TW201216351A - Wafer cleaning method - Google Patents

Abstract

Disclosed is a cleaning method for metallic or silicon wafers (1), which is characterized by: containing a pretreating step for improving a wafer surface; containing a water-repellent protective film formation step, in which a chemical solution for forming the water-repellent protective film containing a water-repellent protective film formation agent for forming the water-repellent protective film (10) on the improved wafer surface is retained in at least the recesses (4) of the wafer, and the water-repellent protective film (10) is formed on the recess surfaces; and by the water-repellent protective film formation agent being a silicon compound represented by R1 aSiX4-a. This method improves the cleaning step susceptible to causing pattern collapse.

Description

[Technical Field] The present invention relates to a cleaning technique of a substrate (wafer) in the manufacture of a semiconductor element or the like. In particular, it relates to a cleaning method for preventing collapse of a concave-convex pattern when a wafer having a concave-convex pattern is formed by washing. [Prior Art] In the manufacture of a semiconductor wafer, a fine concavo-convex pattern is formed on the surface of a germanium wafer by film formation, lithography or etching, and then water (pure water) or an organic solvent is used to clean the surface of the wafer. Wash it out. The components have a tendency to be finer, and the interval between the concave and convex patterns becomes narrower and narrower. Therefore, it is easy to cause the following problem: When water (pure water) is used for washing and water is dried from the surface of the wafer, when the pattern is passed through the gas-liquid interface, the uneven pattern collapses due to capillary action. This problem is particularly a case of a semiconductor wafer having a line width (width of the recess) of 20 nm order and 1 〇 nm level in the case of a wafer in which the pattern of the unevenness is narrowed to a pattern such as a line and a gap shape. More significant. In Patent Document 1 and Patent Document 6, as a method for suppressing pattern collapse, a technique of replacing a cleaning liquid from water into 2-propanol before passing through a concave-convex pattern on a gas-liquid interface is disclosed. However, it is considered that there is a pattern that can be matched. The aspect ratio is limited to 5 or less. Further, in Patent Document 2, as a method for suppressing (4) collapse, a technique targeting a contrast agent pattern is disclosed. This method is a method of suppressing pattern collapse by minimizing capillary force. However, the technique disclosed therein is based on the anti-surname pattern and the anti-reagent itself is modified, and finally the dried treatment agent can be removed together with the resist, so that drying is not required. The removal method of the latter treatment agent cannot be used for this purpose. Further, Patent Document 3 discloses that surface of a wafer having a pattern of irregularities formed by a film containing ruthenium is surface-modified by oxidation or the like, and water-repellent or decane coupling agent is used to form water repellency on the surface. A protective film that reduces capillary force and prevents pattern damage. Further, Patent Literatures 4 and 5 disclose a technique for preventing pattern collapse by hydrophobization treatment using a treatment liquid containing a decylating agent represented by N,N_: methylaminodimethyl decane and a solvent. . [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document No. 2 〇 〇 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 In particular, the cleaning technique of a substrate (wafer) for improving the manufacturing yield of an element having a fine circuit pattern having a relatively high aspect ratio, in particular, the improvement of a concave-convex pattern collapse of a wafer which is liable to cause a surface uneven pattern The technique of the washing step. So far, 'the above wafers are usually wafers with germanium on the surface' but with the diversification of the pattern, the surface has been selected from the group consisting of 157216.doc 201216351 titanium, titanium nitride, tungsten, aluminum, copper, tin, nitrogen. A wafer of at least one metal-based substance in a group consisting of a button and a crucible. When a semiconductor wafer is manufactured, the surface of the wafer is formed to have a surface having a concave-convex pattern. When the surface of the concave-convex pattern is hydrated to prevent the pattern from collapsing, in order to form the water-repellent protective film on the surface of the concave-convex pattern, it is necessary to form a reactive portion such as a hydroxyl group present on the surface of the concave-convex pattern or the surface of the wafer. The compound of the protective film is bonded. When the wafer having the concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing germanium (hereinafter referred to as "wafer only") is washed, the capillary force of the concave-convex pattern portion of the wafer is lowered. The water-based protective film (hereinafter also referred to simply as "protective film") is formed by reacting a telluride such as a decane coupling agent with a hydroxyl group (OH group) introduced on the surface of the wafer. As described above, in order to form a protective film on the uneven pattern containing a ruthenium element, it is necessary to form a reactive site such as a hydroxyl group on the surface of the uneven pattern and to react the compound forming the protective film with the reactive site. The unevenness pattern of the ruthenium-containing element is different in that the degree of difficulty in forming a hydroxyl group or the like differs depending on the type of the material constituting the uneven pattern, and the amount of the hydroxyl group per unit area is surface-treated by water or the like in the case of forming a warp or the like. The conditions make a difference. In the case of a wafer containing a substance having a reactive site such as a stanol group on the surface as in the case of a wafer having the above-described metal-based substance on the surface, the use of any of Patent Documents 3 to 5 is used. The treatment liquid and the treatment method cannot form a water-repellent protective film that prevents pattern damage, and thus there is a problem that the pattern cannot be prevented from being damaged. 157216.doc 201216351 An object of the present invention is to provide a cleaning method for the above-described wafer, which is characterized in that a cleaning step which easily causes pattern collapse is formed by forming a concave-convex pattern on the surface and at least the concave portion I of the (f) convex pattern. - a portion comprising a surface of a concave portion of a wafer selected from the group consisting of titanium, titanium nitride, n, sulphide, copper, tin, nitriding, and a group of materials containing a group of elements The water-repellent protective film (hereinafter, referred to simply as "protective film") is used to reduce the mutual use of the liquid held in the concave portion and the surface of the concave portion. Further, an object of the present invention is to provide a method for cleaning a wafer, which is effective for preventing collapse of a concave-convex pattern, and which is easy to introduce a wafer such as a hydroxyl group on the surface of the concave-convex pattern, even if it is difficult to form a concave-convex pattern. By introducing a wafer such as a hydroxyl group on the surface, the wafer can be cleaned economically and efficiently. Pattern collapse occurs when the gas-liquid interface passes through the pattern as the wafer is dried. The reason for this is considered to be that the difference in the height of the residual liquid occurs between the upper portion and the lower portion of the pattern, whereby the capillary force acting on the pattern is poor. In addition, the expression "collapse" is sometimes referred to as "damage γ. Therefore, if the capillary force is reduced, the difference in capillary force due to the difference in the height of the residual liquid is lowered, and pattern collapse can be expected to be eliminated. Capillary force The absolute value of the enthalpy obtained by the equation shown below can be expected to decrease the capillary force by reducing γ or COS0 according to the formula.

P = 2xyxcos0 / S (where γ is the surface tension of the liquid held in the concave portion, θ is the contact angle between the surface of the concave portion and the liquid held in the concave portion, and S is the width of the concave portion). In the present invention, in order to overcome the above problems, attention has been paid to a pretreatment method for forming a surface of a concavo-convex pattern of a water repellent film and a material for a water repellent protective film. That is, after the surface of the wafer (specifically, for example, the surface of the concave portion of the concave-convex pattern) is reformed (for example, a step of forming an anti-胄 active site by oxidation treatment), the hydrophobicity having a strong hydrophobic property is utilized. • The water-repellent protective film forming agent forms a water-repellent protective film on the surface of the concave portion, thereby imparting water repellency to the surface of the concave portion. The hydrophobic group in the present invention means an unsubstituted thio group, or a smog group in which a part of a nitrogen element in a hydrocarbon group is substituted with a tooth element. The more carbon atoms in the above-mentioned tobacco base, the stronger the hydrophobicity of the hydrophobic group becomes. Further, in the case of a hydrocarbon group in which a part of the nitrogen element in the nicotine group is substituted by a tooth element, there is a case where the hydrophobicity of the hydrophobic group becomes strong. In particular, if the substituted tooth element is a gas element, the hydrophobicity of the hydrophobic group becomes strong, and the more the number of substituted fluorine elements, the stronger the hydrophobicity of the hydrophobic group becomes. The inventors of the present invention conducted intensive studies and found that a water-repellent protective film forming liquid is used by a combination pretreatment (for example, oxidation treatment) and a water-repellent protective film forming agent containing a specific hydrophobic group as a water-repellent protective film forming agent. The surface treatment can be formed on the surface of the concave-convex pattern of the wafer to produce a good water-repellent protective film, which can be efficiently washed. Further, in the present invention, an economical and efficient method of cleaning a wafer having a concave-convex pattern containing a lithium element has been studied. As a result, it has been conceived that an appropriate amount of a hydroxyl group or the like is easily formed on the surface of the concave-convex pattern. Methods were studied. The reason for this is that if a method of forming an appropriate amount of a hydroxyl group or the like on the surface of the concave-convex pattern is provided, the compound forming the water-repellent protective film 157216.doc 201216351 is easily bonded to the surface of the concave-convex pattern, and the water-repellent protective film can be easily obtained stably. According to the first and second aspects of the present invention, there is provided a method of cleaning a wafer (first method), wherein a surface of the concave and convex pattern is formed with a concave-convex pattern, and at least a portion of the concave surface of the concave-convex pattern is selected from the group consisting of titanium a method for cleaning a wafer of at least one of a group consisting of titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, niobium, and a substance containing niobium, including: modifying the surface of the wafer a pre-treatment step; and a water-repellent protective film-forming drug solution containing a water-repellent protective film forming agent for forming a water-repellent protective film on the surface of the wafer to be modified, which is held in at least a concave portion of the wafer, and The water-repellent protective film forming step of forming a water-repellent protective film on the surface of the concave portion; and the water-repellent protective film forming agent is a telluride represented by the following general formula [1]. R1aSiX4.a [1] [In the formula [1], R1 is independent of each other, and is an unsubstituted hydrocarbon group of hydrogen or a carbon number ^~^ or a hydrocarbon group substituted with a hydrogen element via an element, and is selected from an element bonded with an element. In the case of gas, the element of the bond group is a monovalent functional group of oxygen and at least one group of the group consisting of _ groups, and a is an integer in the group 3. Further, in the above wafer crucible, the number of carbons contained in the R of the formula U] is 6 or more in the case of no germanium element. According to the second feature of the present month, the first! The method may be a method for cleaning a wafer (second method), wherein a surface of the concave-convex pattern is formed with at least one surface of the concave portion and a wafer containing a stone element (hereinafter referred to as 'there is a record The cleaning method for "Shi Xi Wa Wa" or only "wafer" includes at least: 157216.doc 201216351 The processing step before the surface of the concave-convex pattern is modified by supplying the pretreatment liquid; f is a water-repellent protective film forming step of forming a water-repellent protective film forming solution on the surface of the modified concave-convex pattern to form a water-repellent protective film on the surface of the concave-convex pattern; and in the above pre-processing step, using Mohr The concentration meter contains 0.001 to 5 m〇l/L of acid and has a pH of 3 or less before the treatment liquid, and the surface of the concave-convex pattern is modified at a temperature of 4 Å or more and less than the boiling point of the pretreatment liquid. The second method may be a method of cleaning a wafer (third method), characterized in that the acid contained in the pretreatment liquid is an organic acid. Any one of the first to third methods may be a method of cleaning a wafer (fourth method), characterized in that at least a part of the uneven pattern is formed of vaporized germanium and/or germanium. The 趵 method may also be a method for cleaning a wafer (the fifth method), characterized in that the surface and the surface thereof are formed with a concave-convex pattern, and at least one of the surfaces of the concave portion of the concave-convex pattern is selected from titanium, f _ titanium hydride , among the groups of tungsten, aluminum, copper, tin, nitride buttons and tantalum, from the "Aβ 7 1 禋 material wafer (hereinafter, there are 5 metal wafers) or only "crystal" In the case of the round method, and in the case of the roundness, the washing party R^SiX [in the formula [2], which is independent of each other, is a hydrocarbon group in which hydrogen, a hydrocarbon group or a hydrogen element is substituted by a halogen element, and the total number is 6 or more, X The water-repellent protective film forming agent is bonded to the ruthenium element and is represented by the following general formula [2]. U] or carbon of 1 to 18 of the unsubstituted formula U], the carbon contained in R1 is a nitrogen monovalent function 157216.doc 201216351 base, and the element bonded with Shi Xi 70 is oxygen 1 Functional group, or dentate base]. According to the first aspect of the present invention, the fifth method may be a method for cleaning a wafer (the sixth method is characterized in that the upper (four) aqueous protection (four) money is a shredded product represented by the following general formula [3]. R2(CH3)2SiX [3] [In the formula m, the V-based unsubstituted hydrocarbyl group having a carbon number of 4 to 18 or the hydrogen-substituted nicotine-substituted nicotinyl group X is bonded to the element of the lithium element. The valence functional group and the element bonded to the dream 70 are a monovalent functional group of oxygen or a dentate group. The fifth or sixth method may also be a method for cleaning a wafer (the seventh method), It is characterized in that the water-repellent protective film forming agent is a compound represented by the following formula [4]. R3(CH3)2SiX [4] is at least a part of nitrogen element having a carbon number of 4 to 18, which is passed through a gas elemental earth. The element in which the X system and the halogen bond are bonded is a valence functional group of nitrogen, and the element bonded to the stone element is a monovalent functional group of oxygen or a dentate group. The first method, the fifth to the seventh Any of the methods can also be a type of wafer

