TW201206949A - Liquid Chemical for Forming Protecting Film - Google Patents

Abstract

Disclosed is a liquid chemical for forming a water-repellent protecting film at least on a surface of a recessed portion of an uneven pattern at the time of cleaning a wafer having a finely uneven pattern at its surface and containing silicon at least a part of the uneven pattern. This liquid chemical contains a silicon compound A represented by the general formula: R1aSi(H)bX4-a-b and an acid A, the acid A being at least one selected from the group consisting of trimethylsilyl trifluoroactate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroactate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroactate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroactate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate and decyldimethylsilyl trifluoromethanesulfonate.

Description

201206949 VI. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a substrate (wafer) which is intended to improve the manufacturing yield of a circuit patterning element which is particularly fine and has a relatively high aspect ratio when manufacturing a semiconductor element or the like. Washing technology. In particular, the present invention relates to a water repellent protective film forming chemical liquid or the like which is intended to improve a cleaning step of ejecting concave and convex patterns of a wafer having a fine uneven pattern on the surface. [Prior Art] For semiconductor components for network or digital home appliances, further high performance, high functionality, or low power consumption are required. Therefore, the miniaturization of the circuit pattern is accompanied by miniaturization of the particle size which causes a decrease in the manufacturing yield. As a result, the purpose of use is to remove the contaminated matter such as the miniaturized particles, and as a result, the washing step occupies 3 to 4% of the entire semiconductor manufacturing step. When the mixed detergent is washed, as the circuit pattern is refined, the damage of the alkali to the wafer becomes a problem. Therefore, it has been developed to replace it with less damaged, for example, dilute hydrofluoric acid detergent. Thereby, although the problem of damage to the wafer by the cleaning is improved, the problem caused by the increase in the aspect ratio of the pattern tends to become apparent as the semiconductor element is miniaturized. That is, after the washing or rinsing, the gas-liquid interface passes through the pattern, causing a pattern depression, and the yield is greatly reduced. The pattern depression is generated when the wafer is lifted from the cleaning liquid or the rinsing liquid. The reason is considered to be that the difference in the height of the residual liquid is formed between the upper and lower portions of the pattern and the lower portion of 156746.doc 201206949, whereby the capillary force acting on the pattern produces a difference. For force, it is expected that the difference in capillary force caused by the difference in the height of the residual liquid is lowered, and the pattern depression is eliminated. Large capillary force

The small value obtained by the following formula is the absolute value of P, and if γ or COS0 is reduced according to the formula, it is expected that the capillary force can be lowered. p = 2 XyXC〇S0/S (γ: surface tension, Θ: contact angle, s: pattern size) In Patent Document 1 _, as a method of reducing γ to suppress pattern depression, it is revealed that before the gas-liquid interface passes through the pattern The technique of replacing the washing liquid with water to form 2-propanol. However, this method is effective for preventing pattern depression, and on the other hand, the usual contact angle of a solvent such as 2-propanol having a small γ is also small, and the result tends to increase C〇W. Therefore, there is a limit that the aspect ratio of the pattern that can be matched is 5 or less. Further, in Patent Document 2, a method of suppressing pattern depression by reducing c 〇 s0 has revealed a technique in which an anti-(4) j pattern is targeted. This method sets the contact angle to 90. In the vicinity, the method of suppressing the pattern depression by "7) "close to the crucible to reduce the capillary force to the limit. However, the disclosed technique uses the resist pattern as a target and the resist itself is modified, Further, it may eventually be removed together with the resist, so that it is not necessary to envisage the removal method of the treatment agent after drying, which cannot be applied to the object. Further, in Patent Document 3, it is disclosed that a concave-convex shape is formed by using a film containing a stone. The surface of the patterned wafer is surface-modified by oxidation or the like, and a water-soluble surfactant or a sulphur coupling agent is used to form a water-repellent protective film on the surface, which reduces the capillary force and prevents the pattern from being washed. However, the water repellent used in the above has insufficient water repellency imparting effect. Further, as a method of preventing pattern depression of a semiconductor element, use of a critical fluid or use of liquid nitrogen is proposed. The method has a certain effect 'but the yield is worse than the previous washing process, and it is difficult to apply to the mass production step. Patent Document No. JP-A-2008-198958 Patent Document 2: Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. No. 4, 403, 336. Patent Document 3: Japanese Patent No. 4,403,202 [Invention] When manufacturing a semiconductor element, The surface of the wafer is a surface having a fine uneven pattern. The object of the present invention is to provide a chemical solution for forming a protective film which uses a wafer having a fine uneven pattern on the surface and at least a part of the uneven pattern containing a germanium element (described below). In the manufacturing method of "defective wafer" or "wafer only", a water repellent protective film is formed on the surface of the concave-convex pattern of the wafer, and the washing step which easily causes pattern depression is improved without impairing the yield. In the surface of the concave-convex pattern of the wafer of the present invention, a protective film forming chemical liquid (hereinafter referred to as "protective film forming chemical liquid" or simply "chemical liquid") is formed on the surface of the concave-convex pattern of the wafer, and is characterized in that it is attached to the surface. When the wafer having the fine concavo-convex pattern and the at least one portion of the concavo-convex pattern contains the germanium element is cleaned, 'the water is formed on the surface of at least the concave portion of the concave-convex pattern. 156746.doc 201206949 Protective film (hereinafter referred to as "water repellent" a protective film or a chemical solution only described as a "protective film" and comprising an anthracene compound A and an acid A represented by the following formula [1], which is selected from trimethyl sulphur trifluoroacetic acid Vinegar, tridecyl sec-alkyl trifluorosulfonate, dimethyl decyl trifluoroacetate, dinonyl decyl trifluoromethanesulfonate, butyl decyl decyl trifluoroacetate , butyl decyl decyl trifluoromethanesulfonate, hexyl decyl decyl trifluoroacetate, hexyl decyl fluorenyl trifluoromethyl phthalate, octyl dimethyl sulphur Trifluoroacetic acid vinegar, octyldidecylfluorenyl trifluoromethanesulfonate, sulfhydryl At least one of the group consisting of methyl sulfosyl trifluoroacetate and decyl dimethyl decyl trifluoromethanesulfonate. R1aSiODbX^.,, [1] (In the formula [1], R1 is each independently selected from a hydrocarbon group having a hydrocarbon group having 1 to 18 carbon atoms and a carbon number of 1 to 1 At least one of the one of the valent alkyl groups of the fluoroalkyl chain, X is independently of each other, and the element bonded to the Si element is a nitrogen atomic organic group 'a is an integer of 1 to 3, and b is 〇~2 The integer, the sum of a and b is 丨~3). R1 of the above formula [1] lowers the surface energy of the above protective film to lower the interaction between water or other liquid and the surface (the interface) of the protective film, for example, a hydrogen bond knife force. In particular, the effect of reducing the interaction with water is large, <the effect of reducing the interaction between the mixture of water and a liquid other than water or a liquid other than water. Thereby, the contact angle of the liquid with the surface of the article can be enlarged. I56746.doc 201206949 The above protective film is formed by chemical bonding of the above-mentioned formula Π]2Χ with the Si element of the ruthenium wafer. Therefore, when the cleaning liquid is removed from the concave portion of the silicon wafer, the protective film is formed on the surface of the concave portion. Therefore, the capillary force on the surface of the concave portion is reduced, and pattern depression is less likely to occur. Further, the above protective film can be removed in the subsequent step. The above acid A is selected from the group consisting of trimethyldecyl trifluoroacetate, trimethyldecyl trifluoromethanesulfonate, dimethyldecyl trifluoroacetate, dimethyl decyl trifluoromethanesulfonate Acid ester, butyl decyl decyl trifluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, hexyl dimethyl decyl trifluoroacetate Mesylate, octyl dimethyl decyl trifluoroacetate, octyl dimethyl decyl trifluoromethane sulfonate, decyl dimethyl decyl trifluoroacetate and mercapto dimethyl At least one of the group consisting of decyl trifluoromethanesulfonate functions to promote the reaction of the bismuth compound VIII with the Si element of the ruthenium wafer. The acid a is present in the above-mentioned chemical solution, whereby the protective film can be formed in a short time. Further, the above acid A may also form part of the protective film. Further, the speed at which the protective film is formed on the surface of the substrate, i.e., the speed at which the surface water repellency is exhibited on the surface of the substrate is determined by the speed at which the component derived from the above cerium compound A is combined with the reaction position of the surface of the substrate. When the acid A is present, the component derived from the ruthenium compound A can be quickly reacted with the reaction site of the surface of the embossed pattern of the ruthenium wafer, that is, the substrate can be sufficiently surface-treated during the surface treatment. Water repellency. When the amount of water present in the chemical solution is increased, the above-mentioned hydrazine compound 8 is hydrolyzed, and the reactivity is liable to lower, and it is difficult to form the protective film. 156746.doc 201206949 Therefore, the total amount of water in the initial raw material is preferably 5 〇〇〇 mass ppm or less with respect to the total amount of the raw material. In the case where the amount of water exceeds 5 by mass, it is difficult to form the above protective film in a short time. Therefore, the total amount of the above-mentioned water is preferably as small as possible, and particularly preferably 1 Å or less, more preferably 5% by mass or less. Further, if the amount of water is present in a large amount, the storage stability of the chemical solution is liable to decrease. Therefore, the amount of water is preferably as small as possible, and preferably 2 Å or less in mass Ppm, more preferably 1 〇〇 ppm by mass or less. Furthermore, the amount of water in the raw material of the above chemical solution may be 〇丨 or more. Further, in the case where the right acid is used in place of the above-mentioned acid A, for example, Brünster's acid is used, the Bronsted acid may be reacted with the above-mentioned Shishi compound A to reduce the Shishi compound A or reduce the reactivity of the ruthenium compound A. Therefore, the acid A is preferably obtained by the reaction of the acid A contained in the protective film forming solution of the present invention. For example, at least one selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride may be obtained from the hydrazine compound B represented by the following formula [2] ( Hereinafter, it is described as "acid B") and it is obtained by carrying out a reaction. R2c(H)dSi-Y [2] (In the formula [2], R2c(8)dSi_ is (CH3)3Si·, (CH3)2(8)Si, (C4H9)(CH3)2Si-, (C6Hl3)(CH3) 2Si-, (c8H17)(CH3)2Si- or (C10H21)(CH3)2Si-. Further, γ is further independent of each other, and the element bonded to the Si element is a one-valent organic group of nitrogen). 156746.doc 201206949 The above chemical solution may also be used to form the above-mentioned accompanying film with respect to the above-mentioned acid-added dream compound which is not consumed in the above reaction, using the acid VIII formed in the above reaction as a catalyst. Namely, the remainder of the above-mentioned reaction which is not consumed, can also be used as the protective medium for the composition of the compound A. Further, the above-mentioned hydrazine compound B is preferably, in terms of a molar ratio, ～(10) 嶋 mole times, preferably G.5 to 5_G moles, and (4) is preferably H0000 moles. The acid A is derived from the electrons of the Shixi compound, and functions as a catalyst to promote the reaction of the surface of the wafer on the surface of the wafer, that is, the reaction of the base alcohol, thereby causing the compound to be oxidized. The bond is chemically bonded to the Si element of the broken wafer. It is considered that the acid A acts as shown in the upper part of the figure below. In addition, the acid A is indicated as "B" in the figure. When the acid is present in the chemical solution, the protective film is formed in the short (four). The amount of water in the chemical solution is increased. The ruthenium compound A is hydrolyzed to reduce the reactivity, and it is difficult to form the protective film. . Therefore, the total amount of water in the starting material is preferably 5 〇〇〇 or less based on the total amount of the raw material. When the amount of water exceeds 5,000 ppm by mass, it is difficult to form the above protective film in a short time. Therefore, the total amount of water is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. Further, when the amount of water is large, the storage stability of the chemical liquid is liable to be lowered. Therefore, the amount of water is preferably as small as possible, and is preferably 2 〇〇 mass ppm or less, and more preferably 100 mass ppm or less. Further, the water content in the raw material of the above chemical liquid may be 0.1 mass ppm or more. In the case of using Buchner's acid instead of 156746.doc 201206949 IA, it is believed that the Brunsert acid acts as shown in the lower part of the diagram below, and the reaction site of the substrate surface, ie, a part of the sterol group, reacts to make the ruthenium compound A is chemically bonded to the yttrium wafer by an element via a decane bond, but the broth in the medicinal solution reacts with the hydrazine compound A to reduce the hydrazine compound A, or the reactivity of the hydrazine compound a decreases. There is a tendency to exhibit sufficient water repellency on the surface of the substrate. [acid 3] acid a Y 矽 compound R ^ si 03⁄4 9H Si wafer

Hair compound

Si wafer

Further, in the liquid phase in the above-mentioned chemical liquid, when the particle is measured by the light scattering type liquid particle detector, the number of particles larger than 〇. 5 μηι is preferably 100 or less per 1 mL of the liquid. If the number of particles larger than 〇·5 μπι exceeds 100 per 1 mL of the drug solution, the pattern damage caused by the particles is caused, and the cause of the decrease in the component yield and the reliability is lowered. good. Further, if the number of particles larger than 〇.5 μιη is 100 or less per 1 mL of the chemical solution, the solvent or water washing of 156746.doc •10-201206949 after the formation of the protective film may be omitted or reduced. Therefore, it is better. Further, the number of particles larger than 〇 5 μm may be one or more per 1 m] L of the drug solution. Further, the particle measurement in the liquid phase in the chemical solution of the present invention is measured by a commercially available measuring device using a light scattering type liquid particle measuring method using a laser as a light source, and the particle size of the four particles means PSL. (p〇lystyrene Latex, polystyrene latex) Light scattering approximate diameter of standard particle reference. Further, it is preferably Na, Mg, K, Ca, Mn, Fe in the above liquid medicine and

