CN111378382B - Chemical mechanical polishing solution and application thereof - Google Patents
Chemical mechanical polishing solution and application thereof Download PDFInfo
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- CN111378382B CN111378382B CN201811639167.7A CN201811639167A CN111378382B CN 111378382 B CN111378382 B CN 111378382B CN 201811639167 A CN201811639167 A CN 201811639167A CN 111378382 B CN111378382 B CN 111378382B
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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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Abstract
The invention discloses a chemical mechanical polishing solution which comprises abrasive particles, a metal corrosion inhibitor, a complexing agent, an oxidant, an anionic fluorocarbon surfactant and water. The polishing solution has high removal rate of the barrier layer and silicon dioxide (TEOS), can well control the removal rate of an ultra-low dielectric constant material (ULK), has strong correction capability on the surface appearance of a semiconductor device, quickly realizes planarization, improves the working efficiency and reduces the production cost.
Description
Technical Field
The invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing solution for flattening a barrier layer and a dielectric layer.
Background
In the manufacture of integrated circuits, as the number of interconnection layers increases and the size of process features decreases, the requirements on interconnection technology and the flatness of the surface of a silicon wafer become higher and higher. Without planarization, it is very difficult to create complex and dense structures on a semiconductor wafer, and Chemical Mechanical Polishing (CMP) is the most effective method to achieve planarization of the entire wafer.
With the development of integrated circuit technology to 45nm and below technology nodes and the sharp increase of interconnection wiring density, the RC coupling parasitic effect brought by resistance and capacitance in an interconnection system is rapidly increased, and the response speed of a device is influenced. To reduce this effect, low dielectric constant materials (k 2.8) must be used to reduce the parasitic capacitance between adjacent metal lines, and currently below the 45nm technology node, ultra low dielectric constant materials (ULK, k 2.5) are commonly used in the industry.
The introduction of ultra low dielectric constant materials (ULK) presents a significant challenge to process technology, particularly Chemical Mechanical Polishing (CMP) processes. In the CMP process, besides strictly controlling surface pollutants and avoiding metal corrosion, the dishing and dielectric layer erosion of the surface of the wafer are lower, the polishing uniformity is high, and the wafer can have reliable electrical property. Particularly in the polishing of barrier layers, rapid removal of the barrier layer and silicon dioxide (TEOS) in a shorter time and at a lower pressure is required, and the residual thickness of ultra low dielectric constant (ULK) materials is well controlled. This presents a higher challenge to CMP. The chemical mechanical polishing solution needs to have strong regulation capability of the removal rate of the ultra-low dielectric constant material (ULK).
There are many chemical mechanical polishing liquids currently on the market for barrier planarization, for example, CN105219274A discloses a chemical mechanical polishing liquid for low-k dielectric material polishing, which employs a combination of a silicone-free nonionic surfactant containing a hydrophilic portion and a lipophilic portion and a silicone-containing nonionic surfactant containing a hydrophilic portion and a hydrophilic portion to control the polishing rate of the low-k dielectric material, but does not mention the influence of the surfactant on the polishing rate of other materials. CN101372089A discloses an alkaline barrier polishing solution, which contains silica abrasive, corrosion inhibitor, oxidizer, nonionic fluorosurfactant, and aromatic sulfonic acid oxidizer compound, and has low barrier polishing rate and low polishing efficiency. CN101016440A discloses an acidic polishing solution for barrier polishing, which contains a silica abrasive, a quaternary ammonium salt, an anionic surfactant, a corrosion inhibitor and an oxidizing agent, wherein the anionic surfactant is used for increasing the polishing rate of a low-k dielectric material. CN102477260A discloses a chemical mechanical polishing solution for shallow trench isolation, which adopts phosphate anionic fluorocarbon surfactant to inhibit the polishing rate of silicon nitride material, the silicon nitride and ULK material belong to two different materials, the surface hydrophilicity and hydrophobicity are different, and the adsorption mechanism of the surfactant on the surfaces of the two materials is different, so the patent does not mention the influence of the phosphate anionic fluorocarbon surfactant on the polishing rate of the ULK material.