The washing method (the eighth method) is characterized in that the round surface of the pretreatment step B holds the oxidation treatment liquid. The eighth method of the above-mentioned day may be a method for cleaning a wafer (the ninth method), wherein the oxidizing treatment liquid used in the hydrazine treatment step is selected from the group consisting of a treatment liquid containing ozone and containing peroxidation. At least one of the treatment liquid of the hydrogen treatment liquid and the group containing the two liquids. The first method and the fifth to ninth methods are related to the first feature of the present invention, and the above! To the fourth method and the second feature (four) of the present invention. * 157216.doc 201216351 The water-repellent protective film of the present invention is a film that is formed on the surface of the wafer to reduce the wettability of the surface of the wafer, that is, to impart 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. Especially for water, the effect of reducing the interaction is large, but the mixture of the water and the liquid mixture other than the phase (4) and the liquid other than the water also have the effect of reducing the interaction. By reducing this interaction, the contact angle of the liquid relative to the surface of the article can be increased. The second feature of the present invention will be described below. For the sake of simplicity, the case where the second feature is described will also be omitted. In the method of cleaning a wafer according to the present invention, a reaction site containing a hydroxyl group or the like can be formed on the surface of the concavo-convex pattern by a liquid containing an acid and a solvent for dissolving the acid, that is, the acid in the pretreatment liquid. In the chemical solution for forming a protective film to be used for forming the water-repellent protective film on the surface of the concave-convex pattern, a compound which forms a protective film such as a zebra coupler and a solvent for dissolving the compound may be contained. When a large number of reactive sites such as hydroxyl groups are present on the surface of the concavo-convex pattern by the pretreatment, the compound forming the protective film contained in the protective film forming chemical solution and the reaction active site are easily reacted. As a result, the water-repellent protective film β can be stably formed on the surface of the uneven pattern. In the method of cleaning the wafer according to the second aspect of the present invention, the molar concentration of the acid in the pretreatment liquid (hereinafter also referred to as " The acid concentration ") is 〜1~5 mol/L. If the molar concentration of the acid in the pretreatment liquid solution is less than mol1 mol/L′, the effect of modifying the surface of the concave-convex pattern cannot be sufficiently obtained, that is, a reactive site such as a hydroxyl group is formed on the surface of the concave-convex pattern. After the 157216.doc 201216351, the molar concentration exceeds f, so it is difficult to remove the metal impurity fruit in the pretreatment treatment liquid. Further, when mol/L is contained in the pretreatment liquid, the concentration of the acid is too high, and it is purified by an ion exchange method in advance from the front. With the drug solution, the above pretreatment is: Γ: . When the enthalpy of the pretreatment liquid exceeds 3, the acidity of the chemical solution is weakened, so that the effect of the second surface of the concave-convex pattern, that is, the formation of the surface of the concave-convex pattern (four) is weak. < In the second feature of the present invention, the surface of the concave-convex pattern is easily reformed in a shorter period of time. On the other hand, if the surface of the concave-convex pattern is modified at a temperature of (4) or more of the pretreatment liquid, the state of the liquid-liquid interface is close to the state of the gas-liquid interface due to the rapid evaporation of the pretreatment liquid. The possibility of bad effects such as pattern damage. According to the second aspect of the present invention, in the method of cleaning a wafer according to the present invention, the surface of the concave-convex pattern is modified at a temperature of 4 〇〇C or more and less than the stagnation point of the pretreatment liquid. It is possible to impart more excellent water repellency to the surface of the above-mentioned concave portion. Therefore, the surface modification of the B 曰 circle by the above-mentioned pretreatment liquid is preferably 65. It is carried out at a temperature above the boiling point of the pretreatment liquid. Further, in the wafer cleaning method according to the second aspect of the present invention, it is preferable that the liquid is held on at least the surface of the concave portion of the concave-convex pattern until the protective film is formed on the surface. In the method for cleaning a wafer according to the second aspect of the present invention, the acid contained in the pretreatment 157216.doc 201216351 is preferably an organic acid. The organic acid mainly contains carbon, hydrogen and oxygen, and is preferably an element which is not suitable for the manufacturing steps of the semiconductor. Further, it is preferred that the organic acid and the inorganic acid phase & have a property of being easily soluble in an organic solvent and difficult to react with a metal. In the method of cleaning a wafer according to a second aspect of the present invention, it is preferable that at least a part of the uneven pattern is formed of tantalum nitride and/or niobium. When the uneven pattern is formed of tantalum nitride or niobium, if the surface of the concavo-convex pattern is not modified, the reactive sites such as hydroxyl groups on the surface of the concavo-convex pattern are small. Therefore, it is difficult to form the water repellent protective film on the surface of the concavo-convex pattern even if the protective film forming chemical solution is applied to the concavo-convex pattern formed by the nitrogen chopping, and the surface of the concavo-convex pattern is modified by the treatment liquid containing the acid. Even when the concave-convex pattern is formed of tantalum nitride or tantalum, a protective film having sufficient water repellency can be formed on the surface of the concave-convex pattern. Advantageous Effects of Invention By using the wafer cleaning method of the present invention (first method), a concave-convex pattern is formed on a surface thereof, and at least a part of a concave portion surface of the concave-convex pattern is selected from titanium, titanium nitride, tungsten, aluminum In the process of cleaning the wafer of at least one of the group consisting of copper, tin, tantalum nitride, niobium, and a substance containing a halogen, the capillary force acting on the concave-convex pattern is lowered and displayed Pattern collapse prevention effect. According to this cleaning method, the cleaning step in the method of manufacturing a wafer having a concave-convex pattern on the surface can be improved without lowering the yield. Therefore, the method for producing a wafer having a concave-convex pattern on the surface by the cleaning method of the present invention is highly productive. 157216.doc -13- 201216351 The cleaning method of the present invention can also be applied to a concave-convex pattern having an aspect ratio of, for example, 7 or more which is expected to become higher and higher in the future, and can reduce the cost of production of a higher density semiconductor element. . Further, the concave-convex pattern can be applied without any major change from the prior art, and as a result, it can be applied to manufacturers of various semiconductor elements. In the method for cleaning a wafer according to the present invention (second method), the protective film formed on the surface of the uneven pattern during the cleaning process is stable and exhibits water repellency. Therefore, collapse of the concavo-convex pattern can be prevented, and the wafer can be stably washed. Further, when the wafer is washed industrially, there are cases in which the types of wafers are different for each production lot. In this case, it is necessary to appropriately utilize the washing conditions corresponding to the production batch, that is, the conditions for forming a water-repellent protective film by forming an appropriate amount of a base or the like on the surface of the concave-convex pattern. However, by appropriately using the second feature of the present invention, it is effective to reduce the washing condition of the yen type of each day by reducing a ® ^ τ. [Embodiment] Before carrying out the method (the method) for cleaning a wafer according to the present invention, the following steps are usually mentioned as follows: Pattern formation on the surface of the wafer as a surface having a fine unevenness Step; Washing step before washing the wafer surface with the pre-treatment cleaning solution. Furthermore, the pre-washing step is sometimes omitted as appropriate. In the pattern forming step, the method is not limited as long as a fine pattern can be formed on the surface of the wafer. As a general method, after the anti-rice agent is applied to the surface of the wafer, the anti-silver agent mask is interposed. The anti-money agent is exposed, and the exposed resist or the unexposed resist is removed, thereby producing a resist having a desired concavo-convex pattern. Further, a resist having a concavo-convex pattern can be obtained by extruding a mold having a pattern on the resist. Then, the wafer is etched. At this time, after selectively resisting the pattern of the residual agent, the resist is peeled off to obtain a wafer having a fine concavo-convex pattern. Further, examples of the wafer include a germanium wafer, a wafer including germanium and/or germanium oxide (a plurality of components of SiOJ, a tantalum carbide wafer, a sapphire wafer, various compound semiconductor wafers, and the like). The surface of the plastic wafer or the like is coated with a layer of a metal material containing a titanium, titanium nitride, tungsten, aluminum, copper, tin, nitride, and tantalum and a tantalum element; or a multilayer film is formed on the wafer, wherein The at least one layer is the material layer or the like; the concave-convex pattern forming step is performed on the layer including the material layer, and the at least one portion of the concave-convex pattern is formed as the substance when the concave-convex pattern is formed. Further, Further, a concave-convex pattern is formed on the wafer, and the material layer is formed on the surface of the concave-convex pattern. Further, the protective film may be formed on the surface of the surface material of the wafer composed of a plurality of components including the above-mentioned substance. As a circle consisting of the plurality of components, the method further includes forming the above-mentioned substance on the surface of the wafer, and forming at least a part of the concave-convex pattern when forming the concave-convex pattern. Further, according to the chemical liquid of the present invention, a protective film can be formed on the surface of a part of the uneven pattern. As an example of the cleaning liquid used in the above-mentioned pre-cleaning step, HI: a mixture of an organic solvent 'water and an organic solvent, and a mixture of at least one of the hydrogen, ozone, acid, and the test 157216.doc -15. 201216351 one. Also, it is also washed. At least a plurality of cleaning liquids in the group consisting of liquids may be sequentially replaced in the cleaning liquid, and after removing the anti-(four)i and removing particles on the surface of the wafer in the pre-cleaning step, by drying, etc. When the above cleaning liquid is removed, if the small 'convex portion is relatively large in aspect, the pattern is likely to collapse. The concave and convex pattern is as shown in Figs. 1 and 2, and the circle 1 indicates that the surface is formed as A schematic plane® of the wafer 1 having the surface of the concave-convex pattern 2, and Fig. 2 shows a part of the cross section in aa of Fig. i. The width 5 of the concave portion is as shown in Fig. 2, and the surface of the convex portion 3 and the convex portion 3 is separated by one. Not ΰ „ (5 aspect ratio is the height of the convex part 6 divided by the width of the convex part 7 In the process of washing, the width of the pattern of the mountain is less than 7 nm, and the aspect ratio is 4 or more, especially above the stone. The first method and the fifth to ninth methods are described in detail. In the following description, in order to simplify, the first feature is omitted. The wafer cleaning method of the present invention (the third method) The method includes: a process step of modifying the surface of the wafer (for example, an oxidation treatment step); and forming a water-repellent (10) film containing a water-repellent protective film forming agent for forming a water-repellent protective film on the surface of the wafer And maintaining at least the concave portion of the wafer, and forming a water-repellent protection (4) water-repellent protective film forming step on the surface of the concave portion. The oxidation treatment step oxidizes the surface of the wafer. In the cleaning method of the present invention, the surface portion has a concave pattern and the at least concave portion of the concave and convex portion comprises a portion selected from the group consisting of titanium, titanium nitride, tungsten, indium, copper, tin, and nitride. Doc -16· 201216351 The wafer of the group consisting of '钌 and the material containing the stone element” is applied to the surface of the wafer to at least partially oxidize the substance. By this oxidation, a radical can be formed on the surface of the above-mentioned substance f, and the aqueous solution for forming a water-repellent protective film which is a water-repellent (tetra) film forming step in the subsequent step can be reacted with the radical. The wafer cleaning method towel of the present invention is efficiently cleaned in order to prevent collapse. Preferably, the step of forming the water-repellent protective film from the oxidation treatment step is such that at least the concave portion of the wafer remains liquid. The shape is off. Further, in the case of performing the above-described pre-cleaning step, it is preferred that the n-water-repellent protective film forming step is performed from the pre-cleaning step to the water-repellent protective film forming step in a state where at least the concave portion of the wafer is always kept liquid. Then, the formation of the liquid-repellent protective film which is held in the concave portion of the wafer by other liquids is also preferably carried out in a state in which at least the concave portion-straight (10) of the wafer is liquid with the upper (four) sample. Furthermore, in the present invention, the method of cleaning the wafer is not particularly limited as long as the oxidation treatment liquid, the chemical liquid or other liquid can be held in at least the concave portion of the concave-convex pattern of the wafer. As a method of cleaning the wafer, a one-piece method in which the wafer is substantially horizontally rotated in a plane-to-surface rotation, and the wafer is washed one by one in the face of the rotation, and the wafer is washed one by one. Or a batch method in which a plurality of wafers are immersed in a cleaning tank and washed. Further, in the form of the chemical liquid or the cleaning liquid when the oxidizing treatment liquid, the chemical liquid or the other liquid is supplied to at least the concave portion of the concave-convex pattern of the wafer, the chemical liquid or the cleaning liquid is held in the concave portion. In the case of a liquid, it is not particularly limited, and examples thereof include a liquid, a vapor, and the like. 157216.doc -17- 201216351, [Oxidation process: Oxidation of the surface of the wafer by Yin, as long as the surface of the wafer is preferably held by the oxidizing treatment liquid, the method of holding the deuterated treatment liquid on the surface of the wafer, In the case of a single-piece method, a method of supplying a liquid in the vicinity of the rotation order, and a liquid flow, and a method of immersing in the oxidation treatment liquid, etc. X, if at least one kind of treatment liquid selected from the group consisting of an old 3 ozone treatment liquid, a hydrogen peroxide treatment liquid, and an acid-containing treatment liquid is used as the oxidation treatment liquid, then the oxidation treatment liquid It is a strong oxidant, so that the wafer table can be selected from at least one of the group consisting of Qin's titanium nitride, crane, Ming, copper, tin, atmosphere group, nail and material containing Shi Xi elements. The material f is preferably used. The oxidation treatment step can be carried out using a normal temperature oxidation treatment liquid, or can be carried out by using an oxidation treatment liquid heated to 30 to 200 C. Generally, metals or nitrides tend to oxidize at higher temperatures, and therefore it is preferred to heat the oxidizing treatment solution to 30 Torr. In the case of treatment with an oxidizing treatment liquid or the like, if the oxidation treatment liquid containing most of the water is used, the treatment liquid is not swelled, so that the temperature cannot be raised under normal pressure. Therefore, use 1〇〇. In the case where the above oxidation treatment liquid is treated, it is preferred to use a solvent different from water. Next, the step of forming the water-repellent protective film will be described. The transfer from the oxidation treatment step to the water-repellent protective film forming step is carried out by replacing the oxidation treatment liquid held in at least the concave portion of the concave-convex pattern of the wafer with the water-repellent protective film forming chemical liquid in the oxidation treatment step. About 18 · 157216.doc 8 201216351 The oxidation treatment liquid is replaced by a liquid solution for forming a water-repellent protective film, and can be directly replaced with a different cleaning liquid A (hereinafter, it is only referred to as "washing liquid A"). In the case where one or more substitutions are made, the aqueous solution for forming a water-repellent protective film is replaced. Preferable examples of the cleaning solution A include water, an organic solvent, a mixture of water and an organic solvent, or at least one of a mixture of an acid, an acid, and a surfactant. Wait. Moreover, examples of the organic solvent which is one of preferable examples of the cleaning liquid A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, and polyols. Derivatives, nitrogen-containing compound solvents, and the like. The formation of the water-repellent protective film in the water-repellent protective film forming step is carried out by holding the water-repellent protective film forming chemical solution in at least the concave portion of the concave-convex pattern of the wafer. Fig. 3 is a view showing a state in which the concave portion 4 holds the chemical liquid 8 for forming the water-repellent protective film. The wafer of the schematic view of Fig. 3 represents a portion of the a-a' section of the figure. In the step of forming the water repellency protection crucible, the water repellent protective film forming chemical solution is supplied to the wafer 1 on which the uneven pattern 2 is formed. At this time, as shown in Fig. 3, the water-repellent protective film forming chemical liquid is maintained in at least the concave portion 4, and the surface of the concave portion 4 is dialed. Further, the protective film of the present invention is not necessarily formed continuously, and it is not necessarily required to be uniformly formed. However, in order to impart more excellent water repellency, it is more preferable to form continuously and uniformly. Further, in the step of forming the water-repellent protective sputum, if the temperature of the chemical liquid is raised, the protective film is likely to be formed in a shorter period of time, but the medicinal liquid is damaged by the tumbling or evaporation of the medicinal solution for forming the water-repellent protective film. The stability of the above solution is preferably maintained at 10 to 16 (rc, especially preferably 15 to 157216.doc -19-201216351 120 ° C 〇, and # in the water-repellent protective film forming step towel The water-repellent protective film forming chemical liquid is described. The chemical liquid contains a water-repellent protective film forming agent represented by the following formula, which corresponds to the above first method. R1aSiX4.a Π] [弋[] towel R knife Independent of each other, it is hydrogen, or a carbon-based unsubstituted hydrocarbon group or a hydrogen-based y-substance-substituted nicotine group. In the case of a metal-based wafer, the number of carbons contained in the R [1] R towel is 6 or more, each of which is selected from the group consisting of a valence functional group in which an element bonded to a halogen element is nitrogen, a monovalent functional group in which an element bonded to a stone element is oxygen, and a base. At least one of the groups, 3 is an integer of 1 to 3.] For example, oxidation treatment is performed on the surface of the material. The oxygen-cut surface obtained is rich in the base of the reactive site, and is usually obtained by subjecting the above-mentioned oxidation treatment to the surface of the Qin, Nitriding, Tungsten, Tin, Nitriding and nail surfaces, respectively. The surface of the oxidized steel, the oxidized steel, the oxygen (4), the oxidized yttrium oxide, and the yttrium oxide has a smaller amount of base than the surface of the oxidized oxidized stone, so that the less base group reacts with the previous sulphur coupling agent and is difficult to surface. Provide sufficient water repellency. However, if the hydrophobic group is a base having stronger hydrophobicity, sufficient water repellency can be imparted. If the total number of carbon atoms is large, Rl is considered to have stronger hydrophobicity. The hydrophobic group, X, R, may also be a hydrocarbon group in which a part or all of the hydrogen 7G element is substituted by a functional element, especially if it has a hydrophobic group having a carbon number of 6 or more and having a strong hydrophobic number of 6 or more. The aqueous protective film forming agent can form a protective film that sufficiently exhibits the water repellency even if it is present on the surface of the wafer. Further, 喟157216.doc 8 •20· 201216351 [1] The total number of carbons contained in R is 6 In the above formula, the total number of carbon atoms of one to three hydrophobic groups included as R1 in the formula [丨] is 6 or more. Further, the X represented by the general formula [1] is bonded to the ruthenium element. The functional group functional group in which the element is nitrogen may be a functional group composed of carbon, hydrogen, boron, nitrogen, argon, oxygen, sulfur, cerium, lanthanum, fluorine, gas, bromine, iodine or the like, and examples thereof include, for example, -NSi(CH3)3 group, -NSi(CH3)2C4H9 group, _NSi(CH3)2C8Hi7 group, -N(CH3)2 group, -N(C2H5)2 group, _n(C3H7)2 group, _n(CH3) (C2H5) group, -NH(C2H5) group, -NCO group, imidazolyl group, etidamine group Further, the element bonded to the yttrium element represented by X of the general formula [1] is a monovalent functional group of oxygen as long as The functional group consisting of carbon, hydrogen, shed, nitrogen, phosphorus, oxygen, sulfur, sulphur, sulphur, chlorine, chlorine, bromine, iodine, etc., for example, -OCH3 group, -〇c2H5 group, -0C3H7 group, -〇COCH3 group, -OCOCF3 group, and the like. In addition, examples of the halogen group represented by X in the general formula [1] include a -F group, a -C1 group, a -Br group, and a -I group. The base represented by X of the above formula [1] and the radical reaction of the surface of the wafer form a bond between the germanium element in the lithiation and the surface of the wafer, whereby a protective film can be formed. Examples of the telluride represented by the general formula [1] include C4H9(CH3)2SiCl, C5Hn(CH3)2SiCl, C6H13(CH3)2SiCl, C7H15(CH3)2SiCl, C8H丨7(CH3)2SiCl, and C9H19 ( CH3) 2SiCl, C10H21(CH3)2Sia, CnH23(CH3)2SiCl, C丨2H25(CH3)2SiCn, Ci3H27(CH3)2SiCl, C14H29(CH3)2SiCl, C15H31(CH3)2Sia, 157216.doc -21 · 201216351 C16H33 (CH3)2SiCn, C17H35(CH3)2SiC, C18H37(CH3)2SiC, C5Hn(CH3)HSiCl, C6H13(CH3)HSiCn, C7H15(CH3)HSiCM, C8H,7(CH3)HSiCl 'C9H19(CH3)HSiCl 'C10H2i (CH3)HSiCl 'CnHyCHOHSiCl, C12H25(CH3)HSiC, C13H27(CH3)HSiCl, C14H29(CH3)HSiCl, C15H31(CH3)HSiCn, C16H33(CH3)HSiC, C17H35(CH3)HSiCl, C18H37(CH3)HSiCl, C2F5C2H4 (CH3)2SiCl, C3F7C2H4(CH3)2Sia, C4F9C2H4(CH3)2SiC, CsFnQHWCH^Sia, C6F13C2H4(CH3)2Sia, C7F15C2H4(CH3)2SiC, C8F17C2H4(CH3)2SiC(C2H5)3SiCl 'C3H7(C2H5)2SiCl &gt ; C4H9(C2H5)2SiCl ' C5H11(C2H5)2SiCl ' C6H13(C2H5)2SiCl, C7H15(C2H5)2SiCM, C8H17(C2H5)2SiCn, C9H19(C2H5)2SiCl ' C10H21(C2H5)2SiCl ' C11H23(C2H5)2SiCl ' C12H25 (C2H5) 2SiCl, C13H27(C2H5)2SiCn, C14H29(C2H5)2Sia, C15H31(C2H5)2SiC, C16H33(C2H5)2SiCn, C17H35(C2H5)2SiCl, C18H37(C2H5)2SiCl, (C4H9)3SiCl, C5Hn(C4H9)2SiCl, C6H13(C4H9)2Sia, C7H15(C4H9 ) 2SiC Bu C8H17(C4H9)2SiCl, C9H19(C4H9)2SiCl, C10H21(C4H9)2SiCl, CnH23(C4H9)2SiCl, C12H25(C4H9)2SiC, C13H27(C4H9)2SiCl, C14H29(C4H9)2SiC, C15H31(C4H9)2SiCl , C16H33(C4H9)2SiCn, C17H35(C4H9)2SiCl, C18H37(C4H9)2Sia, CF3C2H4(C4H9)2Sia, C2F5C2H4(C4H9)2SiCl, C3F7C2H4(C4H9)2Sia, C4F9C2H4(C4H9)2Sia, CsFuQHyC^HASiCn, C6F13C2H4(C4H9 2Sia, C7F15C2H4(C4H9)2SiC, C8F17C2H4(C4H9)2SiC, CsHWCHJSiCh, C6H13(CH3)SiCl2, C7H15(CH3)SiCl2, C8H17(CH3)SiCl2, C9H19(CH3)SiCl2, C1()H21(CH3)SiCl2 CnH23(CH3)SiCl2, C12H25(CH3)SiCl2, C13H27(CH3)SiCl2, •22- 157216.doc 8 201216351 C14H29(CH3)SiCl2, C15H31(CH3)SiCl2, C16H33(CH3)SiCl2, C17H35(CH3)SiCl2 C18H37(CH3)SiCl2, C3F7C2H4(CH3)SiCl2, C4F9C2H4(CH3)SiCl2 'C5F11C2H4(CH3)SiCl2 'C6F13C2H4(CH3)SiCl2 'C7F15C2H4(CH3)SiCl2, C8F17C2H4(CH3)SiCl2, C6H13SiCl3 C7H15SiCl3, C8H17SiCl3, C9H19SiCl3, C10H21SiCl3, CnH23SiCl3, C12H25SiCl3, C13H27SiCl3, C14H29SiCl3, C15H31SiCl3, C16H33SiCl3, C17H35SiCl3, C18H37SiCl3, C4F9C2H4S1CI3 'CsFnCsHJiCb, C6F13C2H4SiCl3, C7F15C2H4SiCl3, C8F17C2H4SiCl3 and other silicon-based compound gas. Further, for example, C4H9(CH3)2SiOCH3, C5H„(CH3)2SiOCH3, C6H13(CH3)2SiOCIi3, C7H15(CH3)2SiOCH3, C8H17(CH3)2SiOCH3, C9H19(CH3)2SiOCH3, C1()H21(CH3) 2SiOCH3, CuHWCHASiOCl·^, C12H25(CH3)2SiOCH3, C13H27(CH3)2SiOCH3, C14H29(CH3)2SiOCH3, C15H31(CH3)2SiOCH3, C16H33(CH3)2SiOCH3, C17H35(CH3)2SiOCH3, C18H37(CH3)2SiOCH3, CsHuCCHDHSiOCHs, C6H13(CH3)HSiOCH3, C7Hi5(CH3)HSiOCH3, C8Hn(CH3)HSiOCH3, C9H19(CH3)HSiOCH3, C10H21(CH3)HSiOCH3, CnH23(CH3)HSiOCH3, C12H25(CH3)HSiOCH3, C13H27(CH3)HSiOCH3, C14H29( CH3)HSiOCH3, C15H31(CH3)HSiOCH3, C16H33(CH3)HSiOCH3, CnH35(CH3)HSiOCH3, C18H37(CH3)HSiOCH3, C2F5C2H4(CH3)2SiOCH3 'C3F7C2H4(CH3)2SiOCH3 'C4F9C2H4(CH3)2SiOCH3 'C5FuC^(CH3 2SiCra3, cut 3 marriage (both 0€113, 15(:2(013)^0013, C8F17C2H4(CH3)2SiOCH3, (C2H5)3SiOCH3, C3H7(C2H5)2SiOCH3, C4H9(C2H5)2SiOCH3, C5H„ (C2H5)2SiOCH3, C6H13(C2H5)2SiOCH3, C7H15(C2H5)2SiOCH3, C8H17(C2H5)2SiOCH3, C9H19(C2H5)2SiOCH3, 157216.doc -23- 201216351 C10H21(C2H5)2SiO CH3, C„H23(C2H5)2SiOCH3, C12H25(C2H5)2SiOCH3, C13H27(C2H5)2SiOCH3, C14H29(C2H5)2SiOCH3, C15H31(C2H5)2SiOCH3, C16H33(C2H5)2SiOCH3, C17H35(C2H5)2SiOCH3, C18H37(C2H5) 2SiOCH3, (C4H9)3SiOCH3, C5Hn(C4H9)2SiOCH3, C6H13(C4H9)2SiOCH3, C7H丨5(C4H9)2SiOCH3, C8H17(C4H9)2SiOCH3, C9H19(C4H9)2SiOCH3, C10H21(C4H9)2SiOCH3, CuH23(C4H9)2SiOCH3 , C12H25(C4H9)2SiOCH3,

