TW201100535A - Cleaning agent for silicon wafer - Google Patents

Abstract

Disclosed is a cleaning agent for a silicon wafer, which contains at least an aqueous cleaning liquid and a water repellent cleaning liquid for providing at least recessed portions in a pattern of projections and recesses with water repellency during a cleaning process. The water repellent cleaning liquid contains a mixture of a water repellent compound, which contains a hydrophobic group and a reactive moiety that can be chemically bonded with Si of a silicon wafer, and an organic solvent that contains at least an alcohol solvent. By using the cleaning agent, the cleaning process, in which a pattern collapse is easily induced, can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning technique for a germanium substrate (wafer), which aims to improve a particularly fine circuit pattern with a relatively high aspect ratio in the manufacture of a semiconductor device. Manufacturing yield of components. [Previous technology year] Currently, semiconductor components for networking and digital home appliances require further improvements in performance, functionality, and power consumption. Therefore, the circuit pattern is continuously finely pulverized, and as a result, the size of the particles which cause a decrease in the manufacturing yield is also miniaturized. Therefore, the washing step for removing the micronized particles is frequently used, and as a result, the washing step accounts for 3 to 4% of the entire semiconductor manufacturing step. On the other hand, in the cleaning by the previously used mixed detergent of ammonia, as the circuit pattern is miniaturized, the damage caused to the wafer by the inspectability gradually becomes a problem. Therefore, it is being developed to replace the less harmful chlorine-based acid scrubbing agent. By this, the problem of damage to the wafer due to cleaning is improved, but the problem caused by the increase in the aspect ratio of the pattern accompanying the miniaturization of the semiconductor element is gradually exposed. That is, when the gas-liquid interface passes through the pattern after washing or rinsing, a pattern collapse occurs, which causes a large drop in yield. This pattern collapse can cause the wafer to be lifted from the cleaning solution or rinse solution. It is generally considered that the reason is that a residual liquid level difference is formed between the lower portion of the upper and lower sides of the pattern, and thus, the capillary force is poorly generated, resulting in pattern collapse. Therefore, if the capillary force is reduced, it is possible to eliminate the pattern collapse due to the difference in capillary force caused by the difference in the southness of the residual liquid. The magnitude of the capillary force is the absolute value of ρ obtained by the formula of the following formula, and according to this formula, if γ or cose is decreased, the capillary force can be expected to be reduced. P=2xr<c〇 secret (γ: surface tension ten contact angle, S:® case size) In Patent Document 1, as a method of reducing γ to suppress pattern collapse, it is shown that before passing through the gas-liquid interface The cleaning solution is changed from water to 2: propanol technology. However, although this method can effectively prevent the pattern from collapsing, the solvent such as 2-propanol having the smaller γ is usually smaller in contact angle, and the result (10) is increased. Therefore, the industry claims that the aspect ratio of the pattern that can cope with this problem is limited to 5 or less. In Patent Document 2, as a method of reducing cos0 and suppressing pattern collapse, a technique in which a resist pattern is targeted is disclosed. This method is achieved by adjusting the contact angle to 9G. In the vicinity, (3)(9) is brought close to q to reduce the capillary force to the limit to suppress pattern collapse. However, the disclosed technology is based on a resist pattern, which is modified against (4) itself, and finally the treatment agent can be removed together with the anti-narrative agent, so that it is not necessary to think of removing the dried treatment agent. The method is therefore not suitable for this purpose. Further, as a method of preventing pattern collapse of a semiconductor element, it is also proposed to use a critical fluid or use liquid nitrogen or the like. However, although the above methods all have certain effects, unlike the previous washing process, these methods all require #closed system or batch processing, so there is a problem in the cost of production, etc. 147937.doc 201100535 Question 0 [Previous [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-198958 [Patent Document 2]

When a semiconductor element is manufactured, the surface of the germanium wafer has a surface having a fine concavo-convex pattern. An object of the present invention is to provide a ruthenium wafer cleaning agent for improving a cleaning step which is likely to cause pattern collapse, in a method for producing a ruthenium wafer having a fine uneven pattern on its surface. The cleaning agent for a silicon wafer according to the present invention is characterized in that the cleaning agent for a wafer having a fine uneven pattern on the surface thereof contains at least a water-based cleaning liquid and a concave-convex pattern for cleaning during the cleaning process. a water repellent aqueous washing solution containing at least a recessed portion, and the water repellent washing liquid mixture contains: a reactive compound containing a reactive portion and a hydrophobic group which can be chemically bonded to Si of Si Shi Jing IB, and An organic solvent containing at least an alcohol solvent. In the cleaning of the present invention, each of the cleaning liquids is used independently and at least two or more of the cleaning liquids are used. In the present invention, the term "water repellency" means reducing the surface energy of the surface of the article, thereby reducing the interaction of water or other liquid with the substance, such as chlorine bonding, intermolecular force and the like. In particular: Two: the effect of interaction is large, and the effect of reducing interaction is also mixed with liquids other than water and water, or liquids other than water. The contact angle of the liquid to the surface of the article can be increased by reducing the interaction. 147937.doc 201100535 The enamel wafer of the present invention is formed by rinsing and rinsing with a embossing pattern/two: the water-based cleaning solution included is formed by having a fine embossing pattern so that the surface of the shixi wafer is formed to be thinner than ten It is then supplied to the recess of the face. In addition, after the water-based washing and rounding is supplied to the water-repellent washing liquid, the above-mentioned Li washing γ/, the upper core crystal 81 H water-repellent washing liquid and the water-based washing liquid may be used in the washing liquid of the same crystal. The state is held with the cleaning liquid not supplied to the wafer surface. Surface replacement of the different cleaning liquids for the Shi Xi 2 invention Dream wafer cleaning agent contains a plurality of cleaning liquids, and the cleaning liquid held in the concave portion is replaced with another cleaning liquid. Use 'and finally remove the detergent from the rounded surface.曰=When the surface of the wafer is washed with a detergent of the present invention, 矽: the surface of the round surface temporarily holds the water-repellent cleaning liquid. The water-repellent surface state is formed by the water-repellent compound of the protective portion: the surface state of the hydration of the moon may not be continuously formed and may be formed uniformly, but in order to impart more excellent water repellency Continuously and uniformly formed. In the present invention, the water-repellent compound is formed to include a reactive portion of the Si chemical bond of the Paneth wafer, so that the surface state of the water repellent can be obtained until the detergent is removed from the concave portion. Keep on the surface of Shi Xi wafer. Therefore, when the cleaning liquid is removed, that is, when the drying is performed, the surface of the concave portion is formed in the surface state of the water repellent, so that the capillary force on the surface of the concave portion is small, and pattern collapse is less likely to occur. If it is assumed that the capillary of the surface of the recessed surface is 1.7937.doc 201100535, the capillary force is less than 2.1 MN/m2 when the water is retained in the concave portion of the surface of the water-repellent stone wafer, the capillary force is small, and pattern collapse is unlikely to occur. good. Further, the surface state of the water repellent may be removed by at least one treatment selected from the group consisting of light irradiation, heating of the stone wafer, and exposure of the stone wafer to ozone. Further, by mixing the water-repellent cleaning liquid with a water-repellent compound containing a reactive portion and a hydrophobic group which can be chemically bonded to Si of the germanium wafer, and an alcohol solvent, the surface of the concave portion can be easily made in a short time. Formed to a fully hydrated surface state.

In the water-repellent washing liquid, if the water-repellent compound is less than 100% by mass based on 100% by mass of the total amount of the water-repellent washing liquid, it is difficult to form the surface of the concave portion into a sufficiently water-repellent surface state. . On the other hand, when it exceeds 99.9% by mass, the effect of the alcohol (the surface of the concave portion can be sufficiently dehydrated in a short time) becomes small. [Embodiment] Since the cleaning agent for ruthenium wafer of the present invention exhibits excellent pattern collapse resistance, when the detergent is used, it is possible to improve the production of a wafer having a fine uneven pattern on the surface without reducing the yield. The washing step in the method. Therefore, the productivity of the method for producing a slab of the surface of the embossed pattern using the surface cleaning agent of the present invention is improved. In the washing (4) of the present invention, it is possible to cope with the unevenness image f having the aspect ratio of the future (fourth) and the aspect ratio of the upper portion, and the production cost of the conductor 4 having a higher density can be further reduced. The cleaning agent of the present invention can be applied to various types of conductor elements without being able to cope with the previous one. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> a step of supplying a water-based cleaning liquid to the surface and holding the aqueous cleaning liquid in the concave portion; and replacing the aqueous cleaning liquid held in the concave portion with the cleaning liquid A different from the aqueous cleaning liquid; a step of retaining the water-repellent cleaning liquid for dehydrating the surface of the concave portion of the concave-convex pattern in the concave portion; and removing the detergent. Further, after the step of holding the water-repellent cleaning liquid in the concave portion, the aqueous repellency liquid solution held in the concave portion may be replaced with the cleaning liquid B different from the water-repellent cleaning liquid. Further, in addition, after the replacement with the different cleaning liquid B, the water-based cleaning liquid containing the water and the liquid is held in the concave portion. In addition, the above steps of removing the detergent include:

By drying, it will remain in the concave portion, Zhu, Luo, and Liu A.ώ. The step of removing the cleaning solution from the concave portion; and at least one treatment of the surface of the stone surface of the Shixi wafer, the first shot, the heating of the wafer, and the rubbing of the wafer to the ozone. The steps. In addition, the above-mentioned removal of the detergent portion: H ή V is performed by drying in the concave ray shot, and is performed on the surface of the wafer opposite to the surface, the wafer is added, and (4) If the cow is exposed to at least one of the steps of burying the ozone, you can also remove the dry wash and remove the wash. After drying up, you will be included in the wash. The water system of the π U 3 aqueous solution is maintained in the concave portion, and the step of removing the aqueous cleaning solution by drying is carried out by I47937.doc 201100535. The above aqueous washing solution is mixed with the above water-repellent compound, And an organic solvent containing at least an alcohol solvent, and the water-repellent compound is 〇丨999% by mass, preferably 0.2-75% by mass, based on 100% by mass of the total of the water-repellent washing liquid. More preferably, 〇.3~5〇% by mass. By containing 〇·1~99.9 mass. /. The water-repellent compound can easily form the surface of the concave portion uniformly in a short time to form a water repellent surface. 〇 The above aqueous washing solution contains at least an alcohol solvent. When the alcohol solvent is present, the reaction between the above water-repellent compound and Si of the Shihwa wafer is accelerated, so that the surface of the concave portion of the tantalum wafer can be formed into a sufficiently water-repellent surface state in a short time. Examples of the alcohol solvent include methanol, ethanol, b propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, isobutanol, hydrazine-pentanol, and hexanol. , 1-heptanol, 1-octyl alcohol, etc., comprising an alkyl group and a hydroxyl group; ethylene glycol, glycerol, 1,2-propanediol, iota, 3-propanediol, anthracene, 2-butanediol, anthracene , % butyl methoxide, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol single sigma, ethylene glycol monobutyrin, propylene glycol monomethyl ketone, propylene glycol monoethyl bond, etc. Things. Further, the above alcohol solvent is preferably an alcohol comprising an alkyl group and a hydroxyl group. At time A, it is easy to form the surface of the concave portion of the tantalum wafer into a sufficiently water-repellent surface state in a short time. Further, in the case of using a mercapto group and an i-based alcohol, it is easy to form the surface of the concave portion of the Shishi wafer into a sufficiently water-repellent surface state in a short period of time when using - mercaptan or a glycol, and thus it is particularly preferable. . Further, the above alcohol solvent preferably has a carbon number of 10, and particularly preferably 147937.doc 201100535 has a carbon number of 6 or less. In addition, the solvent can be used alone or in combination with a plurality of alcohol solvents. When the alcohol solvent is 〇1 (10) (9) by mass, in particular, G_5 to 5 parts by mass, based on the total amount of the water-repellent compound, it is easy to form the surface of the concave portion of the round in a short time. It is preferable to repel the surface state of hydration. Further, the above aqueous washing solution may contain an organic solvent other than the alcohol solvent. Since the above water-repellent compound is easily reacted with the f-substance solvent, it is particularly preferable that the organic solvent other than the alcohol-cooling agent exhibits water repellency in a short time if an aprotic solvent is used. Further, the aprotic solvent means both an aprotic polar solvent and an aprotic nonpolar solvent. Examples of the aprotic solvent include hydrocarbons, esters, ethers, ketones, a solvent containing a sulfoxide, a sulfoxide solvent, a derivative of a polyol having no hydroxyl group, and a nitrogen compound having no NH bond. Solvents, etc. Examples of the above hydrocarbons include: toluene, benzene, xylene, hexyl alcohol, heptane, and octyl; and examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetonitrile. Ethyl esters and the like; examples of the ethers include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, and the like; as examples of the ketones, acetone, ethyl acetonide, methyl ethyl Ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc.; as an example of the above-mentioned self-containing solvent, there are perfluorooctane, perfluoroindene, perfluorocyclopentan , perfluorocyclohexane, hexa-benzene and other perfluorocarbons, 1,1,1,3,3-pentafluorobutane 'octafluorocyclopentane, 2,3 dihydro decafluoropentane, Zeorora Η ( Japan Zeon)) Hydrofluorocarbon, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl I47937.doc •10· 201100535 Ether, Asahiklin AE-3000 (made by Asahi Glass), N〇vec hfe_71〇〇,

Hydrofluoride ether such as Novec HFE-7200, N〇Vec 7300, Novec 7600 (both manufactured by Speaking), gas carbon such as four-gas methane, hydrogen carbon such as chloroform, dichlorodi 1,1,2,2,3-five Fluoropropane, iota-chloro-3,3,3-trifluoropropene, i,2-dichloro-3,3,3-trifluoropropene, hydrochlorofluorocarbon, perfluoroether, perfluoropolyether, etc.; Examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like; and examples of the polyhydric alcohol derivative having no oxindole include diethylene glycol monoethyl ether acetate and ethyl triacetate acetic acid vinegar. Ethylene glycol monobutyrate acetate, propylene glycol monomethyl acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, ethylene Alcohol dimethyl ether, etc.; as an example of a nitrogen-containing compound solvent having no NH bond, there are: n, n-dimethylformamide, N,N-dimethylglyoxime, N•methyl_2 _ Pyrrolidone, triethylamine, pyridine, and the like. Further, when an organic solvent other than the above alcohol solvent is used as a nonflammable solvent, it is preferable that the water-repellent washing liquid becomes a residue, or the phase point is increased, and the risk of the water-repellent cleaning liquid is lowered. The dentate-containing solvent is mostly incombustible, so the incombustible elemental solvent can be preferably used as a nonflammable organic solvent. In this case, the organic solvent other than the above alcohol solvent is preferably 2 to 95 times by weight, more preferably 4 to 5 times by volume, based on the mass ratio of the alcohol solvent. Further, when the wafer is rotated to the wafer to supply the wafer to the wafer, and the hysteresis of the organic solvent is low, the water-repellent cleaning solution is likely to be The cleaning solution spreads over the entire surface of the wafer 147937.doc 201100535. The drying of the outer layer has a tendency to increase in viscosity when the boiling point is high. Therefore, the above organic solvent is preferably one having a boiling point of from 7 〇 to 22 Torr. As such a solvent, in consideration of cost and solubility with other cleaning liquids (replacement degree), the above-mentioned alcohol is preferably propanol or 2-propanol, and it is preferred that the organic solvent other than the above alcohol is Diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl acetic acid s, propylene glycol monomethyl ether acetate vinegar, propylene glycol monoethyl acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl hydrazine (4) Ethylene glycol diethyl ether, ethylene glycol dimethyl ether, cyclohexanone. In the pattern forming step of forming the surface of the Shi Xi wafer into a surface having a fine concavo-convex pattern, first, after the anti-contact agent is coated on the surface of the wafer, the resist is exposed through the resist mask, and the exposed portion is exposed. A resist or an unexposed resist is removed to thereby form a resist having a desired concavo-convex pattern. Further, by pressing the patterned mold against the resist, a resist having a concavo-convex pattern can also be obtained. Then, the wafer is etched. At this time, a portion of the recess of the resist pattern is selectively etched. Finally, the resist is removed to obtain a tantalum wafer having a fine concavo-convex pattern. Furthermore, the 'wafer wafers include: a tantalum oxide film having a natural oxide film, a thermal oxide film or a vapor phase synthetic film (cVD (Chemical Vap〇r Dep〇siti), etc.) formed on the surface. When the concave-convex pattern is formed, at least a part of the concave-convex pattern is an oxidized stone. Further, since the outermost surface of Shixi or tantalum nitride is naturally oxidized by contact with water or the atmosphere to form a tantalum oxide film on the surface, such a tantalum wafer can also be used. In addition, even for a wafer formed of a plurality of components including cerium and/or cerium oxide, the aqueous water-repellent cleaning solution of the present invention can also hydrophobize the cerium and/or oxygen 147937.doc 12 201100535 fossil surface . The wafer formed of the plurality of components further includes an oxygen cut film formed on the surface such as a stone oxide layer, a natural oxide film, a thermal oxide film, or a vapor phase synthetic film (CVD film). In the case of the concavo-convex pattern, at least a part of the concavo-convex pattern is tantalum and/or niobium oxide. After the surface of the crucible wafer is formed into a surface having a fine concavo-convex pattern, the surface is washed with a water-based cleaning solution, and when the aqueous cleaning solution is removed by drying or the like, if the width of the concave portion is small, the longitudinal and lateral portions of the convex portion are relatively large. , it is prone to pattern ◎ collapse. This concave-convex pattern is defined as described in FIG. 1 and FIG. 2 . Figure i is a schematic plan view showing the surface of the stone wafer i after having the surface formed with the fine concavo-convex pattern 2, and Fig. 2 is a view showing aa of Fig. 1 and a portion of the cross section as shown in Fig. 2 The width 5 is expressed by the ratio of the convex portion 3 to the (four) 3, and the aspect ratio of the convex portion is divided by the height 6 of the convex portion. Washing the yak, the pattern in the sudden collapse, it is easy to have a width of 70 nm or less in the concave portion, especially when it is 6 or more, 疋5 (10) or less, and the aspect ratio is 4 or more, especially in the preferred aspect. After the surface of the Shixi wafer is formed to have a fine, night-supporting surface, the water-based cleaning liquid is supplied to the surface, and the water-based cleaning/night is held in the concave portion. state

- ^ w .. . '·,, using a different cleaning solution A than the water-based cleaning solution