The content of the metal impurities of each element of Cu is 1 〇〇 mass Ppb or less with respect to the total amount of the liquid. The metal impurities of the above-mentioned respective elements are all in the form of metal fine particles, ions, colloids, complexes, oxides or nitrides, and are present in the chemical solution regardless of whether they are dissolved or dissolved. When the content of the metal impurities exceeds 1 〇〇 mass ppb with respect to the total amount of the chemical liquid, the junction leakage current of the element increases, which is a cause of a decrease in the component yield and a decrease in the sinfulness, which is not preferable. Further, when the content of the metal impurities is 100 mass ppb or less with respect to the total amount of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Further, the metal impurity content may be 〇〇1 mass ppb or more with respect to the total amount of the chemical liquid. The protective film forming chemical solution of the present invention is used in a wafer forming step in which a concave-convex pattern is formed, and the cleaning liquid is replaced with the chemical liquid. Further, the above-mentioned substituted chemical solution may be replaced with another washing liquid. When the cleaning liquid is replaced with the chemical solution forming liquid solution and the chemical liquid is held on at least the concave portion surface of the uneven pattern as described above, the protective film is formed on at least the concave portion surface of the concave-convex pattern. The protective film of the present invention can be formed without further 156746.doc -11 - 201206949, and it is not necessary to form it uniformly, but it is more preferably continuously and uniformly formed to impart more excellent water repellency. In the present invention, the water repellent protective film for a wafer refers to a film which is formed on the surface of the wafer to reduce the wettability of the surface of the wafer, that is, a film which imparts water repellency. In the present invention, the term "water repellency" means reducing the surface energy of the surface of the article and reducing the interaction between water or other liquid and the surface (interface) of the article such as hydrogen bonding, intermolecular force and the like. In particular, the effect of reducing the interaction with water is greater, but it also has the effect of reducing the interaction between the water and the liquid other than the water or the liquid other than the water. By reducing the interaction, the contact angle of the liquid with the surface of the article can be increased. In the present invention, when the cleaning liquid is removed from the concave portion, that is, when the drying is performed, the protective film is formed on at least the surface of the concave portion of the concave-convex pattern. Therefore, the capillary force on the surface of the concave portion is reduced, and pattern collapse is less likely to occur. Further, the protective film may be at least one selected from the group consisting of a process of performing light irradiation on a surface of a wafer, a process of heating a wafer, a process of exposing ozone to a wafer, and a process of irradiating a surface of the wafer with plasma. Processed and removed. Advantageous Effects of Invention The protective film formed by the chemical solution for forming a protective film of the present invention is excellent in water repellency, thereby reducing the capillary force on the surface of the concave-convex pattern of the wafer and further exhibiting a pattern collapse preventing effect. When the chemical liquid is used, the washing step in the method of manufacturing a wafer having a fine uneven pattern on the surface is not required to be reduced. Therefore, the method for producing a wafer having a fine uneven pattern on the surface of the coating liquid for forming a protective film of the present invention has high productivity. 156746.doc 201206949 The chemical solution for forming a protective film of the present invention can also be used for a concave-convex pattern having an aspect ratio of, for example, 7 or more which is predicted to increase in the future, and can reduce the production cost of a semiconductor device having a higher density. Further, it can be handled without significantly changing the previous device, and the result can be applied to the manufacture of various semiconductor elements. [Embodiment] The wafer cleaning method using the fine concavo-convex pattern on the surface of the protective film forming chemical solution of the present invention and including at least a part of the concavo-convex pattern includes the following steps: (Step 1) setting the surface of the wafer After the surface having the fine uneven pattern, the aqueous cleaning solution is supplied to the surface to protect the surface of at least the concave portion of the concave-convex pattern; # (Step 2) is held on at least the concave surface of the concave-convex pattern. Replacement with the cleaning solution A different from the aqueous cleaning solution; \Step 3) replacing the cleaning solution A with the protective film forming chemical solution, and holding the chemical solution on at least the concave surface of the concave-convex pattern; (Step 4 Removing the liquid from the surface of the relief pattern by drying; and (step 5) removing the protective film. Further, after the step of holding the protective film forming chemical solution on at least the concave portion surface of the concave-convex pattern (step 3), the chemical liquid held on the surface of at least the concave portion of the concave-convex pattern may be replaced with the chemical liquid. After the different cleaning liquid B, the process proceeds to a step of removing the liquid from the surface of the concave-convex pattern by drying (step 4). Further, after the water-based cleaning liquid containing the aqueous solution is held on the surface of at least the concave portion of the concave-convex pattern by the replacement of the cleaning liquid (4), the step of transitioning to removing the liquid from the surface of the concave-convex pattern by drying may be performed 156746.doc 13 - 201206949 (Step) X' When the protective hydrazine forming chemical liquid can be replaced with the aqueous cleaning liquid, the replacement by the cleaning liquid B may be omitted. In the present invention, the cleaning method of the wafer is not particularly limited as long as the chemical liquid or the cleaning liquid can be held on at least the surface of the concave portion of the concave-convex pattern of the wafer. As a method of cleaning the wafer, a wafer in which the wafer is held substantially horizontally and rotated, and a single-piece method in which the liquid is washed in the vicinity of the center of rotation and the wafer is washed one by one is representative, or A batch method in which a plurality of wafers are immersed in a cleaning tank and washed. In addition, the form of the chemical liquid or the cleaning liquid when the chemical liquid or the cleaning liquid is supplied to the surface of at least the concave portion of the concave-convex pattern of the wafer is not particularly limited as long as it is liquid when held on the surface of the concave portion. There are liquids, vapors, etc. The ruthenium compound in the above-mentioned chemical solution is preferably a compound represented by the following formula [丨]. [1] [1] (In the formula [1], R1 is each independently selected from one of a valent alkyl group having a hydrocarbon group having a carbon number of 18 and a fluoroalkyl chain having a carbon number of 丨8. At least one group of the valence organic groups, X is independently of each other, and the element bonded to the Si element is a nitrogen atomic organic group 'a is an integer of U', and b is an integer of 〇~2, which is a total of 1 with b ~3). In the above formula [1], 'the element bonded by X and the element bonded to the element is one of nitrogen. The organic group includes not only hydrogen, carbon, nitrogen, or oxygen, but also contains elements such as Shi Xi, sulfur, and pot sound elements. AO Si Kai. Go to Μ 夕 ,, go to &@; _ 156746.doc •14· 201206949 Examples of machine bases, areocyanate, amine, dialkylamine, isothiocyanate, azide , acetamino group, -n(ch3)c(o)ch3, -n(ch3)c(o)cf3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi( CH3)3, -NHC(0)-0Si(CH3)3, -NHC(0)-NH-Si(CH3)3, ρm® ring (the following formula [3]), 17th stalk ring ( The following formula [4]), morpholine ring (the following formula [5]), -NH-C(0)-Si(CH3)3, -Ν(Η)2·s (Si(H)hR33_h)g(R3 The carbon number of one or all of the hydrogen elements which may be substituted by the Dun element is 1 to 18 one-valent hydrocarbon group, g is 1 or 2, h is an integer of 0 to 2, and the like. X of the ruthenium compound A as a reactive site rapidly reacts with the reaction site of the surface of the embossed pattern of the ruthenium wafer, i.e., the ruthenium alcohol group, thereby causing the ruthenium compound A to be bonded to the ruthenium wafer via a ruthenium oxide bond. The Si element is chemically bonded, whereby the surface of the wafer can be covered by the hydrophobic R1 group, so that the capillary force of the concave surface of the wafer can be reduced in a short time. [Chemical 5]

[4] 〇 [5]

On the other hand, when the X amount of the ruthenium compound a shown by 4-a-b in the above formula [1] is 1, the protective film can be formed homogeneously, which is more preferable. R1 in the above general formula [1] is each independently selected from at least one of v 〜 imn2m + 1 (m-1 to 18) and cnF2n+1CH2CH2 (n = 1 to 8), and When the protective film is formed on the surface of the pattern, the wettability of the surface can be further reduced, that is, it is more preferable because it can impart more excellent water repellency to the surface. Further, since the right m and n are 丨8, it is preferable to form a protective film on the surface of the concave-convex pattern in a short time, 156746.doc •15·201206949. Examples of the dream compound A represented by the above formula [1] include CH3Si(NH2)3, C4H9Si(NH2)3, C7H15Si(NH2)3, C10H21Si(NH2)3, C13H27Si(NH2)3, C16H33Si(NH2). 3, (CH3)2Si(NH2)2, C3H7Si(CH3)(NH2)2 C4H9Si(CH3)(NH2)2 C5HnSi(CH3)(NH2)2 C7H15Si(CH3)(NH2)2 C9H19Si(CH3)(NH2 ) 2 C"H23Si(CH3)(NH2) C13H27Si(CH3)(NH2) C15H31Si(CH3)(NH2) C17H35Si(CH3)(NH2) C2H5Si(NH2)3 C5HnSi(NH2)3 C8H17Si(NH2)3 CnH23Si(NH2 ) 3 C14H29Si(NH2)3 C17H35Si(NH2)3 C2H5Si(CH3)(NH2) C3H7Si(NH2)3 C6H13Si(NH2)3 C9H19Si(NH2)3 C,2H25Si(NH2)3 C15H31Si(NH2)3 C18H37Si(NH2) 3 > (C2H5)2Si(NH2): (C3H7)2Si(NH2)2(C4H9)2Si(NH2)2 C6H13Si(CH3)(NH2)2 C8H17Si(CH3)(NH2)2 C,〇H21Si(CH3) (NH2)2 C12H25Si(CH3)(NH2)2 C14H29Si(CH3)(NH2)2 C16H33Si(CH3)(NH2)2 C18H37Si(CH3)(NH2)2 (CH3)3SiNH2, C2H5Si(CH3)2NH2, (C2H5) 2Si(CH3)NH2(C2H5)3SiNH2, C3H7Si(CH3)2NH2, (C3H7)2Si(CH3)NH2(C3H7)3SiNH2, C4H9Si(CH3)2NH2, (C4H9)3SiNH2 C5HnSi(CH3)2NH2 C7H15Si(CH3)2NH2 C9H19Si (CH3)2NH2 C6H13Si(CH3)2NH2 C8H17Si(CH3)2NH2 C10H21Si(CH3)2NH2 1567 46.doc • 16-201206949

