CN101153205A - Chemical mechanical polishing solution for polishing low dielectric materials - Google Patents
Chemical mechanical polishing solution for polishing low dielectric materials Download PDFInfo
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- CN101153205A CN101153205A CNA2006101167464A CN200610116746A CN101153205A CN 101153205 A CN101153205 A CN 101153205A CN A2006101167464 A CNA2006101167464 A CN A2006101167464A CN 200610116746 A CN200610116746 A CN 200610116746A CN 101153205 A CN101153205 A CN 101153205A
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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
Abstract
The invention discloses chemical mechanical polishing liquid for polishing low-k dielectric materials, which comprises abrasive particles, corrosion inhibitor, oxidizer and water, and is characterized in comprising at least an accelerator agent. The polishing liquid of the invention has a high removing speed of low k dielectric material under lower pressure, and also has the a high removing speed of the other materials such as copper metal (Cu), silicon oxide (Teos), Tantalum metal (Ta)/Tantalum nitride (TaN) blocking layers, etc.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, relate in particular to a kind of chemical mechanical polishing liquid that is used for polishing low dielectric material.
Background technology
Tradition dielectric layer material (as TEOS) is owing to have higher dielectric constant, can cause electric capacity increase between the conducting stratum, thereby influence the speed of unicircuit, efficient is reduced, along with the complicated of unicircuit and becoming more meticulous, this base material can not satisfy more (65nm or 45nm) technical requirements of advanced process all the more, and introducing dielectric materials (as CDO, SOG) in substrate is the inexorable trend of integrated circuit technique development, has produced many polishing slurries that are used for dielectric materials thereupon.
But present low-dielectric material lapping liquid of the prior art does not all reach the perfect adaptation of manufacturing cost and technology performance.Disclose a kind of acid slurry as patent documentation US6046112, adopted ZrO
2Be abrasive material, cooperate azanol, come polishing low dielectric material SOG.The abrasive material price height that is adopted, the production cost height.Patent documentation US6974777 discloses a kind of polishing fluid that is used for dielectric materials for another example, this polishing fluid includes a kind of HLB value greater than 7 nonionogenic tenside, this nonionogenic tenside can suppress the polishing speed of dielectric materials, and little to the removal speed influence of copper and tantalum.
Summary of the invention
The objective of the invention is in order to solve under the lower pressure, problem more rambunctious is selected in the low and polishing of the removal speed of dielectric materials, and a kind of chemical mechanical polishing liquid of novel dielectric materials is provided.This polishing fluid can have the removal speed of higher dielectric materials under lower pressure, to other materials, as metallic copper (Cu), silicon oxide (Teos), smooth (the Ta)/nitrogenize of metal smooth (TaN) blocking layer higher removal speed is arranged also.
Polishing fluid of the present invention comprises abrasive grains, corrosion inhibitor, oxygenant and water, it is characterized in that also comprising at least a rate accelerating material(RAM).
Among the present invention, described rate accelerating material(RAM) can be selected from one or more in following: inorganic phosphate and salt thereof and organic phosphoric acid and salt thereof.Described inorganic phosphate and salt thereof can be the salt of phosphoric acid, phosphorous acid, tetra-sodium, three metaphosphoric acids, hexa metaphosphoric acid, tripolyphosphate, polyphosphoric acid and above-mentioned acid.Described organic phosphoric acid and salt thereof can be 2-phosphonic acids butane group-1; 2; 4-tricarboxylic acid (PBTCA), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic (DTPMP), hydroxy ethylene diphosphonic acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), 2-HPAA (HPAA), polyamino polyether methylene phosphonic acids (PAPEMP), and the salt of above-mentioned acid.What the weight percent concentration of described rate accelerating material(RAM) was preferable is 0.001～2%, and better is 0.01～1%.
Among the present invention, described abrasive grains can be any abrasive grains of the prior art, as the silicon-dioxide of silicon-dioxide, aluminium sesquioxide, cerium dioxide, titanium dioxide, adulterated al, the silicon-dioxide or the high molecular polymerization composition granule of aluminium coating.What the weight percent concentration of described abrasive grains was preferable is 1～20%, and better is 2～15%.That the particle diameter of described abrasive grains is preferable is 20～150nm, and that better is 30～120nm.
