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Publication numberUS20020019202 A1
Publication typeApplication
Application numberUS 09/795,241
Publication dateFeb 14, 2002
Filing dateFeb 28, 2001
Priority dateJun 10, 1998
Publication number09795241, 795241, US 2002/0019202 A1, US 2002/019202 A1, US 20020019202 A1, US 20020019202A1, US 2002019202 A1, US 2002019202A1, US-A1-20020019202, US-A1-2002019202, US2002/0019202A1, US2002/019202A1, US20020019202 A1, US20020019202A1, US2002019202 A1, US2002019202A1
InventorsTerence Thomas, Qianqiu (Christine) Ye, Joseph So, Peter Burke, Vikas Sachan, Elizabeth Langlois, Keith Pierce, Craig Lack, David Gettman, Hiroyuki Senoo, Kouchi Yoshida, Yoshikazu Nishida, Vilas Koinkar, Raymond Lavoie
Original AssigneeThomas Terence M., Qianqiu (Christine) Ye, So Joseph K., Burke Peter A., Vikas Sachan, Langlois Elizabeth A., Pierce Keith G., Lack Craig D., David Gettman, Hiroyuki Senoo, Kouchi Yoshida, Yoshikazu Nishida, Koinkar Vilas N., Lavoie Raymond Lee
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Control of removal rates in CMP
US 20020019202 A1
Abstract
A two-step method for chemical mechanical polishing of a semiconductor substrate having successive layers, comprised of, a metal layer, an underlying barrier film and an underlying dielectric layer. The first polishing step is performed utilizing a slurry composition selective to the metal in the metal layer, to remove the metal at a high removal rate during polishing, and the second polishing step is performed utilizing a slurry composition selective to the barrier film and least selective to the metal layer and the underlying dielectric layer. In an alternate embodiment, the second polishing step is performed with a slurry equally selective to the barrier layer and the underlying dielectric layer and least selective to the metal of the metal layer, to remove the barrier layer at a high removal rate during polishing, and level a surface of the dielectric layer to the surface of the metal interconnection structure in the underlying dielectric layer.
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Claims(25)
What is claimed is:
1. A method for chemical mechanical polishing (CMP) of a semiconductor substrate having a metal layer, an underlying barrier film and an underlying dielectric layer with metal interconnection structures, comprising the steps of:
removing the metal layer by first step CMP utilizing a first step slurry that is highly selective to the metal of the metal layer and less selective to the barrier material of the barrier film to remove the metal of the metal layer with a maximized rate of metal removal by polishing, and to minimize removal of the barrier material of the barrier film; and
removing the barrier material by second step CMP utilizing a second step slurry that is highly selective to the barrier material and is least selective to the metal layer and the dielectric layer, to remove the barrier film with a maximized rate by polishing, with minimized removal of the metal of the metal layer and minimized removal of the dielectric layer to provide the height of the dielectric layer at a surface level with the metal interconnection structures; wherein said second step slurry has a pH greater than 7.
2. The method as recited in claim 1, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having a pH greater than 7, and a dispersion of colloidal silica having a Zeta Potential of negative (20 millivolts or greater) at said pH.
3. The method as recited in claim 1, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having a pH greater than 7, and submicron abrasive particles of colloidal silica comprising up to about 30% by weight of said second step slurry.
4. The method as recited in claim 1, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having a pH greater than 7, a dispersion of colloidal silica having a zeta potential of negative (20 millivolts or greater) at said pH, and submicron abrasive particles of colloidal silica comprising up to about 30% by weight of said second step slurry.
5. The method as recited in claim 1, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry; wherein said second step slurry comprises: submicron abrasive partices of colloidal silica comprising up to about 30% by weight of said second step slurry; a complexing agent up to about 5,000 ppm by weight of said second step slurry; a corrosion inhibitor up to about 110 ppm by weight of said second step slurry; a biocide up to about 200 ppm by weight of said second step slurry; an oxidizing agent up to about 15,000 ppm by weight of said second step slurry; an oxide suppressant up to about 5,000 ppm by weight of said second step slurry; and a chloride salt up to about 200 ppm by weight of said second step slurry.
6. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes said second step slurry having a Zeta Potential of negative (20 millivolts or greater) at said pH.
7. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having a complexing agent selected from the group consisting of: malic acid, tartaric acid, gluconic acid, glycolic acid, citric acid, phthalic acid, pyrocatechol, pyrogallol, gallic acid, and tannic acid.
8. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having a copper corrosion inhibitor.
9. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having hydrogen peroxide as the oxidizing agent.
10. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having ammonium chloride as the chloride salt.
11. The method as recited in claim 5, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having polyvinylpyrrolidone as the oxide suppressant.
12. A method for polishing a semiconductor substrate having a metal layer, an underlying barrier film and an underlying dielectric layer with metal interconnect structures, comprising the steps of:
removing the metal layer by first step CMP utilizing a first step slurry that is highly selective to the metal of the metal layer and less selective to the barrier film to remove the metal of the metal layer with a maximized rate of metal removal by polishing, and to minimize removal of the barrier film; and
removing the dielectric layer and barrier film by second step CMP utilizing a second step slurry that is equally highly selective to the barrier material and the dielectric material and least selective to the metal in the metal layer; wherein said second step slurry comprises a pH greater than 7; submicron abrasive partices of colloidal silica comprising up to about 30% by weight of said second step slurry; a complexing agent up to about 5,000 ppm by weight of said second step slurry; a corrosion inhibitor up to about 110 ppm by weight of said second step slurry; a biocide up to about 200 ppm by weight of said second step slurry; and an oxidizing agent up to about 15,000 ppm by weight of said second step slurry.
13. The method as recited in claim 12, wherein the step of removing the barrier film or alternately the dielectric material by second step CMP utilizes said second step slurry having a Zeta potential of negative (20 millivolts or greater) at said pH.
14. The method as recited in claim 12, wherein the step of removing the barrier film or alternately the dielectric material by second step CMP utilizes a second step slurry having a complexing agent selected from the group consisting of: malic acid, tartaric acid, gluconic acid, glycolic acid, citric acid, phthalic acid, pyrocatechol, pyrogallol, gallic acid, and tannic acid.
15. The method as recited in claim 12, wherein the step of removing the barrier film or alternately the dielectric material by second step CMP utilizes a second step slurry having a copper corrosion inhibitor.
16. The method as recited in claim 12, wherein the step of removing the barrier film by second step CMP utilizes a second step slurry having hydrogen peroxide as the oxidizer.
17. An aqueous polishing composition for polishing semiconductor substrates comprising: a pH greater than 7; submicron abrasive partices of colloidal silica comprising up to about 30% by weight of said second step slurry; a complexing agent up to about 5,000 ppm by weight of said second step slurry; a corrosion inhibitor up to about 110 ppm by weight of said second step slurry; a biocide up to about 200 ppm by weight of said second step slurry; an oxidizing agent up to about 15,000 ppm by weight of said second step slurry; an oxide suppressant up to about 5,000 ppm by weight of said second step slurry; and a chloride salt up to about 200 ppm by weight of said second step slurry.
18. A polishing composition according to claim 17 wherein said complexing agent is citric acid.
19. A polishing composition according to claim 17 wherein said corrosion inhibitor is selected from a group consisting of benzotriazole, tolyltriazole and mixtures thereof.
20. A polishing composition according to claim 17 wherein the oxidizing agent is hydrogen peroxide.
21. A polishing composition according to claim 17 wherein the chloride salt is ammonium chloride.
22. An aqueous polishing composition for polishing semiconductor substrates comprising a pH greater than 7; submicron abrasive partices of colloidal silica comprising up to about 30% by weight of said second step slurry; a complexing agent up to about 5,000 ppm by weight of said second step slurry; a corrosion inhibitor up to about 110 ppm by weight of said second step slurry; a biocide up to about 200 ppm by weight of said second step slurry; and an oxidizing agent up to about 15,000 ppm by weight of said second step slurry.
23. A polishing composition according to claim 22 wherein said complexing agent is citric acid.
24. A polishing composition according to claim 22 wherein said corrosion inhibitor is selected from a group consisting of benzotriazole, tolyltriazole and mixtures thereof.
25. A polishing composition according to claim 22 wherein the oxidizing agent is hydrogen peroxide.
Description

