CN102115637A - Chemical mechanical polishing slurry - Google Patents
Chemical mechanical polishing slurry Download PDFInfo
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- CN102115637A CN102115637A CN2009102476666A CN200910247666A CN102115637A CN 102115637 A CN102115637 A CN 102115637A CN 2009102476666 A CN2009102476666 A CN 2009102476666A CN 200910247666 A CN200910247666 A CN 200910247666A CN 102115637 A CN102115637 A CN 102115637A
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- polishing fluid
- polishing
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- triazole
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Abstract
The invention discloses chemical mechanical polishing slurry. The slurry contains an abrasive material, hydrogen peroxide, a pH regulator, water and one or more of the following complexing agents: triazole, a triazole compound with carbon atom containing donor substituent, pyrimidine, a pyrimidine derivative, piperazine and a piperazine derivative, wherein the particle size of the abrasive material is 10-30nm. The slurry has the following positive effects: the Cu removal rate of the slurry has higher sensitivity to variation of the concentration of the hydrogen peroxide contained in the slurry; and after being polished with the slurry, the copper has smoother surface and better surface topography.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid.
Background technology
In the semiconductor technology processing procedure below 130nm, metallic copper has been widely used as the interconnection line material.The chemically machinery polished of Cu interconnection line (CMP) is the technology of widespread use in the global planarization technology now.Different processing procedures has different technical requirementss to the polishing speed of copper.The removal speed that copper is regulated in the optimization of adopting process condition is industry method commonly used.The existing different polishing fluid prescription of a lot of bibliographical informations is recently regulated the surface topography of Cu and is removed speed to reach different selections.
In the CMP (Chemical Mechanical Polishing) process of Cu, divide two stages: remove stage and landing stage (as shown in Figure 1) fast.Fast the removal stage needs the removal speed of very high copper and higher polishing homogeneity, and landing stage requires lower removal speed and surface topography preferably.The speed of regulating the copper removal by the concentration of hydrogen peroxide is means commonly used on the technology, if the concentration ratio to hydrogen peroxide is responsive, just can improve removal speed fast, can realize the online regulation and control in the stage of removing fast, to reach processing requirement by hydrogen peroxide.And landing stage can reduce the removal that the concentration of hydrogen peroxide reduces metallic copper, and the interpolation tensio-active agent makes polishing stop on the blocking layer.Fig. 1 is big horse scholar process schematic representation.
In the CMP (Chemical Mechanical Polishing) process, the removal speed of Cu directly influences the controllability of CMP (Chemical Mechanical Polishing) process to the sensitivity that hydrogen peroxide concentration changes, thereby influences the stability of polishing performance.Changing too to hydrogen peroxide concentration, sensitivity can cause polishing performance is difficult to accurate control.Suitable susceptibility can be implemented in linear elasticity adjustment polishing and selects ratio, reaches processing requirement.Up to now, the pertinent literature report is not arranged as yet.
Summary of the invention
Technical problem to be solved by this invention is for the requirement to the polishing speed of Cu of the processing procedure that adapts to different CMP (Chemical Mechanical Polishing) process and stage, and the higher chemical mechanical polishing liquid of susceptibility that provides the removal speed of a kind of Cu that hydrogen peroxide concentration is changed.
Polishing fluid of the present invention contains: one or more in abrasive material, hydrogen peroxide, water and the following complexing agent: kind or multiple: contain triazole compounds, pyrimidine, pyrimidine derivatives, piperazine and bridged piperazine derivatives to electron substituent group on triazole, the carbon atom.
Wherein, what described triazole was preferable is 1,2, the 4-triazole; Contain on the described carbon atom to the triazole compounds of electron substituent group preferable for 5-carboxyl-3-amino-1,2,4 triazoles or 3-amino-1,2,4-triazole; What described pyrimidine derivatives was preferable is Pyrimethamine hcl; What described bridged piperazine derivatives was preferable is piperazine six water.
Wherein, what the content of described complexing agent was preferable is mass percent 0.1～5%, and better is mass percent 0.2～3%.
Wherein, described abrasive material can select for use this area to use abrasive material always, as SiO
2And Al
2O
3Deng.What the content of described abrasive material was preferable is mass percent 0.1～20%.
What wherein, the content of described hydrogen peroxide was preferable is mass percent 0.1～10%.