Therefore, aiming at the problem that the polishing rate of the ultra-low dielectric constant material (ULK) in the prior art is not easy to control, a chemical mechanical polishing solution which can be suitable for polishing a barrier layer in an ultra-low dielectric constant material-copper interconnection process, can realize high removal rate of the barrier layer and silicon dioxide (TEOS) and adjustable removal rate of the ultra-low dielectric constant material (ULK) under a mild condition, and can well control Dishing (Dishing), dielectric layer Erosion (Erosion), metal corrosion and surface pollutants is a problem to be solved urgently in the industry.
Disclosure of Invention
In order to solve the above problems, the present invention provides a chemical mechanical polishing solution, which exhibits a high removal rate of a barrier layer and silicon dioxide (TEOS) and an adjustable removal rate of an ultra-low dielectric constant material (ULK) by using a specific anionic fluorocarbon surfactant, thereby well controlling the residual thickness of the ultra-low dielectric constant material (ULK) during polishing, and well correcting Dishing and dielectric Erosion (Erosion) generated during a forward process (copper polishing), while reducing metal corrosion and surface contaminants.
Specifically, the invention provides a chemical mechanical polishing solution, which comprises abrasive particles, a metal corrosion inhibitor, a complexing agent, an oxidizing agent, an anionic fluorocarbon surfactant and water.
Preferably, the anionic fluorocarbon surfactant has a general formula CnF2n+1R, wherein n is more than or equal to 1 and less than or equal to 10, R is-COOM and-SO3M or-OPO3M, M is H, K or NH4。
Preferably, the content of the anionic fluorocarbon surfactant is 0.0001-0.2 percent by mass,
preferably, the content of the anionic fluorocarbon surfactant is 0.001-0.1% by mass.
Preferably, the abrasive particles are selected from one or more of silicon dioxide, aluminum oxide, cerium dioxide, aluminum-doped silicon dioxide and polymethyl methacrylate.
Preferably, the content of the grinding particles is 1-20% by mass.
Preferably, the content of the grinding particles is 2-10% by mass.
Preferably, the particle size of the grinding particles is 20-150 nm.
Preferably, the particle size of the grinding particles is 30-120 nm.
Preferably, the metal corrosion inhibitor is an azole compound.
Preferably, the azole compound is one or more selected from benzotriazole, methyl benzotriazole, 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 5-methyl-tetrazole.
Preferably, the content of the metal corrosion inhibitor is 0.001-2% by mass.
Preferably, the metal corrosion inhibitor is 0.01-1% by mass.
Preferably, the complexing agent is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid, glycine, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, hydroxyethylidene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, polyaminopolyether methylene phosphonic acid, aminotrimethylene phosphonic acid.
Preferably, the content of the complexing agent is 0.01-2% by mass.
Preferably, the content of the complexing agent is 0.05-1% by mass.
Preferably, the oxidant is selected from one or more of hydrogen peroxide, peroxyacetic acid, potassium persulfate and ammonium persulfate.
Preferably, the content of the oxidant is 0.01-1% by mass.
Preferably, the pH value of the chemical mechanical polishing solution is less than or equal to 7.
Preferably, the pH value of the chemical mechanical polishing solution is 2-5.
The chemical mechanical polishing solution of the present invention may further comprise other additives commonly used in the art, such as a pH adjuster and a bactericide.
In another aspect of the invention, an application of the chemical mechanical polishing solution in polishing of barrier layers and dielectric layers is provided.
Compared with the prior art, the invention has the advantages that: the polishing solution has high removal rate of the barrier layer and silicon dioxide (TEOS) and adjustable removal rate of the ultralow dielectric constant material (ULK) under a mild condition, so that the residual thickness of the ultralow dielectric constant material (ULK) can be well controlled in the polishing process, dishing, dielectric layer erosion and metal corrosion can be well controlled in the polishing process, and surface pollutants can be reduced.
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.
Table 1 shows the components and contents of the polishing liquids of comparative examples 1 to 3 and examples 1 to 13 of the present invention. The polishing solutions of examples and comparative examples were prepared according to the table by mixing the components except the oxidizing agent uniformly, using KOH or HNO3Adjusting to the required pH value, adding an oxidant before use, and adding water to complement the mass percent to 100 percent, and uniformly mixing to obtain the various embodiments and comparative examples of the invention.