Cl3H27(C4H9)2SiOCH3, Ci4H29(C4H9)2SiOCH3, Ci5H3i(C4H9)2SiOCH3, Ci6H33(C4H9)2SiOCH3, CnH35(C4H9)2SiOCH3, Ci8H37(C4H9)2SiOCH3, C5Hu(CH3)Si(OCH3)2, C6H〗 3 CH3)Si(OCH3)2, C7H15(CH3)Si(OCH3)2, C8H17(CH3)Si(OCH3)2, C9H19(CH3)Si(OCH3)2, C10H21(CH3)Si(OCH3)2, C„ H23(CH3)Si(OCH3)2, C12H25(CH3)Si(OCH3)2, C13H27(CH3)Si(OCH3)2, C14H29(CH3)Si(OCH3)2, C15H31(CH3)Si(OCH3)2 C16H33(CH3)Si(OCH3)2, C17H35(CH3)Si(OCH3)2 'C18H37(CH3)Si(OCH3)2 'C3F7C2H4(CH3)Si(OCH3)2 'C4F9C2H4(CH3)Si(OCH3)2 C5F! 1C2H4(CH3)Si(OCH3)2, C6F13C2H4(CH3)Si(OCH3)2, C7F15C2H4(CH3)Si(OCH3)2, C8F17C2H4(CH3)Si(OCH3)2, C6H13Si(OCH3)3, C7H15Si( OCH3)3, C8H17Si(OCH3)3, C9H19Si(OCH3)3, C10H21Si(OCH3)3, CnH23Si(OCH3)3, C12H25Si(OCH3)3, C13H27Si(OCH3)3, C14H29Si(OCH3)3, C15H31Si(OCH3) 3. C16H33Si(OCH3)3, C17H35Si(OCH3)3, C18H37Si(OCH3)3, C4F9C2H4Si(OCH3)3, C5F„C2H4Si(OCH3)3, C6F13C2H4Si(OCH3)3, C7F15C2H4Si(OCH3)3, C8F17C2H4Si(OCH3) 3 > C4H9(CH3)2SiOC2H5 'C5H11(CH3)2SiOC2H5 'C6H 13(CH3)2SiOC2H5, C7H15(CH3)2SiOC2H5, C8H17(CH3)2SiOC2H5, C9H19(CH3)2SiOC2H5 > C10H2i(CH3)2SiOC2H5 > 0,^23(^3)2810^5 ' 157216.doc -24- 8 201216351 C 12H25(CH3)2SiOC2H5, C13H27(CH3)2SiOC2H5, C14H29(CH3)2SiOC2H5, C15H31(CH3)2SiOC2H5, C16H33(CH3)2SiOC2H5, CnH35(CH3)2SiOC2H5, C18H37(CH3)2SiOC2H5 'C2F5C2H4(CH3)2SiOC2H5 ' C3F7C2H4(CH3)2SiOC2H5 ^ C4F9C2H4(CH3)2SiOC2H5, C5FuC2H4(CH3)2SiOC2H5, C6F13C2H4 (CH3)2SiOC2H5, C7F15C2H4(CH3)2SiOC2H5, C8F17C2H4 (CH3)2SiOC2H5, (C2H5)3SiOC2H5, C3H7(C2H5)2SiOC2H5, C4H9( C2H5)2SiOC2H5, C5H„(C2H5)2SiOC2H5, C6H13(C2H5)2SiOC2H5, C7H15(C2H5)2SiOC2H5, (:8Κ17((:2Η5)28ίΟ(:2Η5, C9H19(C2H5)2SiOC2H5, C10H21(C2H5)2SiOC2H5, CnHWQHASiOCzHs, C12H25(C2H5)2SiOC2H5, C13H27(C2H5)2SiOC2H5, C14H29(C2H5)2SiOC2H5, C15H31(C2H5)2SiOC2H5, c16H33(C2H5)2SiOC2H5, CnH35(C2H5)2SiOC2H5, Ci8H37(C2H5)2SiOC2H5, (C4H9)3SiOC2H5, CsHWQHASiOCzHs, C6H13(C4H9)2SiOC2H5, C7H15(C4H9)2SiOC2H5, C8Hi7(C4H9)2SiOC2H5, C9H19(C4H9)2SiOC2H5 , C l〇H2i(C4H9)2SiOC2H5, CiiH23(C4H9)2SiOC2H5, Ci2H25(C4H9)2SiOC2H5, C13H27(C4H9)2SiOC2H5, C14H29(C4H9)2SiOC2H5, C15H31(C4H9)2SiOC2H5, C16H33(C4H9)2SiOC2H5, CnH35(C4H9 2SiOC2H5, Ci8H37(C4H9)2§i〇C2H5, (:5Η„((:Η3)8ί(0<:2Η5)2, C6H13(CH3)Si(OC2H5)2, C7H15(CH3)Si(OC2H5)2 , C8H17(CH3)Si(OC2H5)2, C9H19(CH3)Si(OC2H5)2, C1()H21(CH3)Si(OC2H5)2, C„H23(CH3)Si(OC2H5)2, C12H25(CH3) Si(OC2H5)2, C13H27(CH3)Si(OC2H5)2, C14H29(CH3)Si(OC2H5)2, C15H31(CH3)Si(OC2H5)2, C16H33(CH3)Si(OC2H5)2, C17H35(CH3 )Si(OC2H5)2, C18H37(CH3)Si(OC2H5)2, C3F7C2H4(CH3)Si(OC2H5)2, C4F9C2H4(CH3)Si(OC2H5)2, CsFnC:^(CH3)Si(OC2H5)2, C6F13C2H4 (CH3)Si(OC2H5)2, C7F15C2H4(CH3)Si(OC2H5)2, C8F17C2H4(CH3)Si(OC2H5)2, C6H13Si 157216.doc -25.201216351 (OC2H5)3, C7H15Si(OC2H5)3, C8H17Si( OC2H5)3, C9H19Si (OC2H5)3, C10H21Si(OC2H5)3, CnH23Si(OC2H5)3, C12H25Si(OC2H5)3, C13H27Si(OC2H5)3, C14H29Si(OC2H5)3, C15H31Si(OC2H5)3, C16H33Si(OC2H5) 3. C17H35Si(OC2H5)3, C18H37Si (OC2H5)3, C4F9C2H4Si(OC2H5)3, CsFnQI^SKOC^HA, C6F13C2H4Si(OC2H5)3, C7F15C2H4Si(OC2H5)3, C8F17C2H4Si(OC2H5)3 and other alkoxydecane-based compounds. Further, for example, C4H9(CH3)2SiNCO, C5H„(CH3)2SiNCO, C6H13(CH3)2SiNCO, C7H15(CH3)2SiNCO, C8H17(CH3)2SiNCO, C9H19(CH3)2SiNCO, C1()H21(CH3) 2SiNCO, CnH23(CH3)2SiNCO, C12H25(CH3)2SiNCO, C13H27(CH3)2SiNCO, C14H29(CH3)2SiNCO, C15H31(CH3)2SiNCO, C16H33(CH3)2SiNCO, C17H35(CH3)2SiNCO, C18H37(CH3)2SiNCO ' C2F5C2H4(CH3)2SiNCO ' C3F7C2H4(CH3)2SiNCO ' C4F9C2H4(CH3)2SiNCO, C5FnC2H4(CH3)2SiNCO, C6F13C2H4(CH3)2SiNCO, C7F15C2H4(CH3)2SiNCO, C8F17C2H4(CH3)2SiNCO, (C2H5)3SiNCO, C3H7(C2H5 2SiNCO, C4H9(C2H5)2SiNCO, (:5Η„((:2Η5)28ίΝ(:0, C6H13(C2H5)2SiNCO, C7H15(C2H5)2SiNCO, C8H17(C2H5)2SiNCO, C9H19(C2H5)2SiNCO, C1QH21(C2H5 2SiNCO, CnHyC^HASiNCO, C] 2H25(C2H5)2SiNCO, C13H27(C2H5)2SiNCO, C14H29(C2H5)2SiNCO, C15H31(C2H5)2SiNCO, C16H33(C2H5)2SiNCO, C17H35(C2H5)2SiNCO, C18H37(C2H5)2SiNCO , (C4H9)3SiNCO, (:5Η"((:4Η9)28ίΝ(:0, C6H13(C4H9)2SiNCO, C7H15(C4H9)2SiNCO, C8H17(C4H9)2SiNCO, C9H19(C4H9)2SiNCO, C1()H21(C4H9 ) 2SiNCO, C iiH23(C4H9)2SiNCO, C12H25(C4H9)2SiNCO, C13H27(C4H9)2SiNCO, 157216.doc •26- 8 201216351 C14H29(C4H9)2SiNCO, C15H31(C4H9)2SiNCO, C16H33(C4H9)2SiNCO, C17H35(C4H9)2SiNCO , C18H37(C4H9)2SiNCO, C5H„(CH3)Si(NCO)2, C6H13(CH3)Si(NCO)2, C7H15(CH3)Si(NCO)2, C8H17(CH3)Si(NCO)2, C9H19( CH3)Si(NCO)2, C10H21(CH3)Si(NCO)2, CnH23(CH3)Si(NCO)2, C12H25(CH3)Si(NCO)2 'C13H27(CH3)Si(NCO)2 ' C14H29 (CH3)Si(NCO)2 ' C15H31(CH3)Si(NCO)2 ' C16H33(CH3)Si(NCO)2 ' C17H35(CH3)Si(NCO)2 ' C18H37(CH3)Si(NCO)2,C3F7C2H4 (CH3)Si(NCO)2, C4F9C2H4 (CH3)Si(NCO)2 'C5F11C2H4(CH3)Si(NCO)2 'C6F13C2H4(CH3)Si(NCO)2 'C7F15C2H4(CH3)Si(NCO)2, C8F17C2H4 (CH3)Si(NCO)2, C6H13Si(NCO)3, C7H15Si(NCO)3, C8H17Si(NCO)3, C9H19Si(NCO)3, C10H21Si(NCO)3, C„H23Si(NCO)3, C12H25Si(NCO 3, C13H27Si(NCO)3, C14H29Si(NCO)3, C15H31Si(NCO)3, C16H33Si(NCO)3, C17H35Si(NCO)3, C18H37Si(NCO)3, C4F9C2H4Si(NCO)3, CsFuCjRjSKNCOh, C6F13C2H4Si(NCO 3) C7F15C2H4Si(NCO)3, C8F17C2H4Si(NCO)3, etc. Based compound. Further, for example, C4H9(CH3)2SiNH2, C5H„(CH3)2SiNH2, C6H13(CH3)2SiNH2, C7H15(CH3)2SiNH2, C8H17(CH3)2SiNH2, C9H19(CH3)2SiNH2, C10H21(CH3)2SiNH2, CnH23 (CH3)2SiNH2, C12H25(CH3)2SiNH2, C13H27(CH3)2SiNH2, C14H29(CH3)2SiNH2, C15H3(CH3)2SiNH2, C16H33(CH3)2SiNH2, C17H35(CH3)2SiNH2, C18H37(CH3)2SiNH2, C2F5C2H4( CH3)2SiNH2, C3F7C2H4(CH3)2SiNH2, C4F9C2H4(CH3)2SiNH2 > CjFj ^2^(^3)281^2 'C6F13C2H4(CH3)2SiNH2 'C7F15C2H4(CH3)2SiNH2, C8F17C2H4(CH3)2SiNH2, [C4H9( CH3)2Si]2NH, [CsHWCHASihNH, [C6H13(CH3)2Si]2NH, [C7H15(CH3)2Si]2NH, 157216.doc -27- 201216351 [C8H17(CH3)2Si]2NH, [C9H19(CH3)2Si] 2NH, [C1()H21(CH3)2Si]2NH, [CuHdCHASihNH, [C12H25(CH3)2Si]2NH, [C13H27(CH3)2Si]2NH, [C14H29(CH3)2Si]2NH, [C15H31(CH3)2Si ] 2NH, [C16H33(CH3)2Si]2NH, [C17H35(CH3)2Si]2NH, [C18H37(CH3)2Si]2NH, [C2F5C2H4(CH3)2Si]2NH, [C3F7C2H4(CH3)2Si]2NH, [C4F9C2H4 (CH3)2Si]2NH, [C5FnC2H4(CH3)2Si]2NH, [C6F13C2H4(CH3)2Si]2NH, [C7F15C2H4(CH3)2Si]2NH, [C8F17C2H4(CH3)2 Si]2NH, [(C2H5)3Si]2NH, [C3H7(C2H5)2Si]2NH, [C4H9(C2H5)2Si]2NH, [C5Hn(C2H5)2Si]2NH, [C6H13(C2H5)2Si]2NH, [C7H15 (C2H5)2Si]2NH, [C8H17(C2H5)2Si]2NH, [C9Hi9(C2H5)2Si]2NH, [C1()H21(C2H5)2Si]2NH, [C„H23(C2H5)2Si]2NH, [C12H25 (C2H5)2Si]2NH, [C13H27(C2H5)2Si]2NH, [C14H29(C2H5)2Si]2NH, [C15H31(C2H5)2Si]2NH, [C16H33(C2H5)2Si]2NH, [C17H35(C2H5)2Si] 2NH, [C18H37(C2H5)2Si]2NH, [C4H9(CH3)2Si]3N, [CsHWCH^SihN, [C6H13(CH3)2Si]3N, [C7H15(CH3)2Si]3N, [C8H17(CH3)2Si] 3N ^ [C9H19(CH3)2Si]3N > [C10H21(CH3)2Si]3N ^ [C„H23(CH3)2Si]3N, [C12H25(CH3)2Si]3N, [C13H27(CH3)2Si]3N, [C14H29(CH3)2Si]3N ^ [C15H3i(CH3)2Si]3N ' [C16H33(CH3)2Si]3N '[C17H35(CH3)2Si]3N, [C18H37(CH3)2Si]3N, [C2F5C2H4(CH3) 2Si]3N, [C3F7C2H4(CH3)2Si]3N, [C4F9C2H4(CH3)2Si]3N, [C5F„C2H4(CH3)2Si]3N, [C6F13C2H4(CH3)2Si]3N, [C7F15C2H4(CH3)2Si]3N , [C8F17C2H4(CH3)2Si]3N, C4H9(CH3)2SiN(CH3)2, C5H„(CH3)2SiN(CH3)2, C6H13(CH3)2SiN(CH3)2, C7H15(CH3)2SiN(CH3)2 , C8H17(CH3)2SiN(CH3)2, C9H19(CH3)2S iN(CH3)2, C10H21(CH3)2SiN(CH3)2, C„H23(CH3)2SiN(CH3)2, C12H25(CH3)2SiN(CH3)2, C13H27(CH3)2SiN(CH3)2, C14H29 (CH3)2SiN(CH3)2, C15H31(CH3)2SiN(CH3)2, 157216.doc -28 - 8 201216351 C16H33(CH3)2SiN(CH3)2 'C17H35(CH3)2SiN(CH3)2 'C18H37(CH3 ) 2SiN(CH3)2 ' CsHnC^HSiNCCHs^ ' C6H13(CH3)HSiN(CH3)2 ' C7H15(CH3)HSiN(CH3)2 ' C8H17(CH3)HSH3l C9H19(CH3)HSiN(CH3)2, C10H21 (CH3)HSiN(CH3)2

