K along with the content of potassium hydroxide +content), the polishing speed of oxide compound obviously increases, and is up to 3 times of control sample.
Embodiment 2
The colloidal sol type silicon-dioxide of the different sizes containing 6% mass content in this example, 2A ~ 7A is control group, and the potassium hydroxide (providing potassium ion) containing 0.2% mass content in 2B ~ 7B, all the other are water.PH is adjusted to 3 by nitric acid.Polishing condition: polishing machine platform: Logitech LP50, polishing pad is IC1010pad, and downward pressure is 3.0psi, and rotating speed is polishing disk/rubbing head=70/90rpm, and polishing fluid flow velocity is 50ml/min, and polishing time is 1min.
Composition Median size (nm) KOH content (%) SiO 2RR(A/min) Ratio
2A 20 135 1
2B 20 0.2 279 2.1
3A 90 318 1
3B 90 0.2 809 2.5
4A 55 221 1
4B 55 0.2 618 2.8
5A 137 83 1
5B 137 0.2 197 2.4
6A 120 286 1
6B 120 0.2 608 2.1
7A 200 1100 1
7B 200 0.2 1500 1.4
As can be seen from data in table, add the potassium hydroxide of 0.2% mass content in polishing fluid 2B ~ 5B, silicon oxide polishing velocity all can increase to 1.4 ~ 2.8 times of control sample.
Embodiment 3
Colloidal sol type silicon-dioxide 90nm containing 6% mass content in this example, 8A is control group, containing 0.2% quality Al in 8B ~ 8G 2(SO4) 3, MgSO 4, Ca 2nO 3, KNO 3, Na 2sO 4, CuSO 4(providing aluminum ion respectively, magnesium ion, calcium ion, potassium ion, sodium ion, cupric ion), all the other are water.PH is adjusted to 3 by nitric acid.Polishing condition: polishing machine platform: Logitech LP50, polishing pad is IC1010 pad, and downward pressure is 3.0psi, and rotating speed is polishing disk/rubbing head=70/90rpm, and polishing fluid flow velocity is 50ml/min, and polishing time is 1min.
Composition Additive Content (%) SiO2RR(A/min) Ratio
8A Nothing 213 1
8B Al 2(SO 4) 3 0.2 899 4.2
8C MgSO 4 0.2 776 3.6
8D Ca 2NO 3 0.2 970 4.6
8E KNO 3 0.2 1047 4.9
8F Na 2SO 4 0.2 968 4.5
8G CuSO 4 0.2 823 3.9
Add the different metal compound (metal ion is provided) of 0.2% in the polishing fluid of 8B ~ 8G, silicon oxide polishing velocity can be made significantly to improve.
Embodiment 4
Colloidal sol type silicon-dioxide 90nm containing 6% mass content in this example, 9A ~ 13A is control group, and pH is adjusted to 3 ~ 7 respectively by acid or alkali.Potassium hydroxide (providing potassium ion) containing 0.2% mass content in 9B ~ 13B, all the other are water, and pH is adjusted to 3 ~ 7 respectively by nitric acid.Polishing condition: polishing machine platform: Logitech LP50, polishing pad is IC1010pad, and downward pressure is 3.0psi, and rotating speed is polishing disk/rubbing head=70/90rpm, and polishing fluid flow velocity is 50ml/min, and polishing time is 1min.
As can be seen from data in table, polishing component 9B ~ 13B adds the potassium hydroxide (providing potassium ion) of 0.2% mass content, and under the different pH of its correspondence, the removal speed of silicon dioxide layer all can be increased to 2.1 ~ 4.1 times of control group.
Should be understood that, % of the present invention all refers to mass percentage.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.

