This application claims priority to Korean Application Serial No. 2004-35495, filed May 19, 2004, the disclosure of which is hereby incorporated herein by reference.
The present invention relates to methods of forming integrated circuit devices and, more particularly, to methods of cleaning and polishing metal layers on integrated circuit substrates.
Integrated circuit chips frequently utilize multiple levels of patterned metallization and conductive plugs to provide electrical interconnects between active devices within a semiconductor substrate. To achieve low resistance interconnects, tungsten metal layers have been deposited and patterned as electrodes (e.g., gate electrodes), conductive plugs and metal wiring layers. The processing of tungsten and other metal layers frequently requires the use of cleaning compositions to remove polymer and other residues from the metal layers. Such residues may remain after conventional processing steps such as resist ashing. Unfortunately, the use of cleaning compositions that remove residues from metal layers may lead to metal layer corrosion from chemical etchants.
Cleaning compositions configured to inhibit metal corrosion during semiconductor wafer processing have been developed. One such cleaning composition is disclosed in U.S. Pat. No. 6,117,795 to Pasch. This cleaning composition includes using a corrosion inhibiting compound, such as an azole compound, during post-etch cleaning. Corrosion inhibiting compounds may also be used to inhibit corrosion of metal patterns during chemical-mechanical polishing (CMP). Such compounds, which include at least one of sulfur containing compounds, phosphorus containing compounds and azoles, are disclosed in U.S. Pat. Nos. 6,068,879 and 6,383,414 to Pasch. U.S. Pat. No. 6,482,750 to Yokoi also discloses corrosion inhibiting compounds that are suitable for processing tungsten metal layers and U.S. Pat. No. 6,194,366 to Naghshineh et al. discloses corrosion inhibiting compounds that are suitable for processing copper containing microelectronic substrates. Notwithstanding these cleaning and corrosion-inhibiting compositions for semiconductor wafer processing, there continues to be a need for compositions having enhanced cleaning and corrosion-inhibiting characteristics.
Embodiments of the present invention include corrosion-inhibiting cleaning compositions for semiconductor wafer processing. These compositions include an aqueous admixture of at least one metal etchant, first and second different oxide etchants, an azole and water. The azole acts as a chelating agent that binds with and inhibits corrosion of metal layers being cleaned. The azole may be selected from a group consisting of triazole, benzotriazole, imidazole, tetrazole, thiazole, oxazole and pyrazole and combinations thereof. More preferably, the azole is either triazole, benzotriazole or imidazole. A quantity of the azole in the aqueous admixture is in a range from about 0.1 wt % to about 5 wt %.
In additional embodiments of the invention, the first oxide etchant is sulfuric acid, the second oxide etchant is a fluoride and the metal etchant is hydrogen peroxide. A quantity of the metal etchant in the aqueous admixture is in a range from about 0.5 wt % to about 5 wt %. This level of metal etchant is sufficient to have good metal polymer removal rate but not too high to provide metal layer over-etch. A quantity of the sulfuric acid in the aqueous admixture may also be set within a range from about 1 wt % to about 10 wt % and a quantity of the fluoride in the aqueous admixture may be set within a range from about 0.01 wt % to about 1 wt %.
Additional embodiments of the invention include a corrosion-inhibiting cleaning solution that consists essentially of a metal etchant, first and second oxide etchants, a metal chelating agent and water. In these embodiments, the metal etchant can be hydrogen peroxide at a concentration in a range from about 0.5 wt % to about 5 wt % and the first oxide etchant can be sulfuric acid at a concentration in a range from about 1 wt % to about 10 wt %. The second oxide etchant can be hydrogen fluoride at a concentration in a range from about 0.01 wt % to about 1 wt % and the metal chelating agent can be an azole at a concentration in a range from about 0.1 wt % to about 5 wt %.
Still further embodiments of the invention include methods of forming integrated circuit devices by forming a gate oxide layer on an integrated circuit substrate and forming a tungsten metal layer on the gate oxide layer. The tungsten metal layer and the gate oxide layer are patterned to define a tungsten-based insulated gate electrode. The patterned tungsten metal layer is exposed to a cleaning solution containing a metal etchant, at least first and second oxide etchants, a corrosion-inhibiting azole and deionized water. The metal etchant can be a peroxide, the first oxide etchant can be sulfuric acid and the second oxide etchant can be hydrogen fluoride. Methods of forming integrated circuit devices also include methods of forming memory devices by forming an interlayer dielectric layer on an integrated circuit substrate and forming an interconnect opening in the interlayer dielectric layer. The interconnect opening is filled with a conductive plug and then a bit line node is formed on the conductive plug. The bit line node is exposed to a cleaning solution including a metal etchant, at least first and second oxide etchants, a corrosion-inhibiting azole and deionized water.
The present invention now will be described more fully herein with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout.