CuH23Si(CH3)2NH2, C12H25Si(CH3)2NH2, C13H27Si(CH3)2NH2, C14H29Si(CH3)2NH2, C15H31Si(CH3)2NH2, C16H33Si(CH3)2NH2, C17H35Si(CH3)2NH2, C18H37Si(CH3)2NH2, (CH3 2Si(H)NH2, CH3Si(H)2NH2, (C2H5)2Si(H)NH2, C2H5Si(H)2NH2, C2H5Si(CH3)(H)NH2, (C3H7)2Si(H)NH2, C3H7Si(H) 2NH2, CF3CH2CH2Si(NH2)3, C2F5CH2CH2Si(NH2)3, C3F7CH2CH2Si(NH2)3, C4F9CH2CH2Si(NH2)3, CSF, 1CH2CH2Si(NH2)3, C6F13CH2CH2Si(NH2)3, C7F15CH2CH2Si(NH2)3, C8F17CH2CH2Si(NH2) 3, CF3CH2CH2Si(CH3)(NH2)2, C2F5CH2CH2Si(CH3)(NH2)2, C3F7CH2CH2Si(CH3)(NH2)2, C4F9CH2CH2Si(CH3)(NH2)2 'C5F11CH2CH2Si(CH3)(NH2)2 'C6F13CH2CH2Si(CH3 )(NH2)2, C7F15CH2CH2Si(CH3)(NH2)2, C8F17CH2CH2Si(CH3)(NH2)2, CF3CH2CH2Si(CH3)2NH2, C2F5CH2CH2Si(CH3)2NH2, C3F7CH2CH2Si(CH3)2NH2, C4F9CH2CH2Si(CH3)2NH2, C5F" CH2CH2Si(CH3)2NH2, C6F13CH2CH2Si(CH3)2NH2, C7F15CH2CH2Si(CH3)2NH2, C8F17CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2 and other amine decane, or the amine group of the above amino decane (-NH2 group) Substituted into -N=C=0, -N(CH3)2, -N(C2H5)2, -N=c=s '-N3, -NHC(0)CH3, -N(CH3)C(0)CH3 , -N(CH3)C(0)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(0)-0Si(CH3)3, -NHC(0)-NH-Si(CH3)3, imidazole ring, oxazolidinone ring, morpholine ring, -NH-C(0)-Si(CH3)3 -17- 156746. Doc 201206949 , -N(H)2. g(Si(H)hR33_h)g (R3 is a part or all of a hydrogen element which may be substituted by a fluorine element and has a carbon number of 1 to 18, a g-valent hydrocarbon group, g is 1 or 2, and h is an integer of 0 to 2) And so on. Wherein X of the oxime compound A of the above formula [1] is also preferably _n(CH3)2, -NH2, -N(C2H5)2, -N(CH3)C(0)CH3, -n(ch3) c(o)cf3, -NHC(0)-NH-Si(CH3)3, microphone. Ring, -N=C=〇, _NH_c(〇)_Si(CH3)3, -:^(11)2. It must be 1 (11) 洱 434 (114 is a monovalent hydrocarbon group having a carbon number of 1 to 8 in which some or all of the hydrogen elements may be substituted by a fluorine element, 1 is 1 or 2, and j is an integer of 〇 2). In the above liquid, the concentration of the acid A is preferably 1% by mass, preferably 0%, based on the total amount of the above hydrazine compound a. 01~5〇% by mass. If the amount of addition is small, the effect of the acid is lowered, so that it is not preferable, and even if it is excessive, the effect of the acid as a catalyst does not increase, and conversely, there is a concern that the surface of the wafer is eroded or remains as an impurity. Therefore, the concentration of the acid A is preferably 100% by mass based on the total amount of the above ruthenium compound A, and particularly preferably 5% to 25% by mass. Further, in the above chemical solution, the above-mentioned compound A and acid A may be diluted by a solvent. When the total amount of the addition amount of the cerium compound A and the acid A is 〇〇1 to 1% by mass based on the total amount of the above-mentioned chemical liquid, the thickness of at least the concave portion of the concave-convex pattern is apt to be uniform. It is preferred to form a protective film. If it does not reach 0. When the amount is 01% by mass, the protective effect of the uneven pattern tends to be insufficient. Further, if the total amount of the addition of the hydrazine compound A and the acid VIII is large, the cost is increased. Further, the hydrazine compound A and the acid A may be in contact with a protic solvent such as water or an alcohol or the reaction of the sulphur compound A with the acid A to produce a solid matter. If the total is large, the generated Solid 156746. Doc 201206949 The amount of the substance is also increased. The solid matter is more soluble in the above-mentioned liquid, but the risk of remaining as a particle on the wafer after drying increases, so that the operation of the above liquid becomes difficult. The sum of the words is preferably 0. 05 to 50% by mass, more preferably o. Uo quality%. In addition, if the sum of the addition amounts of the compound A and the acid A is large, it is easy to improve the storage stability of the above liquid. Therefore, it is preferably 0. 5 to 3 % by mass, and further preferably 3 % by mass. As a solvent which may be diluted in the above-mentioned chemical liquid, for example, a hydrocarbon, an ester, an ether, a ketone, a solvent containing a crypto element, a sulfoxide solvent, an alcohol, or a derivative of a poly 7 G alcohol may be preferably used. An organic solvent such as a solvent containing a nitrogen element. Wherein, if a hydrocarbon, an ester, a test, a solvent containing a halogen element, a sulfoxide solvent, or a derivative of a polyhydric alcohol is used, the protective film is formed on the surface of the concave-convex pattern. Therefore, it is better. Examples of the hydrocarbons include methyl benzene, benzene, diphenylbenzene, hexane, heptane, and octane; and examples of the ester include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetonitrile. Ethyl ester or the like; as an example of the ether, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.; as an example of the solvent containing the dentate 7C, there are perfluorooctane and perfluoro Perfluorocarbon such as decane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, m3,3_pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Ze 〇r〇ra ΖΕΟΝ (manufactured by 曰本ΖΕΟΝ) and other hydrofluoric ruthenium-fluorenyl perfluoroisobutyl, fluorenyl perfluorobutyl ether, ethyl perfluorobutyl bond, ethyl perfluoroisobutyl ether, Asahiklin ΑΕ-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, N〇vec7300 'N〇Vec7600 (all manufactured by 3M), etc. Hydrofluoroether, tetrachlorodecane 156746. Doc •19· 201206949 such as carbon, gas and other hydrogen and carbon, dichlorodifluoromethane and other gas fluorocarbon, u-dichloro-2'2'3,3,3-pentafluoropropane, 1,3_two gas _1,1,2,2,3_pentafluoropropane, 1_chloro-3'3'3-trifluoropropene, 1>2•dichloro-3,3,3_trifluoropropene, etc. a fluoroether, a perfluoropolyether or the like; and examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like; and as a derivative of the above polyol, and having no 〇h*, there is a diethylene glycol single Ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dioxime ether, diethyl Glycol ethyl decyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol diethyl s-diester, triethylene glycol dimethyl ether, ethylene glycol diacetic acid Ester, ethylene glycol, shii, ethylene glycol, shouting, etc. In addition, when the organic solvent is incombustible, the chemical solution forming liquid is incombustible or the flammable point rises, so that the risk of the chemical liquid is lowered, which is preferable. The solvent containing the dentate element is mostly incombustible, and the solvent of the incombustible element element can be preferably used as a non-combustible organic solvent, and the above liquid is supplied to the crystal while rotating the wafer on the side. In the case of a circle, the above-mentioned organic agent has a low point of the Buddha, and the liquid is easily dried before the solution is wetted and spread to the entire surface of the wafer, which is not preferable. Moreover, if the point of the Buddha is too high, there is a tendency that the viscosity of the liquid is too high, and the viscosity of the liquid is too high. Therefore, it is preferable to use the above-mentioned organic solvent as the grasper. As such a solvent, it is preferable to consider the solubility of the #i @^ 偬烕 or other washing liquid (ease of substitution)', preferably diethyl ethoxylate monoethyl ether acetate, ethylene glycol mono-f ether Acetate, propylene glycol monomethyl early methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl T-ether, di 7 ethyl alcohol monoethyl ether, diethylene glycol mono f ether B 156746. Doc •20· 201206949 Acid bismuth, monoethylene glycol diacetate, triethylene glycol dimethyl scale, ethylene glycol diacetate, ethylene glycol dice. Further, the total amount of water in the starting material of the protective film forming chemical solution is preferably 5,000 ppm by mass or less based on the total amount of the raw material. When the total amount of water = more than 5,000 ppm by mass, the effect of the cerium compound lanthanum and the cerium lanthanum represented by the above formula π] is lowered, and it is difficult to form the protective film in a short time. Therefore, the total amount of the above water content is preferably as small as possible, and particularly preferably 1 〇〇〇 ppm by mass or less, more preferably 5 〇〇 f tppm or less. Therefore, the hydrazine compound A, the acid A contained in the above-mentioned chemical solution, or the solvent contained in the above-mentioned chemical solution is preferably one which does not contain a large amount of water. Further, in the liquid phase in the above-mentioned chemical liquid, when the particle is measured by the light scattering type liquid particle detector, the number of particles larger than 〇·5 μηΐ2 is preferably 100 or less per 丨mL of the liquid. If the number of particles larger than 0 5 μm is more than 100 per 1 mL of the chemical solution, the pattern damage caused by the particles is caused, and the cause of the decrease in the yield of the component and the decrease in the reliability are caused, which is not preferable. . Further, when the number of particles larger than 〇5 μηΐ2 is 100 or less per mL of the chemical liquid, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the above liquid medicine is greater than 0. The number of particles of 5 μηη is preferably as small as 1 or less per 1 mL of the drug solution, and particularly preferably 10 or less, more preferably 2 or less. Further, the number of particles larger than 〇·5 μm may be one or more per i mL of the chemical solution. Further, the content of the metal impurities of each of Na 'Mg, K, Ca, Mn, Fe, and Cu in the above-mentioned chemical liquid is preferably 1 ppb or less per ppb of the total amount of the chemical liquid. If the above metal impurity content is more than 156746 relative to the total amount of the liquid. Doc •21· 201206949 Big 虞, and it is not good. In addition, when 100 ppb is used, the bonding leakage current of the device increases the yield of the device and the reliability decreases. The content of the metal impurity is 1 〇〇 mass _ or less with respect to the total amount of the chemical liquid, and may be omitted. It is preferable to reduce the washing with a solvent or water after the formation of the above protective medium. Therefore, the metal impurity content is preferably as small as possible, and particularly preferably i mass ppb or less, and more preferably 〇1 mass ppt or less. Further, the content of the metal impurities may be 0,01 mass ppb or more with respect to the total amount of the chemical liquid. In the method for preparing a protective film forming liquid containing the mixture of the compound A and the acid VIII represented by the above formula (1), it is preferred to mix the compound A, the acid A and the mixture before mixing. Purification is carried out by at least one of the liquids. Further, when the chemical solution forming solution contains a solvent, the compound A and the acid A before the mixing may be in a solution state containing a solvent. In this case, the above purification may also be carried out before the compound A or At least one of the solution, the acid A or a solution thereof, and the mixed solution after mixing is targeted. The above-mentioned purification uses removal of water by an adsorbent such as a molecular sieve or a vaporizer, and removal of metal impurities of each element of Na, Mg, κ, Shi, FaCu, such as an ion exchange resin or a steaming chamber, and At least one of the removal methods of the pollutants such as the filter smashed particles, etc., preferably: considering the reactivity of the protective film forming liquid or the cleaning of the wafer, removing the water and removing the metal impurities, and removing Contaminants, regardless of the order of removal. The acid A contained in the protective film forming solution for the moon can also be reacted by 156746. Obtained by doc -22- 201206949. For example, it can also be obtained by reacting the hydrazine compound B represented by the following formula [2] with the acid B. R2c(H)dSi-Y [2] (In the formula [2], R2c(H)dSi- is (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3 2Si-, (C6H13)(CH3)2Si-, (C8H17)(CH3)2Si- or (C10H2丨)(CH3)2Si-. Further, Y is independent of each other, indicating that the element bonded to the Si element is one of nitrogen Price organic basis). Further, 'acid B is at least one selected from the group consisting of trifluoroacetic anhydride and trifluoromethanesulfonic anhydride, and reacted with the above-mentioned hydrazine compound B to obtain an acid a, thereby preparing a chemical solution, or the above-mentioned hydrazine compound A and The chemical solution prepared by using the acid A as a starting material is excellent in stability and is therefore more preferable. In the chemical solution for forming a protective film of the present invention, the above-mentioned bismuth compound B may be excessively added to the acid B, and the remaining portion of the ruthenium compound b which is not consumed in the above reaction may also contribute to the formation of the above-mentioned protection as the cerium compound A. membrane. Further, the above hydrazine compound B is preferably 0 in terms of molar ratio with respect to the above-mentioned acid B. 2 to 100,000 moles, preferably 0. 5 to 5 moles, and further preferably 1 to 10,000 moles. Further, as long as the acid A is obtained, a reaction other than the reaction of the above-mentioned compound b and the acid B can be used. The element of the bismuth compound B of the above formula [2] which is bonded to the Si element as Y is a nitrogen monovalent organic group which contains not only hydrogen, carbon, nitrogen or oxygen but also elements such as sulphur, sulfur and halogen. The element bonded to the Si element is nitrogen 156746. Doc -23· 201206949 Examples of monovalent organic groups 'isocyanate group, amine group, dialkylamino group, isothiocyanate group, azide group, etidinyl group, -N(CH3)C(0) CH3, -N(CH3)C(0)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(0)-0Si(CH3)3 , _NHC(0)-NH-Si(CH3)3, imidazole ring, oxazolidinone ring, morpholine ring, _NH-C(0)-Si(CH3)3, -(Si(H)qR53-q) p (R5 is a monovalent hydrocarbon group in which a part or all of hydrogen elements may be substituted by a fluorine element, and the number of carbon atoms is 1 to 18, p is 1 or 2, and q is an integer of 〇 2). Examples of the compound B of the above formula [2] include (CH3)3SiNH2, C4H9Si(CH3)2NH2, C6H13Si(CH3)2NH2, C8H17Si(CH3)2NH2, C10H21Si(CH3)2NH2, (CH3)2Si ( H) Amino decane of NH2, or substituted with the amine group of the above amino decane (_NH2 group) to -N = C = 0, -N(CH3)2, -N(C2H5)2, -N = C = S , -N3, nhc(o)ch3, -n(ch3)c(o)ch3, -n(ch3)c(o)cf3, -N=C(CH3)OSi(CH3)3, -N=C( CF3) OSi(CH3)3, -NHC(0)-OSi(CH3)3, -NHC(0)-NH-Si(CH3)3. Mn ring, p-bit ketone ring, imiline ring, -NH-C(0)-Si(CH3)3, -NH-Si(CH3)3, -NH-Si(H)(CH3)2 , -NH-Si(CH3)2(C4H9), -NH_Si(CH3)2(C6H13), -NH-Si(CH3)2(C8H17), -NH-Si(CH3)2(C10H21), -N- {Si(CH3)3}2 is the so on. Wherein the γ of the oxime compound b of the above formula [2] is preferably _n(CH3)2, -NH2'-N(C2H5)2'-N(CH3)C(0)CH3'-N(CH3)C (0) CF3 '-NHC(0)-NH-Si(CH3)3, imidazole ring, -NH-C(0)-Si(CH3)3, -NH-Si(CH3)3, -NH-Si( H) (CH3)2, -NH-Si(CH3)2(C4H9), -NH-Si(CH3)2(C6H13), -NH-Si(CH3)2(C8H17), -NH-Si 156746. Doc •24· 201206949 (CH3)2(C10H21) ο For example, if hexamethyldiazepine as ruthenium compound B is mixed with di-acetic anhydride as acid B, trifluoroacetic acid will react immediately. Thus, trimethyldecyltrifluoroacetate as the acid A was obtained. Further, for example, if hexamethyldiazepine as the hydrazine compound B is mixed with difluoro sulfonium anhydride as the acid B, the trifluoroanthridine anhydride is immediately reacted to obtain trimethyl decane as the acid A. Trifluorosulfonate. Further, for example, if tetramethyldiazepine as the hydrazine compound B is mixed with difluoroacetic anhydride as the acid B, the trifluoroacetic acid anhydride is immediately reacted to obtain a dimercaptoalkylene group as the acid A. Fluoroacetate. Further, for example, if tetramethyldiazole nitrogen as the hydrazine compound B is mixed with difluoromethanesulfonic anhydride as the acid B, the trifluoromethanesulfonic anhydride is immediately reacted to obtain dimethyl decane as the acid A. Triflate. Further, for example, if 1,3-dibutyltetradecyl ferrocene as the hydrazine compound B is mixed with trifluoroacetic anhydride as the acid B, the trifluoroacetic acid anhydride is immediately reacted to obtain an acid. Butyl dimethyl decyl trifluoroacetate of A. Further, for example, when 1,3-dibutyltetramethyldiazide nitrogen as the hydrazine compound B is mixed with trifluorosulfonium sulfonic acid anhydride as the acid B, the trifluorosulfonium sulfonic acid needle is immediately reacted to obtain The butyl dimercaptoalkylene group of the acid A is tribasic. Further, for example, if 1,3-dihexyltetramethyldiazide nitrogen as the hydrazine compound B is mixed with trifluoroacetic anhydride as the acid B, the trifluoroacetic acid anhydride is immediately reacted to obtain the acid A. Hexyl dimethyl decyl trifluoro 156746. Doc •25· 201206949 Acetate. Further, for example, if 13-dihexyltetradecyldifluorene as the hydrazine compound 8 is mixed with trifluoromethanesulfonic anhydride as the acid B, the trifluorosulfonium sulfonate is immediately reacted to obtain acid A. Hexyl dimethyl sulfonyl difluoromethyl vinegar. Further, for example, if the mixture of 3, di-octyltetramethyldifluorene, and trifluoroacetic anhydride as acid B is mixed as the compound of B, the trifluoroacetic acid anhydride is immediately reacted, thereby obtaining Octyl dimercaptoalkyl trifluoroacetic acid vinegar of acid A. Further, for example, if 1,3-dioctyltetramethyl hexanthene as the compound B of the oxime compound B is mixed with trifluoromethane anhydride as the acid B, the trifluoromethanesulfonic anhydride is immediately reacted. Thus, octyl dimethyl decyl difluoro I 曱 can be obtained as acid A. Further, for example, if octyldidecyl (dimethylamino) as a ruthenium compound B is mixed with trifluoroacetic anhydride as the acid B, the trity acid anhydride is immediately reacted to obtain acid A. Octyl dimethyl decyl trifluoroacetate vinegar. Further, for example, when octyldimercapto (dimethylamino) as the bismuth compound B is mixed with trifluoromethanesulfonic anhydride as the acid B, the trifluoromethyl acid is immediately reacted to obtain As octyl dimethyl decyl dimethyl sulphate of acid A. Further, for example, if the 1,3-dimercaptotetradecyldifluorene as the bismuth compound B is mixed with the difluoroacetic acid acetic acid as the acid B, the tri-acetic acid needle is immediately reacted, thereby obtaining Acid A thiol dimethyl stone kiln base three defeat 156746. Doc -26· 201206949 Acetic acid vinegar. Further, for example, if the fluorene compound dimercaptotetramethyldiazepine is mixed with the trifluoromethanesulfonic anhydride as the acid B, the trifluoromethanesulfonic anhydride is immediately reacted to obtain the thiol group as the acid A. Methyl Shi Xi Xuanmei difluoride I continued to grow vinegar. Further, in the case where the acid hydrazine is obtained by the reaction as described above, the total amount of the water component in the starting material of the protective film forming liquid is preferably 5,000 ppm by mass or less based on the total amount of the raw material. In this case, the amount of water in the raw material is preferably as small as possible, and particularly preferably 1000 ppm by mass or less, and further preferably 500 ppm by mass or less. Further, when the amount of water is large, the storage stability of the above-mentioned chemical liquid is liable to be lowered. Therefore, the amount of water is preferably as small as possible, and is preferably 200 ppm by mass or less, and more preferably 1 〇〇 ppm by mass or less. Further, the total amount of water in the raw material may be 5% by mass or more. Further, in the case where the acid A is obtained by the reaction as described above, when the particle is measured by the particle detector in the light scattering type liquid in the liquid phase in the protective film forming liquid, it is larger than 0. The number of particles of 5 μηι is preferably 100 or less per 1 mL of the drug solution. If the above is greater than 0. When the number of particles of 5 μηι exceeds 1 每 per 1 mL of the chemical solution, the pattern damage caused by the granules is caused, and it is a cause of a decrease in the yield of the component and a decrease in reliability, which is not preferable. Also, if greater than 0. When the number of particles of 5 μηη is 100 or less per 1 mL of the chemical solution, it is preferable to omit or reduce the washing with a solvent or water after forming the protective film. Therefore, the above liquid medicine is greater than 0. The number of particles of 5 μηι is preferably as small as 1 or less per 1 mL of the drug solution, and particularly preferably 10 or less, more preferably 2 or less. Again, the above is greater than 〇 5 156746. The number of particles of doc -27·201206949 μιη may be more than one per 丨mL of the drug solution. Further, when the acid A is obtained by the reaction as described above, the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the protective film forming liquid is relative to the total amount of the liquid It is also preferably 1 〇〇 or less by mass ppb. When the content of the metal impurities on the right side exceeds 1 〇〇 mass ppb with respect to the total amount of the chemical liquid, the junction leakage current of the element increases, which is a cause of a decrease in the yield of the element and a decrease in reliability, which is not preferable. Further, when the content of the metal impurities is 1 〇〇 or less by mass based on the total amount of the chemical liquid, it may be omitted or reduced, and it is preferred to use a solvent or water after the protective film is formed. Therefore, the content of the metal impurities is preferably as small as possible, and particularly preferably, the mass of the metal is less than or equal to 1 ppb, and further preferably, the mass of the metal is equal to or greater than the total amount of the metal. 01 mass ppb or more. In the preparation method of the protective film forming chemical liquid contained in the above-mentioned compound B, the above-mentioned acid B is preferably mixed in the compound B, the acid B, and the mixed liquid before mixing. In the case where at least one of the chemical liquids for forming the H film contains a solvent, the above-mentioned acid B may be a solution containing a solvent, and in this case, the above purification may be mixed before the # The compound/solution, the above-mentioned _ or a solution thereof, and the mixed solution after mixing are used as a target. Further, the acid A obtained by the above reaction is mixed with the compound 8 or a solution thereof to prepare a protective film to form a ruthenium. The above purification may also be carried out by mixing the solution of the compound before, or the acid A obtained by the reaction or At least 156746 of the solution, and the mixed mixture after mixing. Doc -28- 201206949 An object. The above purification system is carried out by removing the water such as an adsorbent such as a molecular sieve or a steaming chamber, removing metal impurities of each element of Na, κ, diFe and Cu such as ion exchange resin or distillation, and by filtering » At least one of the removal of the contaminated material such as the filtered particles is carried out. It is preferable to consider the activity or cleanliness of the protective film forming liquid, remove moisture, remove metal impurities, and remove contaminants regardless of the order of removal. In addition, the chemical solution for forming a protective film of the present invention may contain other additives or the like in addition to the compound A, the acid A or the solvent represented by the above formula (1), without departing from the object of the present invention. The additive may, for example, be an oxidizing agent such as hydrogen peroxide or ozone, or a surfactant. Further, in the case where a portion of the concave-convex pattern of the crystal is not formed of the material of the film of the above-mentioned broken compound A, it is also possible to add a protective medium to the (4). Further, other acids may be added for purposes other than the catalyst. Further, the chemical solution for forming a protective film of the present invention may be stored in a state in which the raw materials are separated into two or more kinds and used in combination before use. For example, when the compound A and the acid A are used as a raw material of the protective liquid for forming a protective film, the compound A and the acid A may be separately stored and mixed before use. In the case of using Shishi Compound B and Acid B, Compound B and Acid B may be separately mixed before use. Further, the ruthenium compound and the acid before mixing may also be in a solution state. Further, the above-mentioned Wei compound and acid may be stored in the same solution and mixed with other raw materials before use. 156,746. Doc •29·201206949 Further, as the chemical solution for forming a protective film of the present invention, for example, a mixture containing the following may be used, or the mixture may be selected from the group consisting of hydrofluoroether, hydrogen fluorocarbon, and ethylene glycol. At least one organic solvent selected from the group consisting of decyl ether acetate, propylene glycol diethylene glycol monoethyl ether acetate monoterpene ether acetate, diethylene glycol diacetate, and diethylene glycol dimethyl ether 76~99. 8999% by mass, selected from hexamethyldioxane, four? Dioxazane, 1,3-dioctyltetramethyldiazepine, An octyldihydrazyl group (at least one or more of the group consisting of dimethylamino group 〇 烧 〇 〇 〜 〜 〜 〜 / / / , , , , , , , , , , , , , , , , , , , , , , , , , Sustained acid, San Dunjia continued heart, dimethyl sulphate, said acetic acid vinegar, trimethyl sulphate trifluoromethyl phthalate, diterpene sulphate trifluoroacetate At least 1 kind of acid 0. 0001 to 4 mass%. In the pattern forming step of forming the surface of the wafer as a surface having a fine concavo-convex pattern, first, after applying a resist on the surface of the wafer, the resist is exposed through a resist mask, and the etching is removed by etching. An exposed resist or an unexposed resist is used to form a resist having a desired concavo-convex pattern. Further, even if a mold having a pattern is pressed against the resist, a resist having a concavo-convex pattern can be obtained. The wafer is then etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is peeled off, a wafer having a fine concavo-convex pattern is obtained. a wafer having a fine concavo-convex pattern on its surface and at least a part of the concavo-convex pattern containing a lithium element, including a film containing a lanthanum element such as lanthanum, cerium oxide or tantalum nitride formed on the surface of the wafer, or forming the above In the concave-convex pattern, at least a part of the surface of the concave-convex pattern contains Shi Xi, Oxide or 156746. Doc •30- 201206949 An element such as tantalum nitride. Further, for a wafer comprising at least one selected from the group consisting of crushed, chopped and nitrided cuts, a protective film may be formed on the surface selected from the group consisting of seconds, oxidized stone, and nitrided (iv). And the at least one portion of the concave-convex pattern includes at least one portion selected from the group consisting of β, oxygen cut, and nitrogen cut formed on the surface of the wafer. At least one of cerium oxide and cerium nitride. Further, the surface of the portion of the concave-convex pattern containing the yttrium element may be formed by the chemical solution of the present invention. When the surface of the wafer is a surface having a fine concavo-convex pattern, if the surface is washed with a water-based cleaning solution and the aqueous cleaning solution is removed by a dry material, the width of the concave portion (four) is larger if the width of the convex portion is larger. It is easy to produce pattern depressions. The concave-convex pattern ' is defined as shown in Fig. 2 and Fig. 2 . Fig. i is a schematic plan view showing a wafer i having a surface having a surface having a fine uneven pattern 2. Fig. 2 is a view showing a portion a-a of Fig. i. The width 5 of the concave portion is also represented by the interval between the convex portion 3 and the convex portion 3 as shown in Fig. 2. The aspect ratio of the convex portion is represented by the height 6 of the convex portion divided by the width 7 of the convex portion. The pattern in the cleaning step is recessed in the width (four) of the concave portion, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more. In the preferred embodiment of the invention, as described above (after the step, the surface of the wafer is set to have a surface having a fine uneven pattern, and then the aqueous cleaning liquid is supplied to the surface to be held on at least the concave surface of the concave-convex pattern. The aqueous cleaning solution: then, as shown in the above (Step 2), the aqueous washing liquid held on the surface of at least the concave portion of the concave-convex pattern is placed on the washing liquid different from the water system. Doc •31· 201206949 Change. Preferred examples of the cleaning solution A include a chemical solution for forming a protective film, water, an organic solvent, or a mixture thereof, which is specifically defined in the present invention, or an acid, a base, or a surfactant mixed therein. At least one of the oxidants and the like. In addition, when the cleaning liquid A is used as the cleaning liquid A, it is preferable to replace the cleaning liquid a with the protective film forming drug in a state in which the cleaning liquid A is held on at least the surface of the concave portion of the concave-convex pattern. liquid. In addition, examples of the organic solvent which is one of preferable examples of the cleaning liquid A include hydrocarbons, esters, ethers, ketones, solvents containing ?I elements, an anthraquinone solvent, and alcohols. , a derivative of a polyhydric alcohol, a solvent containing a nitrogen element, and the like. Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane; and examples of the ester include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Etc.; as an example of the above ethers, there are diethyl ether, dipropyl, dibutyl, and tetrahydrogen. As the above ketones, acetone, ethyl acetonide, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc.; Examples of the solvent containing the dentate element include perfluorooctane, perfluorodecane, perfluorocyclopentane, all-inclusive cyclohexene, /, and a total of fluorocarbons 1, 1, 1, 3, 3 - 5 - Hydrogen fluorocarbon 'methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, such as dibutyl, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora ΖΕΟΝ (made in Japan) Hydrofluoric acid such as ethyl perfluorobutyl ether, ethyl perfluoroisobutyl®, Asahiklin®-3000 (made by Asahi Shiko), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all manufactured by 3M) Ether, four gas methane and other gas carbon, gas imitation and other hydrogen carbon, two gas difluoromethane burning chlorine II carbon '1,1-digas-2,2,3,3,3-pentafluoropropene, 156746. Doc -32· 201206949 1,3·Dichloro-U, 2,2,3·pentafluoropropane m3′3,3_San Dun propylene, & Dichloro-3,3,3-trifluoropropene and other hydrogen Chlorofluorocarbon, perfluoroether, peroxypolyether, etc., as an example of the above-mentioned sub-hard solvent, there are two f-based codes, etc.; as an example of alcohols: there are f-alcohol, ethanol, propanol, butanol , ethylene glycol 'u_propylene glycol, etc.; as an example of the above polyol derivative, there are diethylene glycol monoethyl ether, ethylene glycol single test, ethylene glycol single bond, propylene glycol single test, propylene glycol single B Noodles, diethylene glycol monoacetic acid vinegar, ethylene glycol mono-anthraquinone acetate, ethylene glycol monobutyl-acetic acid 3, propylene glycol mono-ethyl _, propylene glycol monoacetic acid vinegar, diethylene glycol Diethylene glycol ethyl, hydrazine, diethylene glycol-b test, diethylene glycol monoterpene ether acetate vinegar, diethylene glycol diacetate vinegar, diethylene glycol dimethyl ether, ethylene glycol diacetic acid Examples of the solvent of the nitrogen-containing element, such as an ester, ethylene glycol diethyl ether, ethylene glycol-methyl bond, etc., are a kind of amine, N n dimethyl ketoamine H methyl acetamide, N_methyl 〜 Compared with ketone, diethylamine, triethylamine, pyridine, and the like. : 'As an acid sometimes mixed with the cleaning solution A, there is a mineral acid or a. Examples of the inorganic acid include hydrogen acid, buffered hydrogenated acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like. Examples of the organic acid include: an acid, a benzoic acid, a p-toluene acid, and a tri-failure. Carboxylic acid, acetic acid, trifluoromethane-pentafluoropropionate, etc. are used as a base which may be mixed in the cleaning solution A, and the β is tested. Examples of the agent which may be mixed in the cleaning liquid a include ozone, hydrogen peroxide, and the like. Further, when the cleaning liquid A is an organic solvent, the protective film-shaped shirt can be supplied to the concave portion by contact with water*, which is preferable. Among them, ζ organic * agent contains water money organic solvent (dissolved in water (10) parts by mass 156746. Doc • 33 · 201206949 is 5 parts by mass or more), so it is easy to replace it with the cleaning solution A from the aqueous cleaning solution. Further, when the cleaning liquid A contains an aqueous acid solution, the protective film can be formed in a short period of time, which is preferable. Further, a plurality of kinds of cleaning liquids may be used as the cleaning liquid A'. For example, a cleaning solution containing an aqueous acid solution or an aqueous alkali solution and the above organic solvent (preferably containing a water-soluble organic solvent) may be used for the cleaning liquid A, and the cleaning liquid containing an aqueous acid solution or an aqueous alkali solution may be used. - The order of the above organic solvents is washed. Further, a water-based cleaning liquid may be further added and washed in the order of the aqueous solution containing the acid aqueous solution or the aqueous alkali solution, the aqueous cleaning solution, and the organic solvent. FIG. 3 is a schematic view showing a state in which the protective film forming chemical solution 8 is held by the concave portion 4 by the washing step. The wafer of the pattern diagram of Fig. 3 represents a_a of the figure, a part of the section. At the time of the cleaning step, the protective film forming chemical solution is supplied to the wafer 1 on which the uneven pattern 2 is formed. At this time, the chemical liquid is held in the concave portion 4 as shown in Fig. 3, and a protective film is formed on the surface of the concave portion 4, whereby the surface is water-repellent. When the temperature is raised, the protective film forming chemical liquid is liable to form the protective film in a shorter time. The temperature at which the homogeneous protective film is easily formed is preferably 1 (above TC and not at the boiling point of the chemical solution, and particularly preferably maintained at 15 ° C or higher and not lower than the boiling point of the chemical solution (7). The temperature of the chemical liquid is preferably maintained at the temperature of at least the concave portion of the concave-convex pattern. Further, the other cleaning liquid may be held at a temperature of 1 (rc or more and less than the boiling point of the cleaning liquid. The cleaning solution A uses a solution containing an aqueous acid solution, particularly preferably an aqueous solution containing an acid solution and an organic solvent having a boiling point of more than 10 ° C. In the case of doc • 34·201206949, if the temperature of the cleaning liquid is raised to the vicinity of the boiling point of the cleaning liquid, it is easy to form the protective film in a short time, which is preferable. The step of maintaining the protective film forming solution on at least the surface of the concave portion of the concave-convex pattern (step 3), and replacing the chemical liquid held on at least the surface of the concave portion of the concave-convex pattern 1 with the chemical liquid may be replaced. After the cleaning liquid B, the step of transitioning to the liquid from the surface of the concave-convex pattern by drying (step 4), as an example of the cleaning liquid B, an aqueous cleaning solution containing an aqueous solution, or an organic solvent, Or a mixture of the aqueous cleaning solution and the organic solvent, wherein at least one of an acid, an alkali, and a surfactant is mixed, or a stone contained in the protective film forming chemical liquid is added to the chemical liquid. Compound A and acid until the concentration is lower than that of the drug solution. Moreover, examples of the organic solvent which is one of preferable examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, solvents containing element elements, sulfoxide solvents, alcohols, and the like. A derivative of a polyhydric alcohol, a solvent containing a nitrogen element, or the like. Examples of the above hydrocarbons include benzene, benzene, diphenylbenzene, hexanyl, heptane, octane, etc.; as examples of the above esters, there are ethyl acetate, propyl acetate, butyl acetate, and ethyl acetonitrile. Ethyl ester or the like; as an example of the ether, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.; as examples of the ketone, acetone, ethyl acetonide, methyl ethyl ketone, Mercaptopropyl ketone, mercaptobutyl ketone, cyclohexanone, isophorone, etc.; as an example of the above-mentioned solvent containing dentate element, there are all II smoldering, all sputum, perfluorocyclopentan, all Perfluorocarbon such as fluorocyclohexane or hexafluorobenzene, 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora Η (曰本ΖΕΟΝManufacture) isohydrofluorocarbon, mercapto perfluoroisobutyl ether, mercapto perfluorobutyl ether, ethyl perfluorobutyl ether, 156746. Doc •35- 201206949 Hydrofluoroethers such as ethyl perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, N〇vec7600 (all manufactured by 3M), tetrachloro Chlorine and carbon such as methane, hydrogen and carbon such as gas, fluorocarbon such as difluorodifluorodecane, 1,1-dichloro-2,2,3,3,3-pentafluoropropene, 1,3-diox -1,1,2,2,3-pentafluoropropane, 1-gas-3,3,3-trifluoropropene, ^digas-3,3,3-trioxadol, etc. Perfluoro, full y, etc.  Examples of the sulfoxide-based solvent include dimercaptosulfoxide and the like; and examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, and 13-propylene glycol; and as a derivative of the above polyol; For example, there are diethylene glycol monoethyl bond, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethyl Glycol monoethyl ether, diethylene glycol monoterpene ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol Dimethyl bond, etc.; as an example of a solvent for a nitrogen-containing element, there are decylamine, N, n-methylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and Ethylamine, triethylamine, pyridine, and the like. Further, the step of removing the liquid from the surface of the concave-convex pattern may be carried out after the water-based cleaning liquid containing the aqueous solution is retained by the replacement of the cleaning liquid and the surface of the concave-convex portion at least on the surface of the concave portion (step 4). Can: Use! The above washing liquid Β' may also use a plurality of washing liquids. For example, two kinds of liquids. The agent (preferably comprising a water-soluble organic solvent) and the water system are washed 156,746. Doc -36· 201206949 As an example of the water-based cleaning liquid, water or a mixture of water and an organic compound, and at least one of the test substances is used as a main component (for example, the water content is 5 Gf). More than %). In particular, if the water-based cleaning liquid uses water, the contact angle θ of at least the surface of the concave portion of the concave-convex pattern which is repellent by the chemical liquid is increased, and the capillary force p of the surface of the concave portion is lowered, and the dirt is dried. It is difficult to remain on the surface of the wafer, so it is preferable. <A mode diagram in which the water-based cleaning liquid is held in the recessed portion 4 which is water-repellent by the film forming chemical solution, and the wafer in the schematic view of Fig. 4 represents the ? The surface of the concavo-convex pattern is water-repellent by forming the protective film 10 from the above chemical solution. Further, when the protective film 1 is removed from the surface of the uneven pattern, the protective film 1 is also held on the surface of the wafer. "on wafer <At least on the surface of the concave portion of the concave-convex pattern. When the protective film 1G is formed by the protective flag forming chemical liquid, the contact angle is assumed to be 70 to 110 when water is held on the surface. It is difficult to produce pattern depressions, so it is preferable. Also, the contact angle is closer to 9 〇. The smaller the capillary force on the surface of the concave portion, the more difficult it is to form a pattern depression, so that it is preferably 75 to 105. . also,