Among the present invention, described corrosion inhibitor can be azole compounds.Described azole compounds can be benzotriazole, 1-phenyl-5-sulfydryl-tetrazole, 2-sulfydryl-benzothiazole, benzoglyoxaline, 2-mercaptobenzimidazole or 5-amino-1H-tetrazole etc.What the weight percent concentration of described corrosion inhibitor was preferable is 0.001～1%, and better is 0.01～0.5%.
Among the present invention, described oxygenant can be hydrogen peroxide, urea peroxide, Peracetic Acid, Potassium Persulphate or ammonium persulphate.What the weight percent concentration of described oxygenant was preferable is 0.001～5%, and better is 0.05～2%.
Polishing fluid of the present invention is an acidic solution, and what the pH value was preferable is 2.0～7.0, and better is 2.0～5.0.
Polishing fluid of the present invention can also comprise tensio-active agent.Described glass or plastic containers, cats product or anion surfactant.
Polishing fluid of the present invention can also comprise that pH regulator agent, viscosity modifier, defoamer or sterilant wait and reach invention effect of the present invention.
Polishing fluid of the present invention can be made by following method: a certain amount of abrasive grains is added agitator, stirring adds a certain amount of deionized water and various component with given pace down and mixes, and is adjusted to required pH value with pH regulator agent well known in the art and gets final product.
The polishing low dielectric material that polishing fluid of the present invention is preferable, as doping carbon oxides (CDO), such as the silicon-dioxide BD of doping carbon, or low dielectric substrate material such as porous material.
Positive progressive effect of the present invention is: can have the removal speed of higher dielectric materials under lower pressure, to other material, higher removal speed is also arranged as metallic copper (Cu), silicon oxide (Teos), smooth (the Ta)/nitrogenize of metal smooth (TaN) blocking layer etc.Its effect will further specify by the contrast experiment among the embodiment.
Description of drawings
Fig. 1 is the influence to the removal speed of dielectric materials BD (silicon-dioxide of doping carbon) under low polish pressure (1psi) of the polishing fluid 1～13 that contains the different sorts rate accelerating material(RAM) among comparative example 1 polishing fluid and the effect embodiment 1.Be followed successively by the removal speed of 1 to 13 couple of dielectric materials BD of the polishing fluid among comparative example 1 polishing fluid, the effect embodiment 1 (silicon-dioxide of doping carbon) among Fig. 1 from left to right.As seen from the figure, compare with the comparative example 1 who does not add any rate accelerating material(RAM), the polishing fluid 1～13 that has added rate accelerating material(RAM) among the effect embodiment 1 can increase the removal speed of dielectric materials (BD) in various degree.
Fig. 2 is the influence to the removal speed of dielectric materials BD (silicon-dioxide of doping carbon) under low polish pressure (1psi) of the polishing fluid 14～19 of the rate accelerating material(RAM) phosphoric acid that contains different concns among comparative example 1 polishing fluid and the effect embodiment 2.Be followed successively by comparative example 1 polishing fluid, the removal speed of 14～19 couples of dielectric materials BD of the polishing fluid among the effect embodiment 2 (silicon-dioxide of doping carbon) among Fig. 2 from left to right.As seen from the figure, compare, added the polishing fluid 14～19 of the rate accelerating material(RAM) phosphoric acid of different concns among the effect embodiment 2, can increase the removal speed of dielectric materials (BD) in various degree with the comparative example 1 who does not add any rate accelerating material(RAM).
Embodiment
Mode below by embodiment further specifies the present invention, does not therefore limit the present invention among the described scope of embodiments.
Following polishing fluid is made by following method: a certain amount of abrasive grains is added agitator, and stirring adds a certain amount of deionized water and other components with given pace down and mixes, with KOH or HNO
3Being adjusted to required pH value gets final product.