For a good example, please refer to: too: as the different washing liquid A water, right 妩 _ water-repellent washing liquid, water, organic solvent or its equivalent, surfactant in the invention specified in the present invention... It is mixed with acid, slaughter 彳 mt @ / 1 kind of income, etc. In particular, in view of the relationship between the phase damage and the cleanliness, the detergent solution, water, organic II, the water-repellent agent specified in the present invention or a mixture thereof. Further, in the state in which the water-repellent washing liquid other than the 147937.doc -13 - 201100535 is used as the different washing liquid A, the washing liquid A is held in the concave portion 4, and the other is not: The cleaning solution A is replaced with the aqueous washing solution. Further, examples of the organic solvent as a preferred example of the different washing oxime include hydrocarbons, brewing materials, ketones, oximes, dentate-containing solvents, shale-based solvents, alcohols, and polyols. Derivatives, nitrogen-containing compound solvents, and the like. Examples of the hydrocarbons include toluene, benzene, xylene, hexyl alcohol, heptane, and octyl; and examples of the vinegar include: acetic acid, ethyl acetate, propylene acetate, acetic acid, and sodium. Ethyl acetate, etc.; as an example of the above-mentioned _, there are: diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.; as an example of the above ketones, acetone, acetamidine acetone, methyl ethyl Ketone, methyl propyl ketone, decyl butyl ketone 'cyclohexanone, isophorone, etc.; as an example of the above-mentioned i-containing solvent, there are: octane, perfluorodecane, perfluorocyclopentane , perfluorocyclohexane, hexafluorobenzene and other perfluorocarbons, ^13,3" gas butyl, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Ze〇r〇ra H (Japan Ze 〇n)) Hydrofluorocarbon, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, AsahikHn AE_3〇〇〇 (made by Asahi Glass), Novec Hydrofluoride ether such as HFE-7100, Novec HFE-7200, NoVec 73〇〇, N〇vec 7600 (both manufactured by 3M), chlorocarbon such as tetra-methane, hydrogen chloride such as gas, dichlorodifluoromethane, etc. Chlorofluorocarbon, 丨, ^ 2.2.3.3.3- pentafluoropropane, l,3-dichloro-1,1,2,2,3-pentafluoropropane, chloropropene_3.3.3-trifluoropropene, ι,2-diox - Hydrogen chlorofluorocarbon such as 3,3,3-trifluoropropene, perfluoroether, perfluoropolyether, etc.; as an example of the sulfoxide solvent, dimethyl sulphate or the like; as an example of an alcohol, : methanol, ethanol 'propanol, butanol, B 147937.doc • 14- 201100535 diol, 1,3-propanediol, etc.; as examples of the above polyol derivatives, there are: diethylene glycol monoethyl hydrazine, ethylene two Alcohol mono (4), ethylene glycol monotop, propylene glycol monomethyl hydrazine, propylene glycol monoethyl hydrazine, diethylene glycol monoethyl acetonate acetate, ethylene glycol monomethyl acetate, ethylene glycol monobutyl phthalate acetic acid, propylene glycol Acetic acid acetate vinegar, propylene glycol monoethyl ether acetate vinegar, diethylene glycol dimethyl ether, diethylene glycol ethyl methine, ethylene glycol diethylene, ethylene glycol, etc.; as examples of nitrogen-containing compound solvents, there are: Formamide, hydrazine, hydrazine, dimethyl ketone, ν, ν dimethyl hydrazide, hydrazine-methyl, such as diethylamine, triethylamine, etc. Fig. 3 is a view showing a state in which the recessed portion 4 holds the cleaning liquid 8 in the washing step. The Shihwa wafer of the pattern diagram of Fig. 3 represents a part of the cross-section of the figure. When the washing step is performed, the water repellent cleaning liquid is supplied onto the concave wafer 1 to be formed. At this time, as shown in Fig. 3, the water-repellent cleaning liquid is held in at least the concave portion 4, and the concave portion 4 is water-repellent. Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The liquid is replaced with a washing liquid different from the water-repellent liquid. As an example of the different washing liquid, the water-based washing liquid containing the aqueous solution, the organic solvent, the aqueous washing liquid, and the organic solvent Japanese human surfactant are as small as W ^ 5 4 in eight Such as mixing acid, alkali, boundary wounds, and choosing V species, especially considering the damage and cleanliness of the pattern, it is better to say that the washing liquid is organic in the sword washing liquid, organic The solvent, or the above-mentioned water, is used as the different washing agent. In addition, when the water-based cleaning liquid is used as the liquid B, it is preferable to maintain the 147937.doc -15-201100535 in the concave portion*, and replace the cleaning liquid with a washing liquid other than the aqueous washing liquid. Washing solution. Examples of the organic solvent, the halogen-containing solvent, and the nitrogen-containing compound solvent. Further, examples of the preferred agent for the different cleaning liquid B include: a ketone, a vinegar, a domain, a sulfoxide solvent, Alcohols, derivatives of polyols, and the like. Examples of nuclear types include: toluene, stupid, xylene, hexa, geng, xin, etc.; examples of the above vinegars include: acetic acid, acetonitrile, acetic acid, acetoacetate, ethyl acetate, ethyl acetate As an example of the above ethers, there are: diethyl ether, di(10), ditop, tetrahydrofuran, No. 2, etc.; as an example of the above ketones, #: acetone, acetamidine, methyl ethyl ketone , methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc.; as an example of the above-mentioned i-containing solvent 'has: all 1 xin burning, full gas domain, all said 戍 戍: all I cyclohexane, hexafluorobenzene and other perfluorocarbons, such as pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Ze〇r〇ra H (manufactured by 曰本~(10)) Fluorocarbon, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE- 7200, Novec 7300 '

Novec 7600 (both manufactured by 3M) and other hydrofluoroethers, tetragas methane and other gas carbon, chloroform and other hydrochlorocarbons, dichlorodifluoromethane and other gas fluorocarbons, dichloro _ 2,2,3,3,3- Pentafluoropropane, l,3-dichloro-l,i,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, ι,2-digas·3,3, Hydrochlorofluorocarbons such as 3-trifluoropropene, perfluoroethers, perfluoropolyethers, and the like; examples of the sulfoxide-based solvent include dimethyl sulfite and the like; and examples of the alcohols include methanol and ethanol. Propanol, butanol, 147937.doc -16- 201100535 Alcohol 1,3_propanediol, etc.; as an example of the above polyhydric alcohol derivative, there are diethylene glycol monoethyl ether, ethylene glycol monoether, ethylene glycol monobutyl Ether, propylene glycol = hydrazine, propylene glycol, single hexagram, diethylene glycol, single acetyl acetate, ethylene glycol monoterpene ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monoterpene ether acetate, propylene glycol Monoethyl ether acetate, diethylene glycol dimethyl bond, diethylene glycol ethyl sulfonate, ethylene glycol diethyl bond, ethylene glycol dimethyl ether, etc.; as an example of a gas-containing compound solvent, there is: meglumine , Ν, Ν _: methyl amide, hydrazine, hydrazine, hydrazine The phases N_w, [, triethylamine, pyridine and the like than .... Examples of the water-based cleaning solution include water, or a mixture of machine-cooled β, 胄, and at least in water! The obtained water is used as a main component (for example, the water content is 50% by mass or more). Especially in view of cleanliness, it is preferred to use water as a water-based cleaning liquid. Fig. 4 is a schematic view showing a state in which a water-based cleaning liquid is held in a recessed canister which is water-repellent by a water-repellent compound. The Shihwa wafer of the pattern diagram of Fig. 4 represents one of the sections of Fig. 1 . The surface of the concave portion 4 is formed into a water repellent surface state by a water repellent compound. Further, even if the water-based cleaning liquid $ is removed from the concave portion 4 by the chemical bonding unit, the surface state of the water repellent is maintained on the surface of the silicon wafer. It is assumed that the concave portion on the surface of the wafer which is water-repellent by the water-repellent cleaning liquid is accompanied by water, that is, the surface of the concave portion 4 as shown in FIG. 4 is formed into a water-repellent surface by a water repellent compound. When the state is 1 ', the capillary force of the surface of the concave portion when the concave portion is kept with water is preferably 21 m 2 or less. If the gross force is 2·1 Na or less, the pattern collapse is less likely to occur, so that it is preferable. I47937.doc -17- 201100535 In addition, if the capillary force is reduced, the pattern collapse is less likely to occur, so the capillary force is especially! .5 MN/m2 or less is preferred, and more preferably 丨〇 MN/m2 or less. Further, it is desirable to adjust the contact angle with the cleaning liquid to 9 〇. Nearby' makes the capillary force infinitely close to 〇.〇 MN/m2. Further, the water-repellent cleaning liquid contains a reactive portion capable of chemically bonding with Si of the tantalum wafer and a water-repellent compound of a hydrophobic group, and the reactive portion may be a reaction with a sterol group (Si-OH group). As an example thereof, a chlorine group, a bromine-based halogen group, an isocyanate group 'amino group, a dialkylamino group, an isothiocyanate group, an azide group, an etidinyl group, a Shimadzu base, _N(CH3)c〇CH3, -N(CH3)COCF3, imidazole ring, oxazolidinone ring, morpholine ring, etc. si_N bond 'homoyloxy, ethoxylated oxy, trifluoroethenyloxy, _〇 c(ch3)=chcoch3, -OC(CH3)=N-Si(CH3)3, -OC(CF3)=N-Si(CH3)3, -CO-NH-Si(CH3)3 4 Si-OC A bond, a Si_Ο-S bond such as a pyridyl acid ester group or a perfluoroalkyl group acid ester group, or a nitrile group. Further, examples of the hydrophobic group include a monovalent organic group containing a hydrocarbon group or a monovalent organic group containing a C-F bond. The reactive portion of the water repellency compound can rapidly react with the sterol group of the ruthenium oxide layer of the embossed pattern of the ruthenium wafer, and the water repellency compound is chemically bonded to the Si of the Shixi wafer via the Shiqi gas-fired bond. Thereby, the surface of the wafer is covered with a hydrophobic foundation, so that the capillary force of the surface of the concave portion of the wafer can be reduced in a short time. Further, in the water-repellent cleaning solution, a water-repellent compound containing a reactive site and a hydrophobic group which can be chemically bonded to Si of the germanium wafer is contained to comprise a compound selected from the following general formulas [1] and [2]. At least one of the groups is suitable. (R,)aSi(CH3)bHcX4.ab-c [1] 147937.doc -18- 201100535 [R Si(CH3)2_dHd]eNH3-e [2] wherein R is independent, and the carbon number is 丨~ A monovalent organic group of a tobacco group of 18 or an organic group having an i value of a fluoroalkyl chain having a carbon number. R2 is independently an organic group containing a valence of a hydrocarbon group having a carbon number of 18, or a fluoroalkyl chain having a carbon number of 1 to 8! The organic base of the price. In addition, χ is independently selected from the group consisting of halo, alkoxy, ethoxycarbonyl, trifluoroacetoxy, -〇C(CH3)=CHCOCH3, -OC(CH3)=N-Si(CH3)3 , -〇C(CF3)=N-

Si(CH3)3, -CO-NH-SkCH3)3, an alkyl sulfonate group, a perfluoroalkyl sulfonate acrylate group, a nitrile group, and a monovalent organic group in which an element bonded to Si is nitrogen At least one of the group consisting of. 3 is an integer of 1 to 3, and b and c are each an integer of 0 to 2, and the total of a, b, and c is 1 to 3. Further, d is an integer of 0 to 2, and e is an integer of 1 to 3. Further, R1 of the above formula [1] and R2 of the above formula [2] are particularly preferably CmH2m+ to 18) or CnF2n+ to 8). As the water-repellent compound represented by the above formula [1], for example, C18H37S1CI3 'C, 〇H21SiCl3 'C6H13SiCl3 &gt; C3H7SiCl3 'CH3SiCl3 'C18H37Si(CH3)Cl2, C10H21Si(CH3)Cl2, C6H13Si(CH3)Cl2, C3H7Si can be used. (CH3)Cl2, (CH3)2SiCl2, C18H37Si(CH3)2CM, C10H21Si(CH3)2a, C6H13Si(CH3)2a, C3H7Si(CH3)2Cn, (CH3)3SiCl, (CH3)2SiHCl, etc.; C8F 17CH2CH2SiCl3, C6F13CH2CH2SiCl3, C4F9CH2CH2SiCl3, CF3CH2CH2SiCl3, C8F17CH2CH2Si(CH3)Cl2, C6F13CH2CH2Si(CH3)Cl2, C4F9CH2CH2Si(CH3)Cl2, CF3CH2CH2Si(CH3)Cl2, C8F17CH2CH2Si(CH3)2CM, C6F13CH2CH2Si(CH3)2 (M, 147937.doc • 19- 201100535 C4F9CH2CH2Si(CH3)2Cl, CF3CH2CH2Si(CH3)2Cl, CF3CH2CH2Si(CH3)HCl fluoroalkyl gas decane; or a gas group of the above gas oxirane substituted with a chloro group such as a bromo group, isocyanate group , alkoxy, ethoxycarbonyl, trifluoroacetoxy, -OC(CH3) = CHCOCH3, -OC(CH3)=N-Si(CH3)3, -OC(CF3)=N-Si(CH3 3, -CO-NH-Si(CH3)3, alkyl sulfonate group, perfluoroalkyl sulfonate group, nitrile group, -NH2, -N(CH3)2, -N(C2H5) 2. -NHCOCH3, -N3, -N=C=S, -N(CH3)COCH3, -N(CH3)COCF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi a water-repellent compound obtained by (CH3)3, -NHCO-OSi(CH3)3, -NHCO-NH-Si(CH3)3, σmα, ring, sputum ketone ring or miso ring. When the water repellent compound has a plurality of reactive sites, the water repellent compound is easily aggregated, and it is difficult to obtain a surface state in which the water repellent is uniformly repelled. As a result, in the step of irradiating the surface of the crucible wafer or heating the crucible wafer, An additional light irradiation time or heating time is required to remove the portion formed by aggregating the water repellency compound. Therefore, the number of 4-abc indicating the number of the reactive sites is more preferably 1. As the water-repellent compound represented by the above formula [2], for example, (CH3)3SiNHSi(CH3)3, C2H5Si(CH3)2NHSi(CH3)2C2H5, C3H7Si(CH3)2NHSi(CH3)2C3H7, C6Hl3Si(CH3) can be used. 2NHSi(CH3)2C6H〗 3, C6H5Si(CH3)2NHSi(CH3)2C6H5, {(CH3)3Si}3N, {C2H5Si(CH3)2}3N, (CH3)2HSiNHSi(CH3)2H, CF3CH2CH2Si(CH3)2NHSi ( CH3)2CH2CH2CF3, C4F9CH2CH2Si(CH3)2NHSi(CH3)2CH2CH2C4F9, C6F13CH2CH2Si(CH3)2NHSi(CH3)2CH2CH2C6F13,