The capillary force is preferably M MN/m 2 or less. When the capillary force is M MN/rn 2 or less, it is difficult to form a pattern depression, which is preferable. Further, if the capillary force is decreased, it is difficult to cause pattern depression, and therefore the capillary force is preferably 〇, 8 MN/m2 or less. Further, it is preferable to adjust the contact angle with the cleaning liquid to 9 〇. In the vicinity, the capillary force is infinitely close to 〇〇MN/m2, and then, as shown in the above (Step 4), a step of removing the liquid from the surface of the concave-convex pattern by drying is performed. In this step, 156746 is removed by drying. .doc -37- 201206949 : In the concave: the liquid on the surface of the case. The drying is preferably carried out by a known drying method such as a method, a transyl alcohol vapor drying, a marangani dry, a vacuum drying, or a vacuum drying, and the liquid is maintained on the surface when the liquid is removed from the surface of the pattern. The liquid may also be the above-mentioned liquid, washing liquid 3, and aqueous washing liquid. In addition, the mixture of the liquid and the liquid may be a liquid in a state in which the chemical liquid f is replaced with a liquid in the middle of the cleaning liquid, or may be in advance: The liquid is mixed with the mixture obtained in the same washing liquid as the medicinal trousers. Further, after the liquid is temporarily removed from the surface of the embossed pattern, the liquid is selected from the first liquid B, the aqueous cleaning liquid, and the like. At least one of the mixed liquids is described as a surface of the concave-convex pattern, and then dried. ', and the second step is as shown in the above (step 5), and the protective core is removed. When the protective film is removed, It is effective to cut the protective film: CC bond, C_F bond. As a method, the above key can be cut. 'There is not particularly limited, and examples thereof include a process of irradiating a surface of a wafer with light, a process of heating a wafer, a process of exposing the wafer to ozone, a process of irradiating the surface of the wafer with plasma, a process of discharging, and the like. . When the surface of the m circle is corona-treated in the case where the protective film 1Q is cut by light irradiation, it is effective to cut the c_c bond and the CF bond in the protective film ,), and it is preferable to irradiate the ultraviolet ray as follows. The ultraviolet ray has a wavelength equivalent to 34 〇 nm and 24 〇, which is an energy of 83 kcal/mo 卜 116 kcai/m 〇 i as the bonding energy. As the light source, a metal element lamp, a low pressure mercury lamp, a surface pressure mercury lamp, an excimer lamp, a carbon arc lamp, or the like is produced. In the case of a metal dentate lamp, 156746.doc -38· 201206949 ultraviolet irradiation intensity is, for example, an illuminance meter (illumination intensity meter UM-10 manufactured by K〇nica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, The measurement value in the measurement wavelength range: 310 to 400 nm]) is preferably 1 〇〇 mW/cm 2 or more, and particularly preferably 2 〇〇 mw/cm 2 or more. Further, if the irradiation intensity is less than 100 mW/cm2, it takes a long time to remove the above protective film 1〇. Further, in the case of a low-pressure mercury lamp, ultraviolet rays having a shorter wavelength are irradiated. Therefore, even if the irradiation intensity is low, the protective film 10 can be removed in a short time, which is preferable. Further, when the protective film 1 is removed by light irradiation, when the constituent components of the protective film 10 are decomposed by ultraviolet rays, ozone is simultaneously generated, and the constituents of the protective film 10 are oxidized and volatilized by the ozone. , 'The processing time is shortened, so it is especially preferable. As the light source, a low pressure mercury lamp or an excimer lamp is used. Further, it is also possible to heat the wafer while performing light irradiation. In the case of heating the wafer, it is '400 to 70 (rc, preferably 5 〇〇 to 7 〇〇.) The heating of the wafer is performed. The heating time is preferably maintained at 05 to 60 hours, preferably. In this step, it is also possible to use ozone 4 dew, plasma irradiation, corona discharge, etc. in combination, and it is also possible to heat the circle while performing light irradiation on the wafer. In the case of ozone exposure, it is preferred to supply the surface of the wafer to the wafer surface by using ultraviolet light such as a 4-pressure mercury lamp or a low-temperature discharge such as a high-voltage low-temperature discharge. The light can be heated while being exposed to light. The protection of the surface of the wafer can be removed by the combination of: 156746.doc -39- 201206949 irradiation treatment, heat treatment, ozone exposure treatment, The protective film of the surface of the wafer is effectively removed by a plasma irradiation treatment, a corona discharge treatment, etc. The chemical solution of the present invention may be a liquid type which is originally contained by mixing the above-mentioned hydrazine compound with the above-mentioned acid A, or may be used as a liquid type Containing the above-mentioned bismuth compound eight The liquid is mixed with the liquid containing the liquid of the above acid A, and may be mixed at the time of use. Alternatively, it may be a liquid type containing the above-mentioned hydrazine compound B and a liquid containing the liquid of the above-mentioned acid B. The case where the surface having the fine concavo-convex pattern is used, and the case where the cleaning liquid held on the surface of at least the concave portion of the concavo-convex pattern is replaced with another cleaning liquid is a technique that has been established in various other literatures and the like. In the present invention, the evaluation of the above-mentioned chemical solution for forming a protective film is mainly discussed. Further, as described in the prior art and the like according to the present invention,

