SULFURIC ACID COMPOSITION HAVING LOW SURFACE TENSION

Abstract: A surfactant of the general formula: R¹SO²NR²C₂H₄OA (wherein R¹ represents a fluoroalkyl group, R² represents H or a lower alkyl group, and A represents H or SO₂H) is added to a cleaning liquid comprising sulfuric acid or sulfuric acid-hydrogen peroxide, used in the semiconductor industry or the like, to lower the surface tension, thus improving the wettability and enhancing the cleaning effect.

Description: This invention relates to a low surface tension sulfuric acid composition adapted for use in semiconductor manufacturing processes. More particularly, this invention relates to a low surface tension sulfuric acid composition containing specific fluoroalkylsulfonamides. In semiconductor manufacturing processes, sulfuric acid is used, either alone or in combination with other substances, for different purposes, for example, for cleaning silicon substrates, removing resist films or formulating etching solutions. The increased density of integrated circuits nowadays has inevitably led to micronization of patterns and complication of the trench structure (i.e. fine deep grooves) . Use of conventional sulfuric acid under these condition gives rise to inconveniences such as difficult permeation into trenches and insufficient cleaning, due to high surface tension and poor wettability. Accordingly it is now strongly desired to develop a sulfuric acid composition with low surface tension and good wettability. EP-A2-0 182 306 discloses an etchant composition comprising (a) cerium (IV) salt, (b) a nonionic or anionic fluorine-containing surfactant, (c) water, and (d) optionally at least one acid component which could be, among other acids, sulfuric acid. EP-A3-0 276 774 provides a storable semiconductor cleaning solution consisting essentially of sulfuric acid at a concentration of 30% to 70% and hydrogen peroxide at a concentration of 1% to 20% by weight, preferably also containing a pentavalent phosphorous sequestrant and tin ions. The use of fluoroalkylsulfonamide surfactants is not disclosed. Although use of surface-active agent is expected to lower the surface tension of sulfuric acid, only very limited types of surface-active agent are stable in hot sulfuric acid, in particular, in highly oxidizing sulfuric acid/hydrogen peroxide liquid mixtures, with the result that it is in fact extremely difficult to find such surface-active agents that can be put into practical use. As a result of research on a variety of surface-active agents, the inventors have found that specific ones amongst many fluorine-type surface-active agents are stable in hot liquid mixtures of sulfuric acid and hydrogen peroxide and capable of lowering the surface tension. The present invention bases itself on these findings. The object of the present invention is to provide a sulfuric acid composition which has low surface tension and good wettability as well as excellent thermo-stability and oxidation resistance. The present invention is concerned in particular with such low surface tension sulfuric acid composition adapted for use in semiconductor manufacturing processes. The present invention thus provides a low surface tension sulfuric acid composition characterized in that said composition consists essentially of sulfuric acid and a surface-active agent consisting of a fluoroalkylsulfonamide compound of the general formula: R 1 SO 2 NR 2 C 2 H 4 OA wherein R 1 stands for a fluoroalkyl group, R 2 for a hydrogen atom or a lower alkyl group and A for H or SO 3 H. The present invention will now be described below in more detail. The fluoroalkylsulfonamide compounds used in the composition of the present invention are readily available in that they are described for example in U.S. patent 2,803,656 and also commercially available. These sulfonamide compounds, not containing any metal such as sodium, potassium or calcium, exert no adverse effects on semiconductors. The low surface tension sulfuric acid composition of the present invention has an appropriate amount of a sulfonamide compound of formula (I) above added to and dissolved in the sulfuric acid. The amount of the above-mentioned sulfonamides of formula (I) added is in the range of 0.001 - 0.1%, more preferably 0.005 - 0.05% by weight relative to the sulfuric acid. Addition of amounts lower than the lower limit mentioned above was found to give no advantageous effects. Use of amounts higher than the upper limit mentioned above is meaningless because it produces no better effects. The low surface tension sulfuric acid composition of the present invention has a surface tension as low as about one fourth that of conventional sulfuric acid, and a smaller contact angle relative to the silicon substrate, and can easily permeate into fine grooves of the trench structure, thereby significantly enhancing its cleaning effect. Furthermore, it is stable and retains its properties even in the form of liquid mixture with hydrogen peroxide, i.e. even when exposed to highly oxidizing condition. Examples of the present invention will now be shown below together with comparative examples. Examples 1 - 4: Surface Tension Two different compositions were prepared by incorporating into 89% by weight sulfuric acid 0.005% and 0.01% by weight, respectively, of fluoroalkylsulfonamide (of formula (I) wherein R 1 stands for C 8 F 17 , R 2 for C 3 H 7 and A for H or SO 3 H) as fluorine-type surface-active agent, and the surface tension at 20°C of each composition was measured by the Wilhelmy method. Measurement was also made, for comparison, for cases where no fluorine-type surface-active agent was added and where two different types (shown in Table 1 as F1 and F2) of commercially available fluorine-type surface-active agent were added. The results are shown in Table 1. Fluorine-type Surface-active Agent Surface Tension [·10 -3 N/m; or (dyn/cm)] Type Amount Added Example 1 A=H 0.005% 16.4 2 do. 0.01% 16.1 3 A=SO 3 H 0.005% 22.1 4 do. 0.01% 16.5 Comparative Example 1 None None 64.0 2 0.01% 45.6 3 0.01% 51.2 Examples 5 - 7: Stability A test composition was prepared by mixing sulfuric acid having added thereto and dissolved therein 0.01% by weight of fluoroalkylsulfonamide (of formula (I) wherein R 1 is C 8 F 17 , R 2 is C 3 H 7 and A is H) as fluorine-type surface-active agent with 30% by weight aqueous hydrogen peroxide at a ratio by volume of 4:1. The composition was kept heated at the different temperatures of 80°C, 100°C and 130°C. Samples were taken for each temperature after 30, 60, 90 and 120 minutes and their surface tension at 25°C was measured by the wilhelmy method. Measurement was also made, for comparison, for cases where no fluorine-type surface-active agent was added and where two different types (shown in Table 2 as F3 and F4) of commercially available fluorine-type surface-active agent were used. The results are shown in Table 2. Fluorine-type Surface-active Agent Temperature (°C) Change on standing of surface tension [·10 -3 N/m; or (dyn/cm)] 0 min. 30 min. 60 min. 90 min. 120 min. Example 5 Compound (I) 80 14.8 15.1 15.0 15.2 15.3 6 do. 100 15.6 15.4 15.2 15.5 14.8 7 do. 130 15.2 15.4 21.8 18.1 25.5 Comparative Example 4 None 130 65.6 71.7 70.8 71.8 67.6 5 130 20.5 41.6 41.7 60.4 56.0 6 130 20.1 44.0 61.1 59.3 57.5 As is apparent from the results obtained in Examples and Comparative Examples, the low surface tension sulfuric acid composition according to the present invention has excellent properties also in respect of resistance to heating and oxidation. Examples 8 - 12: Cleaning Effect (1) A positive-type photoresist OFPR®-800 (manufactured by Tokyo Oka) was applied onto a bare silicon wafer substrate at a thickness of 1.3 µm and the wafer was subjected to pre-baking at 90°C for 10 minutes followed by pcst-baking at 150°C for 30 minutes. A test composition was prepared by mixing sulfuric acid having added thereto and dissolved therein 0.01% by weight of fluoroalkylsulfonamide (of formula (I) wherein R 1 is C 8 F 17 , R 2 is C 3 H 7 and A is H) as fluorine-type surface-active agent with 30% by weight aqueous hydrogen peroxide at a ratio by volume of 4:1. This composition was used to remove the post-baking resist. The removement was performed for 5, 10 and 15 minutes at 80°C, and for 5 and 10 minutes at 100°C. After removing the resist, the silicon wafer was rinsed with water for 5 minutes, blown with N 2 gas, and checked for particles and haze thereon using a Surface Contamination Analyzer, Surfscan® 4500 (TENCOR INSTRUMENT). Removing test was also conducted, for comparison, for cases where no fluorine-type surface-active agent was added in order to check such silicon wafers for particles and haze thereon. The results are shown in Table 3. Fluorine-type Surface-active Agent Removing Condition Particles (≥0.24 µm) (The Number/Wafer) Haze Area (%) Liquid Temperature Time Example 8 Compound [I] 80°C 5 min. 244 0 9 do. 80°C 10 min. 303 1 10 do. 80°C 15 min. 600 1 11 do. 100°C 5 min. 491 1 12 do. 100°C 10 min. 261 0 Comparative Example 7 None 80°C 5 min. 35805 36 8 do. 80°C 10 min. 34270 63 9 do. 80°C 15 min. 10190 22 10 do. 100°C 5 min. 2133 3 11 do. 100°C 10 min. 1837 7 Examples 13 and 14: Cleaning Effect (2) The silicon substrate with silicon oxide film was treated under the same conditions as in Example 3 to form resist film thereon. A test composition was prepared using the same conditions as in Example 3 to remove the resist. The removement was performed at 80°C and 100°C for 5 minutes. After removing the resist, the silicon wafer was rinsed with water for 5 minutes, spin-dried and checked for particles and haze thereon using Surface Contamination Analyzer, Surfscan® 4500 (TENCOR INSTRUMENT). Removing test was also conducted, for comparison, for cases where no fluorine-type surface-active agent was added in order to check such silicon wafers for particles and haze thereon. The results are shown in Table 4. Fluorine-type Surface-active Agent Removing Condition Particles (≥0.24 µm) (The Number/Wafer) Haze Area (%) Liquid Temperature Time Example 13 Compound [I] 80°C 5 min. 133 0 14 do. 100°C 5 min. 157 0 Comparative Example 12 None 80°C 5 min. ≥14430 84 13 do. 100°C 5 min. 856 1 As is apparent from the results obtained in Examples and Comparative Examples, the low surface tension sulfuric acid composition according to the present invention shows an extremely high cleaning effect upon photoresist removing.