Claims (9)

1. for a chemical mechanical polishing liquid for polishing silicon dioxide base material, comprise metal ion and abrasive grains, it is characterized in that, the pH value of described chemical mechanical polishing liquid is for being less than 7.
2. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, wherein said metal ion is selected from Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, Ba 2+, Al 3+, Cu 2+, Fe2+, Zn 2+, Cr 3+, Ni 2+, Ti 4+, Mn 4+deng one or more.
3. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the content of wherein said metal ion is 0.01 ~ 5wt%.
4. chemical mechanical polishing liquid as claimed in claim 3, it is characterized in that, the content of wherein said metal ion is 0.05 ~ 1wt%.
5. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, wherein said abrasive grains is Silica abrasive particle.
6. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the content of wherein said abrasive grains is 0.5 ~ 30wt%.
7. chemical mechanical polishing liquid as claimed in claim 6, it is characterized in that, the content of wherein said abrasive grains is 3 ~ 15wt%.
8. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the particle diameter of wherein said abrasive grains is 20 ~ 200nm.
9. chemical mechanical polishing liquid as claimed in claim 8, it is characterized in that, the particle diameter of wherein said abrasive grains is 20 ~ 120nm.
CN201310596299.7A 2013-11-22 2013-11-22 Chemical-mechanical polishing solution for polishing silica substrates Pending CN104650739A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153889A (en) * 2016-05-19 2019-01-04 东进世美肯株式会社 Paste compound for chemically mechanical polishing

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US20040082274A1 (en) * 2002-10-24 2004-04-29 Yaojian Leng Polishing slurry used for copper chemical mechanical polishing (CMP) process
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US20080016784A1 (en) * 2006-07-19 2008-01-24 Shoutian Li Tantalum CMP compositions and methods
US20080227297A1 (en) * 2007-03-16 2008-09-18 Yukiteru Matsui Chemical mechanical polishing method and method for manufacturing semiconductor device
CN101649162A (en) * 2008-08-15 2010-02-17 安集微电子（上海）有限公司 Polishing solution used for chemical mechanical grounding
CN101684393A (en) * 2008-09-26 2010-03-31 安集微电子（上海）有限公司 Chemical mechanical polishing sizing agent
CN101684392A (en) * 2008-09-26 2010-03-31 安集微电子（上海）有限公司 Chemical mechanical polishing solution
WO2012051786A1 (en) * 2010-10-22 2012-04-26 安集微电子（上海）有限公司 Chemical-mechanical polishing slurry
CN102559063A (en) * 2010-09-22 2012-07-11 罗门哈斯电子材料Cmp控股股份有限公司 Slurry composition having tunable dielectric polishing selectivity and method of polishing a substrate
CN102559062A (en) * 2010-09-20 2012-07-11 罗门哈斯电子材料Cmp控股股份有限公司 Stabilized, concentratable chemical mechanical polishing composition and method of polishing a substrate
CN102796460A (en) * 2012-08-31 2012-11-28 安特迪（天津）科技有限公司 Silicon dioxide-based CMP (Chemical Mechanical Polishing) solution and preparation method thereof

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CN1307079A (en) * 2000-02-03 2001-08-08 花王株式会社 Polishing composition
US20040082274A1 (en) * 2002-10-24 2004-04-29 Yaojian Leng Polishing slurry used for copper chemical mechanical polishing (CMP) process
US20050092962A1 (en) * 2003-02-14 2005-05-05 Duen-Wu Hua Abrasives for copper CMP and methods for making
CN1849379A (en) * 2003-07-11 2006-10-18 格雷斯公司 Abrasive partilcle for chemical mechanical polishing
CN1637101A (en) * 2003-11-26 2005-07-13 福吉米株式会社 Polishing composition and polishing method
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US20080016784A1 (en) * 2006-07-19 2008-01-24 Shoutian Li Tantalum CMP compositions and methods
US20080227297A1 (en) * 2007-03-16 2008-09-18 Yukiteru Matsui Chemical mechanical polishing method and method for manufacturing semiconductor device
CN101649162A (en) * 2008-08-15 2010-02-17 安集微电子（上海）有限公司 Polishing solution used for chemical mechanical grounding
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153889A (en) * 2016-05-19 2019-01-04 东进世美肯株式会社 Paste compound for chemically mechanical polishing
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CN109153889B (en) * 2016-05-19 2021-10-29 东进世美肯株式会社 Slurry composition for chemical mechanical polishing

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