CN113122142B - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN113122142B CN113122142B CN201911402335.5A CN201911402335A CN113122142B CN 113122142 B CN113122142 B CN 113122142B CN 201911402335 A CN201911402335 A CN 201911402335A CN 113122142 B CN113122142 B CN 113122142B
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention provides a chemical mechanical polishing solution, which comprises silicon dioxide abrasive particles, a corrosion inhibitor, a complexing agent, an oxidant, a metal surface defect improver, a phosphate surfactant and water. The chemical mechanical polishing solution can be applied to polishing of metal copper interconnection, has high copper removal rate and low tantalum removal rate, so that the chemical mechanical polishing solution has higher copper/tantalum removal rate selection ratio, improves dishing and dielectric layer dishing of a polished copper wire, improves the surface roughness of the polished copper, and reduces defects.
Description
Technical Field
The present invention relates to the field of chemical mechanical polishing.
Background
With the development of semiconductor technology, copper, which is a material having good conductivity, has been widely used in electronic element circuits as a material for miniaturization of electronic parts. The small resistance of copper can increase the signal transmission speed between transistors in a circuit, and can provide smaller parasitic capacitance capability and smaller electromigration sensitivity. These electrical advantages have led to copper having a good development prospect in the development of semiconductor technology.
However, during the fabrication of copper integrated circuits, it has been found that copper migrates or diffuses into the transistor regions of the integrated circuits, thereby adversely affecting the performance of the semiconductor transistors, and that copper interconnects can only be fabricated in a damascene process, namely: a trench is formed in the first layer, a copper barrier layer and copper are filled in the trench, and a metal wire is formed and covered on the dielectric layer. The excess copper/copper barrier layer on the dielectric layer is then removed by chemical mechanical polishing, leaving individual interconnect lines in the trenches. The copper chemical mechanical polishing process is generally divided into 3 steps: and 1, removing a large amount of copper on the surface of the substrate with high downward pressure at a high and efficient removal rate and leaving copper with a certain thickness, 2, removing the residual metallic copper with low removal rate and stopping on the barrier layer, 3, and removing the barrier layer, part of the dielectric layer and the metallic copper with a barrier layer polishing solution to realize planarization.
In the copper polishing process, on one hand, redundant copper on the barrier layer needs to be removed as soon as possible, and on the other hand, dishing of the polished copper wire needs to be reduced as much as possible. The metal layer has a partial recess over the copper lines prior to copper polishing. Copper on the dielectric material is easily removed at higher bulk pressures during polishing, while copper in the recess is polished at a lower pressure than the bulk pressure and at a lower copper removal rate. As polishing proceeds, the copper level difference gradually decreases to achieve planarization. However, if the chemical action of the copper polishing liquid is too strong and the static etching rate is too high during polishing, the passivation film of copper is easily removed even under a relatively low pressure (e.g., copper line dishing), resulting in a decrease in planarization efficiency and an increase in dishing after polishing.
With the development of integrated circuits, on the one hand, in the traditional IC industry, in order to improve the integration level, reduce the energy consumption, shorten the delay time, make the line width narrower and narrower, use the low dielectric (low-k) material with lower mechanical strength for the dielectric layer, the number of layers of the wiring is also increasing, and in order to ensure the performance and stability of the integrated circuit, the requirement on copper chemical mechanical polishing is also increasing. It is required to reduce polishing pressure, improve planarization of copper wire surface and control surface defects while ensuring copper removal rate. On the other hand, the line width cannot be scaled down indefinitely due to physical limitations, and the semiconductor industry is no longer solely dependent on integrating more devices on a single chip to improve performance, but is moving toward multi-chip packaging.
Through Silicon Via (TSV) technology is widely accepted in the industry as a latest technology for realizing interconnection between chips by making vertical conduction between chips and between wafers. TSVs enable the density of stacked chips in three dimensions to be maximized, the overall dimensions to be minimized, and chip speed and low power consumption performance to be greatly improved. The conventional TSV process is combined with the conventional IC process to form copper vias penetrating through the silicon substrate, i.e., copper is filled in the TSV opening to realize conduction, and the superfluous copper after filling also needs to be planarized by chemical mechanical polishing removal. Unlike the conventional IC industry, the excess copper filled back surface is typically several to tens of microns thick due to the deep through silicon vias. In order to quickly remove this excess copper. It is generally desirable to have a high copper removal rate while providing good surface flatness after polishing. The existing polishing solution can generate dishing, dielectric layer erosion, copper residue, corrosion and other defects after polishing.