[0001] This application is a continuation-in-part of application Ser. No. 09/693,211, filed Oct. 20, 2000, which claims the benefit of Provisional Application 60/161,242, filed Oct. 22, 1999. This application is a continuation-in-part of application Ser. No. 09/329,225 filed Jun. 10, 1999, which claims the benefit of Provisional Application 60/088,849 filed Jun. 10, 1998. This application is a continuation-in-part of application Ser. No. 09/420,682 filed Oct. 19, 1999, which claims the benefit of Provisional Application 60/104,876 filed Oct. 20, 1998. This application is a continuation-in-part of application Ser. No. 09/439,461 filed Nov. 15, 1999, which claims the benefit of Provisional Application serial number 60/108,656 filed Nov. 16, 1998. This application also claims the benefit of Provisional Application 60/188,421 filed Mar. 10, 2000.

[0002] This invention pertains to polishing methods and slurry compositions or formulations that are used in polishing a semiconductor substrate having successive layers, comprised of, a metal layer, an underlying barrier film or layer, and an underlying dielectric layer.

[0003] Landers et al. in U.S. Pat. No. 5,676,587 discloses a two-step chemical mechanical polishing process for polishing a semiconductor substrate. The first polishing step utilizes an alumina-based slurry to remove a metal layer from an underlying barrier film. The second polishing step utilizes a silica-based slurry to remove the barrier film of tantalum(Ta), tantalum nitride (TaN), titanium (Ti), or titanium nitride (TiN). The silica-based slurry used in the second polishing step is pH neutral and is selective to Ta, TaN, Ti, or TiN to remove the barrier film.

[0004] Chemical mechanical polishing (CMP) is an enabling technology for the production of complex and dense semiconductor structures and is an effective method for the removal and planarization of thin films or layers on semiconductor substrates during the production of semiconductor structures containing integrated circuits such as multi-chip modules, capacitors and the like. During the CMP process, a chemical slurry or polishing fluid (referred to herein as slurry) is used along with a polishing pad. The mechanical motion of the polishing pad relative to the semiconductor substrate in combination with chemical reaction of the polishing fluid with the substrate surface results in material removal from the semiconductor substrate surface. The “damascene” CMP process is employed for forming interconnect lines and vias for multi-layer metal structures that provide the “wiring” of an integrated circuit and involves etching trenches in a planar dielectric (insulator) layer and filling the trenches with a conductive material. The conductive material is typically a metal such as aluminum, copper, or tungsten. To ensure complete filling of trenches, an overlayer of metal, about 10,000 to 15,000 Angstrom in thickness, is required. The dielectric is typically silicon dioxide (SiO2), silicon dioxide derived from tetraethyl orthosilicate (TEOS), phosphosilicate glass (PSG), boron phosphosilicate glass (BPSG), or a low-k dielectric. A technique called “dual-damascene” adds etched vias for providing contact to a lower level as the upper damascene structure is filled. More details are found in “Making the Move to Dual Damascene Processing,” Semiconductor International, August 1997. Typically a layer of another material is first deposited to line the trenches and vias to prevent the migration of metal ions into the dielectric layer. This migration barrier or barrier layer (also referred to as a liner layer) typically comprises tantalum, tantalum nitride, titanium and/or titanium nitride. One or more barrier layers may be provided depending on the specific application. The barrier layer has a thickness up to about 1,000 Angstroms. CMP of such a substrate is performed in two steps to obtain a polished structure with metal circuit interconnect lines in the dielectric layer to generate an integrated circuit.

[0005] As described above, semiconductor substrates used to make integrated circuits typically contain three different layers: a conductive metal layer, a barrier (or liner) film between the conductive metal layer and the underlying dielectric layer, and an underlying dielectric layer. While polishing a semiconductor substrate by CMP, it is desirable for the removal rates of each layer to differ significantly from each other in order to induce planarity and maintain the integrity of the semiconductor substrate during polishing. This difference in removal rates is characterized by a parameter termed the selectivity ratio. For example, the ratio of metal removal rate to the dielectric removal rate is termed the metal-dielectric selectivity ratio. It is also critical to maintain the cross section and planarity of underlying conducting metal interconnect structures (trenches or lines) that provide metal circuit interconnect structures for the integrated circuit, especially when polishing to attain high removal rates of the various layers. Excessive removal of metal from the conducting metal lines is observed as cavities (known as “dishing”) and is undesirable, since it affects the electrical performance of the semiconductor structure (integrated circuit) resulting from CMP of the semiconductor substrate. Similarly, excessive removal of the dielectric layer surrounding the metal lines is observed as cavities (known as “erosion”) and is undesirable, since the dielectric layer should be flawless and free of cavities, adjacent to the side geometry of the metal lines to ensure optimal electrical performance of the semiconductor structure (integrated circuit) resulting from CMP of the semiconductor substrate. Further, CMP polishing is required to polish the semiconductor substrate with a smooth planar polished surface on which are manufactured successive layers, which themselves are polished by CMP. Thus, excessive dishing and erosion in the underlying layers manifests as defects in the upper layers.

[0006] During known CMP, the semiconductor substrate (substrate) to be polished is mounted on a carrier or polishing head of a polishing machine. The exposed surface of the substrate is placed against a rotating polishing pad. The surface of the polishing pad that is in contact with the semiconductor substrate is referred to as the polishing layer. The polishing pad may be a standard pad (without any abrasive in the polishing layer) also referred to as a non fixed-abrasive pad or a fixed-abrasive pad (containing abrasive in the polishing layer). The carrier head provides a controllable pressure (or downforce), on the substrate to bias it towards the polishing pad. A polishing fluid with or without abrasive particles is then dispensed at the interface of the wafer and the polishing pad to enhance removal of the target layer (for e.g., metal layer in first-step CMP or barrier layer in second-step CMP). The polishing fluid is preferably water based and may or may not require the presence of abrasive particles, depending on the composition of the polishing layer of the polishing pad. An abrasive-free polishing fluid also referred to as a reactive liquid is typically used with a fixed-abrasive pad while a polishing fluid containing abrasive particles is typically used with a non fixed-abrasive pad. For polishing softer metal interconnects, such as copper, the polishing fluid can contain up to 3% by weight of abrasive particles.