P=2 xyxcosG/S (γ: surface tension, Θ: contact angle, S: pattern size) It is clear that the pattern depression is largely dependent on the contact angle of the cleaning liquid with the wafer surface, that is, the contact angle of the droplet and the washing The surface tension of the clean liquid. When the cleaning liquid is held in the concave portion 4 of the concave-convex pattern 2, the contact angle of the liquid droplets is correlated with the capillary force of the surface of the concave portion which is considered to be equivalent to the pattern depression, and therefore, according to the above formula and the protective film 10 The evaluation of the contact angle of the droplets leads to capillary forces. Further, in the examples, water as a representative of the aqueous cleaning solution is used as the cleaning liquid. However, in the case of a wafer having a fine concavo-convex pattern on the surface, 156746.doc •40·201206949, since the pattern is very fine, the contact angle of the above-mentioned protective film 10 itself formed on the surface of the concavo-convex pattern cannot be accurately evaluated. . The contact angle of the water droplets is also evaluated by JIS R 3257 "Test method for wettability of the surface of the substrate glass" by adding a few μ of water droplets to the surface of the sample (substrate), and measuring the surface of the water droplets and the substrate. It is carried out at the angle of formation. However, in the case of a patterned wafer, the contact angle becomes very large/the reason is that a Wenzel effect or a Cassie effect is generated, so that the contact angle affects the surface shape (roughness) of the substrate to make the appearance The contact angle of the water droplets increases. Therefore, in the present invention, the above-mentioned chemical liquid is supplied to a wafer having a smooth surface to form a protective film on the surface of the wafer, and the protective film is formed on the surface of the wafer 1 on which the fine uneven pattern 2 is formed. The protective film 10 was formed and subjected to various evaluations. Further, in the present invention, as a crystal having a smooth surface, a tantalum wafer having a thermal oxide film layer or a tantalum nitride layer or a tantalum layer on the surface and having a smooth surface is used. The details are described below. In the following, the evaluation method of the wafer to which the protective film forming chemical solution is supplied, the preparation of the protective film forming chemical liquid, and the evaluation result after the protective film forming chemical liquid is supplied to the wafer will be described. [Evaluation Method of Wafer Provided with Protective Solution Forming Liquid] As an evaluation method of a wafer to which a protective film forming chemical liquid is supplied, the following evaluations (1) to (4) are performed. (1) The contact angle of the protective film formed on the surface of the wafer was evaluated by placing pure water on the surface of the wafer on which the protective film was formed by about 2 μ1, and measuring the water droplets by using a contact angle meter (Kyowa Interface Science: CA_X type). Wafer table 156746.doc 201206949 Angle formed by the surface (contact angle) β (2) Evaluation of capillary force The capillary force (absolute value of ρ) was obtained by calculating ρ ' using the following formula.

P = 2xyxc 〇 s9 / S where 'γ represents the surface tension, e represents the contact angle, and 8 represents the pattern size. In the present embodiment, as an example of the pattern shape, a wafer having a line width (width of the concave portion) of 45 nm and a pattern of a gap (i) shape is assumed. Further, the pattern of the line width: 45 (10) is The tendency is that when the cleaning liquid at the gas-liquid interface passes through the wafer is water, the pattern is liable to sag. When the cleaning solution is 2·propanol, the pattern is difficult to be recessed in the pattern size: 45 nm, crystal Round surface: In the case of cerium oxide, when the washing liquid is 2-propanol (surface tension: 22 mN/m, contact angle with cerium oxide: 1.), the capillary force becomes 0.98 MN/m2. When the washing liquid is the water having the highest surface tension in the liquid other than mercury (surface tension: Μ mN/m, contact angle with cerium oxide: 25), the capillary force becomes 3 2 MN/m 2 . The force is preferably 丨.i MN/m2 or less, particularly preferably 0.8 MN/m2 or less. (3) Removal of Protective Film Under the following conditions, the sample is irradiated with a metal dentate lamp for 2 hours. The contact angle of the water droplets after irradiation is 30. The following are set as qualified (in the table 〇) Lamp: M015-L312 manufactured by EYE GRAPHICS (strength: 1.5 kW) * Illuminance: measured value under the following conditions: 128 mW/cm2 156746.doc -42- 201206949 • Measuring device: UV intensity meter (Konica Manufactured by Minolta Sensing, UM-10) • Light-receiving unit: UM-360 (receiving wavelength: 310 to 400 nm, peak wavelength: 365 nm) • Measurement mode: illuminance measurement (4) Smoothing of the surface of the wafer after removing the protective film The surface was observed by atomic force electron microscopy (manufactured by Seiko Instruments: SPI37〇〇, 2 5 μηι square scan) to obtain the average surface roughness of the center line: Ra (nm). Furthermore, the Ra system defined JIS Β 0601. The center line average roughness is applied to the measurement surface and expanded into three dimensions, and is obtained as the value obtained by averaging the absolute values of the deviations from the reference surface to the designated surface, and is expressed by the following equation. When the Ra value of the wafer is 1 nm or less, the surface of the wafer is not eroded by the cleaning, and the residual film of the protective film does not exist on the surface of the wafer, so it is qualified (the table is 〇). 7]