Disclosure of Invention
In order to solve the problems, the invention provides a chemical mechanical polishing solution, which comprises silicon dioxide abrasive particles, a corrosion inhibitor, a complexing agent, an oxidant, a metal surface defect improver, a phosphate surfactant and water. The phosphate surfactant and the corrosion inhibitor are compounded for use, so that the polishing solution has higher copper removal rate and lower tantalum barrier removal rate, the polishing solution improves the removal rate selection ratio of copper to the tantalum barrier, simultaneously improves dishing and dielectric erosion of the polished copper wire, and simultaneously, the polyol or the hydrophilic polymer is added to improve the surface roughness of the polished copper, so that the defects are reduced.
Further, the structural formula of the phosphate surfactant is as follows:
x is RO, RO- (CH) 2 CH 2 O) n, or RCOO- (CH) 2 CH 2 O) n, R is a C8 to C22 alkyl or alkylbenzene, glyceryl, n=3 to 30; m= H, K, NH 4 Or Na.
Further, the mass concentration of the phosphate surfactant is 0.001-0.1 wt%.
Further, the mass concentration of the phosphate surfactant is 0.005-0.05 wt%.
Further, the metal surface defect improving agent includes a polyol and/or a hydrophilic polymer.
Further, the polyalcohol is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol and glycerol.
Further, the hydrophilic polymer is one or more of polyvinylpyrrolidone, polyacrylamide and polyoxyethylene polyoxypropylene block polymers.
Further, the molecular weight of the hydrophilic polymer is 1000 to 16000.
Further, the molecular weight of the hydrophilic polymer is 1000 to 10000.
Further, the mass concentration of the metal surface defect improving agent is 0.01-3 wt%.
Further, the mass concentration of the metal surface defect improving agent is 0.1-2 wt%.
Further, the silica abrasive particles have an average particle diameter of 20 to 120nm.
Further, the average particle diameter of the silica abrasive particles is 30 to 100nm.
Further, the mass concentration of the silica abrasive particles is 0.05 to 1wt%.
Further, the concentration of the silica abrasive particles is 0.1 to 0.5wt%.
Further, the complexing agent is one or more of glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid, ethylenediamine disuccinic acid, diethylenetriamine pentaacetic acid and triethylenetetramine hexaacetic acid.
Further, the mass concentration of the complexing agent is 0.1-3 wt%.
Further, the mass concentration of the complexing agent is 0.5-1.5 wt%.
Further, the corrosion inhibitor is an azole compound containing no benzene ring.
Further, the azole compound which does not contain benzene rings is one or more of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-carboxyl-3-amino-1, 2, 4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, 5-methyltetrazole and 5-amino-1H-tetrazole.
Further, the mass concentration of the corrosion inhibitor is 0.001 to 0.5wt%.
Further, the mass concentration of the corrosion inhibitor is 0.005-0.2 wt%.
Further, the oxidizing agent is hydrogen peroxide.
Further, the mass concentration of the oxidant is 0.05-3 wt%.
Further, the mass concentration of the oxidant is 0.1-1.5 wt%.
Further, the pH value of the chemical mechanical polishing solution is 5-8.
The chemical mechanical polishing solution of the invention can also contain other additives in the field, such as pH regulator, defoamer, bactericide and the like.
The chemical mechanical polishing solution of the present invention may be prepared by concentrating, diluting with deionized water before use, and adding an oxidizing agent to the concentration range of the present invention.
The reagents of the invention are commercially available.
The weight percent in the invention is the mass percent concentration.
Compared with the prior art, the invention has the advantages that:
compared with the prior art, the invention has the advantages that: 1) The polishing solution has high copper removal rate and low tantalum removal rate, so that the polishing solution has a higher copper/tantalum removal rate selection ratio; 2) The polishing solution can improve dishing and dielectric layer erosion of the polished copper wire; 3) The polishing solution can improve the surface roughness of copper after polishing and reduce defects.
Detailed Description
The advantages of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
Examples
Table 1 shows examples 1 to 17 of the chemical mechanical polishing solutions of the present invention, and the components other than the oxidizing agent were uniformly mixed according to the formulation given in the table, with water being used to make up to 100% by mass. By KOH or HNO 3 Adjusted to the desired pH. Adding oxidant before use, and mixing. The polishing solution can also be prepared into a concentrated sample, and the concentrated sample is diluted by deionized water and added with an oxidant for use.