[0007] A need exists for a method of polishing by CMP to selectively remove (1) the metal layer and the barrier film while minimizing erosion of the dielectric layer in a semiconductor substrate; or (2) selectively remove the barrier film and dielectric layer while minimizing dishing of metal in metal lines (trenches) in a semiconductor substrate.

[0008] A method according to this invention, comprises a two-step CMP process for polishing a semiconductor substrate containing a conducting metal layer, a dielectric layer, and a barrier film or layer between the two. In the first step of the CMP process, the metal layer is removed from the substrate without removing significant amounts of either the barrier film or the underlying dielectric layer. In the second step of the CMP process, the barrier film is removed selectively from an underlying dielectric layer, with minimal removal of metal providing metal lines in the underlying dielectric layer, utilizing a slurry according to this invention, resulting in a smooth planar polished surface.

[0009] In an alternate embodiment, the second step of the CMP process is performed utilizing a slurry according to this invention that is equally highly selective for removal of the barrier film and the dielectric layer but relatively much less selective for removal of the metal providing metal lines in the underlying dielectric layer. In this alternate embodiment, the method of this invention removes any scratches or defects in the underlying dielectric layer.

[0010] The method of this invention is applicable to any semiconductor substrate containing: a conductive metal (such as Cu, Al, W, Pt, Pd, Au, or Ir), a barrier or liner layer (such as Ta, TaN, Ti, or TiN), and an underlying dielectric layer (such as SiO2, TEOS, PSG, BPSG, or any low-k dielectric). Metal line widths, or features, on semiconductor substrates are often around 5 μ. However, new technologies are allowing the size of features to decrease to about 0.18 μ. Such newer, smaller features along with higher feature densities will require more sophisticated and specialized slurries. The method of this invention is suitably performed on a substrate with line widths of about 0.1, 0.13, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 to 0.5 μ. Suitably, the present method is performed on a substrate with line widths of less than 0.4 μ, suitably less than 0.3 μ, suitably less than 0.2 μ, and suitably about 0.18 μ.

[0011] In an embodiment, the method of this invention is used to polish a substrate containing a Cu metal layer, an underlying Ta or TaN barrier layer, and a SiO2 dielectric layer, by a two-step CMP process. In the first step, the Cu overburden layer is removed while removing minimal amounts of the Ta /TaN liner or SiO2. The slurry used in the first step of this process is any conventional slurry that is capable of removing the copper metal overburden layer covering the semiconductor structure, and has a very low rate of material removal on the Ta/TaN barrier film layer and underlying SiO2 layer. Typically, a conventional first step slurry has an acidic pH, and contains oxidizers that enhance the chemical-mechanical removal of Cu at accelerated rates (about 2,000 Angstroms per minute or greater). The second step is performed utilizing a selective slurry according to this invention whereby the barrier layer is removed without removing any remaining metal in metal lines and without removing the underlying dielectric material. In an alternate embodiment, the second step of the method of this invention is performed utilizing a slurry of this invention that removes the barrier layer and the dielectric layer without removing any remaining metal in the metal lines on the semiconductor substrate. This alternate embodiment is utilized to remove scratches and other defects in the dielectric layer to obtain a smooth polished substrate surface.

[0012] The slurry of this invention is alkaline with a pH in a range from about 7.1, 7.3, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 10.5 to 12. In an embodiment, the pH of the slurry is in a range from about 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2 to 9.5, preferably in a range from about 8.5, 8.6, 8.7, 8.9 to 9.0. In another embodiment, the pH of the slurry is in a range from about 9.5, 9.6, 9.7, 9.8, 9.9, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8 to 11.5, preferably in a range from about 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8 to 11.

[0013] The slurry of this invention contains submicron abrasive particles with a particle size up to about 50 nm. Preferably the abrasive particles are non-agglomerated and have a particle size from about 5, 10, 15, 20, 25, 30, 35, 40, 45 to 50 nm. In an embodiment, the submicron abrasive is silica, preferably, colloidal silica.

[0014] Generally, abrasive particles are present in the slurry of this invention at about 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25 to 30% by weight of the slurry. In an embodiment, the abrasive particles are present at about 5, 6, 7, 8, 9, to 9.5% by weight of the slurry, preferably at about 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, to 9% by weight of the slurry. In an alternate embodiment, the abrasive particles are present at about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25 to 30% by weight of the slurry, preferably at about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 to 20% by weight of the slurry.