Polishing fluid of the present invention also can contain one or more in cats product, doped quaternary ammonium salt type tensio-active agent and the nonionic surface active agent.Wherein, described cats product preferable for molecular weight be 2000～50000 polymine; What described doped quaternary ammonium salt type tensio-active agent was preferable is palmityl trimethyl ammonium chloride; What described nonionic surface active agent was preferable is polyoxyethylene glycol.After adding above-mentioned tensio-active agent, polishing fluid of the present invention has lower removal speed to blocking layer Ta, can make the polishing of copper in polishing process on landing stage stops at the blocking layer.That the content of described tensio-active agent is preferable is mass ratio 10～1000ppm, and that better is 50～500ppm.
Polishing fluid of the present invention also can contain other conventional additives of this area, as inhibiter, sterilant, mould inhibitor and organic solvent etc.
What the pH value of polishing fluid of the present invention was preferable is 1～7, and better is 2～5.
Polishing fluid of the present invention by the simple uniform mixing of above-mentioned each composition after, adopt conventional pH agent to be adjusted to be fit to pH and can make.Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: polishing fluid of the present invention is higher to the susceptibility that hydrogen peroxide content changes to the removal speed of Cu.After adding cats product, doped quaternary ammonium salt type tensio-active agent and nonionic surface active agent, polishing fluid of the present invention has lower removal speed to blocking layer Ta, in polishing process, can make the polishing of copper on landing stage stops at the blocking layer, be fit to the polishing on soft landing or blocking layer.Greatly reduce colloidal sol type silica granules particle diameter, reduce over-mastication, make polishing effect finer and smoother polishing material.After adopting polishing fluid polishing of the present invention, copper surface smoother, surface topography is better.
Description of drawings
Fig. 1 is the synoptic diagram in two stages in the CMP (Chemical Mechanical Polishing) process of Cu.
The Cu that Fig. 2 polishes for polishing fluid series among the effect embodiment removes rate diagram.
Fig. 3 is for adopting the photo figure on the preceding copper surface of polishing fluid 2 polishings among the effect embodiment.
Fig. 4 is for adopting the photo figure on copper surface, polishing fluid 2 polishing back among the effect embodiment.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Table 1 has provided polishing fluid embodiment 1～9 of the present invention, and by prescription is with the simple uniform mixing of each composition in the table, surplus is a water, can make the polishing fluid of each embodiment.
Table 1 polishing fluid embodiment 1～9 of the present invention
Table 2 has provided polishing fluid series 1～4 of the present invention, each polishing fluid series is that other compositions are identical, 3 kinds of polishing fluids that contain the hydrogen peroxide of three kinds of different concns respectively, by filling a prescription in the table with the simple uniform mixing of each composition, surplus is a water, adopt potassium hydroxide or nitric acid to be adjusted to and be fit to pH, can make each polishing fluid.
Table 2 polishing fluid series 1～6 of the present invention
Adopt above-mentioned polishing fluid series 1～4, Cu is polished, polishing condition is: overdraft: 2psi; Polishing pad: Politex 14 '; Rotating speed: polishing disk/rubbing head=70/90rpm; Polishing fluid flow velocity: 100ml/min; Polishing time: 2min.The removal speed of Cu such as table 3 and shown in Figure 2.
The Cu of table 3 polishing fluid series 1～4 removes speed
By table 3 data as seen, polishing fluid of the present invention is higher to the susceptibility that hydrogen peroxide concentration changes to the removal speed of Cu.
Wherein, when selecting the 5-carboxyl for use, 3-amino-1,2,4-triazole and/or 3-amino-1,2, during the 4-triazole, the susceptibility that polishing fluid changes with hydrogen peroxide concentration the removal speed of Cu is comparatively responsive when the suboxide agent concentration, and it is higher to remove rate value, susceptibility is not obvious when the high oxidation agent concentration, and total susceptibility variation tendency increases for being tending towards slow after raising fast.
Wherein, when selecting piperazine and Pyrimethamine hcl for use, when hydrogen peroxide concentration was low, the complexing agent molecular adsorption formed dura mater in the metallic surface, slow down the ionization tendency of metal, remove speed and slowly change, when hydrogen peroxide concentration reached 1.5wt%, dura mater was removed under mechanical force, balance is broken, and removes speed and increases fast.
With polishing fluid 2 is example, and the surface picture figure before and after Cu is polished respectively as shown in Figure 3 and Figure 4.By Fig. 3 and 4 contrasts as seen, adopt polishing fluid of the present invention polishing after, the surperficial smoother of copper, surface topography is better.
