JP2002220598A - 1-hydroperfluorocycloalkanol-based detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent capable of being used with no problem in work environments without influencing adverse effects on the ecosystem on the earth. SOLUTION: This detergent comprises 1-hydroperfluorocycloalkanols such as 1-hydrodecafluorocyclohexanol, 1-hydrooctafluorocyclopentanol and 1- hydrododecafluorocycloheptanol as an essential ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent, and more particularly to a cleaning agent effective for cleaning a substrate or the like used in a semiconductor manufacturing process.

[0002]

2. Description of the Related Art Used for manufacturing substrates such as wafers used in the manufacture of semiconductors such as ICs and LSIs, substrates such as quartz substrates used as masks and reticles used in photolithography processes and their precursors, and pellicles. A glass substrate to be manufactured, and furthermore, a substrate used for manufacturing a stamper for an optical disk, and the like, need to be extremely cleanly cleaned due to their properties.

[0003] As a method for cleaning such a substrate, an ultrasonic cleaning method, a scrubbing method using a brush or the like, or a steam cleaning and drying method has hitherto been widely used. Further, as a cleaning agent used in the cleaning method, isopropyl alcohol, chlorofluorocarbons, CF ₃ CF ₂ CH ₂ OH and the like are known. Further, CF ₃ CH (OH) CF ₃ , CF ₃ CH (O
H) CF ₂ CF ₃ , (CF ₃ ) ₃ C (OH), (CF ₃ ) ₂ C
A cleaning agent using (OH) CH ₃ is also known (JP-A-6-346096).

[0004]

However, since isopropyl alcohol is flammable, there is a problem that special consideration must be given to the working environment of the washing process. It has also been pointed out that fluorocarbons such as chlorofluorocarbons, when released into the atmosphere, destroy the ozone layer in the stratosphere and, as a result, adversely affect ecosystems on the planet. Is regulated. Also, CF ₃ CF ₂ CH ₂
Since the hydroxyl group in OH is a primary hydroxyl group, there is a problem that cleaning properties are poor. Further, CF ₃ CH (OH) CF ₃ ,
CF ₃ CH (OH) CF ₂ CF ₃ , (CF ₃ ) ₃ C (O
H) and (CF ₃ ) ₂ C (OH) CH ₃ are compounds having a secondary hydroxyl group, but have the drawback that they are difficult to obtain.

An object of the present invention is to provide a cleaning agent which can be used without problems in the working environment and which does not adversely affect the ecosystem on the earth.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems. As a result, 1-hydroperfluorocycloalkanols are nonflammable and contain no chlorine atom, so that ozone They found that their contribution to global warming was small due to their short lifetime in the atmosphere without destroying the layers.

Further, 1-hydroperfluorocycloalkanols have an extremely polar hydroxyl group due to secondary alcohols having a perfluoroalkyl group, and are therefore excellent against ionic contaminants and fluxes. It was found to be a cleaning agent. That is, the present invention provides a detergent containing 1-hydroperfluorocycloalkanol as an essential component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The 1-hydroperfluorocycloalkanols of the present invention include those having 5 to 10 carbon atoms.
1-hydroperfluorocycloalkanol is particularly preferable, and in particular, 1-hydroperfluorocycloalkanol having 5 to 7 carbon atoms (ie, 1-hydrooctafluorocyclopentanol, 1-hydrodecafluorocyclohexanol, 1-hydrododecafluorocycloheptanol) Is preferred.

[0009] 1-Hydroperfluorocycloalkanols are non-flammable and therefore have no inconvenience in the working environment and are easy-to-use detergents. Further, 1-hydroperfluorocycloalkanols have a structure in which a fluorine atom is bonded to a carbon atom adjacent to a carbon atom to which a hydroxyl group is bonded, and the properties of the hydroxyl group are different from those of a normal alcoholic hydroxyl group. In addition, it is a compound that can exhibit high detergency to ionic substances and polar compounds.

The detergent of the present invention contains 1-hydroperfluorocycloalkanol as an essential component,
Preferred are those composed of only one or more 1-hydroperfluorocycloalkanols, or those composed of one or more 1-hydroperfluorocycloalkanols and one or more other solvents, particularly 1- It is preferable to consist of only one or more hydroperfluorocycloalkanols. The cleaning agent of the present invention may contain a compound that enhances the stability of the cleaning agent.

Examples of the other solvent include at least one selected from the group consisting of hydrocarbons, alcohols, ketones, ethers and esters, and alcohols are preferred. The amount of the other solvent contained in the detergent is preferably 40% or less, more preferably 20% or less, and further preferably 10% or less.

The hydrocarbons are preferably chain or cyclic saturated or unsaturated hydrocarbons having 5 to 15 carbon atoms, such as n-pentane, cyclopentane, n-hexane, cyclohexane and n-heptane. 5-7 hydrocarbons are particularly preferred.

The alcohols are alcohols other than 1-hydroperfluorocycloalkanols, and are preferably chain or cyclic saturated or unsaturated alcohols having 1 to 16 carbon atoms, such as methanol, ethanol,
n-propyl alcohol, isopropyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-
Pentanol, 2-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2- Methyl-
1-pentanol, 4-methyl-2-pentanol, 2
-Ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2
-Octanol, 2-ethyl-1-hexanol, 1-
Nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol,
Benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol,
3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, 2,6-dimethyl-4
-Heptanol, nonyl alcohol, tetradecyl alcohol and the like. More preferably, methanol,
It is an alkanol having 3 or less carbon atoms such as ethanol and isopropyl alcohol.