Each compounds content per-cent is weight percentage in the following example.
Embodiment 1 1%CeO
2(particle diameter is 30nm), 0.001%1-phenyl-5-sulfydryl-tetrazole, 0.2% DAP, 0.001% urea peroxide, water is surplus, pH=2.
Embodiment 2 2%Al
2O
3(particle diameter is 20nm), 0.01%2-sulfydryl-benzothiazole, 0.2% tetra-sodium, 0.05% Peracetic Acid, 0.02% polyacrylic acid (molecular weight is 3000), water is surplus, pH=3.
Embodiment 3 10%TiO
2(particle diameter is 150nm), 0.2% benzoglyoxaline, 0.2% polyphosphoric acid, 0.5% Potassium Persulphate, 0.02% Macrogol 200 (molecular weight is 200), water is surplus, pH=4.
The SiO of embodiment 4 15% doped with Al
2(particle diameter is 30nm), 0.5%2-mercaptobenzimidazole, 0.2% ethylenediamine tetraacetic subunit phosphonic acids potassium, 2% ammonium persulphate, 0.02% polyacrylic acid (molecular weight is 10000), water is surplus, pH=5.
Embodiment 5 20% covers the SiO of Al
2(particle diameter is 70nm), 1%5-amino-1H-tetrazole, 0.1% phosphoric acid, 0.1% potassiumphosphate, 5% hydrogen peroxide, 0.02% cetyl trimethylammonium bromide, water is surplus, pH=6.
Embodiment 6 10% polymethylmethacrylates (particle diameter is 120nm), 0.2% benzotriazole, 0.1% Amino Trimethylene Phosphonic Acid (ATMP), 0.1% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=7.
Comparative example 1 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% hydrogen peroxide, water are surplus, pH=3.
Effect embodiment 1
Polishing fluid 1 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 2 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% potassium pyrophosphate, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 3 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% phosphorous acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 4 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% 3 metaphosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 5 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% Sodium hexametaphosphate 99,0.2% hydrogen peroxide, water are surplus, pH=3.
Polishing fluid 6 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% tripolyphosphate, 0.2% hydrogen peroxide, water are surplus, pH=3.
Polishing fluid 7 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2%2-phosphonic acids butane group-1,2,4-tricarboxylic acid (PBTCA), 0.2% hydrogen peroxide, water are surplus, pH=3.
Polishing fluid 8 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% polyamino polyether methylene phosphonic acids (PAPEMP), 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 9 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% hydroxy ethylene diphosphonic acid (HEDP), 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 10 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% Amino Trimethylene Phosphonic Acid (ATMP), 0.2% hydrogen peroxide, water are surplus, pH=3.
Polishing fluid 11 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% ethylenediamine tetraacetic subunit phosphonic acids (EDPMP), 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 12 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2%2-hydroxyl see acyl acetic acid (HPAA), 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 13 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% diethylene triamine pentamethylene phosphonic (DTPMP), 0.2% hydrogen peroxide, water is surplus, pH=3.
Adopt polishing fluid and 1～13 couple of low dielectric material BD of the polishing fluid among the effect embodiment 1 (silicon-dioxide of doping carbon) among the comparative example 1 under low polish pressure (1psi), to polish, remove speed as shown in Figure 1.As seen from the figure, compare with the comparative example 1 who does not add any rate accelerating material(RAM), the polishing fluid 1～13 that has added rate accelerating material(RAM) among the effect embodiment 1 can increase the removal speed of dielectric materials (BD) in various degree.
Polishing material: BD (dielectric materials, the silicon-dioxide of doping carbon); Polishing condition: 1Psi, polishing disk and rubbing head rotating speed 70/90rpm, polishing pad Politex, polishing fluid flow velocity 100ml/min, Logitech PM5 Polisher.
Effect embodiment 2
Polishing fluid 14 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.001% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 15 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.01% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 16 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 17 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 1% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 18 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 1.5% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Polishing fluid 19 10%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 2% phosphoric acid, 0.2% hydrogen peroxide, water is surplus, pH=3.