Ra= J Xr IFix.yj-ZoidXdY

YT XL Here, XL, Xr, YB, and YT indicate the measurement range of the X coordinate and the γ coordinate, respectively, s〇 is the area when the measurement surface is ideally flat, and is set to a value of (xr_Xl)x(Yb_Yt). Further, F(X, Y) represents the height of the measurement point (χ, γ), and Zq represents the average height in the measurement plane. [Example 1] (1) Preparation of chemical solution for forming a protective film 156746.doc • 43· 201206949 Hexamethyldiazepine [(H3c)3si-NH-Si (CH3)3] which is a hydrazine compound A: 1 g, trimethyldecyl trifluoroacetate as acid A [(CH3)3Si-OC(O)CF3]: 0.1 g, propylene glycol monoacetic acid acetonitrile (PGMEA) as an organic solvent: 98.9 g The mixture was mixed to obtain a chemical solution for forming a protective film. Further, it was confirmed that the total amount of water in the starting material of the above-mentioned chemical solution was 5,000 ppm by mass or less based on the total amount of the raw material. The molecular sieve 4A (manufactured by Showa Co., Ltd.) removes moisture from the chemical solution, and then removes metal impurities from the chemical solution by ion exchange resin (ION-CLEAN SL manufactured by Nihon Pall), which is then filtered by a filter. (The optimizer manufactured by Entegris) removes particles from the liquid and purifies them. The amount of water in the purified liquid is measured by a Karl Fischer type moisture meter (manufactured by Kyoto Electronics, ADP·5 11 type), and as a result, the amount of water in the purified liquid is relative to the drug. The total amount of the liquid was 6 mass ppm. Further, the content of the metal impurity in the purified liquid solution was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical System, Agilent 7500cs type), and the purified Na, Mg, K, The content of metal impurities of each element of Ca, Mn, Fe and Cu is Na=2 mass ppb, Mg=0.04 mass ppb, K=0.2 mass ppb, CIa=l mass ppb, Mn= relative to the total amount of the liquid solution. 0.005 mass ppb, Fe=0.08 mass ppb, Cu=0.06 mass ppb. In the case of "particle measurement by a light scattering type liquid particle detector in the liquid phase", a particle larger than 〇·5 μιη is measured by a light scattering type liquid particle measuring device (manufactured by Ri〇n Co., Ltd., Model KS-42AF) For the number, the number of particles larger than 〇.5 μιη is 2 per 1 mL of the drug solution. Further, in the examples after the present embodiment, the following chemical liquid is also used: the total amount of water in the starting material 156746.doc 201206949 of the chemical solution is determined to be 5000 mass ppm or less with respect to the total amount of the raw materials, and the same is performed. Purification and confirmation that the amount of water relative to the total amount of the chemical solution is 5,000 ppm by mass or less, and the content of the metal impurities of each of Na, Mg, K, Ca, Mn, Fe, and Cu is 100% by mass relative to the total amount of the liquid. The number of particles below ppb and larger than 〇'5 μιη is 100 or less per 1 mL of the drug solution. (2) <5th wafer cleaning will be smoothed with a thermal oxide film on the wafer (Si wafer with a thermal oxide film layer of 1 μηι thickness on the surface)' is immersed at room temperature at 1 The mass% of the aqueous hydrogen acid solution was incubated for 2 minutes, then immersed in pure water for 1 minute, and immersed in 2-propanol (iPA) for 1 minute. (3) The surface treatment of the surface of the wafer by the use of the protective film-forming chemical solution. The protective film of the Shihwa wafer is immersed in 2 (the preparation of the (1) protective film forming solution). The solution was formed for 1 minute. Thereafter, the wafer was immersed in iPA for 1 minute, and then immersed in pure water as a water-based cleaning solution for 1 minute. Finally, the wafer was taken from pure water. The air is removed by spraying air to remove the surface of the wafer. The wafer obtained by the evaluation of the method for evaluating the wafer for the protective film forming liquid is evaluated as shown in Table ,, before the surface treatment. The initial contact angle was less than 1 〇. The contact angle after surface treatment was 84. 'The water repellency imparting effect was exhibited. χ, the capillary force when water was held was calculated using the formula disclosed in "Evaluation of Capillary Force", As a result, the capillary force becomes 0.3 MN/m2', and the capillary force is small. Moreover, the contact angle after (10) irradiation is less than 10. The protective film can be cut. Further, the Ra value of the wafer after uv exposure is less than 0.5 nm. Confirm that the wafer was not invaded during cleaning. 156746.doc •4 5·201206949 Eclipse, and the residue of the protective film does not remain after uv irradiation. The liquid used in this example does not change in appearance even after being stored at 45 ° C for 1 week, and the contact angle after surface treatment is 84°, no performance degradation found. 156746.doc • 46· 201206949 «! f in' >Λ in ί?Γ •Λ1 ίο* in' in' in' fT •Λ ίη 2. in' in' »Λ in '•Λ* iTt in' (η in' *?Γ in' in •o' m < + δ % 1 ο 〇〇Ο ? ο ο ο % 〇〇ο Ο o Ο 〇ο ? ? ο ο ο ? ο 〇ο ο 〇〇0 0 Ο ο ο 0 〇0 〇ο Ο o Ο 〇0 0 Ο ο ο ο 〇ο m «! £ Composition: 屮珥S- S- S- S- g\ s- g » S- g» S- S, ss s- gv gv s, s, gg S- s, g, )LV, ° ° V, ° B V, ν^ VVV, V, VV V. £ ο 0 0 0 o ο 0 0 〇ο o 0 0 0 0 0 ο 0 ο 0 ο 0 0 ο ί=ΐ Λ 15 m ο rs o' m 〇(N d CN o ο ο m ο r> dd νο v〇s〇Ο Ό Ο (η (N <Ν dmdmd <Ν d <Ν Ο dmd <Ν女S女5=ί V Contact angle after surface treatment (Η) Chigne 00 00 SO 00 sv〇00 00 00 Ζ s S sg S g U 芸ss〇00 z Chignière s Nie initial <Β: 珥C ball ο V Ο V ο V 〇V 〇V o V o V ο V ο V ο V o V ο V o V o V ο V ο V o V Ο V ο VOV o V ο V ο V Ο V ο V ο V Ο V SU 姊Ancestral dry cups cups cups cups cups cups cups hard to pile up vg cups cups difficult< level SI cups are difficult to dry and difficult to dry 墉墀 墀 墀 碟 埤磲 2 2 2 (S < i2 i i 萑7100 〇ΰ 8 Γ» 芝 u 1 s Ο § S 1 IS | ο § 〇 | t S 〇白〇g pM S Ο Ρ 窆ί g I 〇 Λ 2 2 〇 CU ώ Γγ Η U s CU ti] S 卜 P υ g £ Η Ο 8 〇 CU Ο eu 8 Ρ*» 6 eu 8 〇 CU 8 6 0. ί 1 i υ Q i US by ί ί by < tu UU: U 〇CJ 〇υ tC U 〇tC υ . 6* \C u OU: CJ ο U: UU 〇UU: υ 〇υ .Λ tC o O tC υ ΕΛ tC υ ο 5Λ U: υ on tC υ U: 〇 § tC u I 9 U: υ 〇U tt: υ ο π U 〇ct {) u υ 〇π U: υ 〇ct iC υ Ο 〇〇ο ο VV ο V 〇• Λ 9 9 Ο 9 9 〇〇ο 9 9 9 9 9 Ο w (Λ 00 L0 ΙΛ ΕΛ (Λ 03⁄4 ΕΛ W !£ CO CO Λ 00 (Λ 00 ΕΛ &〇0Λ ίΛ Λ CO CO CO ΕΛ W ΕΛ cone t XX i' XX ΐ XXS Κ £ X £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £合: 浓茂 [quality 1 " «Γ» ο " »Λ 〇£ X Λ X r> X 1 X ο u X u U < X X £ £ X £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ X υ 茗 茗X uw X Ο ώ υ ά u 00 i υ XU 巧X in X Ζ X υ 汔X 2 u Co i (Λ X 1 lo X 5 u op i Ιο X 2 έ 2 芩2 % 2 芩2芩芩X + 芩 芩 &Q ϋ CO CO ς〇ίΛ U ς〇G Λ Λ CJ 00 00 υ to υ w 00 CO CO 00 00 C CO ϋ w 00 U CO υ CO U (Λ υ a XX £ £ X £ £ £ £ £ £ £ £ £ £ £ £ £ OS N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 I§ i§ ¥ ♦ <V; ¥ ¥ -47- 156746.doc 201206949 [Examples 2 to 56] The concentrations of hydrazine compound A, hydrazine compound A, acid A, and organic solvent used in Example 1 were appropriately changed. And processing conditions such as the treatment process after the surface treatment of the protective film forming chemical liquid, and performing surface treatment of the wafer, and further performing the same Evaluation. The results are shown in Tables 1 to 2. 156746.doc -48- 201206949 斗CN<] 1 Evaluation result 1 Surface smoothness (Ratnm) 〇 (<〇·5) 〇(〇5) | 〇(<0.5) | 〇(<0.5) in ' Ο in' ? 〇 (<〇·5) | 〇(<0·5) | 〇(<0.5) 1 〇(<〇5) I 1 〇(<〇-5) I 〇( <〇-5) 〇(<〇-5) 丨〇(<0·5) | 〇(<〇.5) 1 〇(<0.5> 1 1 〇(<〇5) I卜(0.5) I | 〇(<0.5> | 〇(<0.5) | 〇(<0-5) | 〇(<0.5) 1 °(<〇.5) 1 in' ο 〇 (<0.5) | 〇(<0.5) 1 ◦ (<0.5) | 〇(<〇-5) I ο (<0.5) 2 Visit I-45 ® Male W § 〇 (<!〇 ) 〇 (<!〇) I 〇(<!〇) I 〇(<!〇) 1 I 〇(<!0) 1 〇(<!〇) I 〇(<!〇) I 〇(<!〇) V, 1 〇(<!0) I 〇(<!〇) i 1 〇(<!〇) II 〇(<!〇) I | I 〇(<! 0) 1 ! 〇(<!〇) I 〇(<!〇) I 〇(<!〇) IV 〇(<!〇) I 〇(<!〇) 1 〇(<!〇 1 S' 7 〇 (<!〇) 1 〇 (<!〇) 1 〇 (<!〇) 1 〇 (<!〇) 〇 (<!0) Capillary force ([MN/m2 ]) <calculated value> rs m ο ΓΝ 〇d CN Ο o Rs d <so (N 〇rn d inch 〇〇do VO ο inch〇TT 〇do 00 ο 00 ο ov〇o (Ν Ο v〇o <N d contact angle after surface treatment ([°]) S So 00 00 Z SO 00 00 SO 00 z CS 00 rs 00 zg CM 00 CS OO «Ν 〇\ <N 〇\ ss OO Θ0 沄00 s 00 Ζ f ε 〇V ο V 〇V 〇V ο V o V o V o V 〇V 〇V ο V 〇V ο V ο V o V ο V 〇V 〇V 〇V Ο V o V ο V ο V o V o V ο V o V ο V Ο VI protective film formation After treatment with the surface treatment of the liquid medicine, cup, cup, cup, cup, cup, cup, cup, water, cup, cup, cup, cup, cup, crucible, m, m, m /PGMEA | PGMEA | PGMEA | PGMEA 1 PGMEA 1 PGMEA 1 PGMEA 1 PGMEA 1 HFE-7100/PGMEA | PGMEA | HFE-7100/PGMEA | | PGMEA 1 HFE-7100/PGMEA | 1 PGMEA 1 1 HFE-7100/PGMEA | • PGMEA HFE-7100/PGMEA] [ PGMEA 1 ! HFE-7100/PGMEA | PGMEA 1 HFE-7100/PGMEA | PGMEA | HFE-7100/PGMEA | PGM EA | PGMEA 1 PGMEA 1 HFE-7100/PGMEA | HFE-7100/PGMEA | PGMEA < | (CH3)3Si-0C(0)CF3 | (CH3)3Si-0C(0)CF3 1 (CH3)3Si-0C (0)CF3 | (CH3)3Si-0C(0)CF3 1 (CH3)3Si-OC(0)CF3 1 (CH3)3Si-0C(0)CF3 1 (CH3)3Si-0C(0)CF3 U: Dad 9 (Λ X υ | (CH3)3Si-0C(0)CF3 U 9 ΕΛ 1 (CH3)3Si-OC(0)CF3 | | (CH3)3Si-OC(0)CF3 1 (CH3)3Si-0C (0)CF3 [(CH3)3Si-0C(0)CF3 | [(CH3)3Si-OC(0)CF3n ! (CH3)3Si-0C(0)CF3 1 (CH3)3Si-0C(0)CF3 | (CH3)3Si-0C(0)CF3 1 (CH3)3Si-0C(0)CF3 | .(CH3)3Si-0C(0)CFi 1 (CH3)3Si-0C(0)CF3 1 (CH3)jSi- 0C(0)CF3 1 (CH3)3Si-0C(0)CF3 | (CH3)3Si-0C(0)CF3 | u ο (Λ 5 (CH3)3Si-0C(0)CF3 | Ο υ 9 Ιο X υ u: υ ο υ 9 «Λ Λ XU (CH3)3Si-OC(0)CF3' (CH3)3Si-0S(02)CF3 矽 compound Α concentration [% by mass] 矽 compound A 1 (H3C) 2Si (H> NH-Si(H)(CH3)2 | (H3C)3Si-NH-Si(CH3)3 | (H3C)2Si(H>NH-Si(H)(CH3)2 1 (H3C)3Si-NH-Si (CH3)3 Λ υ g ζΛ X 1 w CO 1 (H3C)3Si-NH-Si(CH3)3 ! | (H3C)2Si(H>NH-Si(H)(CH3)2 I 1 C6H5Si(CH3) rNH-Si(CH3)2C6H5 | | C6H5Si(CH3)2-NH-Si(CH3)2C6H3 | | CF3C2H4Si (CH3)rNH-Si(CH3)2C2H4CF3 | CF3C2H4Si(CH3)2-NH-Si(CH3)2C2H4CF3 1 (CH3)3Si-N(CH3)2 1 [(CH3)3Si-N(CH3)2 1 | ( CH3)3Si-N(C2H5)2 | 1 Z (Λ X υ '(CH3)3Si-NCO 1 (CH3)3Si-NCO 1 Trimethyldecyl imidazole 1 Trimethyldecyl imidazole IX CJ u 芎XJ C4H9Si (CH3)2-N(CH3)2 1 C8H17Si(CH3)rN(CH3)2 1 C8H17Si(CH3)2-N(CH3)2 1 5 5* XUX £ ο εό X 芩X (H3C)3Si-NH- Si(CH3)3 | (H3C)3Si-NH-Si(CH3)3 1 (H3C)3Si-NH-Si(CH3)3 | (H3C)3Si-NH-Si(CH3)3 1Example 28 1 Implementation Example 29 1 Example 30 1 Example 31 ! | Example 32 ! I Example 33 1 | Example 34 | 1 Example 35 ] | Example 36 1 | Example 37 ^ Example 38 | 1 Example 39 1 1 Embodiment 40 | 丨 Embodiment 41 | 1 Embodiment 42 1 1 Embodiment 43 1 1 Embodiment 44 1 | Example 45 | | Example 46 | | Example 47 I 1 Example 48 1 1 Example 49 1 1 Embodiment 50 | | Example 51 1 1 Example 52 1 | Example 53 | 1 Example 54 1 1 Example 55 1 Example 56 156746.doc • 49- 201206949 Furthermore, in the table, r ( H3C)2Si(H)-NH-Si(H)(CH3)2" means tetramethyldiazepine, "C6H5Si(CH3)2-NH-Si(CH3)2C6H5 Means diphenyltetradecyldioxane, "CF3C2H4Si(CH3)2-NH-Si(CH3)2C2H4CF3" means 1,3-bis(trimethylpropyl)tetramethyldiazepine , "(CH3)3Si-N(CH3)2" means trimethylsulfonylalkyldiamine, "(CH3)3Si-N(C2H5)2" means trimethyldecyldiethylamine, "(CH3 "3Si-NCO" means trimethyldecyl isocyanate, "C4H9Si(CH3)2-N(CH3)2" means butyldiindenyl (dimethylamino)chamane, "C8H17Si(CH3)2- N(CH3)2" means octyldimethyl (diammonium) decane. Further, in Examples 45 to 46, as the compound A in the chemical solution for forming a protective film, trimethyldecyl imidazole represented by the following formula was used. [化8]