Table 4 has provided polishing fluid series 5～8 of the present invention, each polishing fluid series is that other compositions are identical, contain and do not contain 2 kinds of polishing fluids of tensio-active agent respectively, by filling a prescription in the table with the simple uniform mixing of each composition, surplus is a water, adopt potassium hydroxide or nitric acid to be adjusted to and be fit to pH, can make each polishing fluid.
The Cu of table 4 polishing fluid series 5～8 removes speed
Adopt above-mentioned polishing fluid series 5～8, Ta is polished, polishing condition is: overdraft: 2psi; Polishing pad: Politex 14 '; Rotating speed: polishing disk/rubbing head=70/90rpm; Polishing fluid flow velocity: 100ml/min; Polishing time: 2min.The removal speed of Ta is as shown in table 5.
The Cu of table 5 polishing fluid series 5～8 removes speed
By table 5 data as seen, behind the interpolation tensio-active agent PEI3500, polishing fluid of the present invention obviously reduces the removal speed of Ta.
Claims (14)
1. chemical mechanical polishing liquid, contain: one or more in abrasive material, hydrogen peroxide, pH regulator agent, water and the following complexing agent: contain triazole compounds, pyrimidine, pyrimidine derivatives, piperazine and bridged piperazine derivatives to electron substituent group on triazole, the carbon atom, the grain diameter of described abrasive material is 10～30nm.
2. polishing fluid as claimed in claim 1 is characterized in that: described triazole is 1,2, the 4-triazole; The triazole compounds that contains on the described carbon atom to electron substituent group is 5-carboxyl-3-amino-1,2,4 triazoles or 3-amino-1,2,4-triazole; Described pyrimidine derivatives is a Pyrimethamine hcl; Described bridged piperazine derivatives is piperazine six water.
3. polishing fluid as claimed in claim 1 is characterized in that: the content of described complexing agent is mass percent 0.1～5%.
4. polishing fluid as claimed in claim 3 is characterized in that: the content of described complexing agent is mass percent 0.2～3%.
5. polishing fluid as claimed in claim 1 is characterized in that: described abrasive material is SiO
2Or Al
2O
3
6. polishing fluid as claimed in claim 1 is characterized in that: the content of described abrasive material is mass percent 0.1～20%.
7. polishing fluid as claimed in claim 1 is characterized in that: the content of described hydrogen peroxide is mass percent 0.1～10%.
8. polishing fluid as claimed in claim 1 is characterized in that: the pH value of described polishing fluid is 1～7.
9. polishing fluid as claimed in claim 8 is characterized in that: the pH value of described polishing fluid is 2～5.
10. polishing fluid as claimed in claim 1 is characterized in that: described chemical mechanical polishing liquid also contains one or more in the following tensio-active agent: cats product, doped quaternary ammonium salt type tensio-active agent and nonionic surface active agent.
11. polishing fluid as claimed in claim 10 is characterized in that: described cats product is that molecular weight is 2000～50000 polymine; Described doped quaternary ammonium salt type tensio-active agent is a palmityl trimethyl ammonium chloride; Described nonionic surface active agent is a polyoxyethylene glycol.
12. polishing fluid as claimed in claim 10 is characterized in that: the content of described tensio-active agent is mass ratio 10～1000ppm.
13. polishing fluid as claimed in claim 12 is characterized in that: the content of described tensio-active agent is mass ratio 50～500ppm.
14. polishing fluid as claimed in claim 1 is characterized in that: described pH regulator agent is potassium hydroxide or nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102476666A CN102115637A (en) | 2009-12-30 | 2009-12-30 | Chemical mechanical polishing slurry |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102476666A CN102115637A (en) | 2009-12-30 | 2009-12-30 | Chemical mechanical polishing slurry |
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|---|---|
| CN102115637A true CN102115637A (en) | 2011-07-06 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423819A (en) * | 2020-04-17 | 2020-07-17 | 深圳市朗纳研磨材料有限公司 | Polishing solution and preparation method thereof |
-
2009
- 2009-12-30 CN CN2009102476666A patent/CN102115637A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423819A (en) * | 2020-04-17 | 2020-07-17 | 深圳市朗纳研磨材料有限公司 | Polishing solution and preparation method thereof |
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Application publication date: 20110706 |