Cleaning agent composition comprising an alkylamide solvent and a fluorine-containing quaternary ammonium salt

Abstract

A cleaning agent composition for use in removing an adhesive residue, characterized in that the composition contains a quaternary ammonium salt and a composition solvent including a first organic solvent and a second organic solvent; the first organic solvent is an amide derivative represented by formula (Z) (wherein R.sup.0 represents an ethyl group, a propyl group, or an isopropyl group; and each of R.sup.A and R.sup.B represents a C1 to C4 alkyl group); the second organic solvent is a non-amide organic solvent other than the amide derivative; and the composition has a water content less than 4.0 mass %. ##STR00001##

Claims

1. A cleaning agent composition for use in removing an adhesive residue, the composition comprising a quaternary ammonium salt and a composition solvent including a first organic solvent and a second organic solvent; the first organic solvent is an amide derivative represented by formula (Z): ##STR00021## wherein R.sup.0 represents an ethyl group, a propyl group, or an isopropyl group; and each of R.sup.A and R.sup.B represents a C1 to C4 alkyl group; the second organic solvent is a non-amide organic solvent other than the amide derivative; the quaternary ammonium salt includes a fluorine-containing quaternary ammonium salt; and the composition has a water content less than 4.0 mass %.

2. The cleaning agent composition according to claim 1, wherein the amide derivative includes at least one species selected from the group consisting of N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide.

3. The cleaning agent composition according to claim 2, wherein the amide derivative includes at least one species selected from the group consisting of N,N-dimethylpropionamide, N,N-diethylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N,N-dimethylisobutyramide, and N,N-diethylisobutyramide.

4. The cleaning agent composition according to claim 3, wherein the amide derivative includes at least one species selected from the group consisting of N,N-dimethylpropionamide and N,N-dimethylisobutyramide.

5. The cleaning agent composition according to claim 1, wherein the fluorine-containing quaternary ammonium salt includes a tetra(hydrocarbyl)ammonium fluoride.

6. The cleaning agent composition according to claim 5, wherein the tetra(hydrocarbyl)ammonium fluoride includes at least one species selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.

7. The cleaning agent composition according to claim 1, wherein the second organic solvent includes at least one species selected from the group consisting of an alkylene glycol dialkyl ether, an aromatic hydrocarbon compound, and a ring-structure-having ether compound.

8. The cleaning agent composition according to claim 1, wherein the composition solvent is formed only of an organic solvent.

9. The cleaning agent composition according to claim 1, wherein the composition solvent has an amide derivative content of 30 to 90 mass %.

10. The cleaning agent composition according to claim 1, which has a water content less than 3.0 mass %.

11. The cleaning agent composition according to claim 10, which has a water content less than 2.0 mass %.

12. The cleaning agent composition according to claim 11, which has a water content less than 1.0 mass %.

13. A cleaning method, comprising removing an adhesive residue remaining on a substrate by use of the cleaning agent composition as recited in claim 1.

14. A method for producing a processed semiconductor substrate, the method comprising: producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer formed from an adhesive composition; processing the semiconductor substrate of the produced laminate; separating the semiconductor substrate after processing; and removing an adhesive residue remaining on the separated substrate with a cleaning agent composition, wherein the cleaning agent composition as recited in claim 1 is used as the cleaning agent composition.

Description

EXAMPLES

(1) The present invention will next be described in detail by way of Examples and Comparative Examples, which should not be construed as limiting the invention thereto. The apparatuses employed in the present invention are as follows.

(2) (1) Agitator: Planetary centrifugal mixer ARE-500 (product of Thinky Corporation)

(3) (2) Viscometer: Rotary viscometer TVE-22H (product of Toki Sangyo Co., Ltd)

(4) (3) Agitator: Mix Roter Variable 1-1186-12 (product of As One Corporation)

(5) (4) Agitator H: Heating Rocking Mixer HRM-1 (product of As One Corporation)

(6) (5) Contact-type film thickness meter: Wafer thickness meter WT-425 (product of Tokyo Seimitsu Co., Ltd.)

(7) [1] Preparation of Adhesive Compositions

Preparation Example 1

(8) To a 600-mL agitation container dedicated for a planetary centrifugal mixer, there were added a base polymer formed of linear-chain polydimethylsiloxane having vinyl groups (viscosity: 200 mPa.Math.s) and an MQ resin having vinyl groups (product of WACKER Chemie AG) (a1) (150 g), linear-chain polydimethylsiloxane having Si—H groups (viscosity: 100 mPa.Math.s) (product of WACKER Chemie AG) (a2) (15.81 g), and 1-ethynyl-1-cyclohexanol (product of WACKER Chemie AG) (A3) (0.17 g), and the resultant mixture was agitated by means of a planetary centrifugal mixer for 5 minutes.