Adopt polishing fluid and 14～19 couples of low dielectric material BD of the polishing fluid among the effect embodiment 2 (silicon-dioxide of doping carbon) among the comparative example 1 under low polish pressure (1psi), to polish, remove speed as shown in Figure 2.As seen from the figure, compare, added the polishing fluid 14～19 of the rate accelerating material(RAM) phosphoric acid of different concns among the effect embodiment 2, can increase the removal speed of dielectric materials (BD) in various degree with the comparative example 1 who does not add any rate accelerating material(RAM).
Polishing material: BD (dielectric materials, the silicon-dioxide of doping carbon); Polishing condition: 1Psi, polishing disk and rubbing head rotating speed 70/90rpm, polishing pad Politex, polishing fluid flow velocity 100ml/min, Logitech PM5 Polisher.
Effect embodiment 3
Polishing fluid 20 20%SiO
2(particle diameter is 100nm), 0.8% benzotriazole, 2% phosphoric acid, 5% hydrogen peroxide, water are surplus, pH=3
Polishing fluid 21 15%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 0.2% phosphoric acid, 0.2% hydrogen peroxide, water are surplus, pH=3
Polishing fluid 22 15%SiO
2(particle diameter is 100nm), 0.2% benzotriazole, 1% phosphoric acid, 0.2% hydrogen peroxide, water are surplus, pH=3
Adopt the polishing fluid of the polishing fluid 20～22 among the effect embodiment 3 that low dielectric material BD (silicon-dioxide of doping carbon), metallic copper (Cu), silicon oxide (Teos), metal smooth (Ta) are polished under low polish pressure (1psi), it is as shown in table 1 to remove speed.
By table 1 as seen, polishing fluid 20-22 among the effect embodiment 3 is except having higher removal speed to dielectric materials BD (silicon-dioxide of doping carbon), to other material, higher removal speed is also arranged as metallic copper (Cu), silicon oxide (Teos), metal smooth (Ta).
20～22 couples of BD of polishing fluid among the table 1 effect embodiment 3 (dielectric materials, the silicon-dioxide of doping carbon), the removal speed of metallic copper (Cu), silicon oxide (Teos) and metal smooth (Ta)
| Polishing fluid | BD removes speed (A/min) | Cu removes speed (A/min) | Teos removes speed (A/min) | Ta removes speed (A/min) |
| 20 | 859 | 742 | 1026 | 835 |
| 21 | 562 | 332 | 681 | 585 |
| 22 | 763 | 401 | 834 | 513 |
Polishing material: BD (dielectric materials, the silicon-dioxide of doping carbon), metallic copper (Cu), silicon oxide (Teos), metal smooth (Ta); Polishing condition: 1Psi, polishing disk and rubbing head rotating speed 70/90rpm, polishing pad Politex, polishing fluid flow velocity 100ml/min, Logitech PM5 Polisher.
Raw material used in the present invention and reagent are the commercially available prod.
Claims (22)
1. a chemical mechanical polishing liquid that is used for polishing low dielectric material comprises abrasive grains, corrosion inhibitor, oxygenant and water, it is characterized in that: also comprise at least a rate accelerating material(RAM).
2. polishing fluid according to claim 1 is characterized in that: described rate accelerating material(RAM) is selected from one or more in following: inorganic phosphate and salt thereof and organic phosphoric acid and salt thereof.
3. polishing fluid according to claim 2 is characterized in that: described inorganic phosphate and salt thereof are phosphoric acid, phosphorous acid, tetra-sodium, three metaphosphoric acids, hexa metaphosphoric acid, tripolyphosphate, polyphosphoric acid, and the salt of above-mentioned acid.
4. polishing fluid according to claim 2; it is characterized in that: described organic phosphoric acid and salt thereof are 2-phosphonic acids butane group-1; 2; 4-tricarboxylic acid, ethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic, hydroxy ethylene diphosphonic acid, Amino Trimethylene Phosphonic Acid, 2-HPAA, polyamino polyether methylene phosphonic acids, and the salt of above-mentioned acid.