C8F17CH2CH2Si(CH3)2NHSi(CH3)2CH2CH2C8F17, {CF3CH2CH2Si(CH3)2}3N 147937.doc -20- 201100535 and the like. It is particularly preferable that the above-mentioned general formula [2] is a two of two. Among the water-repellent compounds exemplified above, it is preferable that the surface of the concave portion is formed into a sufficiently water-repellent surface state in a short time, and it is particularly preferable that the X of the above formula [1] is a chlorine-based gas decane. .

Further, when water is contained in the aqueous washing solution, the reactive portion of the water repellent compound is hydrolyzed to form a sterol group (Si_〇H). The reactive site also reacts with the alkaloid group, and as a result, the water-repellent compounds are bonded to each other to form a polymer. The dimer has a lower reactivity with the sterol group of the ruthenium oxide layer of the tantalum wafer. Therefore, the time required for the surface of the dream wafer to be water-repellent becomes longer. Therefore, the solvent of the above aqueous repellency washing liquid is not limited to water, that is, the above organic solvent containing at least an alcohol solvent. Further, a trace amount of water may be present in the solvent of the aqueous water-repellent cleaning solution. However, when the water is contained in a large amount in the solvent, the water-repellent compound is hydrolyzed by the moisture, and the reactivity is lowered. Therefore, the amount of water in the solvent is preferably lower, and the moisture content is preferably less than 3 moles per mole of the water-repellent compound when mixed with the above water-repellent compound. The good is 1 mole, especially good is less than 5 moles. Further, in order to promote the reaction between the water repellent compound and the surface of the wafer, a catalyst may be added to the water repellent cleaning solution. As such a catalyst, it can be preferably used: trifluoroacetic acid, tri-glycolic acid liver, pentafluoropropionic acid, pentafluoropropane-, monofluoromethyl-acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride, etc., without water. Determination of hydrazine, alkylamine, dialkylamine, etc., sulphide, sulphuric acid, methyl sulphate hydrochloride, etc., metal complex or gold di-salt of tin, tin, titanium, etc. Decane, trimethyldecyl trifluoropyruvate, trifluoromethane 147937.doc -21- 201100535 acid dimethyl; epsilon ester and the like. In particular, considering the effect of the catalyst and the cleanliness, it is preferably: trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, trifluorosulfonate, sour, acid, hydrogen and other non-aqueous acids, And chlorodecane, tri-n-decyl sulphate, trimethyl sulfonium triflate, and the like. The amount of the catalyst added is preferably 疋O.OOid% by mass based on 100 parts by mass of the total amount of the above water-repellent compound. If the amount of addition is small, the catalyst effect is not good. In addition, even if it is too much, the effect of the catalyst will not be improved. On the contrary, there will be a flaw in the surface of the wafer or as an impurity remaining on the wafer. Therefore, the amount of the above-mentioned catalyst added is particularly preferably 5 to 3 mass%. Further, when the temperature of the water repellent cleaning liquid is increased, it is easy to form the surface of the concave portion in a surface state which is water repellent in a shorter period of time. The temperature at which the surface state of the water repellent uniformly is easily obtained is preferably maintained at 0 to 16 Torr, and particularly preferably at 1 G to 12 n:. The temperature of the water repellent cleaning liquid is preferably maintained at this temperature when it is held in the recess 4. Then, a step of removing the cleaning liquid held by the recessed portion 4 which is water-repellent by the water-repellent compound and removing the detergent is carried out. Preferably, the step comprises: removing the cleaning liquid held in the concave portion from the concave portion by drying; and selecting the light to irradiate the surface of the wafer, heating the 11 wafer, and exposing the Shixi wafer to At least one step of treatment of ozone. When the cleaning liquid is removed from the concave portion, the cleaning liquid held in the concave portion is preferably a water-based cleaning liquid. In this case, it is preferred to carry out the following step 1 after the aqueous water-repellent cleaning liquid is held in the concave portion, and the aqueous washing liquid held in the concave portion and the cleaning liquid B different from the (four) aqueous washing liquid are preferably subjected to the following step 1. 147937.doc • 22· 201100535 After the replacement, the aqueous cleaning solution containing the aqueous solution is held in the recess. Further, when the cleaning liquid is removed from the concave portion, the washing liquid held in the concave portion may be a water repellent washing liquid or the different washing liquid B. In the step of removing the cleaning liquid from the concave portion, the cleaning liquid is removed by drying. The drying is preferably carried out by the method known in the following (four): spin drying, IPA (2-propanol) steam drying, marangani drying, heat drying, hot air drying, vacuum drying, and the like. In the step of at least the old treatment of illuminating the surface of the wafer, heating the germanium wafer, and exposing the germanium to ozone, the surface state 10 of the surface of the stone wafer is removed. When the surface state of the water repellent state is removed by light irradiation, it is effective to cut off the S^c bond, the CC bond, and the C_F in the surface state 10 which is not repelled by the water repellency. For this purpose, it is preferred to irradiate ultraviolet rays as described below, that is, the ultraviolet rays contain a bond energy equivalent to the bond of 58 to 80 kcal/mol, 83 kcal/m〇1, 116 kcal/m. w ◎ Wavelengths of 350 to 45 〇 nm, 340 nm, and 240. As the light source, a metal element lamp, a low pressure mercury lamp, a high pressure mercury lamp, an excimer lamp, a carbon arc lamp or the like can be used. The ultraviolet irradiation intensity is preferably, for example, an illuminance meter (luminescence intensity meter UM-10 manufactured by Konica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400 nm]). The value is 100 mW/cm2 or more, particularly preferably 200 mW/cm2 or more. Further, if the irradiation intensity is less than 1 〇〇mW/cm2, it is necessary to remove the surface state of the above-mentioned water repellent. In addition, if a low-pressure mercury lamp is used, the ultraviolet light of a shorter wavelength is irradiated, so 147937.doc -23·201100535 and even if the A?, the intensity of the shot is low, the surface state of the water-repellent surface can be removed in a short time. In addition, in the case where the surface state of the water repellent is removed by light irradiation, when the constituent component of the surface state 10 of the water repellent is decomposed by ultraviolet rays, Ozone is generated, and the ozone oxidizes and volatilizes the constituent components of the water-repellent surface state 10, so that the treatment time is shortened, which is particularly preferable. As the light source, a low-pressure mercury lamp or an excimer lamp can be used. Side surface of the light irradiation heating the wafer stone evening.

In the case of heating the Shi Xi wafer, it is carried out at 4 〇〇 to 7 ,, preferably at 500 to 700 ° C for heating of the ruthenium wafer. For the heating time, it is preferred to maintain heating for 1 to 60 minutes, more preferably 1 to 3 minutes. Further, in the step towel, ozone exposure, «irradiation' corona discharge, and the like can be produced. In addition, it is also possible to heat the stone wafer while heating. In the case of exposing Shi Xijing® to ozone, it is preferred to irradiate with a low-mercury material or (4) a high-voltage (four) low-temperature discharge.

The generated ozone is supplied to the surface of the round. It is also possible to expose or heat the Shi Xi wafer by exposing it to ozone. In the surface state 10 of the water repellent surface of the wafer, the above-mentioned surface state 可 can be efficiently removed by combining the above-described light irradiation treatment, the above-described heat treatment, and the above-described odor treatment. In addition, in this step, plasma irradiation, corona discharge, or the like may be used in combination. For example, it is described in the publicly-known literature, and the like: no-return-shaped 面 is a surface having a fine concavo-convex pattern' and is replaced by another cleaning liquid in the concave portion. 147937.doc -24-201100535 The cleaning liquid system has been obtained. Since the technique is established, the present invention is carried out centering on the price of the water-repellent washing liquid. Further, according to the formula P=2xYxcose/S (Y: surface tension, Θ: contact angle, s: pattern size) described in the prior art and the like, it is clear that the pattern collapse largely depends on the cleaning liquid and the ruthenium wafer. The contact angle of the surface is the contact angle of the droplets and the surface tension of the cleaning liquid. In the case of the cleaning liquid held in the concave portion 4 of the concave-convex pattern 2, the contact angle of the droplet is related to the capillary force of the surface of the concave portion, and the capillary force of the surface of the concave portion can be considered to be equivalent to the pattern collapse. Therefore, the capillary force can be derived from the evaluation of the contact angle of the droplets in the above-described formula and the surface state 10 of the water repellent. Further, in the examples, the above-mentioned washing liquid used water as a representative of the aqueous washing liquid. However, in the case of a tantalum wafer having a fine uneven pattern on the surface, since the pattern is extremely fine, the water repellency of the surface portion 10 of the water repellent itself cannot be accurately evaluated. The evaluation of the contact angle of the water-repellent water droplets was carried out in the following manner. As described in JIS R 3257 "Test method for wettability of substrate glass surface", a few drops were applied to the surface of the sample (substrate). A water droplet of μ1 measures the angle formed by the water droplets on the surface of the substrate. However, in the case of a patterned stone wafer, the contact angle becomes very large. The reason for this is that the contact angle of the surface of the substrate is increased by the influence of the surface shape (roughness) of the substrate due to the Wenzel effect or the Cassie effect. Therefore, in the present invention, the water repellent cleaning liquid is supplied to the smooth surface of the stone wafer to form a water repellent surface state, and the surface state is regarded as a wafer on which the fine concavo-convex pattern 2 is formed. The surface state of the water repellent of 1 147937.doc 25- 201100535 ίο was evaluated. Details (4) Description of the next financial statement. Coincidentally, the evaluation method of the Shixi wafer with the water-repellent cleaning solution, the preparation of the water-repellent cleaning liquid, and the evaluation of the water-repellent liquid after the Shi Xiyuan were evaluated. [Evaluation method of the enamel wafer with the water-repellent cleaning liquid] As the evaluation method of the 7-wafer supplied with the water-repellent cleaning liquid, the following evaluations (1) to (4) were carried out. (1) The contact angle of the surface state of the water repellent by the water-repellent cleaning solution is evaluated by adding a contact angle meter to the surface of the repellent wafer by about 2 _丨u, ''μ pure water' ( Concord interface science manufacturing: CA-X^iJ Ning 匕 匕 ))) measured the angle formed by the water droplets and the surface of the wafer (contact angle). Here, the contact angle of the surface state of the water repellent liver is 50. Those who are within the range are evaluated as qualified (in the table, it is noted as ten (2) Evaluation of capillary force The P is calculated by the following formula, and the capillary force (absolute value of P) is obtained.