CuH23(CH3)HSiN(CH3)2 ' Ci2H25(CH3)HSiN(CH3)2 ' C13H27(CH3)HSiN(CH3)2 ' ' C15H3,(CH3)HSiN(CH3)2 ' C16H33(CH3)HSiN(CH3) 2 ' C17H35(CH3)HSiN(CH3)2, C18H37(CH3)HSiN(CH3)2, C2F5C2H4 (CH3)2SiN(CH3)2, C3F7C2H4(CH3)2SiN(CH3)2, C4F9C2H4 (CH3)2SiN(CH3) 2 > C5F11C2H4(CH3)2SiN(CH3)2 'C6F13C2H4 (CH3)2SiN(CH3)2, C7F15C2H4(CH3)2SiN(CH3)2, C8F17C2H4 (CH3)2SiN(CH3)2, (C2H5)3SiN(CH3) 2. C3H7(C2H5)2SiN(CH3)2, C4H9(C2H5)2SiN(CH3)2, C5H„(C2H5)2SiN(CH3)2, C6H13(C2H5)2SiN(CH3)2, C7H15(C2H5)2SiN( CH3)2, C8H17(C2H5)2SiN(CH3)2, C9H19(C2H5)2SiN(CH3)2, C1GH21(C2H5)2SiN(CH3)2, C„H23(C2H5)2 SiN(CH3)2, C12H25(C2H5 2SiN(CH3)2, C13H27(C2H5)2SiN(CH3)2, C14H29(C2H5)2SiN(CH3)2, C15H31(C2H5)2SiN(CH3)2, C16H33 (C2H5)2SiN(CH3)2, C17H35(C2H5 2SiN(CH3)2, C18H37(C2H5)2 SiN(CH3)2, (C4H9)3SiN(CH3)2, C6H13(C4H9)2SiN(CH3)2, C7H15(C4H9)2SiN(CH3)2, C8Hl7 ( C4H9)2SiN(CH3)2, C9H19(C4H9)2SiN(CH3)2, C1(jH21(C4H9)2 SiN(CH3)2 'C11H23(C4H9)2SiN(CH3)2 'C12H25(C4H9)2SiN(CH3)2 ' C13H27(C4H9)2SiN(C H3)2, C14H29(C4H9)2SiN(CH3)2, C15H31 (C4H9)2SiN(CH3)2, C16H33(C4H9)2SiN(CH3)2, C17H35(C4H9)2 SiN(CH3)2 'C18H37(C4H9)2SiN (CH3)2 'C5H11(CH3)Si[N(CH3)2]2 'C6H13(CH3)Si[N(CH3)2]2, C7H15(CH3)Si[N(CH3)2]2, C8H17(CH3 ) -29- 157216.doc 201216351

