# Patent

## Title
Cleaning solution and damascene process using the same

## Abstract

A cleaning solution is provided. The cleaning solution includes an aliphatic polycarboxylic acid, a chain sulfonic acid substantially less than 4 wt % and an amine containing buffer agent.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation-in-part (CIP) application of U.S. application Ser. No. 13/293,282, filed Nov. 10, 2011, which is a continuation application of U.S. application Ser. No. 12/830,566, filed Jul. 6, 2010. The entirety of each of the above-mentioned patent applications are hereby incorporated by reference herein and made a part of this specification.


FIELD OF THE INVENTION
The present invention relates to a cleaning solution and a damascene process using the same.
BACKGROUND OF THE INVENTION
A Dual damascene process is a technology widely applied in a semiconductor process. To reduce the RC delay caused by a parasitic capacitance, the current dual damascene process adopts an ultra low-k (ULK) material as a dielectric layer. Further, with the minimization of the device, a titanium nitride (TiN) hard mask layer is formed on the dielectric layer, and then the required patterns are precisely transferred to the dielectric layer by utilizing different etching selectivities of the TiN hard mask layer and the dielectric layer.
The pattern transfer is usually achieved by a dry etching process. However, during the dry etching process, the reactive gases passing into a reaction chamber may also undergo a polymerization reaction. Therefore, the organic polymer formed from the polymerization reaction is deposited on the surface of the device. Moreover, the reactive gases used for etching the dielectric layer are mostly fluorine-containing gases. These fluorine-containing gases may react with the TiN hard mask layer to produce titanium fluoride (TiFx) on the surface of the device, and thus, a profile change of the device, abnormal conduction, leakage or short circuiting between film layers is thereby caused, and the reliability of the device is accordingly reduced.
The effect produced by the polymer and titanium fluoride residues is particularly significant in the deep sub-micro fabrication process. Further, upon the study thereof, the post-etch cleaning process may affect the conduction ability of the device by etching the exposed metal lines below the dual damascene opening, thereby causing a profile change by swelling the dielectric layer with the cleaning solution, or leading to an increase in the dielectric constant. Therefore, the post-etch cleaning process has become a very important step in the duel damascene process.
SUMMARY OF THE INVENTION
The present invention provides a cleaning solution to effectively remove the residues containing a plurality of residual species.
The present further invention provides a damascene process to reduce the surface damage (copper loss) of the conductive layer, avoid damages of the dielectric layer or an increase in the dielectric constant, or prevent bridges forming between the dual damascene structures, and thus, the reliability of the semiconductor device is enhanced.
The present invention provides a cleaning solution including a fluorine containing compound, an inorganic acid, a chelating agent containing a carboxylic group and water for balance. The content of the fluorine containing compound is 0.01-0.5 wt % of the cleaning solution. The content of the inorganic acid is 1-5 wt % of the cleaning solution.
According to an embodiment of the present invention, the inorganic acid includes sulfuric acid (H2SO4) or hydrochloric acid (HCl).
According to an embodiment of the present invention, the chelating agent containing the carboxylic group includes oxalic acid.
According to an embodiment of the present invention, the cleaning solution consists of 0.01-0.5 wt % of the fluorine containing compound, 1-5 wt % of the inorganic acid, the chelating agent containing the carboxylic group, and water for balance.
According to an embodiment of the present invention, the fluorine containing compound includes hydrofluoric acid (HF) and ammonium fluoride (NH4F).
According to an embodiment of the present invention, the cleaning solution further includes ethylenediaminetetraacetic acid (EDTA).
According to an embodiment of the present invention, the cleaning solution further includes triethanolamine (TEA).
The present invention further provides a damascene process. The process includes the following steps. A substrate having a conductive layer thereon is provided. A dielectric layer and a metal hard mask layer are sequentially formed on the substrate. The metal hard mask layer and the dielectric layer are sequentially etched so as to form an opening exposing the conductive layer. A post-etch cleaning process using a cleaning solution is performed. The cleaning solution includes 0.01-0.5 wt % of a fluorine containing compound, 1-5 wt % of an inorganic acid, a chelating agent containing a carboxylic group, and water for balance.
According to an embodiment of the present invention, the inorganic acid includes sulfuric acid (H2SO4) or hydrochloric acid (HCl).
According to an embodiment of the present invention, the chelating agent containing the carboxylic group includes oxalic acid.
According to an embodiment of the present invention, the cleaning solution consists of 0.01-0.5 wt % of the fluorine containing compound, 1-5 wt % of the inorganic acid, the chelating agent containing the carboxylic group, and water for balance.