P = 2xyxcos0 / S where 'γ denotes the surface tension, θ 矣 denotes a contact angle, and S denotes a pattern size. Furthermore, the line width is 45 nm, and the aspect ratio of the pattern of 6 has the following tendency: if the circle is washed through the gas-liquid interface, the ginseng is planted in the rain, and the 四(4) "the liquid is water, the pattern is easy. Collapse, if it is 2_propanol, the pattern is not easy to be a thousand easy to use. In the case where the pattern size surface is oxidized stone, 3(10)B曰 round table M/ , ^ 冼孑, night is 2_propanol (surface Tension: 22 mN/m 'contact with phlegm and phlegm, on the other hand, 贝! hair, thin tube force is 0.98 (10) surface tension: 72mN mercury, the surface tension of the largest liquid in the liquid... m 'and oxygen cut Contact angle::5.), 'The capillary force is 3.2 MN/m2. Therefore, 'with 2.1 MN/m2 between t 147937.doc &quot;26 - 201100535 mark 'If the capillary force is maintained when there is water When the value is 2.1 MN/m2 or less, the evaluation is acceptable (indicated as 〇 in the table). (3) The removal of the surface state of the water-repellent surface by the water-repellent cleaning liquid is irradiated for 2 hours under the following conditions. UV (ultravi〇let, ultraviolet) light of a metal halide lamp. The contact angle of the water droplet after irradiation is changed to 30° or less. 〇) • Lamp: M015-L312 manufactured by Eye Graphics (strength: 1.5 kW) • Illuminance • The measured value under the following conditions is 128 mW/cm2 • Measuring device: UV intensity meter (manufactured by Konica Minolta Sensing, UM- 10) • Light receiving unit: UM-360 (receiving light wavelength: 310 to 400 nm, peak wavelength: 365 nm) • Measurement mode: illuminance measurement (4) Removal of the surface state after hydration The surface smoothness evaluation was performed by atomic force electron microscopy (manufactured by Seiko Instruments: SPI3700, scanning range of 2.5 μπι square), and the center line average surface roughness (Ra) was determined. Further, the Ra system was applied to the measurement surface. The average roughness of the center line defined in 〇601 is obtained by three-dimensional expansion, and is calculated as the value obtained by averaging the absolute values of the deviations from the reference surface to the designated surface by the following equation. If the surface value of the wafer after removing the water repellent surface state is 1 nm or less, it is considered that the surface of the wafer is not rotted by the cleaning, and the residue of the water-repellent cleaning liquid on the surface of the wafer is evaluated as qualified ( The table is marked as 〇). [Number 1]

Ra=t〇x’Y)_Z()|dxdY 147937.doc •27- 201100535 where xL, xR, ΥΒ, Υτ are measured in the range of coordinates and γ coordinates, respectively. SQ is a degree at which the measurement surface is a flat surface which is ideal, and the surface area 'z〇 indicates the average height in the measurement surface. VIII [Example 1] (1) Preparation of water-repellent cleaning solution Trimethyl chlorite [(CH3)3sicl] 3 g as a water-repellent compound, and 2-propanol (ipA) as an alcohol solvent 5 g is mixed with a mixed solvent of 92 g of toluene as an organic solvent other than an alcohol solvent, and (iv) a concentration of the water-repellent compound relative to the total amount of the water-repellent washing liquid is obtained for about 5 minutes (hereinafter referred to as "water-repellent compound concentration" ") is a water-repellent washing liquid having a concentration of 3% by mass of the alcohol solvent relative to the total amount of the water-repellent washing liquid (hereinafter referred to as "alcohol concentration") of 5% by mass. (2) Cleaning of the shredded wafer is carried out with a smooth thermal oxide film of the Shihwa wafer (the surface of the Si wafer W having a thickness of the thermal oxide film layer is immersed in a hydrofluoric acid aqueous solution of 2 mm in size] Then, imin is immersed in pure water and immersed in acetone! (10). (3) Surface treatment of the surface of ruthenium wafer with water-repellent cleaning solution. Preparation of Shixi wafer in the above (1) Preparation of water-repellent cleaning solution The water-repellent washing solution in the middle, dipping 1〇mip under 20〇c, silly, soaking the wafer in the crucible for i min, and then immersing it in pure water as a water-based cleaning solution for (5) min. Finally, 'take the wafer from the pure water and blow off the air to remove the pure water from the shell surface.'' In the above "Evaluation method for the supply of water-repellent cleaning liquid wafer" 147937.doc -28- 201100535 The key points of the evaluation were evaluated on the wafers obtained. The results are as shown in Table 1. The initial contact angle before surface treatment is less than 10. However, after surface treatment: the contact angle becomes 70. The water-based effect is added. In addition, the formula described in "Evaluation of the above-mentioned hair: tube strength" is used to calculate the water retention. The capillary force results in a capillary force of la MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation is less than 10. The surface state of the water repellent is removed. Further, the Ra value of the wafer after UV irradiation is not Up to 05 nm, 晶圆 确 先 晶圆 晶圆 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 ' ίη in' in' (r\ in' in' in in ίτΓ « S, 〇VV 'o' VVVV 'o' VV 'ο&quot; VVVVVV 'o V 'o VVVVVV 'ο&quot; V Hydrating surface ti ^ ^ C 斗&lt;sc 鹆埤s- s- ss S, sssss § s s- sss· s ss sss § Evaluation result V ^0 VV 'o VVV 'o' VV 'ο' VV 'ο VVV 'ο&quot VVVVVV 'o&quot; V 'o' V 0^ VVVV Capillary force (_/m2)) &lt; i calculated value > CA 1 Q(ll) i 1 1 00 0 1 | 5 is: 3 S' 0 0^ 0 0 'o' rn 〇〇T 〇'o' 0(0.7) (0 0 'o' 5Γ ο 'ο&quot; Contact angle after surface treatment ([°]) ίο 公〇〇\〇0 o(70) 邑1 pan 'ο 1 1 I 'o 〇〇* tN 00^ R 00^ 1 S' 1 ?戒戒: ο ο 0 0 0 O 0 ο ο ο 〇 〇 〇 〇 ο 0 0 0 〇 0 0 o 0 0 ο 吞! g VVVVVVVVVVVVVVVVVVVVVV VVVV 怼* Cup Vr 杷 cup cup cup + F 杷杷杷% W % ^ • Vi Bhl Washed handle · 4»r 4r 4r Solvent wash sister dry 1_ Disc 碡墀墀 墉Μ 墀墀 time [min] 〇〇ο ο ο ο 〇〇〇〇〇〇〇ο 〇〇ο Ο ο Ο ο ο 〇ο ο Temperature [°C] SSS ss S s SS ssss S s 15« : Tea效^ W 4茫% m % E s S ί £ s ss SS 冢 Μ 埤 埤 i i i i i i i i i i i i i i i H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CTFP DCTFP 曱 benzene \_ιά_1 1 _ _ 曱 _ 1" HFE-7100 CTFP HFE-7100 CTFP HFE-7100 HFE-7100 HFE-7100 &lt; - HFE-7100 Organic Solvent Fermentation (% by mass) VJ Wl ο » Nmm νη «/&gt; ui «η »n ΙΛ \η mm *Τί un Wl Vi 〇sg »n £ SS 丁丁雔ϊϋ雔ϊϋ SE SE 2 2 1 ί iPA iPA iPA iPA — 二荽孑r, ^ 3S w - ri mmm Γ *Ί mm ΓΛ η fn 0 沄«Π 0 m water repellent compound y ίΛ X uy ϋ〇X u U .3⁄4 X u U on £ u (CH milk SiCI y (Λ I Uy ΙΛ X υ u 1 υ y (Λ X uy .3⁄4 X uy on XU 〇X 〇ϊλ X 0 X U. U ΰ XU Λ £ υ £ υ S υ u U Λ υ υ ΪΛ X uy X uu ΙΛ u U ΪΛ £ u U 〇X υ y ΪΛ £ uy ΪΛ 1 CJ y &amp; £ uy [Λ £ υ y ΕΛ XU y (Λ u Example 1 Example 2 1 Example 3 I Example 4 Example 5 1 Embodiment 6 I Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Example Π Example 18 1 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25-30-147937.doc 201100535 [Example 2] Operations were carried out in the same manner as in Example 1 except that the concentration of the water-repellent compound was changed to i% by mass. As a result of the evaluation, the contact angle after the surface treatment was changed to 66. It shows the water repellency imparting effect. In addition, the capillary force when holding water was 13 MN/m2, and the capillary force was small. In addition, the contact angle after uv irradiation is less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the UV circle after the UV,, and after the shot is less than 5 nm, and it can be broken that the crystal circle does not reach the rot after washing, and the residual residue of the water-repellent washing liquid remains after the UV irradiation. [Example 3] Operations were carried out in the same manner as in Example 除 except that the alcohol concentration was changed to 10% by mass. As a result of the evaluation, the contact angle after the surface treatment became M. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 1.2 MN/m2 ’capillary force is small. 3, the contact angle of UVM after shooting is less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the wafer after the shot is less than 0.5 nm, and the wafer is not corroded during the cleaning, and the residue of the water-repellent cleaning liquid remains after the UV irradiation.