Si[N(CH3)2]2, C9H19(CH3)Si[N(CH3)2]2, C1GH21(CH3)Si[N(CH3)2]2, CuH23(CH3)Si[N(CH3)2] 2, C12H25(CH3)Si[N(CH3)2]2, C13H27(CH3)Si[N(CH3)2h, C14H29(CH3)Si[N(CH3)2]2, C15H31(CH3)Si[N( CH3)2]2, C16H33(CH3)Si[N(CH3)2]2, C17H35(CH3)Si[N(CH3)2]2, C18H37(CH3)Si[N(CH3)2]2, C3F7C2H4( CH3)Si[N(CH3)2]2, C4F9C2H4(CH3)Si[N(CH3)2]2, CsFnQzHdCHOSinSKCHAh, C6F13C2H4(CH3)Si[N(CH3)2]2, C7F15C2H4(CH3)Si[N( CH3)2]2, C8F17C2H4(CH3)Si[N(CH3)2]2, C6H13Si[N(CH3)2]3, C7H15Si[N(CH3)2]3, C8H17Si[N(CH3)2]3, C9H19Si[N(CH3)2]3, C10H21Si[N(CH3)2]3, CnHuSitl^CHsKh, C12H25Si[N(CH3)2]3, C13H27Si[N(CH3)2]3, C14H29Si[N(CH3) 2]3, C15H31Si[N(CH3)2]3, C16H33Si[N(CH3)2]3, C17H35Si[N(CH3)2]3, C18H37Si[N(CH3)2]3, C4F9C2H4Si[N(CH3) 2]3, C5FnC2H4Si [N(CH3)2]3, C6F13C2H4Si[N(CH3)2]3, C7F15C2H4Si[N(CH3)2]3, C8F17C2H4Si[N(CH3)2]3, C4H9(CH3)2SiN( C2H5)2, C5Hn (CH3)2SiN(C2H5)2, C6H13(CH3)2SiN(C2H5)2, C7H15(CH3)2 SiN(C2H5)2, C8H17(CH3)2SiN(C2H5)2, C9H19(CH3)2SiN (C2H5) 2, C10H21 (CH3)2SiN(C2H5)2 > C11H23(CH3)2SiN(C2H5)2 'C12H25 (CH3)2SiN(C2H5)2, C13H27(CH3)2SiN(C2H5)2, C14H29(CH3)2 SiN(C2H5)2 , C15H31(CH3)2SiN(C2H5)2, C16H33(CH3)2SiN(C2H5)2, C17H35(CH3)2SiN(C2H5)2, C18H37(CH3)2SiN(C2H5)2, C2F5C2H4(CH3)2SiN(C2H5)2 , C3F7C2H4(CH3)2SiN(C2H5)2, C4F9C2H4(CH3)2 SiN(C2H5)2, CsFuCzHJCHASil^C^HA, C6F13C2H4(CH3)2 SiN(C2H5)2, C7F15C2H4(CH3)2SiN(C2H5)2, C8F17C2H4 (CH3)2 157216.doc •30· 8 201216351