Methods of cleaning metal layers on semiconductor substrates include cleaning tungsten-based gate electrodes. As illustrated by
Additional methods of cleaning metal layers on semiconductor substrates may also include cleaning metal-based bit lines in semiconductor memory devices. As illustrated by
The above-described corrosion-inhibiting cleaning solutions include an aqueous admixture of at least one metal etchant, first and second different oxide etchants, an azole and deionized water. The azole acts as a chelating agent that binds with and inhibits corrosion of metal layers (e.g., tungsten metal layers) being cleaned. The azole may be selected from a group consisting of triazole, benzotriazole, imidazole, tetrazole, thiazole, oxazole and pyrazole and combinations thereof. More preferably, the azole is either triazole, benzotriazole or imidazole. A quantity of the azole in the aqueous admixture is in a range from about 0.1 wt % to about 5 wt %. In some embodiments of the present invention, the first oxide etchant is sulfuric acid (H2SO4) and the second oxide etchant is a fluoride. The fluoride may be hydrogen fluoride, ammonium fluoride, tetramethyammonium fluoride, ammonium hydrogen fluoride, fluroroboric acid and tetramethylammonium tetrafluoroborate. The metal etchant is a peroxide. The peroxide may be hydrogen peroxide, ozone, peroxosulfuric acid, peroxoboratic acid, peroxophosphoric acid, peracetic acid, perbenzoic acid and perphthalic acid. A quantity of the metal etchant in the aqueous admixture is in a range from about 0.5 wt % to about 5 wt %. This level of metal etchant is sufficient to have good metal polymer removal rate but not too high to provide metal layer over-etch. A quantity of the sulfuric acid in the aqueous admixture may also be set within a range from about 1 wt % to about 10 wt % and a quantity of the fluoride in the aqueous admixture may be set within a range from about 0.01 wt % to about 1 wt %. TABLE 1 illustrates the compositions in a plurality of example cleaning solutions containing equal amounts of sulfuric acid (H2SO4), hydrogen peroxide (H2O2) and hydrogen fluoride (HF), with different quantities of deionized water (H2O) and different quantities of different azole compounds. In particular, example solutions 1-5 contain triazole, examples 6-10 contain benzotriazole and example solutions 11-15 contain imidazole. Example solutions 16-18 contain tetrazole, thiazole and oxazole, respectively. The constituents of a comparison cleaning solution (Comparison 1), which contains no azole compound, is also illustrated by TABLE 1.
TABLE 2 illustrates the BPSG (borophosphosilicate glass) etch rates that were achieved with a plurality of the cleaning solutions illustrated by TABLE 1. In particular, TABLE 2 illustrates a highest oxide etch rate for the comparison solution (Compare 1), which contains no corrosion-inhibiting agent. TABLE 2 also illustrates how higher concentrations of the corrosion-inhibiting agent (triazole, benzotriazole and imidazole) result in lower oxide etch rates. For example, the oxide etch rate using the 3rd example solution (2 wt % triazole) is less than the oxide etch rate for 1st example solution (0.1 wt % triazole); the oxide etch rate for the 8th example solution (2 wt % benzotriazole) is less than the oxide etch rate for the 6th example solution (0.1 wt % benzotriazole); and the oxide etch rate for the 13th example solution (2 wt % imidazole) is less than the oxide etch rate for the 11th example solution (0.1 wt % imidazole).
TABLE 3 illustrates the cleaning ability of a plurality of the cleaning solutions illustrated by TABLE 1. In particular, TABLE 3 illustrates better cleaning ability for example solutions 3, 8 and 13, which include 2 wt % of a respective azole compound, relative to example solutions 1, 6 and 11, which only include 0.1 wt % of an azole compound. TABLE 3 also illustrates that poor cleaning ability is present in the comparison solution (Compare 1), which is devoid of an azole compound.
TABLE 4 illustrates the tungsten etch rates associated with the cleaning solutions illustrated by TABLE 1. In particular, TABLE 4 illustrates that for a given one of the most preferred azole compounds (triazole, benzotriazole and imidazole), the tungsten etch rate decreases (to some saturated level) as the quantity of azole compound is increased. TABLE 4 also illustrates a highest tungsten etch rate for the comparison solution (Compare 1), which is devoid of an azole compound.
Analysis of additional example solutions demonstrates that using less than 0.01 wt % of the corrosion-inhibiting agent (azole) results in poor corrosion inhibition and that a degree of corrosion inhibition saturates at levels greater than about 10 wt %. A more preferred range for the corrosion-inhibiting agent extends from about 0.1 wt % to about 5 wt %. This analysis also demonstrates that using less than 0.05 wt % of peroxide results in poor polymer removal ability and using greater than 10 wt % of peroxide results in metal layer over-etch. A more preferred range for the peroxide extends from about 0.5 wt % of about 5 wt %. The analysis further demonstrates that using less than 0.001 wt % of fluoride results in poor oxide polymer removal ability and using greater than 2 wt % of fluoride results in oxide layer over-etch and lifting of metal patterns. A more preferred range for the fluoride extends from about 0.01 wt % to about 1 wt %.
In the drawings and specification, there have been disclosed typical preferred embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being set forth in the following claims.
Number | Date | Country | Kind |
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2004-35495 | May 2004 | KR | national |
This application is related to U.S. application Ser. No. ______, filed Dec. 23, 2004, entitled Corrosion-Inhibiting Cleaning Compositions for Metal Layers and Patterns on Semiconductor Substrates (Attorney Docket No. 5649-1361).