[Example 4J] The operation was carried out in the same manner as in Example 以外 except that hydrazine and propanol (nPA) were used as the alcohol solvent. As shown in the table, the contact angle after the surface treatment was changed to: 〇 ’ showed a water repellency imparting effect. In addition, when the water is kept, the capillary &amp; force is 1 · 1 MN/m 2 , and the capillary force is small. In addition, the contact angle after uv irradiation is less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the roundness after Uv irradiation was less than 5 nm, and it was confirmed that the wafer was not subjected to corrosion by the sinter J47937.doc -31 - 201100535, and the residue of the water-repellent cleaning liquid remained after the uv irradiation. [Example 5] Operations were carried out in the same manner as in Example i except that ethanol was used as the alcohol solvent. The evaluation results are shown in Table 1, and the contact angle after the surface treatment was changed to 7 Å. , showing the water repellency imparting effect. In addition, when the water is kept, the capillary force is U, and the capillary force is small. In addition, the contact angle after uv irradiation is less than 1 〇. The surface state of the hydration is removed. Further, after the uv irradiation, the Ra value of the wafer was less than 55 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the UV-free and residual water-repellent cleaning liquid remained after the irradiation. [Example 6] The same procedure as in Example i was carried out except that i-butanol was used as the alcohol solvent. As a result of the evaluation, as shown in Table 1, the contact angle after the surface treatment was changed to exhibit a water repellency imparting effect. In addition, the capillary force when water is maintained is U MNW, and the capillary force is small. The contact angle after uv irradiation was less than 1〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 7] Operations were carried out in the same manner as in Example ] except that 1-hexanol was used as the alcohol solvent. The evaluation results are shown in Table 1, and the contact angle after the surface treatment was changed to 7 Å. , showing the water repellency imparting effect. In addition, the capillary force when water was maintained was 1.1 MN/m2, and the capillary force was small. The contact angle after n uv irradiation was less than 1 〇 ° The surface state of the water repellent was removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0_5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residual edge of the water-repellent cleaning liquid remained after the irradiation of 147937.doc -32 - 201100535 uv. [Example 8] The same procedure as in Example 1 was carried out except that a fluorine-based solvent (Asahiklin AE3000: gas i ether manufactured by Asahi Glass Co., Ltd.) was used as the organic solvent other than the alcohol solvent in the water-repellent cleaning liquid. As a result of the evaluation, the contact angle after the surface treatment was changed to 72. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 1.0 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The hydration expression is removed. Further, after the UV irradiation, the Ra value of the wafer was less than 5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 9] The same procedure as in Example 1 was carried out except that a gas solvent (Novec HFE-71 〇〇: gas ether manufactured by Sumitomo 3M) was used as the organic solvent other than the alcohol solvent in the water-repellent cleaning liquid. Take action. The evaluation results are shown in Table ,, and the contact angle after the surface ◎ was changed to 76. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 〇 8 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the Uv irradiation, the Ra value of the wafer did not reach nm 5 nm, and it was confirmed that the wafer was not subjected to sulphur during cleaning, and the residue of the water repellent cleaning liquid remained after the uv irradiation. [Example 10] The same procedure as in Example i was carried out except that the use of Bugas·3,3,3·sanacene (CTFP) as an organic solvent other than the alcohol solvent in the water-repellent cleaning liquid was carried out. Doc -33- 201100535 Operation. As a result of the evaluation, the contact angle after the surface treatment in Table 1 was changed to 2, and the water repellency imparting effect was exhibited. In addition, the capillary 1 when water is present is "io MW, and the capillary force is small. In addition, the contact angle after υν irradiation is less than 1 G. The surface state of the water repellent is removed. Further, the day after the irradiation of υν The Ra value of the Japanese yen is less than 0_5 nm, and the wafer is not corroded when the ink is removed, and the residue of the water-repellent cleaning liquid remains after the UV irradiation. [Example 11] The operation results were the same as in Example 使用 except that 1,2-digas-3,3,3-trifluoropropene (DCTFp) was used as the organic solvent other than the alcohol solvent in the water-repellent cleaning solution. As shown by W, the contact angle after kneading treatment was changed to 72. It showed an effect of imparting water repellency. In addition, the capillary force when water was held was 1_0 MN/m2, and the capillary force was small. The contact angle is less than 10. The surface state of the water repellent is removed. The Ra value of the wafer after the shot is less than 〇5 nm, which confirms that the wafer is not subjected to the rot after washing and does not remain after UV irradiation. The residue of the aqueous washing liquid [Example 12] The water-repellent compound was used as a water-repellent compound, and trifluoropropyl fluorene-based gas stone was used [C The operation was carried out in the same manner as in Example 以外 except for F3CH2CH2Si(CH3)2C1. The evaluation results are shown in Table 1, and the contact angle after the surface treatment was changed to 66. The water repellency imparting effect was exhibited. The capillary force is 1.3 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation is less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the wafer after UV irradiation is less than 0.5 nm. It was confirmed that the wafer was not corroded during the cleaning, and the residue of the aqueous washing solution remained after the UV irradiation. 147937.doc 34· 201100535 [Example 13] The non-aqueous compound was used to use nonafluorohexyldimethylchlorodecane. The operation was carried out in the same manner as in Example 1 except that [cF3(CF2)3CH2CH2Si(CH3)2C丨]. The evaluation results are shown in Table 1. The contact angle after the surface treatment was changed to 70, and the water repellency imparting effect was not exhibited. When the water is kept, the capillary force is 1.1 MN/m2', and the capillary force is small. ^, the contact angle after irradiation is less than 10. The surface state of the water repellent is removed. Further, after the irradiation The Ra value of the wafer is less than 0.5 nm, and it can be confirmed that the crystal is washed. It was not corroded, and the residue of the aqueous repellency washing liquid remained after UV irradiation. [Example 14] The ruthenium wafer was immersed in a hydrofluoric acid aqueous solution in addition to the above "(2) 矽 wafer cleaning". After 2 min, immerse in pure water! _, the same as in Example 浸 except that the heart was immersed for 1 mm. The evaluation results are shown in Table 1, and the contact angle after the surface treatment was changed to 7 Å. It shows the effect of water repellency. In addition, the capillary force when holding water is M MN/m2, and the capillary ◎ is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm, and it was confirmed that the wafer was not subjected to rot* during the cleaning, and the residue of the water-repellent cleaning liquid was not left after the uv irradiation. [Example 15] The operation was carried out in the same manner as in Example 14 except that the organic solvent other than the alcohol solvent in the aqueous washing solution was replaced with HFE-7100. Evaluation results As shown in Table 1, the contact angle after the surface treatment was changed to 74. , showing water repellency MN/m2, giving effect. In addition, the capillary force when holding water is 〇 9 147937.doc •35- 201100535 Mao, 'Tian Hao's force is small. In addition, the contact angle after irradiation of u v did not reach 丨〇. The surface state of the water repellent is removed. Further, after the υν irradiation, the Ra value of the wafer is less than 0.5 nm, and it is confirmed that the wafer is not corroded during the cleaning and the residue of the water repellent cleaning liquid remains after the irradiation. [Example 16] The operation was carried out in the same manner as in Example 14 except that the organic solvent other than the alcohol solvent in the water-repellent cleaning solution was replaced with CTFP. The evaluation results are shown in Table 1, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, the capillary force when water is maintained is 丨〇 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm5 nm, and it was confirmed that the wafer was not subjected to rot # during the cleaning, and the residue of the water-repellent cleaning solution was not left after the uv irradiation. [Example 17] Operations were carried out in the same manner as in Example 15 except that i-propanol (nPA) was used as the alcohol solvent. As a result of evaluation, the contact angle after the surface treatment was changed to 80. ' shows a water repellency imparting effect. In addition, when the water is kept, the capillary force is 0.6 MN/V, and the capillary force is small. In addition, the contact angle after strontium irradiation is less than 10. The surface state of the water repellent is removed. Further, the Ra value of the wafer after the shot was less than 0.5 nm, and it was confirmed that the wafer was not corroded and etched during the cleaning, and the residue of the water-repellent cleaning liquid remained after the UV irradiation. [Example 18] Operations were carried out in the same manner as in Example 17 except that the organic solvent other than the alcohol solvent in the aqueous washing solution was replaced with CTFP. Evaluation result ^ 147937.doc * 36 - 201100535 Table: The contact angle after surface treatment was changed to 78. It shows that the water repellency imparting effect has a capillary force of 0.7 in the case of maintaining water, and the capillary force is small. In addition, the contact angle after uv irradiation was less than 1 〇. The surface state of the water repellent is wrong. Further, after the uv irradiation, the value of the wafer is less than Μ(10)', and the wafer is not taken care of, and (4) the residual water of the water-repellent cleaning liquid is not left after the irradiation.