(9) Separately, a platinum catalyst (product of WACKER Chemie AG) (A2) (0.33 g) and linear-chain polydimethylsiloxane having vinyl groups (viscosity: 1,000 mPa.Math.s) (product of WACKER Chemie AG) (a1) (9.98 g) were added to a 50-mL screw tube, and the contents were agitated for 5 minutes by means of a planetary centrifugal mixer. A portion (0.52 g) of the thus-agitated mixture was added to the above mixture, and the resultant mixture was agitated for 5 minutes by means of a planetary centrifugal mixer. Finally, the product mixture was filtered through a nylon filter (300 mesh), to thereby prepare an adhesive composition having a viscosity of 9,900 mPa.Math.s as determined by means of a rotary viscometer.

Preparation Example 2

(10) To a 600-mL agitation container dedicated for a planetary centrifugal mixer, a base polymer formed of an MQ resin having vinyl groups (product of WACKER Chemie AG) (a1) (95 g), p-menthane (product of Nippon Terpene Chemicals, Inc.) (93.4 g) serving as a solvent, and 1,1-diphenyl-2-propyn-1-ol (product of Tokyo Chemical Industry Co., Ltd.) (A3) (0.41 g) were added, and the resultant mixture was agitated for 5 minutes by means of a planetary centrifugal mixer.

(11) To the thus-prepared mixture, there were added linear-chain polydimethylsiloxane having Si—H groups (viscosity: 100 mPa.Math.s) (product of WACKER Chemie AG) (a2), linear-chain polydimethylsiloxane having vinyl groups (viscosity: 200 mPa.Math.s) (product of WACKER Chemie AG) (a1) (29.5 g), polyorganosiloxane (polydimethylsiloxane, viscosity: 1,000,000 mm.sup.2/s) (AK1000000, product of WACKER Chemie AG) (B), and 1-ethynyl-1-cyclohexanol (product of WACKER Chemie AG) (A3) (0.41 g), and the resultant mixture was further agitated for 5 minutes by means of a planetary centrifugal mixer.

(12) Separately, a platinum catalyst (product of WACKER Chemie AG) (A2) (0.20 g) and linear-chain polydimethylsiloxane having vinyl groups (viscosity: 1,000 mPa.Math.s) (product of WACKER Chemie AG) (a1) (17.7 g) were added to a 50-mL screw tube, and the contents were agitated for 5 minutes by means of a planetary centrifugal mixer. A portion (14.9 g) of the thus-agitated mixture was added to the above mixture, and the resultant mixture was further agitated for 5 minutes by means of the planetary centrifugal mixer. Finally, the product mixture was filtered through a nylon filter (300 mesh), to thereby prepare an adhesive composition having a viscosity of 4,600 mPa.Math.s as determined by means of a rotary viscometer.

(13) [2] Preparation of Cleaning Agent Compositions

Example 1

(14) N,N-Dimethylpropionamide (14.25 g) and 1,2-diethoxyethane (14.25 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.50 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 2

(15) N,N-Dimethylpropionamide (11.18 g) and tetrahydrofuran (11.18 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.18 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 3

(16) N,N-Dimethylpropionamide (20.08 g) and tetrahydropyran (20.08 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (2.11 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 4

(17) N,N-Dimethylpropionamide (17.81 g) and cyclopentyl methyl ether (17.81 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.88 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 5

(18) N,N-Dimethylpropionamide (10.25 g) and mesitylene (10.25 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.08 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 6

(19) N,N-Dimethylisobutylamide (12.52 g) and 1,2-diethoxyethane (12.52 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 7

(20) N,N-Dimethylisobutylamide (12.52 g) and tetrahydrofuran (12.52 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 8

(21) N,N-Dimethylisobutylamide (12.52 g) and tetrahydropyran (12.52 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 9

(22) N,N-Dimethylisobutylamide (12.52 g) and cyclopentyl methyl ether (12.52 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Example 10

(23) N,N-Dimethylisobutylamide (12.52 g) and mesitylene (12.52 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Comparative Example 1

(24) N,N-Dimethylacetamide (9.50 g) was added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (0.50 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Comparative Example 2

(25) 1,3-Dimethyl-2-imidazolidinone (95 g) was added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (5 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Comparative Example 3

(26) N-Methyl-2-pyrrolidone (dehydrated) (95 g) was added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (5 g), and the thus-obtained mixture was agitated, to thereby prepare a cleaning agent composition.