SiN(C2H5)2, (C2H5)3SiN(C2H5)2, C3H7(C2H5)2SiN(C2H5)2, C4H9(C2H5)2SiN(C2H5)2, CsHWCzHASil^C^HA, C6H13 (C2H5)2SiN(C2H5)2 , C7H15(C2H5)2SiN(C2H5)2, C8H17(C2H5)2 SiN(C2H5)2, C9H19(C2H5)2SiN(C2H5)2, C10H21(C2H5)2SiN(C2H5)2, C11H23(C2H5)2SiN(C2H5) 2 ' C12H25(C2H5)2SiN(C2H5)2 ' C13H27 (C2H5)2SiN(C2H5)2, C14H29(C2H5)2SiN(C2H5)2, C15H31(C2H5)2 SiN(C2H5)2, C16H33(C2H5)2SiN(C2H5 2, C17H35(C2H5)2SiN (C2H5)2, C18H37(C2H5)2SiN(C2H5)2, (C4H9)3SiN(C2H5)2, C5H11(C4H9)2SiN(C2H5)2 'C6H13(C4H9)2SiN(C2H5) 2 ^ C7H15 (C4H9)2SiN(C2H5)2, C8Hi7(C4H9)2SiN(C2H5)2, C9H19(C4H9)2 SiN(C2H5)2, C1QH21(C4H9)2SiN(C2H5)2, C12H25(C4H9)2SiN( C2H5)2, C13H27(C4H9)2SiN(C2H5)2, C14H29 (C4H9)2SiN(C2H5)2, C15H3丨(C4H9)2SiN(C2H5)2, C16H33(C4H9)2 SiN(C2H5)2, C17H35(C4H9) An amine decane compound such as 2SiN(C2H5)2, Cl8H37(C4H9)2SiN(C2H5)2. Further, a of the general formula [1] may be an integer of 1 to 3, and when the & is 1 or 2, if the chemical liquid is stored for a long period of time, the above-mentioned telluride is liable to be caused by the incorporation of moisture or the like. In the polymerization reaction with each other, there is a tendency that it is difficult to stably form the water-repellent protective film on the surface of the wafer. In consideration of this aspect, it is preferable that the a of the general formula [1] is three, that is, the following general formula [2] The telluride represented. It corresponds to the above fifth method. R^SiX [2], [in the formula m, r1 are independent of each other, and are hydrogen, or an unsubstituted hydrocarbon group of carbon number 18 or a hydrocarbon group in which a hydrogen element is substituted by a tooth element, and 157216 included in the formula [2]. .doc •31 - 201216351 The total carbon number is 6 or more (in the case of a metal-based wafer), the element bonded to the lanthanide element and the lanthanum element is a valence functional group of nitrogen, and the element bonded to the yttrium element is oxygen. a monovalent functional group, or a radical of the above formula Π], wherein H@Rl is an unsubstituted hydrocarbon group having a carbon number of 4 to 18 or a hydrocarbon group substituted with a halogen element and It is preferable that the telluride represented by the following general formula [3] has a high reactivity with the hydroxyl group on the surface of the wafer, and is preferable (corresponding to the above-described sixth method because the wafer surface is In the reaction between the hydroxyl group and the group represented by the above-mentioned telluride, the steric damage caused by the hydrophobic group has a great influence on the reactivity, and in the alkyl chain bonded to the ruthenium element, except for the longest one. The shorter two are as short as possible. R2(CH3)2SiX [3] [In the formula [3], R2 is an unsubstituted hydrocarbon group or hydrogen element having a carbon number of 4 to 18 a hydrocarbon group substituted with a halogen element, an element in which the X system is bonded to a ruthenium element is a valence functional group of nitrogen, an element bonded to a ruthenium element is a valence functional group of oxygen, or a dentate group. Further, in the formula [1] In the telluride represented by the following formula [4], it is a hydrocarbon group in which at least a part of hydrogen elements having a carbon number of 4 to 18 are substituted with a fluorine element and both of the Ris contain a methyl group. Therefore, it is preferable to impart more excellent water repellency to the surface of the wafer, and at least a part of the hydrocarbon group substituted with a fluorine element as described above is a hydrophobic group which is particularly hydrophobic, so that the result can be obtained. The protective film imparts more excellent water repellency. It corresponds to the above-mentioned seventh method. R3(CH3)2SiX [4] [In the formula [4], R3 is at least a part of argon element having a carbon number of 4 to 18, and fluorine element 157216 .doc 8 •32- 201216351 Substituted hydrocarbyl group, the X-bonding element bonded to the lanthanum element is a valence functional group of nitrogen, and the element bonded to the yttrium element is oxygen! valence functional group, or dentate base" The water-based film forming agent may be contained in at least the drug solution for forming a protective film. The organic solvent may be diluted with the organic solvent (4). The organic solvent may be dissolved in the above-mentioned water-repellent protective film forming agent. For example, hydrocarbons, vinegars, ethers, ketones, tooth-containing solvents, and sulfoxide-based solvents can be preferably used. , _, a derivative of a polyhydric alcohol, a solvent of a nitrogen-containing compound, etc. When water is used as a solvent for dilution, water causes hydrolysis of a group represented by X of the above-mentioned telluride to become a stanol group (Si_〇H), The resulting stanol groups are subjected to a condensation reaction with each other, whereby the above-mentioned tellurides are bonded to each other to form a dimer. The dimer has a low reactivity with a hydroxyl group on the surface of the wafer, so that the wafer surface cannot be sufficiently dialed. The time required for hydration, or hydration becomes longer, so the use of water as a solvent is not good. Further, since the above-mentioned telluride is easily reacted with a protic solvent, it is particularly preferable to use an aprotic solvent (four) as the organic solvent to exhibit water repellency on the surface of the wafer in a short period of time. Further, the non-fionic solvent includes an aprotic polar solvent and an aprotic nonpolar solvent (IV). Examples of such an aprotic solvent include hydrocarbons, vinegars, ethers, ketones, a tooth-containing solvent, a sulfoxide-based solvent, a derivative of a polyol having no hydroxyl group, and a nitrogen-containing compound having no NH bond. Solvent. Examples of the hydrocarbons include toluene benzene, toluene, heptane, and octyl; and as an example of the vinegar, there are ethyl acetate, acetonitrile, butyl acetate, and ethyl acetate. And as an example of the above ethers, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.; as an example of the above ketones, there are acetamidine, ethyl 157216.doc • 33·201216351 醯 acetone, Methyl ethyl ketone 'methyl propyl ketone, methyl butyl ketone, etc.; as an example of the above-mentioned solvent, there are perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, Perfluorocarbon such as hexafluorobenzene, m3, % pentafluorobutane, octafluorocyclopentane, 2,3-dihydro decafluoropentane, Zeorora H (manufactured by ZE〇N, Japan), methyl all Fluoroisobutyl ether, decyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl sulphate, Asahiklin AE_3 〇〇〇 (made by Asahi Glass), Novec HFE-7100, Novec HFE_72〇〇, N〇vec 73 Oh,