5. polishing fluid according to claim 1 is characterized in that: the weight percent concentration of described rate accelerating material(RAM) is 0.001～2%.
6. polishing fluid according to claim 5 is characterized in that: the weight percent concentration of described rate accelerating material(RAM) is 0.01～1%.
7. polishing fluid according to claim 1 is characterized in that: described abrasive grains is the silicon-dioxide of silicon-dioxide, aluminium sesquioxide, cerium dioxide, titanium dioxide, adulterated al, the silicon-dioxide or the high molecular polymerization composition granule of aluminium coating.
8. polishing fluid according to claim 1 is characterized in that: the particle diameter of described abrasive grains is 20～150nm.
9. polishing fluid according to claim 8 is characterized in that: the particle diameter of described abrasive grains is 30～120nm.
10. polishing fluid according to claim 1 is characterized in that: the weight percent concentration of described abrasive grains is 1～20%.
11. polishing fluid according to claim 10 is characterized in that: the weight percent concentration of described abrasive grains is 2～15%.
12. polishing fluid according to claim 1 is characterized in that: described corrosion inhibitor is an azole compounds.
13. polishing fluid according to claim 12 is characterized in that: described azole compounds is benzotriazole, 1-phenyl-5-sulfydryl-tetrazole, 2-sulfydryl-benzothiazole, benzoglyoxaline, 2-mercaptobenzimidazole or 5-amino-1H-tetrazole.
14. polishing fluid according to claim 1 is characterized in that: the weight percent concentration of described corrosion inhibitor is 0.001～1%.
15. polishing fluid according to claim 14 is characterized in that: the weight percent concentration of described corrosion inhibitor is 0.01～0.5%.
16. polishing fluid according to claim 1 is characterized in that: described oxygenant is hydrogen peroxide, urea peroxide, Peracetic Acid, Potassium Persulphate or ammonium persulphate.
17. polishing fluid according to claim 1 is characterized in that: the weight percent concentration of described oxygenant is 0.001～5%.
18. polishing fluid according to claim 17 is characterized in that: the weight percent concentration of described oxygenant is 0.05～2%.
19. polishing fluid according to claim 1 is characterized in that: the pH value of described polishing fluid is 2.0～7.0.
20. polishing fluid according to claim 19 is characterized in that: the pH value of described polishing fluid is 2.0～5.0.
21. polishing fluid according to claim 1 is characterized in that: described polishing fluid also comprises surfactant.
22. polishing fluid according to claim 21 is characterized in that: described tensio-active agent is nonionogenic tenside, cats product or anion surfactant.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101167464A CN101153205A (en) | 2006-09-29 | 2006-09-29 | Chemical mechanical polishing solution for polishing low dielectric materials |
| PCT/CN2007/002808 WO2008040183A1 (en) | 2006-09-29 | 2007-09-24 | A chemical-mechanical polishing liquid for polishing low-dielectric material |
| CNA2007800291081A CN101541902A (en) | 2006-09-29 | 2007-09-24 | A chemical-mechanical polishing liquid for polishing low-dielectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101167464A CN101153205A (en) | 2006-09-29 | 2006-09-29 | Chemical mechanical polishing solution for polishing low dielectric materials |
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|---|---|
| CN101153205A true CN101153205A (en) | 2008-04-02 |
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|---|---|---|---|
| CNA2006101167464A Pending CN101153205A (en) | 2006-09-29 | 2006-09-29 | Chemical mechanical polishing solution for polishing low dielectric materials |
| CNA2007800291081A Pending CN101541902A (en) | 2006-09-29 | 2007-09-24 | A chemical-mechanical polishing liquid for polishing low-dielectric material |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800291081A Pending CN101541902A (en) | 2006-09-29 | 2007-09-24 | A chemical-mechanical polishing liquid for polishing low-dielectric material |
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| WO (1) | WO2008040183A1 (en) |
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| Publication number | Publication date |
|---|---|
| WO2008040183A1 (en) | 2008-04-10 |
| CN101541902A (en) | 2009-09-23 |
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