[0015] In an embodiment, the slurry of this invention contains a complexing agent at about 0.5, 1, 10, 20, 30, 50, 75, 100, 125, 150, 175, 200, 300, 400, 500, 600, 700, 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500 to about 5,000 parts per million (ppm) by weight of the slurry, preferably at about 3,000, 3,100, 3,200, 3,300, 3,400, 3,500, 3,600, 3,700, 3,800, 3,900, 4,000, 4,500 to about 5,000 ppm by weight of the slurry. In an alternate embodiment, the complexing agent is present at about 10, 20, 30, 50, 75, 100, 125, 150, 175, 200, 300, 400 to 500 ppm by weight of the slurry, preferably at about 100, 125, 150, 175, 200 to 300 ppm by weight of the slurry.

[0016] In an embodiment, a corrosion inhibitor is added to the slurry of this invention at about 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 to 110 ppm by weight of the slurry, preferably at about 70, 75, 80, 85, 90, 95, 100, 105 to 110 ppm by weight of the slurry.

[0017] In an embodiment, an oxidizing agent is added to the slurry of this invention at about 1, 100, 500, 750, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000 to 15,000 ppm by weight of the slurry, preferably at about 5,000, 6,000, 7,000, 8,000, 9,000 to 10,000 ppm by weight of the slurry.

[0018] In an embodiment, the slurry of this invention contains an oxide suppressant present at about 1, 10, 20, 30, 40, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500 to 5,000 ppm by weight of the slurry, preferably at about 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, 2,000, 2,100, 2,200, 2,300, 2,400, to 2,500 ppm by weight of the slurry.

[0019] In an embodiment, the slurry of this invention contains chloride ions at about 0.01, 0.15, 0.2, 0.25, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 150, 175 to 200 ppm by weight of the slurry, more preferably at about 50, 75, 100, 125 to 150 ppm by weight of the slurry.

[0020] In an embodiment, the slurry of this invention contains a biocide present at about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 to 200 ppm by weight of the slurry, preferably at about 90, 100, 110 to 150 ppm by weight of the slurry.

[0021] The method of this invention utilizes a two-step CMP process for polishing a semiconductor substrate containing a conducting metal layer, a dielectric layer, and a barrier film or layer between the two. In the first step of the CMP process, the metal layer is removed from the substrate without removing significant amounts of either the barrier film or the underlying dielectric layer. In the second step of the CMP process, the barrier layer is removed selectively utilizing a slurry of this invention without removing the dielectric material or the metal of the metal lines in the underlying dielectric layer. In an alternate embodiment, the second step of the CMP process is performed utilizing a slurry according to this invention that is equally highly selective for removal of the barrier film and the dielectric layer but relatively less selective for removal of the metal providing metal lines in the underlying dielectric layer. In this alternate embodiment, the method of this invention removes any scratches or defects in the dielectric layer. The second polishing step is performed at an alkaline pH since the barrier metal removal rate is enhanced in the alkaline range. Typically, barrier metal removal rates above 1000 Angstroms per minute are desired during the second polishing step with relatively low dielectric and metal removal rates. Second-step polishing slurries that are basic and contain fumed silica are disclosed in U.S. application Ser. No. 09/420,682 filed Oct. 19, 1999, which is herein incorporated by reference.

[0022] Abrasives used in CMP slurries include alumina, silica, ceria, germania, titania, zirconia, diamond, boron nitride, boron carbide, silicon carbide and combinations thereof. Preferably, the slurry used in the method of this invention contains abrasive colloidal silica particles. As disclosed in U.S. application Ser. No. 09/439,461 filed Nov. 15, 1999, slurries comprised of colloidal silica particles with a primary particle size of about 10 to about 50 nanometers and a surface area of about 40 to about 600 m2/g provide high selectivity for removal of the barrier layer versus the dielectric layer. U.S. application Ser. No. 09/439,461 is herein incorporated by reference.

[0023] The abrasive used in the slurry of this invention has a Zeta Potential of negative (20 millivolts or greater) at the pH of use, i.e. pH>7. Zeta Potential is a measure of surface charge density of abrasive particles in dispersion in an aqueous solution of alkaline pH, i.e. pH>7. A more negative Zeta Potential value, typically about −70 millivolts to about −20 millivolts is indicative of a better dispersed slurry with none to extremely low levels of agglomeration of abrasive particles.

[0024] Typical dielectric materials used in composite semiconductor substrates include SiO2, TEOS, phosphosilicate glass (PSG), boron phosphosilicate glass (BPSG), or a low-k dielectric. Low-k dielectrics include porous silica, organic low-k dielectrics such as fluoro polymers and copolymers. Suppression of the dielectric layer removal rate is achieved through passivation of the dielectric layer surface. U.S. Pat. No. 5,614,444, “Method of Using Additives with Silica-Based Slurries to Enhance Selectivity in Metal CMP,” teaches an additive comprising at least one polar and one apolar component to suppress oxide removal. However, the patent claims the necessity of both a polar and an apolar group to be present. U.S. Pat. No. 5,391,258 and U.S. Pat. No. 5,738,800 teach the use of various compounds to suppress the rate of dielectric removal during chemical-mechanical polishing of semiconductor substrates and are herein incorporated by reference for all useful purposes. U.S. Pat. No. 5,770,103 teaches the use of mono-, di-, or tri-substituted phenols for removing a titanium barrier layer from a semiconductor substrate and is herein incorporated by reference for all useful purposes.