Novec 7600 (all manufactured by 3M) such as hydrofluoroether, tetrachloromethane and other gas carbon, chloroform and other hydrochlorocarbon 'di-halogen difluorocarbon chlorofluorocarbon, pentafluoropropane, 1,3-dichloropentafluoropropane,丨Chlorine_3,3,3·Trifluoropropene, 1,2, dichloro-3,3,3-trifluoropropene, etc. Hydrochlorofluorocarbon, perfluoroether, perfluoropoly _, etc.; In the case of a solvent, there is a di-subunit hard or the like; as an example of the above-mentioned non-base acetal polyol derivative, there is a diethylene glycol monoethyl (10) acetic acid S, an ethylene glycol monomethyl (tetra) acetic acid, and a third Alcohol monobutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; as an example of a nitrogen-containing compound solvent having no Ν_Η bond, ν, ν dimethyl amide, Ν , Ν-dimethylacetamide, Ν_methyl_2• 吼洛烧嗣, triethylamine,. ratio. Order. Further, if the organic solvent towel is used as the flame retardant, the water-repellent protective film-forming drug solution becomes inflammable, or the ignition point becomes high, and the risk of the water-repellent protective film-forming drug solution is lowered. . Most of the tooth-containing solvents are flame retardant. The flame retardant tooth-containing solvent is preferably used as a flame retardant organic solvent. A trace amount of water may also be present in the organic life agent. However, if a large amount of the water is contained in the solvent 157216.doc -34 - 201216351, the cut product is hydrolyzed by the moisture, and the reactivity is lowered. Therefore, it is preferred to reduce the water content in the solvent. When the water content is mixed with the above-mentioned telluride, it is preferably set to be less than 1 mole of the telluride, and more preferably set to less than 5 moles. Times. In the above-mentioned water-repellent protective film forming agent having a total amount of 丨(9)% by mass of the water-repellent protective film forming liquid, and having 0.1 to 50 mass% of 质/〇, the liquid is preferably used with respect to the above-mentioned liquid The total amount 丨〇〇 mass%, more preferably the content of the water-repellent protective film forming agent is Q 3 2 2 Qf. When the water-repellent protective film forming agent is less than G.1% by mass, the water-repellent imparting effect tends to be insufficient. When it is more than 50% by mass, it is obtained from the water-repellent ores 4 after washing. The component of the forming agent remains as a #质 residue on the wafer surface. Therefore, it is not preferable because the amount of the use of the water-repellent protective film is increased, so that it is not preferable from the viewpoint of cost. Further, in order to promote the reaction between the telluride and the hydroxyl group on the surface of the wafer, a catalyst may be added to the chemical solution. As such a catalyst, a non-aqueous acid such as fluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic acid anhydride, trifluoromethyl K^-fluoromethyl anhydride, sulfuric acid or hydrochloric acid can be preferably used. , aprotic nitrogen-containing solvents such as ammonium, pyridylamine, etc., aprotic nitrogen-containing solvents such as ammonium sulfonate, potassium sulfide, potassium hydroxylamine hydrochloride, and metal sigma such as tin and aluminum Or metal salt. In particular, in view of the catalytic effect, it is preferably an acid such as triacetic acid, trifluoroacetic anhydride, trifluorosulfoniumsulfonic acid, trifluorosulfonium sulfonic acid anhydride, sulfur, or hydrochloric acid. The acids preferably do not contain water. X, the above catalyst may also be a part of the water-repellent protective film formed by the reaction. In particular, if the carbon number 157216.doc -35 - 201216351 of the hydrophobic group R1 of the telluride represented by the general formula [1] becomes large, there is a steric damage, so that the ceramsite is present with respect to the wafer table. The situation of reduced reactivity. In this case, by adding a non-acid as a catalyst, there is a case where the reaction between the radical on the surface of the wafer and the above-mentioned dream compound is promoted, and the complement is caused by the steric damage of the hydrophobic group as described above. Reduced reactivity. The addition 1 of the above catalyst is preferably 0.01 to 100 mass with respect to the total amount of the above-mentioned telluride π θ ^ ^. / Mang Right Adding less, the catalyst effect is reduced