TABLE 1 polishing solutions for comparative examples 1 to 3 and inventive examples 1 to 13
Effect example 1:
the chemical mechanical polishing solutions of comparative examples 1 to 3 and examples 1 to 13 were used to polish copper (Cu), tantalum (Ta), silicon dioxide (TEOS), and ultra low dielectric constant (ULK) under the following conditions: polishing was performed using a 12 "Reflexion LK polisher using a Fujibo pad at a polishing pressure of 1.5psi, a polishing rotation speed of 93/87rpm for the polishing platen/head, a polishing slurry flow rate of 300ml/min, and a polishing time of 1 min. The polishing rates of the polishing solutions of each example for the four materials were obtained and are shown in Table 2.
TABLE 2 removal rates for copper (Cu), tantalum (Ta), silicon dioxide (TEOS) and ultra low dielectric constant (ULK) materials for the polishing solutions of comparative examples 1-3 and inventive examples 1-13
As shown in Table 2, the polishing solution of comparative example 1 does not contain anionic surfactant, and the polishing rate of ULK is greater than that of TEOS, so that the removal rate of the material with ultralow dielectric constant cannot be well controlled in the polishing process; the polishing solution of the comparative examples 2 to 3 added with the conventional anionic surfactants such as dodecylbenzene sulfonic acid and polyacrylic acid has no influence on the polishing rate of the ULK, and the problem of wafer morphology defect is easily caused due to uncontrollable removal rate of the ULK in the polishing process. Compared with the comparative example, the polishing solution of the examples 1 to 13 of the invention has high polishing rate for tantalum and TEOS, and meanwhile, due to the addition of the anionic fluorocarbon surfactant, the polishing rate of ULK can be controlled, and the polishing rate of tantalum and TEOS is not influenced, so that in the polishing process, tantalum and TEOS can be removed rapidly, the residual thickness of the material with ultra-low dielectric constant can be well controlled, and the process requirements can be met. In addition, it can be seen from embodiments 1 to 13 of the present invention that the polishing rate of ULK can be adjusted by selecting different types of anionic fluorocarbon surfactants and adjusting the concentration of the anionic fluorocarbon surfactants, so as to meet the requirements of different processes for the removal rate of the ULK material.
Effect example 2:
the polishing slurry of comparative example 1 and examples 1-3 above was used to polish patterned copper wafers, which are commercially available as 12 inch Sematech754 patterned wafers, with the film material on the wafers being copper/tantalum nitride/TEOS/ULK from top to bottom. The polishing process comprises the following steps: 1) removing most of the copper by using a commercially available copper polishing solution; 2) removing residual copper by using a commercially available copper polishing solution; 3) the tantalum/tantalum nitride/TEOS layer was removed with the polishing solutions of comparative example 1 and examples 1 to 3 described above, stopping the polishing at the ULK layer, and the dishing and erosion of the polished wafer surface were examined. Wherein, the polishing conditions of the step 3) are as follows: polishing was performed using a 12 "Reflexion LK polisher using a Fujibo pad at a polishing pressure of 1.5psi, a polishing rotation speed of 93/87rpm for the polishing disk/head, a polishing slurry flow rate of 300ml/min, and a polishing time of 70 s. Dishing (discing) and dielectric Erosion (Erosion) of the patterned wafer after polishing were measured with an atomic force microscope. Before and after polishing, the dishing and dielectric erosion values of the wafer and their variation from those before polishing are shown in Table 3.
In table 3, the disching indicates a recess formed on the surface of a copper block of 100 × 100 μm after polishing a copper or barrier layer, Erosion indicates dielectric Erosion of the barrier layer on a dense line region (50% copper/50% dielectric layer) with a line width of 0.18 μm and a density of 50%, a positive value indicates a copper recess, and a negative value indicates a copper protrusion.
TABLE 3 results of polishing patterned wafers with the polishing solutions of comparative examples 1 to 3 and inventive examples 1 to 13
As can be seen from Table 3, the polishing solutions of examples 1 to 3 according to the present invention exhibited better abilities to improve dishing and dielectric layer erosion than those of comparative example 1. As shown in table 2, the polishing solution in the embodiment of the present invention can effectively control the polishing rate of ULK, so as to meet the removal rate selection ratio of the material required by the process, obtain a flat wafer surface, meet the application requirements of the polished wafer, and represent excellent market application prospects.
It should be noted that the contents in the present invention are all contents by mass percentage, if not specifically stated.