[Example 19J Ο Ο The operation was carried out in the same manner as in Example 17 except that the concentration of the water repellent compound was changed to 5% by mass. As a result of the evaluation, the contact angle after the surface treatment became 82. It shows the water repellency imparting effect. In addition, the capillary force when water is maintained is Q4 _m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 G. The surface state of the water repellent is removed. The Ra value of the wafer after the irradiation of uv was less than ( 5 (10), and it was confirmed that the wafer was not subjected to rot # ' during the cleaning and the residue of the water-repellent cleaning liquid remained after the irradiation of Uv. [Example 20] Operations were carried out in the same manner as in Example 除 except that the concentration of the water-repellent compound was changed to 1% by mass. As a result of the evaluation, the contact angle after the surface treatment was changed to 82. ' shows a water repellency imparting effect. In addition, the capillary force when holding water was 0.4 MN/m2, and the capillary force was small. In addition, the contact angle after uv irradiation is less than 1 〇. The surface state of the water repellent is removed. Further, after the wafer irradiation, the value of the wafer was less than G 5 (10), and it was confirmed that the wafer was not subjected to the ruin at the time of cleaning, and the residue of the water-repellent cleaning liquid remained after the uv irradiation. 147937.doc -37·201100535 [Example 21] The operation was carried out in the same manner as in Example 17 except that the concentration of the water-repellent compound was changed to 5% by mass. As a result of evaluation, as shown by w, the contact angle at the surface of the film became 84°', showing a water repellency imparting effect. In addition, the capillary force when water is maintained is 〇·3 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the hydration is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach (5 (10), and it was confirmed that the wafer was not subjected to the cleaning during the cleaning, and the residue of the water-repellent cleaning liquid remained after the UV irradiation. [Example 22] The same procedure as in Example 19 was carried out except that the organic solvent in the water-repellent cleaning liquid was only propanol (npA). As a result of the evaluation, the contact angle after the surface treatment was changed to 74. It shows the water repellency imparting effect. In addition, the capillary force when holding water is Q 9 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1G. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach G5 (10), and it was confirmed that the wafer was not purified at the time of cleaning, and the water-repellent cleaning liquid did not remain after the uv irradiation. [Example 23] Operations were carried out in the same manner as in Example 22 except that the concentration of the water-repellent compound was changed to 10% by weight. The tf price result shows that the contact angle after the surface treatment becomes 78. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 0·7 MN/m2, and the capillary force is small. In addition, the contact angle of UV,,, and after shot is less than 1〇. The surface state of the water repellent is removed. 147937.doc -38- 201100535 It can be confirmed that the water-based washing liquid is cleaned, and the Ra value of the wafer after the UV irradiation is not 曰-丄 nm. The round is not corroded, and no residue remains after the uv irradiation. [Example 24] The same operation as in the operation of the column 22 was carried out except that the concentration of the water-repellent compound was changed to 5% by mass. As a result of the evaluation, the contact angle after the surface treatment was changed to 80. , showing the effect of water-repellent duty. In addition, the capillary force when the water is kept is 〇6 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the hydration is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach 〇·5 (10), and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 25] In the above-mentioned "(3) Surface treatment of the surface of the wafer by the water-repellent cleaning liquid", the germanium wafer was immersed in the water-repellent cleaning liquid, and then immersed in pure water. The operation was carried out in the same manner as in Example 15 except that the wafer was taken out from the pure water and the air was blown to obtain a water-repellent surface state. The evaluation results are shown in Table 1. The contact angle after the surface treatment was changed to 74. , showing the water repellency imparting effect. In addition, the capillary force when holding water was 0.9 MN/m2, and the capillary force was small. Further, the contact angle after UV irradiation was less than 10°, and the surface state of the water repellent was removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 26] 147937.doc -39- 201100535 The operation was carried out in the same manner as in the Example except that the organic solution CTFP other than the solvent of the water-repellent cleaning solution was used. The evaluation results are shown in Table: The contact angle after surface treatment was changed to 72. , showing repulsion: = effect. In addition, when the water is kept, the capillary force is 1.0 MN/m2, and the capillary force is small. In addition, the contact angle after uv irradiation was less than 10. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm', and it was confirmed that the wafer was not corroded during the cleaning and the residue of the water repellent cleaning liquid remained after the uv irradiation. 147937.doc -40· 201100535

&lt;N

Evaluation result Surface smoothness (Ra[nm]) 〇 (&lt;0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇(&lt;;0.5)〇(&lt;0.5)〇(&lt;0.5)〇(&lt;0.5)〇(&lt;0.5) 〇«0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇(&lt;0.5) 〇 «0.5) 〇 (&lt;0.5) 〇 (&lt;0.5) 〇 (&lt;0.5) :. (&lt;0.5). (&lt;0.5) • « ±1 ^ The monument you E: V Ήί «: An W logic ¥ 鹆 ball. (&lt;1〇) ! 〇(&lt;!0)' 〇(&lt;!0) 〇(&lt;10);〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0)〇(&lt;!0) 〇 {&lt;!0) 〇(&lt;!0) 〇(&lt;!0) 〇(&lt;!0) 〇(&lt;!0) 〇(&lt;!0) Capillary force (_/m2))&lt Calculated value &gt; I 1 ο I | α: ο 1 &amp; 〇, 1 0 5Γ 〇1 3 〇(0.9) ? 1 ΐη Ο CN cn Contact angle after surface treatment 〇Μ 0(74) 1 Μ o 〇(74) 〇&quot; § 0? γΤ S 1 initial contact angle [°]i &lt;10 &lt;10 1 &lt;10 ί &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;;10&lt;10&lt;10&lt;10&lt;10&lt;10&lt;10&lt;10&lt;10 1 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 Electricity%% 1 ^ 1 ^ Rebel 4sf Water碡 磲碡墀 磲碡墀 磲碡墀 墀 墀 墀 磔 磔 磔 磔 min min [ [ [ [ [ [ [ [ [ [ [ [ min min [ [ [ [ [ [ [ [ [ [ [ [ • Robbery S! ^ ^ 5 ti « ^ Miscellaneous BE 2 S5 ί ί iPA, A stupid iPA ' HFE-7100 墀 1 1 acetone acetone water-repellent washing liquid organic solvent 3 effect chill cold CTFP DCTFP HFE-7100 HFH-7100 CTFP HFE-7100 CTFP HFE-7100 CTFP DCTFP HFE-7100 CTFP DCTFP "甲笨_ Γ HFE-7100 HFE-7100 CTFP "DCTFP HFE-7100 HFE-7100 • Fermentation concentration (% by mass) m •Τί W1 •η ml〇w&gt; V) u-ϊ «Λ V) »n ΙΛ In IT) v&gt; m S yeast solvent ί ί ί SS s s s ί s S5 SSSS ί 2 water-reducing compound concentration (% by mass) mf·&quot;) ΡΛ ro mmmm cn m cn mm cn m water-repellent compound U μ £ ο U .3⁄4 δ U (Λ X u U .3⁄4 〇y ΪΛ 1 uy (Λ X u U (Λ £ ο y ΚΛ £ uy £ u U ΪΛ X u U £ ay ΰό 1 ο U ao X uy go X u (CH3)3SiCI y ΰο X υ Ο ΕΛ s U 00 £ u Ο X υ £ 0 XU £ untreated (hydrolyzate of CH^Sia Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 1 Example 38 Example 39 Example 40 Implementation 41 1 贲 Example 42 1 贲 Example 43 Example 44 1 Example 45 1 Comparative Example 1 Comparative Example 2 147937.doc -41- 201100535 [Example 27] Except the alcohol solvent in the water-repellent cleaning solution The operation was carried out in the same manner as in Example 25 except that the organic solvent was replaced with FP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. It shows that the water repellency gives a fruit. In addition, when the water is kept, the capillary force is 1. 〇 MN/m2, and the capillary force is small. In addition, the contact angle after uv irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the uv irradiation. [Example 28] After the above-mentioned "(3) Surface treatment of the surface of the wafer by the water-repellent cleaning liquid", the silicon wafer was immersed in the water-repellent cleaning liquid, and then air was blown to remove the water repellency of the surface. Washing solution. Then, immersed in iPA in 丨min, and immersed in pure water for 1 min. Finally, the ruthenium wafer was taken out from the pure water, and air was blown to remove the pure water on the surface, thereby obtaining the crystal of the surface state of water repellency. All of the operations were carried out in the same manner as in Example 15 except for the above. The evaluation results are shown in Table 2. The contact angle after the surface treatment was changed to 74. It shows the effect of water repellency. In addition, the capillary force when water is maintained is 〇 9 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the wafer after the UV irradiation was less than 0 5 nm, and it was confirmed that the wafer was not ruined at the time of washing, and the residue of the water-repellent cleaning liquid was not left after the UV irradiation. [Example 29] After the above-mentioned "(3) Using the water-repellent cleaning liquid on the surface of the surface of the wafer, 147937.doc • 42-201100535", the crystal is immersed in the water-repellent washing liquid, and then blown. With air, remove the water-repellent cleaning solution from the surface. Then, the iPA is immersed in the iPA wall, and finally, the Shihwa wafer is taken out from the iPA, and the ipA of the air-removing surface is removed, thereby obtaining the wafer having the surface state of water repellency, and the examples are the same as the examples. 15 operation was performed in the same manner. The results are shown in Table 2. The contact angle after the surface treatment was changed to 72. ' shows a water repellency imparting effect. In addition, keep there

The capillary force in water is 丨.0 MN/m2, and the capillary force is small. In addition, UV