As the ketone, a chain or cyclic saturated or unsaturated ketone having 3 to 9 carbon atoms is preferable, and a ketone having 3 to 4 carbon atoms such as acetone and methyl ethyl ketone is particularly preferable.

As the ethers, chain or cyclic saturated or unsaturated ethers having 2 to 8 carbon atoms are preferable.
Ethers having 4 to 6 carbon atoms, such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, are particularly preferred.

As the esters, chain or cyclic saturated or unsaturated esters having 2 to 19 carbon atoms are preferable, and esters having 3 to 4 carbon atoms such as methyl acetate and ethyl acetate are particularly preferable.

The object to be cleaned with the cleaning agent of the present invention is not particularly limited as long as it is stable to 1-hydroperfluorocycloalkanols, and includes various objects to be cleaned. Among these, 1-hydroperfluorocycloalkanols are very effective as a cleaning agent for a substrate for a semiconductor because they can satisfactorily clean ionic contaminants and fluxes, and are preferred.

Examples of the object to be cleaned include glass, quartz, or those obtained by depositing chromium or the like on the surface thereof to form a coating, resin, or those having a circuit pattern or the like on the resin. Specific examples of the object to be cleaned include a substrate such as a wafer used in semiconductor manufacturing, a mask or reticle used in a photolithography process and a quartz substrate as a precursor thereof, and a glass substrate used in manufacturing a pellicle. And a substrate used for manufacturing a stamper for an optical disk.

The method of cleaning with the cleaning agent of the present invention is not particularly limited, and includes a method of immersing the object to be cleaned in the cleaning agent, a method of spraying the cleaning object on the object to be cleaned, and a method of cleaning the object to be cleaned in the vapor of the cleaning agent. A steam washing and drying method for drying after washing the surface of the object to be washed, and the like, is particularly preferable. In these methods, when the melting point of 1-hydroperfluorocycloalkanol used as a cleaning agent is higher than room temperature, it is used after being heated to the melting point or higher.

As a specific method for performing the cleaning by the steam cleaning and drying method, it is preferable to first perform a pretreatment for removing most of the stains. As a method of the pretreatment, there is a method of immersing an object to be cleaned in a detergent or ultrapure water and removing foreign substances adhering to the object to be cleaned by ultrasonic vibration, and rubbing with a brush using a detergent or ultrapure water. Or a method in which an object to be cleaned is immersed in a solution of sulfuric acid-hydrogen peroxide solution, ammonium hydroxide-hydrogen peroxide solution or the like to remove organic substances by an oxidation reaction.

Next, cleaning by a steam cleaning and drying method is performed using the cleaning agent of the present invention. As the steam cleaning and drying method,
Place the object to be cleaned at a temperature lower than the vapor in the steam, condense the vapor on the surface of the object to be cleaned, and wash off the surface of the object to be cleaned,
A method in which the time when the temperature of the object to be cleaned becomes equal to the temperature of the steam is set to a dry state and the process is terminated at this time may be exemplified.

When cleaning is performed by the steam cleaning and drying method using the cleaning agent of the present invention, there is an advantage that the cleaning agent does not remain on the cleaned and dried substrate surface. Further, there is an advantage that the time required for drying after washing is short, and drying can be performed in a short time. And, the advantage is extremely remarkably recognized when the cleaning agent of the present invention is used as compared with the conventional cleaning agent.

[0023]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. [Examples 1 to 3 (Examples)] A reticle glass substrate was washed with sulfuric acid (120 ° C., 5 minutes), washed with water (3 minutes), and further ultrasonically washed in water (3 minutes). After this preliminary washing, using 1-hydrodecafluorocyclohexanol (Example 1), 1-hydrooctafluorocyclopentanol (Example 2), and 1-hydrododecafluorocycloheptanol (Example 3) as detergents, The substrate was cleaned by a steam cleaning and drying method, and the dried state after drying was visually observed. Table 1 shows the results.

[0024]

[Table 1]

Example 4 (Example) A flux washing test was performed using 1-hydrodecafluorocyclohexanol. Flux (Tamura FA) on the entire surface of the printed circuit board
L-4, manufactured by Tamura Seisakusho Co., Ltd.), baked in an electric furnace at 200 ° C. for 2 minutes, and immersed in 1-hydrodecafluorocyclohexanol heated to 70 ° C. for 3 minutes. Table 2 shows the results.

Example 5 (Comparative Example) 1-hydrodecafluorocyclohexanol was converted to 1,1,2-trichloro-1,
A flux washing test was performed in the same manner as in Example 4 except that the flux was changed to 2,2-trifluoroethane. Table 2 shows the results.

[0027]

[Table 2]

[0028]

According to the present invention, 1-hydroperfluorocycloalkanols, which are nonflammable and have excellent cleaning ability, are used as a cleaning agent, so that they are superior to conventional cleaning agents without any problem in working environment. Washing can be performed. Further, since the cleaning agent of the present invention has excellent drying properties, the drying time can be shortened, and when the steam cleaning and drying method is performed, cleaning can be performed under more advantageous conditions.

Claims (4)

[Claims] 1. A cleaning agent containing 1-hydroperfluorocycloalkanols as an essential component. 2. The cleaning agent according to claim 1, wherein the 1-hydroperfluorocycloalkanol is 1-hydroperfluorocyclohexanol. 3. The cleaning agent according to claim 1, which is used for cleaning a semiconductor substrate. 4. The cleaning agent according to claim 3, which is used for cleaning by a steam cleaning and drying method.