TABLE 1 polishing liquid compositions of examples 1 to 17 of the invention
Table 2 shows examples 18 to 29 and comparative examples 1 to 6 of the chemical mechanical polishing liquid of the present invention, and the components other than the oxidizing agent were uniformly mixed according to the formulations given in the table, with water being used to make up to 100% by mass. By KOH or HNO 3 Adjusted to the desired pH. Adding oxidant before use, and mixing.
TABLE 2 comparative example polishing solutions 1 to 6 and example 18 to 29 polishing solution compositions
Effect example 1
The polishing solutions of comparative examples 1 to 6 and inventive examples 18 to 29 were used to polish bare copper (Cu) and tantalum (Ta) under the following conditions. Specific polishing conditions: cu polishing pressures were 1.5psi and 2.0psi, tantalum polishing pressures were 1.5psi; the rotation speed of the polishing disk and the polishing head is 73/67rpm, the polishing pad IC1010 and the flow rate of the polishing liquid are 350mL/min, the polishing table is 12' reflexion LK, and the polishing time is 1min. The copper/tantalum removal rates for each example were measured separately and the removal rate selection ratios were calculated for both and the results are set forth in table 3.
Table 3 removal rates and removal rate selection ratios for comparative polishing solutions 1 to 6 and examples 18 to 29
As can be seen from Table 3, the polishing solutions of the examples of the present invention have a higher copper/tantalum removal rate selection ratio than the comparative examples. The polishing solution in comparative example 1 only contains grinding particles, complexing agent and oxidant, and has higher copper and tantalum removal rates, so that the copper/tantalum removal rate selection ratio is low; the polishing solution of comparative example 2 was added with a corrosion inhibitor based on comparative example 1, thereby reducing the removal rate of tantalum and improving the removal rate selection ratio of copper/tantalum by the polishing solution to some extent. However, the polishing solution of comparative example 2 still has not a sufficiently high copper/tantalum removal rate selection ratio to meet the polishing requirements for tantalum as a barrier layer.
In comparative examples 3 and 4, a combination of azole corrosion inhibitor and phosphate surfactant without benzene ring was added as compared to inventive example 18, but comparative example 3 had too low a pH and higher copper and tantalum removal rates, resulting in a low selectivity for copper/tantalum removal rate. However, the pH of comparative example 4 was too high, resulting in a significant reduction in copper removal rate, and the copper could not be removed effectively. As can be seen from a comparison of the components of example 18 and comparative example 5, the selection of the combination of benzotriazole, an azole corrosion inhibitor having a benzene ring, and a phosphate surfactant, while reducing the tantalum removal rate, greatly inhibited the copper removal rate and was not effective. From comparative example 6 and examples 18-29, it is clear that the addition of the polyol or hydrophilic polymer does not affect the copper and tantalum removal rates.
Effect example two
The patterned copper wafers were polished using the polishing solutions of comparative examples 2, 3, 6 and inventive examples 18 to 29 under the following conditions. Polishing conditions: the rotation speed of the polishing disk and the polishing head is 73/67rpm, the polishing pad IC1010 and the flow rate of the polishing liquid is 350mL/min, and the polishing table is 12' reflexion LK. Polishing the patterned copper wafer to about residual copper with a downforce of 2psi on polishing pad 1The residual copper was then removed on polishing pad 2 with a down force of 1.5 psi. Dishing values (Dishing), dielectric layer Erosion (Erosion), and copper surface Roughness (roughess) of 5um/1um (line width of copper/dielectric material) copper line array regions on patterned copper wafers were measured using a Dektak-XT steppers, and the number of surface defects of the polished copper blank wafer was measured using a surface defect scanner SP2, and the Dishing values and dielectric layer Erosion values, and the copper surface Roughness and number of surface defects of the resulting copper lines are shown in table 4.
TABLE 4 polishing effects of comparative polishing solutions 2, 3, 6 and examples 18 to 29
As can be seen from Table 4, compared with the comparative example, the polishing solution of the embodiment of the invention has less dishing and dielectric erosion of the copper wire, less surface roughness and surface defects of the copper wire after polishing, and greatly improved surface morphology. The polishing solution of comparative example 2 was added with a corrosion inhibitor based on comparative example 1, thereby reducing the removal rate of tantalum and improving the removal rate selection ratio of copper/tantalum by the polishing solution to some extent. However, dishing and dielectric erosion of the copper wire polished with the polishing liquid of comparative example 2, and copper surface roughness and defects after polishing were large, and the copper wire surface morphology was poor.