接触 The contact angle after irradiation is less than 10. The surface state of the water repellent is removed. Further, after the uv irradiation, the Ra value of the wafer did not reach 〇·5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water-repellent cleaning liquid remained after the UV irradiation. [Example 30] The organic solvent other than the alcohol solvent in the aqueous cleaning solution was replaced with the CTFP, and the same operation as in Example 29 was carried out. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. It shows a water repellency imparting effect. In addition, when the water is kept, the capillary force is 1 〇 MN/m2, and the capillary force is small. In addition, the contact angle after uv irradiation was less than 10. The surface state of the water repellent is removed. After the UV irradiation, the Ra value of the wafer is less than 5 nm. It is confirmed that the wafer is not subjected to corrosion when the cleaning is performed, and the residue of the water-repellent cleaning liquid remains after the irradiation. Crush. [Example 31] In the above (3) Surface treatment of the surface of the crucible wafer by the water repellent cleaning liquid, the crucible wafer was immersed in the water repellent cleaning liquid, and then air was blown to remove the water repellency of the surface. Washing solution. Then, after immersing in pure water, the most 147937.doc -43-201100535, the ruthenium wafer is taken out from the pure water, and the air is removed by air to remove the pure water on the surface, thereby obtaining the crystal of the surface state of water repellency. The same operation as in Example 15 was carried out except for the circle. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 74. ' shows a water repellency imparting effect. In addition, the capillary force when water is maintained is 〇·9 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV sputtering, the Ra value of the wafer was less than 0 5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 32] The organic solvent other than the alcohol solvent in the water-repellent cleaning solution was replaced with the CTFP, and the operation was carried out in the same manner as in Example 31 (10). The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, the capillary force when water is maintained is i Q MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, the Ra value of the wafer after the uv irradiation was less than (5 (10)', and it was confirmed that the wafer was not subjected to rot # during the cleaning, and the residue of the water-repellent cleaning liquid was not left after the uv irradiation. [Example 33] In addition to the above-mentioned "(3) Surface treatment of the surface of the stone substrate by the water-repellent cleaning liquid", the silicon wafer was taken out from the aqueous washing liquid, and then air was blown to obtain water repellent. Except for the wafer in the surface state, Γ was operated in the same manner as in Example 15. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 74. , He replied with water to give effect. In addition, keep the hair when there is water 147937.doc -44· 201100535 The fine official force is 0.9 MN/m2, and the capillary force is small. In addition, the contact angle after Uv irradiation was less than 10. The surface state of the water repellent is removed. Further, the Ra value of the post-fired wafer was less than 55 nm, and it was confirmed that the wafer was not subjected to rot at the time of washing and that the residue of the water-repellent cleaning liquid remained after the UV irradiation. [Example 34] Operations were carried out in the same manner as in Example 33 except that the organic solvent other than the alcohol solvent in the aqueous washing solution was replaced with CTFP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, the capillary force when holding water is i · 〇 MN / m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 10. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm5 nm', and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the uv irradiation. [Example 35] Operations were carried out in the same manner as in Example 33 except that the organic solvent other than the alcohol solvent in the aqueous washing solution was replaced with Q DCTFP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, the capillary force when holding water is 丨〇 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 10. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the UV irradiation. [Example 36] After immersing the ruthenium wafer in the water-repellent washing liquid in the above-mentioned "(3) Using a water-repellent cleaning liquid on the surface of the surface of the ruthenium wafer, H7937.doc-45-201100535" The i min was immersed in the iPA, and finally, the ruthenium wafer was taken out from the iPA, and the iPA of the surface was removed by air to obtain a wafer having a surface state of repelling water, and otherwise, the same as in the fifteenth embodiment. Perform operations. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 74. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 0·9 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer was less than nm5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the uv irradiation. [Example 37] The operation was carried out in the same manner as in Example 36 except that the organic tanning agent other than the alcohol solvent in the water-repellent cleaning was replaced with the CTFP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, when the water is kept, the capillary force is i g and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the uv irradiation, the value of the wafer was less than 〇5 (10), and it was confirmed that the wafer was not rotted during the cleaning, and the residue of the water repellent cleaning liquid was not left after the irradiation of w. [Example 38] The same procedure as in Example 36 was carried out except that the organic solvent other than the alcohol solvent in the water-repellent cleaning solution was replaced with DCTFP. The evaluation results are shown in Table 2. The contact angle after the surface treatment was changed to 72. , showing repulsion: sexual effect. In addition, the capillary force when holding water is j 〇 Μ*, and the hair 147937.doc •46· 201100535 has a small tube force. In addition, the contact angle after UV irradiation did not reach i〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm', and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the uv irradiation. [Example 39] In addition to the above "(2) Washing of wafers, the wafer was immersed in pure water for 1 min in hydrofluoric acid water/glutamine &amp;&gt; Dip in ipA ◎ 1 mm and impregnate in toluene! Except for the example, the operation is performed in the same manner as the embodiment. As a result of the δ parity, as shown in Table 2, the contact angle after the surface treatment became 70 Å, and the water repellency imparting effect was exhibited. In addition, the capillary force when holding water was 1.1 MN/m2, and the capillary force was small. In addition, the contact angle after υν irradiation was less than 10, and the surface state of the water repellent was removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not subjected to corrosion at the time of cleaning and the residue of the water-repellent cleaning liquid remained after the irradiation of IJV. [Example 40] ❹ In the above "(2) Washing of wafers, the germanium wafer was immersed in a hydrofluoric acid aqueous solution for 2 minutes, and then immersed in pure water for minmin, dipped in ipA The mixture was immersed for 1 min and immersed in HFE_71 】. The operation was carried out in the same manner as in Example I except for the mash. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 74. It shows the water repellency imparting effect. In addition, when there is water, the hair and b force are 0.9 MN/m2, and the capillary force is small. In addition, the contact angle after uv irradiation is less than 1 〇. The surface state of the water repellent is removed. Further, after the uv irradiation, the Ra value of the wafer did not reach 〇·5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the uv irradiation. 147937.doc •47- 201100535 [Example 41] In addition to the above “(2) Washing of wafers], the wafer was placed in hydrofluoric acid water/guar solution/X &gt; The same operation as in Example 15 was carried out except that the pure water was immersed for 1 min. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 74. It shows the water repellency imparting effect. In addition, the capillary force when holding water is 0.9 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation did not reach 丨〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the UV irradiation. [Example 42] Operations were carried out in the same manner as in Example 4 except that the organic solvent other than the alcohol solvent in the water-repellent cleaning solution was replaced with CTFP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of water repellency. In addition, the capillary force when holding water is 〇 MN/m2, and the capillary force is small. In addition, the contact angle after UV irradiation was less than 1 〇. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer did not reach nm 5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the uv irradiation. [Example 43] Operations were carried out in the same manner as in Example 41 except that the organic solvent other than the alcohol solvent in the aqueous washing solution was replaced with DCTFP. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was changed to 72. , showing the effect of repudiation. In addition, the capillary force when holding water is 1.0 MN/m2, and the capillary force of 147937.doc •48-201100535 is small. In addition, the contact angle after υν irradiation is less than 10. The surface state of the water repellent is removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid was not left after the UV irradiation. [Example 44] Ο 〇 The same procedure as in Example 15 was carried out except that ethyl dimethyl chloromethane [CsH^SiCCH^Cl] was used for the water-repellent compound. The sweat price results are shown in Table 2, and the contact angle after surface treatment became 78. , showing the water repellency imparting effect. In addition, the capillary force when water is maintained is 〇·7 MN/m2, and the capillary force is small. Further, the contact angle after υν irradiation was less than 1 〇, and the surface state of the water repellent was removed. Further, after the υν irradiation, the Ra value of the wafer did not reach 55 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the water repellent cleaning liquid remained after the υν irradiation. [Example 45] Operations were carried out in the same manner as in Example 15 except that the water-repellent compound was propyl dimethyl chlorite [CbHAKCHACI]. The evaluation results are shown in Table 2, and the contact angle after the surface treatment was 82. , showing the water repellency imparting effect. In addition, the capillary force when holding water is MN/m2, and the capillary force is small. In addition, the contact angle after uv irradiation was less than 1 〇 ° The surface state of the water repellent was removed. Further, after the UV irradiation, the Ra value of the wafer was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residual water-repellent cleaning liquid remained after the UV irradiation. [Comparative Example 1] The same operation as in Example i was carried out except that the water repellent cleaning liquid was not supplied to the crucible wafer. 147937.doc • 49·201100535 was operated. That is, the % 'in the case of the 'in the case' is evaluated on the wafer that is not repelled to the outer + main state. The left hydration table of 卞禾 is the lower 3 of the tentacles. With Lagu, 4 fruits as shown in Table 2, the wafer is connected to MW. Capillary force when there is water is larger 3.2 U匕 Comparative Example 2] Trimethyl gas oxirane 3.0 g, 丨 θ

Edi high score k~ _ 6 g this &amp; ’ then add 0 1 n

Aqueous acid solution (pH 1) 24 -1 N , θ . „ ) g was stirred at room temperature for about 24 hours, and the water-repellent washing solution was applied, and the same procedure as in Example 1 was carried out except that this was obtained. That is, in this comparative example, the water repellency, the volume, and the (4) aqueous washing liquid containing the reactive site hydrolyzable compound were used. The evaluation results are as shown in Table 2. 3.1: When water is maintained Capillary force is a simple schematic view of Fig. 1 which is a schematic plan view of the W circle 1 after the surface is formed into a surface having a fine concavo-convex pattern 2; Fig. 2 shows a_a in the figure, a part of the section FIG. 3 is a schematic view showing a state in which the cleaning liquid 8 is held in the recessed portion 4 in the washing step; and FIG. 4 is a view showing that the recessed portion 4 in the surface state of the water repellent state is maintained with the aqueous washing liquid. Diagram of the pattern diagram of the state. [Description of main component symbols] 1 矽 Wafer 2 Fine embossed pattern on the surface of the wafer 3 3 The convex part of the pattern 147937.doc -50- 201100535 4 The concave portion of the pattern 5 The width of the concave portion 6 convex Height of the section 7 Width of the projection 8 Retaining liquid held in the recess 4 • 9 Water-based cleaning solution 10 in the recess 4 Surface state repellent by water-repellent compound 147937.doc •51 -

Claims (1)

201100535 VII. Patent application scope: 1. A cleaning agent for enamel wafers, characterized in that it is a cleaning agent for wafers having a fine concave-convex pattern on the surface, and the cleaning agent for the ruthenium wafer contains at least a water system. a cleaning solution, and a water-repellent cleaning solution for dehydrating at least the concave portion of the concave-convex pattern during the cleaning process, and the water-repellent cleaning liquid mixture comprises: chemical bonding with the silicon wafer a water-repellent compound of a reactive site and a hydrophobic group; and an organic solvent containing at least an alcohol solvent. 〇 2 3. The wafer cleaning agent according to claim 1, wherein the alcohol solvent is at least one selected from the group consisting of alcohols having 10 or less carbon atoms. The cleaning agent for wafers according to claim 1 or 2, wherein the water repellent compound is at least one selected from the group consisting of the following general formulae (1) and [2]: [1] [R2Si(CH3)2 .dHd]eNH3.e [2] wherein 'Rl independently represents a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having a carbon number of 丨8 R is independent of each other, and represents a monovalent organic group containing a hydrocarbon group having a carbon number of 丨18 or an organic group having an valence of a fluoroalkyl chain having a carbon number of 1 to 8. Further, 'X is independent, indicating Free halo, alkoxy, ethoxylated, trisethoxycarbonyl, -0(:((:113)=0:11(:0(:113,-0(:(〇13)#- Si(CH3)3, _〇c(CF3)=N-Si(CH3)3, -CO-NH-Si(CH3)3, alkyl acid vinegar group, perfluoroalkyl sulfonate group, nitrile group And at least one group consisting of a monovalent organic group in which the element bonded to Si is nitrogen; a is 147937.doc 201100535 An integer of 'b and C' is an integer of 〇~2, a, The total value of b and c is 1 to 3, and further, d is an integer of 〇 2 and 2, and e is an integer of 1 to 3. The cleaning agent for wafers according to any one of the preceding claims, wherein the organic solvent is the above-mentioned alcohol solvent and an aprotic solvent. 5. The cleaning agent for wafers according to any one of claims 1 to 4, wherein The organic solvent is the above-mentioned alcohol solvent and the incombustible gas-containing solvent. 6. The cleaning agent for wafers according to any one of claims 5 to 5, which is assumed to be repelled by the above-mentioned water-repellent cleaning liquid. The capillary force on the surface of the recess when the recessed portion of the surface of the wafer is hydrated reaches 2.1 MN/m2 or less. 7. A water-repellent cleaning liquid which is used by the user during the cleaning process of the wafer It is characterized in that it is used to repel at least the concave portion of the concave-convex pattern during the cleaning process of the stone wafer having a fine concave-convex pattern on the surface, and the water-repellent cleaning liquid contains: a "water-repellent compound of a reactive bond and a hydrophobic group of a chemical bond; and an organic solvent containing at least an alcohol solvent. 8. A method for cleaning the surface of a tantalum wafer, characterized in that it is used as in claim 1 Washing the Shixi wafer to any of the 6 To clean the surface of the stone wafer, and the method comprises the following steps: (4) after removing the cleaning liquid on the surface of the wafer, performing light irradiation on the surface of the stone wafer, heating the stone wafer, and scraping the wafer At least one treatment that is exposed to ozone. 147937.doc