According to an embodiment of the present invention, the opening includes a dual damascene opening, a via opening or a contact opening.
According to an embodiment of the present invention, the metal hard mask layer includes titanium, titanium nitride, tantalum, tantalum nitride, tungsten, tungsten nitride, or a combination thereof.
According to an embodiment of the present invention, the damascene process further includes the step of forming a buffer layer after the step of forming the dielectric layer and before the step of forming the metal hard mask layer and forming a cap layer after the step of forming the metal hard mask layer, wherein the cap layer includes silicon carbide, silicon nitride or silicon oxynitride.
According to an embodiment of the present invention, the buffer layer includes silicon oxide or silicon oxynitride.
According to an embodiment of the present invention, the fluorine containing compound includes hydrofluoric acid (HF) and ammonium fluoride (NH4F).
According to an embodiment of the present invention, hydrofluoric acid (HF) is 0.01-0.1 wt %.
According to an embodiment of the present invention, ammonium fluoride (NH4F) is 0.05-0.5 wt %.
According to an embodiment of the present invention, the cleaning solution further includes ethylenediaminetetraacetic acid (EDTA).
According to an embodiment of the present invention, the cleaning solution further includes triethanolamine (TEA).
The present invention provides a cleaning solution comprises an aliphatic polycarboxylic acid, a chain sulfonic acid substantially less than 4 wt %; and an amine containing buffer agent.
According to an embodiment of the present invention, the aliphatic polycarboxylic acid comprises an alkyl polycarboxylic acid selected from a group consisting of tartaric acid, maleic acid, malic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, maleic anhydride, citric acid, adipic acid, azelaic acid, sebacic acid, 1,13-tridecanedioic acid and the arbitrary combinations thereof.
According to an embodiment of the present invention, the aliphatic polycarboxylic acid is an aromatic polycarboxylic acid comprising phthalic acid or isophthalic acid.
According to an embodiment of the present invention, the chain sulfonic acid is selected from a group consisting of mesylic acid, esylic acid, tosylic acid, taurine and the arbitrary combinations thereof.
According to an embodiment of the present invention, the amine containing buffer agent comprising Triethanolamine (TEA), Monoethanolamine (MEA), Diethanolamine (DEA), Methyl Diethanolamine (MDEA) or monoisopropanolamine (MIPA).
According to an embodiment of the present invention, the cleaning solution further comprises an oxidizing agent selected from a group consisting of H2O2, Fe(NO3)3, KIO3, KMnO4, HNO3, NH4ClO2, NH4ClO3, NH4IO3, NH4BO3, NH4ClO4, NH4IO3, (NH4)2S2O8, (N(CH3)4)ClO2, (N(CH3)4)ClO3, (N(CH3)4)IO3, (N(CH3)4)BO3, (N(CH3)4)ClO4, (N(CH3)4)IO4, (N(CH3)4)S2O2, (CO(NH2)2)H2O2, CH3(CO)OOH and the arbitrary combinations thereof.
According to an embodiment of the present invention, the cleaning solution further comprises a co-solvent selected from a group consisting of ethylene glycol, propylene glycol (PG), neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol, formamide, acetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide (DMSO), y-butyrolactone, propylene carbonate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, butyl carbitol, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether and the arbitrary combinations thereof.
According to an embodiment of the present invention, the cleaning solution further comprises a chelating agent selected from a group consisting of oxalic acid, 1,2,4-triazole (TAZ), benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles, naphthotriazole, thyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, ben-50 zothiazole, tritolyl phosphate, indiazole, ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′,N′tetraacetic acid (CDTA), 2-mercaptobenzoimidizole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dime and the arbitrary combinations thereof.
According to an embodiment of the present invention, the cleaning solution further comprises a weak acid selected from a group consisting of acetic acid, lactic acid, glyconic acid, gluconic acid, ascorbic acid, benzoic acid and the arbitrary combinations thereof.
According to an embodiment of the present invention, the cleaning solution further comprises HF or NH4F.
According to an embodiment of the present invention, the cleaning solution has a pH substantially less than or equal to 7.
The present invention further provides a damascene process. The process includes the following steps. A substrate having a conductive layer thereon is provided. A dielectric layer and a metal hard mask layer are sequentially formed on the substrate. The metal hard mask layer and the dielectric layer are sequentially etched so as to form an opening exposing the conductive layer. A post-etch cleaning process using a cleaning solution is performed. The cleaning solution includes an aliphatic polycarboxylic acid, a chain sulfonic acid substantially less than 4 wt % and an amine containing buffer agent.
The present invention further provides a cleaning method. The cleaning method includes the following steps. A cleaning solution comprising an aliphatic polycarboxylic acid, a chain sulfonic acid substantially less than 4 wt %, and an amine containing buffer agent is firstly provided, and the cleaning solution is applied onto a surface of a semiconductor substrate by a liner cleaning tool or a spin/spry tool.



BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed description and accompanying drawings, in which:
FIGS. 1A to 1E schematically illustrate cross-sectional views of a damascene process according to an embodiment of the present invention.



DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of preferred embodiments of this invention are presented herein for purpose of illustration and description only. It is not intended to be exhaustive or to be limited to the precise form disclosed.
An embodiment of the present invention provides a cleaning solution. The cleaning solution includes hydrofluoric acid (HF), an inorganic acid, ammonium fluoride (NH4F), a chelating agent containing a carboxylic group, triethanolamine (TEA), ethylenediaminetetraacetic acid (EDTA) and water.
In the cleaning solution, the content of hydrofluoric acid is 0.01-0.1 wt %. The content of the strong acid is 1-5 wt %. The strong acid is an inorganic acid with pKa value less than −1.74, such as sulfuric acid (H7SO4) or hydrochloric acid (HCl). The content of ammonium fluoride is 0.05-0.5 wt %. The chelating agent containing the carboxylic group includes oxalic acid, for example. The rest or balance of the cleaning solution is water. The water is de-ionized (DI) water. In an embodiment, the cleaning solution consists of hydrofluoric acid, the strong acid, ammonium fluoride, the chelating agent containing the carboxylic group, triethanolamine, ethylenediaminetetraacetic acid and water, and other components are not included.
The cleaning solution can be applied in a damascene process. A dual damascene process is taken as an example in the following.
FIGS. 1A to 1E schematically illustrate cross-sectional views of a damascene process according to an embodiment of the present invention.
Referring to FIG. 1A, a substrate 10 having a conductive layer 20 and a cap layer 30 sequentially formed thereon is provided. The conductive layer 20 includes Cu, CuAl alloy or CuAlSi alloy, for example. The cap layer 30 includes silicon nitride, silicon oxynitirde or silicon carbide, for example. Thereafter, a dielectric layer 40, a buffer layer 50, a metal hard mask layer 60, and a cap layer 65 are sequentially formed on the cap layer 30. The dielectric layer 40 includes an ultra low-k (ULK) material, for example. The ultra low-k material is a material with a dielectric constant of 2.5 ̃2.7 or lower. The ultra low-k material includes Black Diamond (Trademark of AMAT), or Dense ULK (Trademark of NOVELLUS) for example. The material of the buffer layer 50 is different from that of the dielectric layer 40. The buffer layer 50 includes silicon oxide or silicon oxynitride, for example. The metal hard mask layer 60 includes metal or metal nitride, such as titanium, titanium nitride, tantalum, tantalum nitride, tungsten, tungsten nitride, or a combination thereof. The cap layer 65 is adapted to protect the metal hard mask layer 60 and includes silicon nitride, silicon oxide, silicon oxynitirde or silicon carbide, for example.
Referring to FIG. 1B, a dual damascene opening 70 is formed in the cap layer 65, the metal hard mask layer 60, the buffer layer 50, the dielectric layer 40 and the cap layer 30 by photolithography and etching processes. The bottom of the dual damascene opening 70 exposes the conductive layer 20. The dual damascene opening 70 is formed by a laterally extending trench 72 disposed at an upper position or location thereof and a vertically extending via opening 74 disposed at a lower position or location thereof. The method of forming the dual damascene opening 70 includes forming the via opening 74 prior to forming the trench 72, or alternatively, forming the trench 72 prior to forming the via opening 74. The etching gases for the etching process usually include fluorine, so as to remove the metal such as refractory metal in the metal hard mask layer 60. During the etching process, polymer is usually formed on the sidewall of the dual damascene opening 70. Moreover, in the etching process, the copper loss problem occurs due to the formation of copper oxide (CuOx) or CuOxFy on the surface of the conductive layer 20 (e.g. copper layer) exposed by the dual damascene opening 70. Therefore, after the step of forming the dual damascene opening 70, the to-be-removed residual species include refractory metal, fluorine, oxygen, silicon, carbon and copper.
Referring to FIG. 1C, a chemical cleaning process 80 (or a post-etch cleaning process) is performed with the above-mentioned cleaning solution, so as to remove the residues on the substrate 10 as well as the damaged surface of the conductive layer 20. The cleaning solution consists of hydrofluoric acid, the strong acid, ammonium fluoride, the chelating agent containing the carboxylic group, triethanolamine, ethylenediaminetetraacetic acid and water, and other components are not included. The components and contents of the cleaning solution are described above, and the details are not iterated herein. The chemical cleaning process 80 can be performed at room temperature, such as 20 to 50° C., for example. The time period of the chemical cleaning process 80 is 60 to 120 seconds, for example.