Compared with the invention of the example 18, the combination of the azole corrosion inhibitor without benzene ring and the phosphate surfactant is adopted in the comparative example 3, but the pH value of the comparative example 3 is too low, the copper and tantalum removal rate is also higher, and the dishing and the medium layer erosion of the copper wire are both larger. The blank copper wafers polished in comparative example 6 and example 18 were subjected to defect scanning by the defect scanner SP2, and as a result, it was found that the number of defects on the surface of the polished copper wafer in comparative example 6, to which the metal surface defect improver was not added, was significantly higher than in example 18. Therefore, the addition of the metal surface defect improving agent can further improve the copper surface roughness and surface defects after polishing. From comparative example 6 and examples 18-29, it is seen that the addition of the polyol or hydrophilic polymer significantly reduces the post-polishing copper surface roughness and surface defects, thereby improving the post-polishing copper surface morphology.
According to the polishing solution disclosed by the embodiment of the invention, the polishing solution is prepared by using the abrasive particles with the particle size and the particle size distribution index within a certain range and adding the combination of the azole corrosion inhibitor without benzene ring, the phosphate surfactant and the metal surface defect improver into the polishing solution at a proper pH value, so that the high copper removal rate is maintained, the tantalum barrier layer removal rate is reduced, and the effect of improving the removal rate selection ratio of the polishing solution to the copper and tantalum barrier layers is realized; meanwhile, the polishing method can be used for polishing the wafer, can improve Dishing (Dishing) and dielectric layer Erosion (Erosion) of the polished copper wire, can obviously improve the surface roughness of the polished copper wire, and can reduce surface defects.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (9)
1. A chemical mechanical polishing solution comprises silicon dioxide abrasive particles, a corrosion inhibitor, a complexing agent, an oxidant, a metal surface defect improver, a phosphate surfactant and water;
the mass concentration of the silicon dioxide grinding particles is 0.05-1wt%;
the corrosion inhibitor is an azole compound without benzene ring, and the mass concentration of the corrosion inhibitor is 0.001-0.5 wt%;
the mass concentration of the complexing agent is 0.1-3wt%;
the metal surface defect improver comprises a polyol and/or a hydrophilic polymer, wherein the polyol is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol and glycerol; the hydrophilic polymer is one or more of polyvinylpyrrolidone, polyacrylamide and polyoxyethylene polyoxypropylene block polymers, and the mass concentration of the metal surface defect improver is 0.01-3wt%;
the mass concentration of the phosphate surfactant is 0.001-0.1wt%;
the mass concentration of the oxidant is 0.05-3 wt%.
2. The chemical mechanical polishing solution according to claim 1, wherein the phosphate surfactant has a structural formula:
and/or->
X is RO, RO- (CH) 2 CH 2 O) n, or RCOO- (CH) 2 CH 2 O) n, R is a C8 to C22 alkyl or alkylbenzene, glyceryl, n=3 to 30; m= H, K, NH 4 Or Na.
3. The chemical mechanical polishing liquid according to claim 1, wherein the hydrophilic polymer has a molecular weight of 1000 to 16000.
4. The chemical mechanical polishing liquid according to claim 3, wherein the hydrophilic polymer has a molecular weight of 1000 to 10000.
5. The chemical mechanical polishing liquid according to claim 1, wherein the silica abrasive particles have an average particle diameter of 20 to 120nm.
6. The chemical mechanical polishing solution according to claim 1, wherein the complexing agent is one or more of glycine, alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartic acid, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid, ethylenediamine disuccinic acid, diethylenetriamine pentaacetic acid, and triethylenetetramine hexaacetic acid.
7. The chemical mechanical polishing liquid according to claim 1, wherein the benzene ring-free azole compound is one or more of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-carboxy-3-amino-1, 2, 4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, 5-methyltetrazole, and 5-amino-1H-tetrazole.
8. The chemical mechanical polishing solution according to claim 1, wherein the oxidizing agent is hydrogen peroxide.
9. The chemical mechanical polishing liquid according to any one of claims 1 to 8, wherein the pH of the chemical mechanical polishing liquid is 5 to 8.
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