Further, in the table, "(CH3)3Si-OS(〇2)CF3" means trimethylsulfonyltrifluoromethyl acid. In the table, "PGMEA" means propylene glycol monomethyl ether acetate, "HFE-7100" means hydrofluoroether (HFE-7100 manufactured by 3Μ), and "HFE-7100/PGMEA" means mass ratio. A mixed solution of HFE-7100: PGMEA = 95:5 was counted. "CTFP" means 1-gas-3,3,3-trifluoropropene roast, and "CTFP/PGMEA" means a mixed solution of CTFP:PGMEA=95:5 156746.doc -50-201206949 in mass ratio. "DCTFP" means cis-1,2_digas_3,3,3_trifluoropropene, and "DCTFP/PGMEA" means a mixed solution of DCTFp: PGMEA = 95:5 by mass ratio. Further, in Example 56, as the acid A, trimethylsulfonyltrifluoroacetate and trimethyltinyltrifluoromethylenecarboxylate were used as each of 5 g. In the above-mentioned "(3) surface treatment by the chemical liquid for forming a protective film on the surface of the wafer," the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then immersed in After simmering in pure water, the wafer was finally taken out of pure water and air was sprayed to remove pure water from the surface. In the above-mentioned "(3) surface treatment by the chemical liquid for forming a protective film on the surface of the wafer," the ruthenium wafer was immersed in the chemical solution for forming a protective film, and then immersed in In iPA for i minutes, finally remove the sand wafer from ipA and spray air to remove the surface ipA. In the above-mentioned "25 (3) surface treatment by the chemical liquid for forming a protective film on the surface of the wafer," the liquid crystal of the protective film is taken out and the air is sprayed off to remove the air. In the protective film forming agent of the surface/Examples 29 to 3, the above-mentioned "(the surface treatment of the surface of the wafer: the surface treatment by the film forming liquid) is performed, and the germanium wafer is immersed in the protective film forming liquid. After the middle, the 喷 ± 喷 喷 喷 虱 虱 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 去除 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Round, and air is sprayed to remove the pure water on the surface. In Examples 31 to 32, L'i ", the use of m on the surface of the wafer is guaranteed. "Surface treatment", the enamel wafer is immersed in the protective film 156746.doc • 51. 201206949 After the film formation liquid, the air is sprayed to the main hole _ 7 hole to remove the protective film forming liquid on the surface. Crash in iPA for 1 minute, fight for 6 · ϋΑ士免, knife title, dare to take out Shi Xi from uPA Circumference 'and air is sprayed to remove the surface ipA. In the examples 33 to 34, the above-mentioned "(3) surface treatment using the protective film forming liquid on the surface of the stone wafer," After immersing in the protective film-forming chemical solution, the protective film for spraying the air to remove the surface is formed by immersing in pure water for 1 minute, and the drug solution is then immersed in iPA for 1 minute and finally taken out from the pure water. The wafer 'and the air is sprayed to remove the pure water of the surface. In the embodiment 51, the smoothing of the wafer with the thermal oxide film is provided by the above-mentioned "(2) cleaning of the wafer" (the surface contains The Si wafer of the thermal oxide film layer having a thickness of 丨μηη is immersed in a hydrofluoric acid aqueous solution of 丨% by mass for 2 minutes at room temperature, and immersed in pure water for 1 minute. Further, at 98<> The mixture was immersed in 〇3 mass% aqueous hydrochloric acid solution for 1 minute, and then immersed in pure water for 1 minute at room temperature, and then immersed in 2-propanol (iPA) for tl minutes. Further, in Example 52 In the embodiment 54, a smooth tantalum nitride film (having a thickness of 0.3 μm of a tantalum nitride layer on the surface) is used. For the Si wafer, the same processing as described above is performed. In Example 53, Example 55, 'cleaning with the above r (2) 矽 wafer'' will be smoothed with a tantalum nitride film. The Si wafer having a thickness of 〇3 μηη on the surface was immersed in a 1% by mass aqueous solution of nitrogenic acid for 2 minutes at room temperature, and immersed in pure water for 1 minute. Further, at 98 The underarm is immersed in a mixture of 0.6% by mass aqueous hydrochloric acid and ethylene glycol in a mass ratio of 50:50 for i minutes, and then immersed in pure water at room temperature. 156746.doc • 52· 201206949 After the clock, 'immerse in 2-propanol (iPA) for 1 minute. [Example 57] Hexamethyldiazepine [(H3C)3Si-NH-Si(CH3)3] as a ruthenium compound B: 1 g, trifluoroacetic anhydride as acid b [{CF3C(0) }20]: 0.1 g, PGMEA as an organic solvent: 98.9 g, and mixed and reacted, thereby obtaining a dimercapto-based trifluoroacetate as acid A and hexamethyldiazepine as hydrazine The compound A and PGMEA were used in the same manner as in Example 丨 as the chemical solution for forming a protective film of an organic solvent. The hexamethyldioxane contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which has not been consumed in the above reaction of the acid VIII, and this component functions as the hydrazine compound A. The evaluation results are shown in Table 3. The contact angle after surface treatment was 82. , showing the water repellency effect. Further, when the water is held, the capillary force becomes 〇 4 MN/m, and the capillary force is small. χ, the contact angle after uv irradiation is not up to remove the protective film. Further, the value of the wafer after the uv irradiation is less than 0.5 nm, and it is confirmed that the wafer is etched away during the cleaning, and the residue of the protective film does not remain after the UV irradiation. 156746.doc 53· 6 20 1X 20 [εί Evaluation result, surface smoothness (Ra[nm]) 〇(<〇-5) ο (<0.5) ! ί 〇(<〇·5) 〇(&lt ;0.5) 〇(<0.5) o (<0.5) 〇(<0.5) 〇(<0.5) o (<0.5) 〇(<0.5) 〇(<0.5) 〇(<0.5 〇 (<0.5) o (<0.5) 〇 (<0.5) Removability of protective film i (contact angle Π) 〇 (<!0) 〇 (<!0) 〇 (<!0 )〇(<!0) 〇(<!0) 〇(<!0) 〇(<!0) 〇(<10) 〇(<!0) 〇(<!0) 〇 (<!〇) I 〇(<!0) 〇(<!0) 〇(<10) 〇(<!0) Hair I» Tube force ([MN/m2]) <Calculated value > 〇τΓ Ο o' vp NO d \qr* CN d (N dood 5 v〇o Contact angle after surface treatment Ν 00 <Ν 〇0 fN 00 gs vo 00 v〇00 s〇00 (N 00 Rs 00 § 00 00 § 00 On initial contact angle [.] <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 1 〇V Treatment of the surface of the silver film for forming a protective film, drying, cup, water, cup, cup, lysing, washing cup Cup dry quasi-mm quasi-protection "Formation of liquid acid A (CH3) 3Si-OC(0)CF3 (CH3)3Si-0C(0)CF3 (CH3)3Si-0C(0)CF3 (CH3)3Si-OS (〇2) CF3 (CH3)3Si-OS(〇2)CF3 (CH3)3Si-0S(02)CF3 (H3C)2Si(H)-OC(0)CF3 (H3C)2Si(H)-0C(0 ) CF3 (H3C)2Si(H)-OC(0)CF3 (H3C>2Si(H>OS(02)CF3(H3C)2Si(H)-OS(〇2)CF3 C4H9Si(CH3)2-0C(0 ) CF3 C*H9Si(CH3)2-〇S(〇2)CF3 C8H17Si(CH3)r〇C(0)CF3 C8Hl7Si(CH3)2-OS(02)CF3 Starting material organic solvent PGMEA HFE-7100 HFE. 7100/PGMEA HFE-7100 HFE- 7100/PGMEA CTFP/PGMEA PGMEA HFE-7100 HFE· 7100/PGMEA HFE-7100 HFE- 7100/PGMEA PGMEA PGMEA PGMEA PGMEA C0 {CF3C(0)}20 {CF3C(0)}20 {CF3C(0)}20 {CF3S(02)}2〇{CF3S(02)}2〇{CF3S(02)}2〇{CF3C(0)h〇{CF3C(0)}20 {CF3C(0) }20 {CF3S(02)}2〇{CF3S(02)h〇{CF3C(0)}20 {CF3S(〇2)h〇{CF3C(0)>2〇{CF3S(02)h〇矽 compound B concentration [mass%] - 矽 compound BI (H3C) 3Si-NH-Si(CH3)3 (H3C)3Si-NH-Si(CH3)3 (H3C)3Si-NH-Si(CH3)3 (H3C) 3Si_NH, Si(CH3>3(H3C)3Si-NH-Si(CH3)3(H3C)3Si-NH-Si(CH3)3(H3C)2Si(H)~NH-Si( HXCH3)2 (H3C)2Si(H>NH-Si(H)(CH3)2(H3Q2Si(H>NH-Si(H)(CH3)2(H3C)2Si(H>NH-Si(H)(CH3>;2 (HjChSKHyNH-SKHXCH^ C4H9Si(CH3)2-NH-Si(CH3)2C4H9 C4H9Si(CH3)2-NH-Si(CH3)2C«H9 CgHiTSKCHah-NH-SiiCHj^CgHn CjHpSiiCHj^NH-SKCHB^CsH, Embodiment 57 Embodiment 58 Embodiment 59 Embodiment 60 Embodiment 61 Embodiment 62 Embodiment 63 Embodiment 64 Embodiment 65 Example 66 Example 67 Example 68 Example 69 Example 70 I56746.doc - 54-201206949 [Examples 58 to 71] The conditions of the ruthenium compound b, the acid b, and the organic solvent used in Example 57 were appropriately changed, and the surface treatment of the wafer was carried out, and the evaluation was further carried out. The results are not shown in Table 3. Further, in the table, "C4H9Si(CH3)2-NH-Si(CH3)2C4H9" means 1,3-dibutyltetramethyldiazepine ''c8Hl7Si(CH3)2_NH_si(CH3)2C8H丨7" means 1,3-dioctyltetramethyldiazepine. Further, 'in the table' "{CF3S(〇2)}2〇" means trifluorosulfonate anhydride. Further, in Examples 58 to 59, if trifluoroacetic anhydride used as the acid B is mixed with hexamethylenediazane as the hydrazine compound B, the reaction is immediately changed to trimethyl decyl Fluoroacetate, and this example shows the same meaning as in the case of using trimethyldecyltrifluoroacetate as the acid A. Further, in Examples 60 to 62, when the trifluoromethyl acid anhydride used as the acid B was mixed with hexamethylene diazoxide as the hydrazine compound B, the reaction was immediately changed to trimethyl decyl Fluoromethanesulfonate, and this example shows the same meaning as in the case of using trimethyldecyltrifluoromethanesulfonate as the acid A. Further, in Examples 63 to 65, when trifluoroacetic anhydride used as the acid B was mixed with tetramethyldiazepine as the hydrazine compound B, the reaction was immediately changed to didecyl decyl group III. Fluoroacetate, and this example shows the same meaning as in the case of using dimethyl decyl trifluoroacetate as the acid A. Further, in Examples 66 to 67, if the trifluoromethanesulfonic anhydride used as the acid B is mixed with tetramethyl dimethyl sulphur which is 156746.doc-55-201206949 as the hydrazine compound B, the reaction is immediately carried out. It was changed to dimethyl decyltrifluorosulfonate, and this example shows the same meaning as in the case of using dimercaptodecyltrifluorosulfonate as the acid A. Further, in Example 68, if trifluoroacetic anhydride used as the acid B is mixed with 1,3-dibutyltetradecyldioxane as the compound of the compound B, the reaction is immediately changed to a change. Since the present invention is the same as the case of using butyl decyl decyl trifluoroacetate as the acid A, this example shows the same meaning as in the case of using butyl decyl decyl trifluoroacetate. Further, in Example 69, if the trifluoromethanesulfonic anhydride used as the acid B is mixed with the 1,3-dibutyltetradecyl diruthenium as the compound of the Shishi compound B, the reaction is immediately changed. This is the same meaning as in the case of using butyl dimethyl decyl trifluoromethylene vinegar as the acid A, in the form of butyl decyl fluorenyltrifluoromethanesulfonate. Further, in Example 70, if trifluoroacetic anhydride used as the acid b is mixed with 1,3-dioctyltetramethyldiazane as the hydrazine compound B, the reaction is immediately changed to an octyl group. Dimercaptoalkyltrifluoroacetate, this example shows the same meaning as in the case of using octyldimethylsulfonyltrifluoroacetate as the acid A. Further, in Example 71, if trifluoromethanesulfonic anhydride used as the acid B was mixed with 1,3-dioctyltetramethyldiazane as the hydrazine compound B, the reaction was immediately changed to octane. The dimethyl decyl trifluorosulfonate is the same as in the case where octyl dimethyl decyl trifluoromethanesulfonate is used as the acid A. I56746.doc -56 - 201206949 [Example 72] Hexamethyldiazepine [(H3C)3Si-NH-Si(CH3)3] as ruthenium compound B: 1 g, trifluoroacetic acid as acid B [CF3C(0)-OH; h〇.lg, PGMEA as an organic solvent: 98.9 g, mixed, and reacted as shown in the following formula, thereby obtaining trimethylsulfonyltrifluoroacetate as acid A The hexa-nonyldiazane was used in the same manner as in Example 1 except that the hydrazine compound A and the PGMEA were used as the protective liquid for forming a protective film of an organic solvent. The hexamethyldiazepine contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which is not consumed in the reaction of the above acid A, and this component functions as the hydrazine compound A. The evaluation results are shown in Table 4. The contact angle after the surface treatment was 84. , showing the water repellency imparting effect. Further, when the water is kept, the capillary force is 0.3 MN/m2, and the capillary force is small. Also, the contact angle after UV irradiation is less than 10. , the protective film can be 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 corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation. (H3C)3Si_NH-Si(CH3)3 + 2 CF3C(0)0H-2CF3C(0)0Si(CH3)3+NH3 156746.doc ·57· 201206949 Inch _ id ? in' «λ' in ' *rv «Λ1 in' in' *Λ in' in' in' «λ' in' in' in' •o' in' in' in' *n •o' Ϊλ' π «o' ίο* 5 ite | < + g 〇〇0 Art ο 1, ο ? ot 〇Ο 1 l Ο ? ? 0 1 ο ? 〇? Ο ? >w/ ? 0 ? ο ? 0 t £ 0 1 ? 0 i 0 t 0 1 1 0 1 1 % 〇? 0 21« s- S- g· £ S- § s s- sr S' S- S- S- g. s· s- s s- s- s- s· § S- s- S- S- s- 5 ΐ ® V^ 〇ο ο ° ° 0 V, v^ o V^ V^ 0 v^. 0 iL 么 0 ° Ο λ Λ Λ £Με ^ « § 5 Rn mdm ο γ〇o (Ν ο <N o ο <Ν Ο O rn r*1 rn r〇«〇vq Ο ο oc ο 00 (Ν (Ν 00 o (N Γ** ο Γ<ί Ο Γ» d ro Ο vq fO ο St 5 17 Contact angle after surface treatment (Π) zs S s 沄 This SS This ss Niss S s Μ Si Si ss 鸢ss CO s 00 S s 芝 ο V o V ο V Ο V o V o V Ο V ο V o V ο V Ο V o V o V 〇V 〇V 〇V o V Ο V ο V ο V ο V ο V Ο V Ο V o V 〇V ο V ο ν ο V ο V a ft! Mg V «ί Dry body cup body cup body cup cup cup cup cup cup cup cup B? ttg a body cup Cup < dissolve ffl wash e male ttp body cup up 碡 difficult to 墀墀 碡 碡 碡 碡 U U U U U: k Ο 〇ο pC υ u: δ Ο δ 6 iC 〇δ ο & S ο ?r 6 u: 6 u: u Ο u: u Ο u: u U: 〇U: each ςΤ U: U 1 uC υ i δ δ 〇U: υ 1 tC US ΧΛ u: u δ έ 〇U : υ 〇〇U: ο uC U: 〇ί a 9 § ? i square 9 δ έ 〇έ 1 〇έ 1 I 1 i 9 0* 9 9 a 9 VV 9 £ p Μ a 9 SV Λ σ 9 〇tr 9 ts ο σ 9 σ 9 tr 9 00 I CO 1 ς〇 IX υ II 1 Wu 1 I 1 II ο II « I <Λ I όό 1 00 IU % 5 JC 〇CO υ to υ W i (Λ I δ U5 DC J ο Ιο i υ ΰο S (Λ I 0Λ 1 to I ϊό X u οό U to i <<<<<< C <<<< Organic solvent < § § ο PGMEA < i § I < S § <<> 7100 • -7100 % § ο % I -7100 § § ο < § § § Ο 1 SI 1 S 1 i 1 s ο <<<< § i < § i. \ s I << 镰C Province 2 iii i i 2 2 g — 卜 i r- ii 2 i 2 *7 1 S Γ- i 2 i 2 2 2 2 2 2 r- ir*> i 2 g X o K ϊ ο X ο re oo X ϊ XX Ο ο X 〇Ο ο X 9 X 9 X oo K 2 κ XX oo κ 9 X Ο X 9 X 〇〇X 9 3: 〇A κ ο X s X s X 2 X Ο X 〇re ο έ* X o X 9 ffi ϊ Ο X o 丄2 o ό* 〇Ο Ο ΰ Ο 〇〇ο 1 Tf ο 〇S 琏雄 G 0 Q 0 Si νί ζΓ 0 0 0 0 w5* This a 0 Q <1 0 0 0 0 Si 0 tr 0 σ 0 b* b 6 u. & δ 匕δ ϋ U u u. & b & 6 && 5 6 & gs bu U 6 &&&& 6 eu 6 6 «? QQ 吞彡- XX XX gt gt υ υ XX XX υ υ 矽 X υ XX XX XX 矽 矽 矽 C C C C / / / C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C 1 £ 1 IS 'i Μ 1 g 1 g I Dad 5 1 i Μ i X u % Λ X u ζ 1 ζ Si υ z U on X κ υ 2 on X £ υ 芊λ f υ to X uz Ji. £ υ AS z ύ A £ y, X 3C U ffi υ io ί i-NH-Si(CHi)., i-NH-Si(CH3)3 i-NH-Si(CH3)3 i-NH-Si(CH 〇3 i-NH-Si(CH〇3 X υ CO i to (Λ ς〇CO Λ w to Μ w W ws (Λ % CO ΧΛ 00 00 w 荠\7) w 00 wo CO ς〇ΙΛ υ υ UUU X r υ υ X X £ X UU 4 U Si E £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ £ ;N to *ns〇p 00 〇\ όο This SS S 涅 00 SS is in On S! at 5; & % % g: 0 1 i S ί si 诔 诔 婼诘 婼 婼 婼4c »Κ *Κ ·« ♦« VK «>;:: 156746.doc .58 - 201206949 [Examples 73 to 103] The concentration of the hydrazine compound B and the hydrazine compound B used in the example 72 was appropriately changed. The surface treatment of the wafer was carried out under conditions such as an organic solvent, and the evaluation was carried out. The results are shown in Table 4. Further, in the table, "CF3C(0)-0H" means trifluoroacetic acid, and "CF3S(02)-0H" means trifluoromethanesulfonic acid. In Example 78, a protective liquid for forming a protective film containing dimercaptodecyltrifluoroacetate as the acid A or tetramethyldiazepine as the hydrazine compound A was obtained by the reaction of the following formula. The tetramethyldiazepine contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which is not consumed in the reaction of the above acid A, and this component functions as the hydrazine compound A. (H3C) 2Si(H)-NH-Si(H)(CH3)2 + 2 CF3C(0)0H-2 2 CF3C(0)0Si(H)(CH3)2 + NH3 In Example 86 By the reaction of the following formula, a protective liquid for forming a protective film containing trimethyl decyl trifluoroacetate as the acid A or trimethyl decyl dimethylamine as the hydrazine compound A is obtained. The trimethyldecyldiamine which is contained in the chemical solution of the present embodiment is used to obtain the compound B which is not consumed in the reaction of the above acid A, and this component functions as the hydrazine compound A. [化11]