Hydrofluoric acid, sulfuric acid and ammonium fluoride in the cleaning solution are configured for providing fluorine ions and adjusting the pH value. The chelating agent containing the carboxylic group, triethanolamine and ethylenediaminetetraacetic acid in the cleaning solution serve as a chelating agent, resolve the metal complexes in the aqueous solution, and stabilize the surface of the conductive layer to avoid re-oxidation of the conductive layer, and thus, they are regarded as a surface oxidation inhibitor.
In details, sulfuric acid in the cleaning solution hardly reacts with the dielectric layer 40, so that damages of the dielectric layer 40 do not occur. However, sulfuric acid can react with CuOx or CuOxFy on the surface of the conductive layer 20 to form water-soluble copper ions (Cu2+). The copper ions can chelate with the chelating agent containing the carboxylic group, so as to avoid copper loss caused by re-oxidation of the conductive layer 20. Further, sulfuric acid, hydrofluoric acid and ammonium fluoride in the cleaning solution are mixed to form SO3F−, which is a strong nucleophilic reagent to make the Cu−R bonds break and achieve the purpose of removing the residues.
However, the contents of the cleaning solution may be modified, for example, the chelating agent containing a carboxylic group (oxalic acid) may be replaced by other polycarboxylic acid, and the sulfuric acid (H2SO4) may be replaced by a sulfonic acid. In some other embodiments, the cleaning solution may comprises an aliphatic polycarboxylic acid, a chain sulfonic acid substantially less than 4 wt %, an amine containing buffer agent and water for balance. Besides, in the purpose for proving fluorine ion, the cleaning solution may optionally include HF or NH4F.
In some embodiments of the present invention, the aliphatic polycarboxylic acid comprises an alkyl polycarboxylic acid selected from a group consisting of tartaric acid, maleic acid, malic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, maleic anhydride, citric acid, adipic acid, azelaic acid, sebacic acid, 1,13-tridecanedioic acid and the arbitrary combinations thereof. In some other embodiments of the present invention, the aliphatic polycarboxylic acid is an aromatic polycarboxylic acid comprising phthalic acid or isophthalic acid. In the present embodiment, the cleaning solution comprises 2 wt % of 1,13-tridecanedioic acid.
The chain sulfonic acid is selected from a group consisting of mesylic acid, esylic acid, tosylic acid, taurine and the arbitrary combinations thereof. The amine containing buffer agent comprising Triethanolamine (TEA), Monoethanolamine (MEA), Diethanolamine (DEA), Methyl Diethanolamine (MDEA) or monoisopropanolamine (MIPA). In the present embodiment, the cleaning solution comprises 4 wt % of taurine substantially and 5 wt % of Methyl Diethanolamine (MDEA).
To enhance the cleaning performance, in some embodiment, the cleaning solution further comprises an oxidizing agent selected from a group consisting of H2O2, Fe(NO3)3, KIO3, KMnO4, HNO3, NH4ClO2, NH4ClO3, NH4IO3, NH4BO3, NH4ClO4, NH4IO3, (NH4)2S2O8, (N(CH3)4)ClO2, (N(CH3)4)ClO3, (N(CH3)4)IO3, (N(CH3)4)BO3, (N(CH3)4)ClO4, (N(CH3)4)IO4, (N(CH3)4)S2O8, (CO(NH2)2)H2O2, CH3(CO)OOH and the arbitrary combinations thereof. In the present embodiment, the cleaning solution comprises 8 wt % of (N(CH3)4)ClO2, (N(CH3)4)ClO3 and (N(CH3)4)ClO4.
The cleaning solution may further comprises a co-solvent selected from a group consisting of ethylene glycol, propylene glycol (PG), neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol, formamide, acetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide (DMSO), y-butyrolactone, propylene carbonate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, butyl carbitol, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether and the arbitrary combinations thereof.
In addition, the cleaning solution may further comprise other chelating agent and a weak acid. Wherein the chelating agent may be selected from a group consisting of oxalic acid, 1,2,4-triazole (TAZ), benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br or I), naphthotriazole, thyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, ben-50 zothiazole, tritolyl phosphate, indiazole, ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′,N′tetraacetic acid (CDTA), 2-mercaptobenzoimidizole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dime and the arbitrary combinations thereof; and the weak acid may be selected from a group consisting of acetic acid, lactic acid, glyconic acid, gluconic acid, ascorbic acid, benzoic acid and the arbitrary combinations thereof.