Comparative Example 4

(27) N,N-Dimethylpropionamide (product of Tokyo Chemical Industry Co., Ltd.) (47.5 g) and tetrahydrofuran (product of Kanto Chemical Co., Inc.) (47.5 g) were added to tetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co., Inc.) (5 g), and the thus-obtained mixture was agitated. Subsequently, pure water (5 g) was further added thereto, and the resultant mixture was further agitated, to thereby prepare a cleaning agent composition.

Comparative Example 5

(28) A commercial silicone cleaner “KSR-1” (product of Kanto Chemical Co., Inc.) was used as a cleaning liquid composition.

(29) [3] Evaluation of Performance of Cleaning Agent Compositions

(30) Generally, the excellent cleaning agent composition is required to exhibit such a high cleaning speed that it can dissolve an adhesive residue immediately after contact therewith, and excellent persistency in cleaning speed. Thus, the following tests were performed. When a tested cleaning agent composition exhibits both higher cleaning speed and more excellent persistency in cleaning performance, more effective cleaning can be expected.

(31) [3-1] Determination of Water Content

(32) The water content of each cleaning agent composition was determined by means of a Karl Fischer moisture meter CA-200 (product of Mitsubishi Chemical Analytech).

(33) [3-2] Determination of Etching Rate

(34) Each of the prepared cleaning agent compositions was evaluated in terms of cleaning speed by measuring the etching rate. Specifically, the adhesive composition obtained in Preparation Example 1 was applied onto a 12-inch silicon wafer by means of a spin coater so as to adjust the coating thickness to 100 μm, and cured at 150° C. for 15 minutes, then 190° C. for 10 minutes. The thus-coated wafer was cut into square chips (4 cm×4 cm), and the layer (film) thickness of one of the chips was measured by means of a contact-type film thickness meter. Thereafter, the chip was placed in a 9-cm Petri dish made of stainless steel, and the cleaning agent composition (7 mL) was added, followed by closing the dish. The closed Petri dish was placed on Agitator H, and the chip was cleaned through agitation at 23° C. for 5 minutes. After cleaning, the chip was removed and washed with isopropanol and pure water, and then dry-baked at 150° C. for 1 minute. The layer (film) thickness of the chip was measured again by means of the contact-type film thickness meter. Through dividing the decrease in layer (film) thickness after cleaning by the cleaning time, etching rate [μm/min] was calculated. The etching rate was employed as an index for cleaning performance. Table 1 shows the results.

(35) [3-3] Evaluation of Dissolution Property

(36) For determining the persistency in cleaning performance of each of the prepared cleaning agent compositions, the following adhesive dissolution test was conducted. Specifically, the adhesive composition obtained in Preparation Example 2 was applied onto a 12-inch silicon wafer by means of a spin coater and cured at 120° C. for 1.5 minutes and 200° C. for 10 minutes. Subsequently, the cured adhesive composition was scraped off by use of a cutter blade from the 12-inch wafer. A portion (1 g) of the cured adhesive composition was transferred to and weighed in a 9-mL screw tube, and then the cleaning agent composition (2 g) was added to the tube. The dissolution state of the cured product was observed at 23° C. When the cured product was completely dissolved within 1 to 2 hours, the state was rated as “Excellent.” When the cured product was completely dissolved within 2 to 12 hours, the state was rated as “Very good.” When the cured product was substantially dissolved within 12 to 24 hours, the state was rated as “Good.” When the cured product was substantially not dissolved over a long period of time, the state was rated as “Bad.” Table 1 shows the results.

(37) TABLE-US-00001 TABLE 1 Water content Etching rate Dissolution (%) [μm/min] test Ex. 1 0.67 10.8 Excellent Ex. 2 0.65 14.72 Excellent Ex. 3 0.67 10.62 Excellent Ex. 4 0.63 11.51 Excellent Ex. 5 0.63 8.72 Excellent Ex. 6 0.63 10.28 Excellent Ex. 7 0.78 13.85 Excellent Ex. 8 0.73 9.93 Excellent Ex. 9 0.71 10.26 Excellent Ex. 10 0.72 8.32 Very good Comp. Ex. 1 — 8 Bad Comp. Ex. 2 — 4 Bad Comp. Ex. 3 — 5.1 Bad Comp. Ex. 4 5.36 0.69 — Comp. Ex. 5 — 2.3 Bad

(38) As shown in Table 1, the cleaning agent compositions, each containing a quaternary ammonium salt (i.e., tetrabutylammonium fluoride), an amide derivative represented by formula (Z) (i.e., N,N-dimethylpropionamide), and a non-amide solvent, fell within the scope of the present invention and were found to exhibit excellent cleaning speed and favorable persistency in cleaning performance, as compared with those of cleaning agent compositions each containing a solvent formed only of an amide derivative not represented by formula (Z) and a cleaning agent composition containing intentionally added water.