It should be understood that the embodiments of the present invention have been described in terms of preferred embodiments, and not as limitations of the invention, and that those skilled in the art may readily modify or modify the embodiments in accordance with the teachings herein without departing from the scope of the invention.
Claims (12)
1. A chemical mechanical polishing liquid for polishing barrier layer and ULK material with ultra-low dielectric constant contains abrasive particles
Particles, a metal corrosion inhibitor, a complexing agent, an oxidant, an anionic fluorocarbon surfactant and water;
the general formula of the anionic fluorocarbon surfactant is CnF2n +1R, wherein n is more than or equal to 1 and less than or equal to 10, R is-COOM,
-SO3M or-OPO 3M, M is H, K or NH 4; the mass of the anionic fluorocarbon surfactant
The percentage content is 0.0001 percent to 0.2 percent;
the abrasive particles are selected from silicon dioxide, aluminum oxide, cerium dioxide, aluminum-doped silicon dioxide, polymethyl methacrylate
One or more of methyl methacrylate; the content of the grinding particles is 1-20% by mass; the above-mentioned
The particle size of the grinding particles is 20-150 nm;
the metal corrosion inhibitor is an azole compound;
the complexing agent is selected from oxalic acid, malonic acid, succinic acid, citric acid, glycine and 2-phosphonobutane-1, 2,
one or more of 4-tricarboxylic acid, hydroxyethylidene diphosphonic acid, ethylene diamine tetramethylene phosphonic acid, polyaminopolyether methylene phosphonic acid and amino trimethylene phosphonic acid;
the oxidant is selected from one or more of hydrogen peroxide, peroxyacetic acid, potassium persulfate and ammonium persulfate;
the PH value of the chemical mechanical polishing solution is less than or equal to 7.
2. The chemical mechanical polishing solution according to claim 1,
the content of the anionic fluorocarbon surfactant is 0.001-0.1% by mass.
3. The chemical mechanical polishing solution according to claim 1,
the content of the grinding particles is 2-10% by mass.
4. The chemical mechanical polishing solution according to claim 1,
the particle size of the grinding particles is 30-120 nm.
5. The chemical mechanical polishing solution according to claim 1,
the azole compound is one or more selected from benzotriazole, methyl benzotriazole, 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 5-methyl-tetrazole.
6. The chemical mechanical polishing solution according to claim 1,
the mass percentage content of the metal corrosion inhibitor is 0.001-2%.
7. The chemical mechanical polishing solution according to claim 1,
the mass percentage content of the metal corrosion inhibitor is 0.01-1%.
8. The chemical mechanical polishing solution according to claim 1,
the mass percentage content of the complexing agent is 0.01-2%.
9. The chemical mechanical polishing solution according to claim 1,
the mass percentage content of the complexing agent is 0.05% -1%.
10. The chemical mechanical polishing solution according to claim 1,
the mass percentage content of the oxidant is 0.01-1%.
11. The chemical mechanical polishing solution according to claim 1,
the pH value of the chemical mechanical polishing solution is 2-5.
12. Use of a chemical mechanical polishing liquid according to any one of claims 1 to 11 for ULK polishing of barrier layers and ultra low dielectric constant materials.
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| CN115365996A (en) * | 2022-08-23 | 2022-11-22 | 福建省南安市宏炜新材料有限公司 | Chemical mechanical polishing process of N-Si substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372089A (en) * | 2006-12-21 | 2009-02-25 | 杜邦纳米材料气体产品有限公司 | Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing |
| CN101623843A (en) * | 2009-07-31 | 2010-01-13 | 昆山光爱电子材料有限公司 | Manufacturing method of ultrathin crystal plate of low-pass optical filter |
| CN102329572A (en) * | 2011-09-20 | 2012-01-25 | 深圳市力合材料有限公司 | Copper chemical and mechanical polishing combination |
| CN102477260A (en) * | 2010-11-26 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372089A (en) * | 2006-12-21 | 2009-02-25 | 杜邦纳米材料气体产品有限公司 | Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing |
| CN101623843A (en) * | 2009-07-31 | 2010-01-13 | 昆山光爱电子材料有限公司 | Manufacturing method of ultrathin crystal plate of low-pass optical filter |
| CN102477260A (en) * | 2010-11-26 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
| CN102329572A (en) * | 2011-09-20 | 2012-01-25 | 深圳市力合材料有限公司 | Copper chemical and mechanical polishing combination |
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