In the present embodiment, the cleaning solution has a pH substantially less than or equal to 7, more preferably about 4, and the cleaning process 80 is preferably performed at 30° C. ̃50° C., more preferably at 40° C. However, it should be appreciated that the optimal pH and the temperature for performing the chemical cleaning process 80 may be adjusted in accordance with the content of the cleaning solution. For example, the cleaning solution may further comprise H2O2, and the applicants found that the residues on the substrate 10 and the damaged surface of the conductive layer 20 may be efficiently removed, while the pH of the cleaning solution is maintained within a range from 7 to 9; as well as when the chemical cleaning process 80 is performed at a temperature substantially ranging from 30° C. to 50° C.
Referring to FIG. 1D, a cleaning process 90 is performed after the step of performing the chemical cleaning process 80. In an embodiment, the cleaning process 90 is performed immediately after the step of performing the chemical cleaning process 80, and no other processes between the cleaning process 90 and the chemical cleaning process 80 are present or performed. The cleaning process 90 is performed with DI water only, and no other components are used. The cleaning process 90 can be performed at room temperature, such as 20 to 30° C., for example. The time period of the cleaning process 90 is 30 to 90 seconds, for example. Thereafter, a baking process is performed. The temperature of the baking process is 200 to 300° C., and the time period of the same is 30 to 60 minutes, for example.
Referring to FIG. 1E, a conductive material (not shown) is formed on the cap layer 65 and the metal hard mask layer 60 filling in the dual damascene opening 70. The conductive material includes copper, for example. Thereafter, a chemical mechanical polishing (CMP) or an etching back process is performed to remove the conductive material on the cap layer 65 and the remaining conductive material 100 in the dual damascene opening 70. Afterwards, the cap layer 65, the metal hard mask layer 60, and the buffer layer 50 are removed.
The dual damascene process in the above-mentioned embodiment is provided for illustration purposes, and is not construed as limiting the present invention. The above-mentioned dual damascene opening can also be a via opening or a contact opening only. Therefore, the above-mentioned cleaning solution can be applied to a single damascene process.
Further, the cleaning solution is not limited to apply to a damascene process. The cleaning solution of the present invention can be applied to a semiconductor process with to-be-removed residual species that includes refractory metal, fluorine, oxygen, silicon, carbon and copper. For example, the cleaning solution set forth in the aforementioned embodiments can be applied to cleaning any surface of a semiconductor substrate by a liner cleaning tool or a spin/spray tool.
EXAMPLE
An ultra low-k dielectric layer, a silicon oxynitride layer and a titanium nitride layer are sequentially formed on a substrate having a copper layer and a carbide silicon nitride layer thereon. Thereafter, a photolithography process is performed and followed by a dry etching process with fluorine containing gases, so as to form a dual damascene opening. Afterwards, a chemical cleaning process is performed with the cleaning solution set forth in the aforementioned embodiments (e.g. 0.06 wt % of hydrofluoric acid, 3 wt % of sulfuric acid, 0.1 wt % of ammonia fluoride, 10 wt % of oxalic acid, 10 wt % of TEA, 0.2 wt % of EDTA and water for balance, but not limited), and then another cleaning process is performed immediately with DI water.
The result shows that the residues in the process can be effectively removed by performing the chemical cleaning process with the cleaning solution and followed by another cleaning process with DI water. Moreover, damages are not found on the surface of the dielectric layer or the copper layer, or an increase in the dielectric constant is not caused or resulted. Bridges are not observed between the formed dual damascene structures. Thus, the reliability of the semiconductor device can be accordingly enhanced.
Besides, since the cleaning solution set forth in some embodiments are aqueous solution and contain organic acid and buffer agent that is degradable by microorganisms, thus the cleaning solution may be more eco-friendly than the conventional cleaning solution in the art. Thus, the cleaning solution set forth in the aforementioned embodiments is preferably applied to cleaning any surface of a semiconductor substrate by a liner cleaning tool, e.g. Cleaner with Confined Chemical Cleaning, Trademark of Lam Research Corporation.
Comparative Examples 1 to 6
A dual damascene opening is formed by the method of the above-mentioned Example. Thereafter, a post-etch cleaning process is performed with different cleaning solutions including different components, and immediately followed by another cleaning process with DI water. The results are shown in Table 1.