[0025] As disclosed in U.S. application Ser. No. 09/329,225 filed Jun. 10, 1999, polishing compositions (i.e. slurries) containing an organic polymer with a degree of polymerization of 3 and a molecular weight greater than 10,000 provide a selectivity between the metal and the dielectric layer in excess of 20:1. Exemplary organic polymers for use as oxide suppressants in the slurry of this invention include but are not limited to poly vinyl alcohol, polyvinyl pyrrolidone, polymethyl methacrylate, poly formaldehyde, poly ethylene glycol and polymethacrylic acid. U.S. application Ser. No. 09/329,225 is herein incorporated by reference.

[0026] A complexing agent is added to the slurry of this invention to increase the solubility of metal residuals on the semiconductor substrate at the start of the second CMP polishing step and the barrier metal during the remainder of the second CMP polishing step. U.S. application Ser. No. 09/329,225 provides additional details on the mechanism of interaction of complexing agents with metal atoms and a list of compounds for use as complexing agents. Exemplary complexing agents for use in the polishing composition of this invention include acetic acid, citric acid, ethyl acetoacetate, glycolic acid, lactic acid, malic acid, oxalic acid, salicylic acid, sodium diethyl dithiocarbamate, succinic acid, tartaric acid, thioglycolic acid, glycine, alanine, aspartic acid, ethylene diamine, trimethylene diamine, malonic acid, gluteric acid, 3-hydroxybutyric acid, propionic acid, phthalic acid, isophthalic acid, 3-hydroxy salicylic acid, 3,5-dihydroxy salicylic acid, gallic acid, gluconic acid, pyrocatechol, pyrogallol, gallic acid, tannic acid and salts thereof. Preferably, the complexing agent used in the slurry of this invention is citric acid.

[0027] In an embodiment, the polishing composition of this invention contains a choride salt. Chloride ions are highly mobile species that bond to the semiconductor substrate being polished at high surface energy sites such as edges and defects to minimize the local surface energy. Attainment of a uniform surface energy greatly minimizes localized non-uniform processes and variations in the surface of the semiconductor substrate being polished.

[0028] Often oxidizing agents, such as hydrogen peroxide, are added to CMP slurries so that any metal in the substrate being polished is converted to an oxide during the CMP process thereby enhancing metal removal rates. A general review of this art is provided by F. Kaufman et al., J. Electrochem. Soc., vol. 138, p. 3460, 1991, incorporated by reference herein. Common oxidizing agents used in slurries are nitrates, iodates, chlorates, perchlorates, chlorites, sulfates, persulfates, peroxides, ozonated water and oxygenated water. Oxidizing agents are typically used in CMP slurries at about 0.01% (1,000 ppm by weight of the slurry) to about 7% (7,000 ppm by weight of the slurry) by weight of the slurry. An oxidizing agent is used in the slurry of this invention to remove metal residuals from the substrate surface and to enhance barrier layer metal removal rates. Preferably, hydrogen peroxide is used as the oxidizing agent in the slurry of this invention.

[0029] Corrosion inhibitors are also added to the slurry of this invention to prevent static etching of metal in the semiconductor substrate. Corrosion inhibitors are typically effective at concentrations in a range from about 0.001% (100 ppm) to about 4% (40,000 ppm) by weight of the slurry. Suitable corrosion inhibitors for use in the slurry of this invention include benzotriazole (BTA), mercaptobenzotriazole (MBT), tolyltriazole and other inhibitors typically used with the metal present in the semiconductor substrate being polished. Preferably, the corrosion inhibitor used in the slurry of this invention is benzotriazole.

[0030] Biocides are added to the slurry of this invention to prevent bacterial and fungal growth. An exemplary biocide being Neolone™ Microbicide (major ingredients: 2-methyl-4-isothiazolin-3-one and propylene glycol) available from Rohm and Haas Company, Philadelphia, Pa. Further information, pertaining to compounds that are suitable for use as biocides in the polishing composition of this invention, is found in US Utility Application filed on Feb. 2, 2001 (awaiting a filing receipt/Serial No. from the US PTO) which claims the benefit of US Provisional Patent Application Serial No. 60/182,960 filed on Feb. 16, 2000 which is incorporated herein by reference.

[0031] The ionic strength of the slurry of this invention is adjusted through the use of agents such as acids, bases and salts. Exemplary agents include ammonium hydroxide, ammonium chloride, ammonium bromide, ammonium acetate, ammonium sulfate, citric acid, etc. A suitable ionic strength is necessary to prevent agglomeration of abrasive particles in the slurry of this invention. A suitable range of ionic strength in the context of this invention is from about 0.01M to 10 M. A lower ionic strength, up to about 0.01M, is desired in an embodiment of the slurry of this invention having a high abrasive content from about 8 to 30% by weight of the slurry.