(H3C)3Si-N(CH3)2 + CF3C(0)0H -CF3C(0)0Si(CH3)3 + HN(CH3)2 156746.doc -59- 201206949 In Example 88, by the following formula The reaction solution obtained was a protective film for forming a protective film containing trimethylsulfonyltrifluoroacetate as the acid A or trimethyldecyldiethylamine as the hydrazine compound A. The tridecylsulfonyldiethylamine contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which is not consumed in the reaction of the above acid A, and this component functions as the hydrazine compound A. (H3C) 3Si-N(C2H5)2 + CF3C(0)OH -CF3C(0)0Si(CH3)3+HN(C2H5)2 In Example 90, the inclusion was obtained by the reaction of the following formula Butyl dimethyl decyl trifluoroacetate is used as a protective liquid for forming a protective film of hydrazine compound A as acid A or butyl dimethyl (dimethylamino) decane. The butyldimethyl(diguanylamino)decane contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which is not consumed in the reaction of the above acid A, and this component functions as the hydrazine compound A. C4H9Si(CH3)2-N(CH3)2 + CF3C(0)0H-CF3C(0)〇Si(CH3)2C4H9 + HN(CH3)2 In Example 92, the reaction by the following formula A chemical solution for forming a protective film containing octyldimercaptoalkyltrifluoroacetate as the acid A or octyldimethyl(dimethylamino)decane as the hydrazine compound A was obtained. The octyl dimethyl (dimethylamino) decane contained in the chemical solution of the present embodiment is used to obtain the hydrazine compound B which is not consumed in the reaction of the above acid A, and the component is used as the hydrazine compound A to issue 156746. Doc -60- 201206949 Wave function. C8H17Si(CH3)rN(CH3)2 + CF3C(0)〇H CFaC^OSiiCHs^QHn + HNiCHa^ In Example 97, 'washing with the above (2) wafer, smoothing A dream wafer with a thermal oxide film (a Si wafer containing a thermal oxide film layer having a thickness of 1 on the surface) is immersed in a hydroquinone aqueous solution of 丨 mass % for 2 minutes at room temperature and immersed in 1 minute in pure water, and further, immersed in 〇3 mass ° / at 98 < t. The aqueous solution of hydrochloric acid was incubated for 1 minute, and then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol (iPA) for 1 minute. Further, in Example 98 and Example 1, a smooth silicon nitride film with a tantalum nitride film (a Si wafer having a tantalum nitride layer having a thickness of 0.3 μm on the surface) was used, and the same procedure as described above was carried out. deal with. Further, in Example 1 and 2, the same treatment as described above was carried out using a smooth silicon wafer with a polycrystalline germanium film (a "wafer" having a polycrystalline germanium layer having a thickness of 0.3 μm on the surface). In Example 101, the above-mentioned "(2) 矽 wafer cleaning j, smoothing a tantalum nitride film with a tantalum nitride film (the surface contains a thickness of ΐ3 μΐη of the nitride layer of the crystallization layer), Immersed in a 1% by mass aqueous solution of nitrogen acid at room temperature for 2 minutes' and was immersed in pure water for a minute. Further, the mass ratio of the aqueous solution of 0.6% by mass of hydrochloric acid to ethylene glycol was 50 under air. :50 minutes in a mixture of 50 minutes, then immersed in pure water at room temperature " after a minute 'immersion in 2-propanol (iPA) fl minutes. Again, in Example 1〇3, use smoothing A polycrystalline (tetra)-cut wafer (Si wafer having a polysilicon layer having a thickness of 156746.doc • 61·201206949) is attached, and the same treatment as described above is performed. [Example 104] Hexadecyldioxane [(H3C)3Si_NH_si(CH3)3]: 1 g, difluoroacetic acid [CF:jC(〇)〇H] as acid B: lg, PGMEA as an organic solvent: In the same manner as in the first embodiment, the contact angle of the surface treatment was 84. The water repellency imparting effect was exhibited, and the capillary force at the time of holding water was 0.3. MN/m2, the capillary force is small. Moreover, the contact angle after uv irradiation is less than 10. The protective film can be removed. Further, the wafer after Uv irradiation has a value of less than 0.5 nm, and the wafer can be confirmed at the time of cleaning. It is not corroded, and the residue of the protective film does not remain after the uv irradiation. However, if it is used at 45. After the liquid storage for i weeks, the contact angle after the surface treatment is 10. The reason is as follows: Trifluoroacetic acid is reacted with hexamethyl-indolizane to consume hexamethylene diazoxide. Further, an example using acid A as a starting material is used, and even after being stored at 45 for one week, it is stored for one week. The contact angle after the surface treatment was 84 Å, and no deterioration in performance was observed. Therefore, the chemical solution prepared by using the compound A and the acid A as the starting material is more excellent in stability and therefore more preferable. Example 105] In the first embodiment, 'by the above "(7)矽The "washed round" will be smoothed with a thermal oxide film on the Shi Xi wafer (the surface contains a thickness of 1 called a thermal oxide film Si wafer), and is immersed in a w mass % aqueous solution at room temperature. 2 minutes and dipped in pure water for 1 minute. Further, the above-mentioned "(3) surface treatment by the chemical liquid for forming a protective film on the surface of the _ round surface" is provided on the spin coater by the shishi wafer wetted by 156746.doc • 62·201206949 water. While rotating at a speed of the surface, the surface of the wafer was supplied with 2-propanol (iPA) 1* clock', and then the protective film forming chemical solution was supplied for 1 minute, and then supplied for _ minute, and then pure water was supplied! In the minute, the rotation was continued for 1 minute in a state where no liquid was supplied, thereby removing the pure water of the surface. The evaluation of the obtained wafer was "the contact angle after surface treatment was 82. , showing the water repellency effect. Further, when the water is held, the capillary force becomes 〇·4 MN/m2, and the capillary force is small. Moreover, the contact angle after UV irradiation was less than 1 〇. , the protective film can be removed. Further, the value of the wafer after the uv irradiation was less than 5 nm, and it was confirmed that the wafer was not invaded during the cleaning, and the residue of the protective film did not remain after the uv irradiation. [Example 106] The same procedure as in Example 2 was carried out except that the total amount of water in the starting material was W (10) ppm by mass based on the total amount of the raw material. As a result of the evaluation, the contact angle after the surface treatment was 70. , showing the water repellency imparting effect. Further, when the water is held, the capillary force becomes kl MN/m2, and the capillary force is small. Moreover, the contact angle after UV irradiation was less than 1 〇. , the protective film can be removed. Further, the Ra value of the wafer after the irradiation was less than 0.5 nm, and it was confirmed that the wafer was not corroded during the cleaning, and the residue of the protective film did not remain after the UV irradiation. Comparative Example 1 The same procedure as in Example 1 was carried out except that the protective film forming chemical liquid was not supplied to the silicon wafer. That is, in this comparative example, the wafer in the surface state which was not water-repellent was evaluated. The evaluation results are shown in Table 5. The contact angle of the wafer was as low as 3°. The capillary force at the time of holding water was 3 2 MN/m 2 . 156746.doc •63- 201206949 [s<] Evaluation result Surface smoothness (Ra[nm]) 1 1 • 1 1 1 1 1 Removal of protective film (contact angle [°]) 1 1 will 1 1 1 1 1 Capillary force ([MN/m2]) <calculated value><N rS 00 <S CS Ο cn (S contact angle after surface treatment ([°]) 00 (N 00 ss 宕00 VO Ο 〇V 〇〇〇o Ο 0 Treatment after surface treatment of protective film forming solution 哉•VF VtP cup Washing solvent wash 5 墀Protective film forming liquid starting material! Organic solvent 1 PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA Acid A, acid B other than acid 1 1 ch3s(o2)-oh X 〇〇UX u h2so4 H3P〇4 X HNO3 矽Compound A concentration [% by mass] 1 — — «Μ — 矽 compound A untreated (H3C) 3Si -NH-Si(CH3)3(H3C)3Si-NH-Si(CH3)3(H3C)3Si-NH-Si(CH3)3(H3C)3Si-NH-Si(CH3)3(H3C)3Si-NH -Si(CH3)3(H3C)3Si-NH-Si(CH3)3(H3C)3Si-NH-Si(CH3)3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 • 64- 156746.doc 201206949 Comparative Example 2 An acid-free protective film was used in the comparative example except that the quinone diazane: 1·0 g and PGMEA: 99.0 g were mixed to obtain a protective film forming chemical solution. The drug solution was formed. As shown in Table 5, the contact angle after the surface treatment was as low as 28. The capillary force at the time of holding water was as large as 2.8 MN/m 2 [Comparative Examples 3 to 8] Modified Example 1 The acid A used in the process was subjected to surface treatment of the wafer, and the evaluation was carried out. The results are shown in Table 5. In the table, "CH3S(02)-0H" means nail sulfonic acid, and "CH3CO〇H" means acetic acid. '"HzSO4" means sulfuric acid (water content is 2% by mass), "H3P04" means phosphoric acid (water content is 15% by mass), and "HC1" means hydrochloric acid (water content is 65% by mass), " HN〇3" means nitric acid (water content is 31% by mass). The surface treatment was carried out under the same conditions except that acid A was used in Example 1, and an acid other than acid A was used in Comparative Examples 3 to 8. It was confirmed that Example 1 using only trimethyldecyltrifluoroacetate as the acid A imparted excellent water repellency to the surface of the wafer. On the other hand, it was confirmed that Comparative Examples 3 to 8 could not impart sufficient water repellency to the silicon wafer. A sufficient water repellency liquid can be applied to the surface of the ruthenium wafer, that is, the oxime group which is the reaction site on the surface of the ruthenium wafer can rapidly react with the ruthenium compound A to cause the ruthenium compound A to pass through the oxime bond. The Si element of the wafer is chemically bonded, so it is suggested that the trimethylsulfonyltrifluoroacetate as the acid A significantly increases the reaction rate of the chemical solution. 156746.doc •65-201206949 In Examples 35-38, 47-50, 68-71, 90-93, and 95-96, a ruthenium compound having a relatively large hydrocarbon group as the Ri of the above formula [1] was used. A, such ruthenium compound A can react with the ruthenium group at the reaction site of the ruthenium wafer surface and cover the wafer with a larger hydrocarbon group via a siloxane bond.

The Si element is effective for repelling the surface of the wafer. Of course, such a compound A having a relatively large hydrocarbon group can be combined with an acid A which can significantly increase the reaction speed of the chemical solution, thereby effectively achieving water repellent of the wafer surface. [Reference Examples 1 to 4] The Shishi compound a and the organic solvent used in the implementation of m are appropriately changed, and tridecyl gas decane [(CH3)3Sicl] is further used as an acid other than the acid VIII, and the surface treatment of the wafer is performed. And further evaluate it. The results are shown in Table 6. When the chemical solution used in the present reference example is whitened, the appearance becomes white $, and the precipitated component is found. However, if the chemical solution is subjected to surface treatment for purification, the contact angle is 78 84 and there is no change. Effect of the liquid phase of the embodiment, etc. 156746.doc 66-201206949 (¥Μ) (0>) ▲ (·0>) ▲ (ον) <(·0>)<(2>l· ( Ol>)<(οιν)<(οι>)< ^珑1-|

Asf ρε/_]) (u) U § s $1 s [%_- s ν#φ-^ ·0 ·0 9Ό 2 8 Bu 0l>

VIS lys-HU) " olv V3wod/oou_3 by G!S-HU) ο00

Ol> VHWOd I3!S-H3) 00

01V gravel

VHSDd/ool'HdH 03⁄43⁄4}) [9ΐ 156746.doc "Ηυ)! ·Η2·-^(υ*) "Hu)IS-HM,!sm(u£) "hu)ch)! S-hm-(h)! S-u£) -H3)(H)! S-HM-(H)! S"(U£) I?%^ $s •67- 201206949 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic plan view showing a wafer crucible having a surface having a fine concavo-convex pattern 2. Figure 2 shows a-a of Figure 1, a portion of the section. FIG. 3 is a schematic view showing a state in which the protective film forming chemical solution 8 is held by the concave portion 4 by the washing step. Fig. 4 is a schematic view showing a state in which a water-based cleaning liquid is held in the concave portion 4 in which the protective film is formed. [Description of main component symbols] 1 Wafer 2 Fine concavo-convex pattern on the surface of the wafer 3 Patterned convex portion 4 Patterned concave portion 5 Width of the concave portion 6 Height of the convex portion 7 Width of the convex portion 8 Protective film forming medication held in the concave portion 4 Liquid 9 Water-based cleaning solution held in the recess 4 10 Protective film 156746.doc • 68-

Claims (1)

201206949 VII. Patent application scope: 1. A chemical solution for forming a protective film, which is characterized in that it is used for cleaning a wafer having a fine uneven pattern on its surface and at least a part of the concave-convex pattern containing a yttrium element. The surface of at least the concave portion of the concave-convex pattern is formed into a chemical solution for repellency of the aqueous protective film, and comprises a chemical compound A and an acid A represented by the following general formula [1], which is selected from a trimethyl sulfonyl group. Trifluoroacetate, trimethyldecyl trifluoromethanesulfonate, dinonyl decyl trifluoroacetate, dimethyl decyl trifluoromethanesulfonate, butyl fluorenyl sulfoxide In the group consisting of acetic acid vinegar, butyl dimethyl decyl trifluoromethanesulfonate, octyl decyl decyl trifluoroacetate and octyl decyl decyl trifluorosulfonate At least one. R aSi(H)bX4^.b [1] (In the formula [1], R1 is independently from each other selected from the group consisting of carbon number is ～18 In the drug night, when the liquid detector in the above liquid solution is used for particle measurement, the number of particles larger than 0.5 μm in 156746.doc 201206949 is less than loo per mL of the liquid. 4. The protective film forming solution according to claim 2, wherein the particles in the liquid phase in the liquid phase are measured by a particle detector in a light scattering type liquid, and the number of particles larger than 0.5 μm is in each! The amount of mL in the drug solution is less than one. 5. The protective film forming liquid according to any one of claims 1 to 4, wherein a metal impurity content of each of elements of Na, Mg, K, Ca, Mn, Fe, and Cu in the liquid is relative to the liquid The total amount is 1 〇〇 mass ppb or less. 6. A method of modulating a protective film forming solution according to any one of claims 1 to 2, which is to prepare a compound before the mixing of the raw material for forming the protective film. Purification is carried out by at least one of A and acid A, and the mixed solution after mixing. 7. A method of cleaning a wafer surface having a fine concavo-convex pattern on the surface by using the protective film forming solution according to any one of claims 5 to 5, The method includes the step of removing the protective film from the surface of the wafer after removing the cleaning liquid from the surface of the wafer. The cleaning method of claim 7, wherein the step of removing the protective film from the surface of the wafer is selected from the steps of performing light irradiation on the surface of the wafer, processing the heated wafer, performing ozone exposure on the wafer, and At least one of the processes of plasma irradiation of the wafer surface. A chemical solution for forming a protective film, which is characterized in that it has a fine concavo-convex pattern on a surface thereof and is cleaned at least at least a part of the concave portion of the concave-convex pattern. 156746.doc 201206949 A chemical solution for repellency of a water-repellent protective film, comprising hydrazine compound A and acid A as shown by the following general formula [丨] selected from cesium trimethyl decyl trifluoroacetate, Methyl carbaryl trifluoromethane vinegar, dimethyl sulphur trifluoroacetic acid vinegar, dimethyl decyl trifluoromethyl canthate, butyl dimercapto fluorenyl trifluoroacetate, Butyl decyl decyl trifluoromethanesulfonate, hexyl decyl decyl trifluoroacetate, hexyl dimethyl decyl trifluoromethanesulfonate, octyl dimethyl decyl trifluoroacetate Ester, octyl dimethyl decyl difluoro sulfonate, decyl dimethyl decyl trifluoroacetate and fluorenyl dimethyl decyl dioxide S At least - species, [Chem. 16] Coffee (8) ^ seven [13 (in the formula [1], R1 is independent of each other from the carbon number a monovalent organic group of a hydrocarbon group of 18 and at least one group of a monovalent organic group having a carbon number of 丨8, wherein each of X is independently a value of one of nitrogen bonded to the Si element The organic group, a is an integer of Bu 3, and b is an integer of o 2 to 2 'the total of a and b is 1 to 3). Ίο. 11. The protective film forming liquid solution of claim 9, wherein the total amount of water in the starting material of the above-mentioned chemical liquid is 5 〇〇〇 mass ppm or less based on the total amount of the raw material. The protective film forming solution according to claim 9, wherein the particle in the liquid phase in the liquid solution is measured by a particle detector in a light scattering type liquid, and the amount of particles larger than 〇. The liquid is below one. 156746.doc 201206949 12·When the liquid film for protective film formation of 〇 求 , , , , , , , , , , , , , , , , , , , 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 保护 保护 保护One or less of this liquid per i mL. 13. The protective film forming solution according to any one of claims 9 to 12, wherein a metal impurity content of each of elements of Na, Mg, κ, Ca, Mn, Bu and Cu in the above liquid is relative to the liquid The total amount is l〇〇 mass ppb or less. A method of preparing a chemical solution for forming a protective film according to any one of claims 9 to 3, which is a compound before the mixing of the raw material for forming a protective film. Purification is carried out with at least one of acid A and a mixed mixture. A method of cleaning, characterized in that it is used for forming a wafer surface having a fine concavo-convex pattern on a surface of a protective film for use in any one of claims 9 to 13, wherein the method comprises self-crystallizing The step of removing the protective film from the surface of the wafer after removing the cleaning liquid from the round surface. 16. The method of claim 15, wherein the step of removing the protective film from the surface of the wafer is selected from the group consisting of a process of irradiating the surface of the wafer with light, a process of treating the wafer, and performing ozone exposure on the wafer. And at least one of the treatments of plasma irradiation of the wafer surface. 156746.doc