TABLE 1







Components of cleaning solution
Results


















Comparative
10 wt % of oxalic acid, 0.1 wt % of
Copper surface


example 1
ammonia fluoride, 3 wt % of
damage



sulfuric acid, 0.06 wt % of



hydrofluoric acid and water for



balance


Comparative
10 wt % citric acid, 0.1 wt % of
Polymer residue


example 2
ammonia fluoride, 3 wt % of



sulfuric acid, 0.06 wt % of



hydrofluoric acid and water for



balance


Comparative
5 wt % of iminodiacetic acid
Polymer residue


example 3
(IDA), 0.1 wt % of ammonia
Dielectric layer



fluoride, 3 wt % of sulfuric acid,
damage



0.06 wt % of hydrofluoric acid and



water for balance


Comparative
10 wt % of oxalic acid, 0.2 wt % of
Copper surface


example 4
EDTA, 3 wt % of sulfuric acid,
damage Polymer



0.06 wt % of hydrofluoric acid and
residue



water for balance


Comparative
10 wt % of TEA, 0.1 wt % of
Copper surface


example 5
ammonia fluoride, 3 wt % of
damage



sulfuric acid, 0.06 wt % of



hydrofluoric acid and water for



balance


Comparative
5 wt % of iminodiacetic acid, 1 wt
Dielectric layer


example 6
% of NH4HF2, 3 wt % of sulfuric
damage Copper



acid, 0.06 wt % of hydrofluoric
surface damage



acid and water for balance









While the invention has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention needs not be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.

## Claims

1. A cleaning solution, comprising:
(a) an aliphatic polycarboxylic acid;
(b) a chain sulfonic acid substantially less than 4 wt %; and
(c) an amine containing buffer agent;
wherein the amine containing buffer agent comprising Triethanolamine (TEA), Monoethanolamine (MEA), Diethanolamine (DEA), Methyl Diethanolamine (MDEA) or monoisopropanolamine (MIPA).

2. The cleaning solution of claim 1, wherein the aliphatic polycarboxylic acid comprises an alkyl polycarboxylic acid selected from a group consisting of tartaric acid, maleic acid, malic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, maleic anhydride, citric acid, adipic acid, azelaic acid, sebacic acid, 1,13-tridecanedioic acid and the arbitrary combinations thereof.

3. The cleaning solution of claim 1, wherein the aliphatic polycarboxylic acid is an aromatic polycarboxylic acid comprising phthalic acid or isophthalic acid.

4. The cleaning solution of claim 1, wherein the chain sulfonic acid is selected from a group consisting of mesylic acid, esylic acid, tosylic acid, taurine and the arbitrary combinations thereof.

5. The cleaning solution of claim 1, further comprising an oxidizing agent selected from a group consisting of H2O2, Fe(NO3)3, KlO3, KMnO4, HNO3, NH4ClO2, NH4ClO3, NH4IO3, NH4BO3, NH4ClO4, NH4IO3, (NH4)2S2O8, (N(CH3)4)ClO2, (N(CH3)4)ClO3, (N(CH3)4)IO3, (N(CH3)4)BO3, (N(CH3)4)ClO4, (N(CH3)4)IO4, (N(CH3)4)S2O8, (CO(NH2)2)H2O2, CH3(CO)OOH and the arbitrary combinations thereof.

6. The cleaning solution of claim 1, further comprising a co-solvent selected from a group consisting of ethylene glycol, propylene glycol (PG), neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol, formamide, acetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide (DMSO), y-butyrolactone, propylene carbonate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, butyl carbitol, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether and the arbitrary combinations thereof.