[0032] Various embodiments of this invention are illustrated in the following examples.

EXAMPLE 1

[0033] Method 1 in Table 1 refers to a second step method trial that was performed utilizing a slurry of this invention and shows high barrier removal rates with low metal and dielectric removal rates. Method 2 in Table 1 refers to a second step method trial that was performed utilizing a slurry of this invention, and shows high barrier removal rates while metal removal rates are moderate, between high (about 400 A/min) and low (about 150 A/min), with a low dielectric removal rate (<250 A/min).

TABLE 1
(Å = Angstroms)
TaN RR
Method (A/min) Ta RR (Å/min) Cu RR (Å/min) SiO2RR (Å/min)
1 >700 >400 <150 <250
2 >700 >400 <150-400 <250

[0034] In each method trial, a Ta removal rate above 400 Å/min and a TaN removal rate above 700 Å/min was observed. The two methods trials of Table 1 resulted in good planarity without significant dishing or erosion. The method trials utilized a slurry, according to this invention, highly selective to the barrier film (illustrated by high removal rates of Ta or TaN) and least selective to the metal and the dielectric layer, to provide the first method trial with desired minimized removal rates of both Cu and SiO2. The removal rates of Ta or TaN were maximized (>700 Å/min) with a minimized lower removal rate of Cu (<150 Å/min) and SiO2 (<250 Å/min).

[0035] With proper application of the slurry of this invention, semiconductor substrates can be polished with low observed dishing or recess of the interconnect structures (metal lines), in particular Cu, as well as low erosion of the underlying dielectric layer (i.e., SiO2). For example, the second step slurry can be selected according to this invention to compensate for any dishing resulting from the first step, by selecting a slurry with an increased selectivity to SiO2 which removes the SiO2 to the level of the Cu interconnect structures that have undergone dishing during the first step polishing.

EXAMPLE 2

[0036] Polishing of 6″ wafers containing Cu, TaN, and SiO2 (TEOS) films was performed on a WESTECH 372U polisher (available from IPEC/Planar). An IC1000 XY-grooved primary polishing pad, a Politex Regular Embossed secondary polishing pad, and a DF200 carrier film were used (all available from Rodel, Inc.). A TBW 100 Grit Diamond conditioner was employed. The IC grooved pad was mounted on the primary platen of the polishing machine and 20 precondition sweeps were carried out with deionized (DI) water to precondition the polishing pad. The conditioning parameters for the primary polishing pad were a downforce (DF) of 7 psi, 3 platen sweeps (post with DI water), 70 rpm platen speed, and 75 rpm disk speed. The Politex pad was mounted to the secondary table and preconditioned with a 6″ stiff bristle hand brush and DI water with 8 scrapes and 8 brushes performed manually. The following conditions were used during the polishing tests depending on the semiconductor substrate being polished:

TABLE 2
Polishing Test Conditions
Parameter First Step Second Step
Time (seconds) 60 10
DF (psi) 2 0.5
Back Pressure (psi) 1 0
DF Ramp (sec) 5 5
Carrier (rpm) 60 40
Table (rpm) 60 40
Slurry Flow (ml/min) 150 0
Rinse Off On
# polar measurement site map on the CDE and SM-300. Edge exclusion was 10 mm for Cu and 10 for TaN and TEOS.

[0037]

TABLE 3
Slurry Formulations
Colloidal
Particle Silica (wt
Slurry1 Diameter % of
Tested CA BTA (nm) slurry) pH
1 0.192 0.1 12 8 to 9 8.0
2 0.192 0.1 12 8 to 9 8.5
3 0.192 0.1 12 8 to 9 9
4 0.192 0.1 12 8 to 9 9.5
5 0.192 0.1 12 8 to 9 10
6 0.192 0.1 12 8 to 9 10.5

[0038] The slurry formulations listed in Table 3 were utilized to polish 6″ wafers containing Cu, TaN, and SiO2(TEOS). The metal, barrier and dielectric removal rates are summarized in Table 4, along with calculated selectivity ratios based on the observed removal rates.

TABLE 4
Removal Rates and Selectivity Ratios
SiO2 Selectivity Selectivity
Slurry (TEOS) Ratio Ratio
Tested Cu RR TaN RR RR (TaN:Cu) (TaN:TEOS)
1 55 983 220 17.9:1 4.5:1
2 84 1260 245   15:1 5.1:1
3 86 1411 140 16.4:1 10.1:1 
4 106 1126 175 10.6:1 6.4:1
5 123 1189 187  9.7:1 6.4:1
6 194 1305 156  6.7:1 8.4:1

[0039] Slurry formulations, A and B, of this invention are provided in Table 5, with suitable and preferred ranges for various additives, in % or ppm by weight by the slurry.