Claims: A low surface tension sulfuric acid composition characterized in that said composition consists essentially of sulfuric acid and a surface-active agent consisting of a fluoroalkylsulfonamide compound of the general formula R 1 SO 2 NR 2 C 2 H 4 OA wherein R 1 stands for a fluoroalkyl group, R 2 for a hydrogen atom or a lower alkyl group and A for H or SO 3 H. A low surface tension sulfuric acid composition as claimed in claim 1, wherein the amount of the fluoroalkylsulfonamide compound added is 0.001 - 0.1% by weight relative to the sulfuric acid. A low surface tension sulfuric acid composition as claimed in claim 1 or 2, wherein the sulfuric acid is in the form of liquid mixture with hydrogen peroxide.

Inventors: HARA HISAO, MORI K, SHIHOYA T, HARA, HISAO, MORI, K, SHIHOYA, T, MORI, K KANTO KAGAKU KK CHUOKENKYUSHO-NAI
Applicants: KANTO KAGAKU, NISSAN CHEMICAL IND LTD, KANTO KAGAKU KABUSHIKI KAISHA, NISSAN CHEMICAL INDUSTRIES LTD.
Application year: 1990
Main classification: C23F1
IPC codes: H01L21, C11D1, C09D9, C23F1, C23G1, C09K13