7. The cleaning solution of claim 1, further comprising a chelating agent selected from a group consisting of oxalic acid, 1,2,4-triazole (TAZ), benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles, naphthotriazole, thyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, ben-50 zothiazole, tritolyl phosphate, indiazole, ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′,N′ tetraacetic acid (CDTA), 2-mercaptobenzoimidizole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dime and the arbitrary combinations thereof.

8. The cleaning solution of claim 1, further comprising a weak acid selected from a group consisting of acetic acid, lactic acid, glyconic acid, gluconic acid, ascorbic acid, benzoic acid and the arbitrary combinations thereof.

9. The cleaning solution of claim 1, further comprising HF or NH4F.

10. The cleaning solution of claim 1, wherein the cleaning solution has a pH substantially less than or equal to 7.

11. A cleaning method, comprising steps of applying the cleaning solution in accordance with claim 1 onto a surface of a semiconductor substrate by a liner cleaning tool or a spin/spray tool.

12. A damascene process, comprising:
providing a substrate having a conductive layer thereon;
sequentially forming a dielectric layer and a hard mask layer on the substrate;
sequentially etching the hard mask layer and the dielectric layer, so as to form an opening exposing the conductive layer; and
performing a post-etch cleaning process with a cleaning solution, wherein the cleaning solution comprises:
(a) an aliphatic polycarboxylic acid;
(b) a chain sulfonic acid substantially less than 4 wt %; and
(c) an amine containing buffer agent;
wherein the amine containing buffer agent comprising Triethanolamine (TEA), Monoethanolamine (MEA), Diethanolamine (DEA), Methyl Diethanolamine (MDEA) or monoisopropanolamine (MIPA).

13. The damascene process of claim 12, wherein the aliphatic polycarboxylic acid comprises an alkyl polycarboxylic acid selected from a group consisting of tartaric acid, maleic acid, malic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, maleic anhydride, citric acid, adipic acid, azelaic acid, sebacic acid, 1,13-tridecanedioic acid and the arbitrary combinations thereof.

14. The damascene process of claim 12, wherein the aliphatic polycarboxylic acid is an aromatic polycarboxylic acid comprising phthalic acid or isophthalic acid.

15. The damascene process of claim 12, wherein the chain sulfonic acid is selected from a group consisting of mesylic acid, esylic acid, tosylic acid, taurine and the arbitrary combinations thereof.

16. The damascene process of claim 12, wherein the cleaning solution further comprises an oxidizing agent selected from a group consisting of H2O2, Fe(NO3)3, KIO3, KMnO4, HNO3, NH4ClO2, NH4ClO3, NH4IO3, NH4BO3, NH4ClO4, NH4IO3, (NH4)2S2O8, (N(CH3)4)ClO2, (N(CH3)4)ClO3, (N(CH3)4)IO3, (N(CH3)4)BO3, (N(CH3)4)ClO4, (N(CH3)4)IO4, (N(CH3)4)S2O8, (CO(NH2)2)H2O2, CH3(CO)OOH and the arbitrary combinations thereof.

17. The damascene process of claim 12, wherein the cleaning solution further comprises a co-solvent selected from a group consisting of ethylene glycol, propylene glycol (PG), neopentyl glycol, 1,3-propanediol, diethyleneglycol, dipropyleneglycol, glycerol, formamide, acetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfoxide (DMSO), y-butyrolactone, propylene carbonate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, butyl carbitol, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether and the arbitrary combinations thereof.

18. The damascene process of claim 12, wherein the cleaning solution further comprises a chelating agent selected from a group consisting of oxalic acid, 1,2,4-triazole (TAZ), benzotriazole (BTA), tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles, naphthotriazole, thyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione, mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, ben-50 zothiazole, tritolyl phosphate, indiazole, ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N′,N′ tetraacetic acid (CDTA), 2-mercaptobenzoimidizole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dime and the arbitrary combinations thereof.

19. The damascene process of claim 12, wherein the cleaning solution further comprises a weak acid selected from a group consisting of acetic acid, lactic acid, glyconic acid, gluconic acid, ascorbic acid, benzoic acid and the arbitrary combinations thereof.

20. The damascene process of claim 12, wherein the cleaning solution further comprises HF or NH4F.

21. The damascene process of claim 12, wherein the cleaning solution has a pH substantially less than or equal to 7; and the post-etch cleaning process is performed at a temperature ranging from 30° C. to 50° C.