TABLE 5
Slurry Formulations of This Invention
Preferred Preferred
Additive A Range for A B Range for B
pH ≧7 10-11 ≧7 8.5-9.5
Colloidal ≦30 10-20 ≦30 8-9
Silica (%)
Complexing ≦500 100-300 ≦5,000 3,000-5,000
Agent (ppm)
Corrosion ≦110  70-110 ≦110  70-110
Inhibitor
Oxidizing ≦15,000  5,000-10,000
Agent (ppm)
Chloride Salt ≦200  50-150
(ppm)
Oxide ≦5,000 1,000-2,500
Suppressant
Biocide (ppm) ≦200  90-150 ≦200  90-150

[0040] Although preferred embodiments are disclosed, other embodiments and modifications of this invention are intended to be covered by the spirit and scope of the appended claims.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6783432 *Jun 4, 2001Aug 31, 2004Applied Materials Inc.Additives for pressure sensitive polishing compositions
US6786944Apr 14, 2003Sep 7, 2004Jsr CorporationFor use in micro isolating step or a planarizing step of an inter layer dielectric in production of semiconductor devices
US6916742Feb 27, 2003Jul 12, 2005Rohm And Haas Electronic Materials Cmp Holdings, Inc.Modular barrier removal polishing slurry
US7144816 *Mar 12, 2004Dec 5, 2006Intel CorporationPolysilicon opening polish
US7241725Sep 25, 2003Jul 10, 2007Rohm And Haas Electronic Materials Cmp Holdings, Inc.comprising imine compounds and hydrazine compounds; for polishing tantalum-containing barrier; abrasive free
US7291280 *Dec 28, 2004Nov 6, 2007Rohm And Haas Electronic Materials Cmp Holdings, Inc.Multi-step methods for chemical mechanical polishing silicon dioxide and silicon nitride
US7294575 *Jan 5, 2004Nov 13, 2007United Microelectronics Corp.Chemical mechanical polishing process for forming shallow trench isolation structure
US7300480Sep 25, 2003Nov 27, 2007Rohm And Haas Electronic Materials Cmp Holdings, Inc.Comprises oxidizer (hydrogen peroxide), inhibitor of nonferrous metal, abrasive, complexing agent, imine derivatives (acetamidine hydrochloride), hydrazine derivatives (carbohydrazide), and water; for use with polyurethane polishing pads; for semiconductor substrates
US7381647 *Apr 21, 2005Jun 3, 2008Micron Technology, Inc.Methods and systems for planarizing microelectronic devices with Ge-Se-Ag layers
US7491252Mar 25, 2003Feb 17, 2009Rohm And Haas Electronic Materials Cmp Holdings, Inc.Tantalum barrier removal solution
US7659975 *Sep 19, 2006Feb 9, 2010Kla-Tencor Technologies Corp.Methods and systems for inspection of a wafer or setting up an inspection process
US8304345Jun 9, 2009Nov 6, 2012SoitecGermanium layer polishing
US8763428 *Mar 16, 2007Jul 1, 2014Hoya CorporationMethod for producing glass substrate for magnetic disk and method for manufacturing magnetic disk
US20090158775 *Mar 16, 2007Jun 25, 2009Hoya CorporationMethod For Producing Glass Substrate For Magnetic Disk And Method For Manufacturing Magnetic Disk
US20100086864 *Dec 11, 2009Apr 8, 2010Asahi Glass Company, LimitedMethod of polishing glass substrate
US20100102268 *Nov 9, 2007Apr 29, 2010Evonik Degussa GmbhDispersion comprising cerium oxide and colloidal silicon dioxide
US20100307068 *Dec 1, 2008Dec 9, 2010Evonik Degussa GmbhDispersion comprising cerium oxide and colloidal silicon dioxide
EP1357161A2 *Apr 17, 2003Oct 29, 2003JSR CorporationAqueous dispersion for chemical mechanical polishing
WO2006133249A2 *Jun 6, 2006Dec 14, 2006Advanced Tech MaterialsIntegrated chemical mechanical polishing composition and process for single platen processing
WO2010001028A1 *Jun 9, 2009Jan 7, 2010S.O.I.Tec Silicon On Insulator TechnologiesGermanium layer polishing
WO2010037265A1 *Sep 25, 2009Apr 8, 2010Anji Microelectronics (Shanghai) Co., LtdChemical-mechanical polishing liquid
Classifications
U.S. Classification451/57, 257/E21.304, 257/E21.244
International ClassificationH01L21/3105, C09G1/02, H01L21/321
Cooperative ClassificationC09G1/02, H01L21/31053, H01L21/3212
European ClassificationH01L21/321P2, C09G1/02, H01L21/3105B2
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