Low' is therefore not good. In addition, even if the above-mentioned catalyst is added to the kAI, the catalyst effect will not rise. If it is more than the hairs, there will be a catalyst effect instead of the moon. At the top of the wafer surface. Therefore, the amount of the above-mentioned catalyst added is preferably -HH)% by mass, more preferably 0.150% by mass. More preferably 〇 2~2〇% by mass. Fig. 4 shows a case where the liquid portion 9 is immersed in the concave portion 4 which is water-repellent by the water-repellent protective film forming agent, and is not intended to be _ _ 立 _ _. The wafer of the schematic diagram of Figure 4 is a portion of the a a section of Figure 1. A water-repellent protective film 1 is formed on the surface of the concave portion 4 by a water-repellent film forming agent. At this time, the liquid 9 held in the concave portion 4 may be a liquid that has been replaced by the above-mentioned wrap-around liquid, and the washing liquid B (hereinafter, only Z is used; the first clean liquid B). The liquid B) may also be a liquid in which the liquid in the g (mixture of the liquid medicine and the washing liquid) is replaced. The water-repellent protective film H) is also held on the wafer surface when the liquid 9 is removed from the concave portion 4. As a preferable example of the above-mentioned cleaning liquid B, water, an organic solvent, a mixture of water and an organic solvent, or at least at least an acid, a test, and a surfactant are mixed therein! Kinds of above, etc. Further, examples of the organic solvent of the right t which is one of preferable examples of the cleaning liquid B described in the above-mentioned 157, 216, doc 8 * 36 - 201216351 include hydrocarbons, anthraquinones, ethers, ketones, and polyalkanols. A_coolant, sulfoxide solvent, alcohol, multicomponent SM. a. λ/ * If there is a liquid in the concave portion of the circle Then, a capillary force acts on the recess. Cars 丨 The size of the capillary force is as described above, and is the absolute value of ρ obtained by the formula shown below.

P = 2xyxc 〇 s0 / S (wherein γ is the surface tension of the liquid held in the concave portion, and θ is the contact angle between the surface of the concave portion and the liquid held in the concave portion, and s is the width of the concave portion). On the right, as shown in the recess 4 of FIG. 4, a water-repellent protective film is present on the surface of the concave portion, and the absolute value of the increase is reduced. From the viewpoint of suppressing the collapse of the pattern, the value of ρ, and ^ is preferably as good as possible. It is preferable to adjust the contact angle with the liquid to be removed to about 90 ° to make the capillary force infinitely close to 0.0 Μ N / m 2 . = As shown in Fig. 4, when a protective film 1 is formed on the surface of the concave portion, the contact angle is assumed to be 5 〇 to 13 〇 when water is held on the :: surface. It is difficult to cause the pattern to collapse, so it is preferable. The closer the contact angle is to 9〇. The smaller the capillary force acting on the concave portion is, the more difficult it is to cause the pattern to collapse, and it is particularly preferable to be u〇. Further, for example, in the case of a wafer having a line width (width of the concave portion) of 45 and a pattern of a gap shape, if the capillary force is 2.1 MN/m or less, pattern collapse is less likely to occur, which is preferable. Further, if the hair 's force is small, it is more difficult to cause pattern collapse (four), so the capillary force is preferably 1.1 MN/V or less. Further, it is preferable to adjust the contact angle with the cleaning liquid to a vicinity of 9 G° so that the capillary force is infinitely close to 0·0 MN/m 2 . Then, the washing method (the third method) using the wafer of the present invention is washed.

157216.doc -37· 201216351 A method of removing the liquid held by the concave portion of the wafer after the cleaning will be described. This description is the same as the first and second features of the present invention. Further, the liquid held in the concave portion is the above-mentioned chemical liquid, the washing liquid 0, or a mixture of the chemical liquid and the washing liquid. As a method of removing the above liquid, it is preferred to dry by nature. Drying by air (d), nitrogen drying, spin drying, Π> Α(2-propanol) vapor drying, malangani drying, heat drying, hot air drying, vacuum drying, etc. Further, in order to efficiently remove the liquid, the remaining liquid may be dried after draining and removing the held liquid. Finally, a method of removing the water-repellent protective film from the surface of the wafer after removing the liquid is performed. This description is also the same as in the third and second features of the present invention. In order to remove the material of the riding water (4) Wei, it is more effective to cut off the C rhyme in the protective film. The method is not particularly limited as long as the above-mentioned key can be cut, and for example, the surface of the wafer is heated to 曰B, the wafer is exposed to ozone, the plasma is irradiated onto the surface of the wafer, and the wafer surface is exposed. Corona discharge, etc. When the protective film is removed by light irradiation, it is preferred to irradiate the bond energy having a CC bond or a CF bond in the ruthenium protective film, that is, an energy equivalent to 83 kcai/m〇i and 1 i6 kcal/mol. 34 〇 (10), 24 紫外线 dirty short wavelength of ultraviolet light. As the light source, a metal element lamp, a low pressure mercury lamp, a high pressure mercury lamp, an excimer lamp, a carbon arc lamp or the like can be used. In the case where the protective film is removed by light irradiation, ozone is generated while decomposing the constituent components of the protective film by ultraviolet rays, and the constituent components of the protective film are oxidized and volatilized by the ozone, so that the treatment time is shortened. Preferably. As the light source, it is preferable to use a low-pressure mercury 157216.doc 8 • 38 - 201216351 lamp or an excimer lamp or the like, and it is also possible to heat the crystal while heating the wafer while performing light irradiation. . c 'preferably to ~7〇 generation = row wafer heating. The heating time is preferably carried out by holding a knife clock, preferably 1 G to 3 G minutes. Further, in this step, ozone exposure, plasma irradiation, corona discharge, or the like may be used in combination. Alternatively, the wafer may be heated while being heated on one side. The method of removing the protective film by heating may be a method of bringing a wafer into contact with a heat source, a method of placing the wafer in a heated environment such as a heat treatment furnace, or the like. Furthermore, as for the method of placing the wafer in a heating environment, even when processing a plurality of wafers, it is easier to uniformly apply a W to the surface of the wafer to remove the protective film H. The method is simple in operation, processed in a short time, and has a high processing capability in an industrially advantageous method. In the case where the wafer is exposed to ozone, ozone generated by ultraviolet irradiation using a low-pressure mercury lamp or the like or low-temperature discharge using a high voltage or the like can be supplied to the wafer surface. The wafer-surface can be exposed to light while being exposed to ozone or heated.保护 By combining the above-described light irradiation, heating, ozone exposure, electropolymerization irradiation, and corona discharge, the protective film on the wafer surface can be efficiently removed. Hereinafter, the second feature of the present invention (the above-described first to fourth methods) will be described in detail. In the following description, 4 is simplified, and the case where the second feature is omitted is also omitted. Further, the description of the detailed description of the ith feature will be omitted.

157216.doc -39· 201216351 A preferred method of cleaning a wafer relating to an embodiment of the second feature of the present invention comprises: (step) having a concave-convex pattern on the surface and at least a portion of the concave-convex pattern containing a halogen The surface of the wafer (hereinafter also referred to as "the surface of the concave-convex pattern") is a step of supplying a liquid and holding the liquid on at least the surface of the concave-convex pattern; (Step 2) forming a liquid for the water-repellent protective film (hereinafter also referred to as a "protective film forming chemical solution") a step of replacing the liquid and holding the chemical solution on at least the concave portion surface of the concave-convex pattern; ^ (step 3) a step of removing liquid from the surface of the concave-convex pattern; and (step 4) removing the dial The step of the water-based protective film (hereinafter also referred to as "protective film"). 'As the liquid in (Step 1), at least the pre-treatment liquid is used. In addition to the pre-treatment liquid, it is also possible to use a water-based washing system containing an aqueous solution. At least one of the cleaning liquid and the cleaning liquid A different from the pretreatment liquid and the aqueous cleaning liquid. When a plurality of liquids are used, the pretreatment medicine can be combined. In combination with at least one of the aqueous cleaning solution and the cleaning liquid A, a mixed liquid containing at least one of the pretreatment liquid, the aqueous cleaning solution, and the cleaning liquid may be used. For example, the pretreatment liquid can be used only for the surface cleaning of the wafer and the surface of the G3 convex pattern. Further, after the water H cleaning liquid is held on at least the surface of the concave portion of the concave-convex pattern, the cleaning liquid A can be replaced with the water system. The cleaning solution can be replaced with the pretreatment liquid to replace the cleaning solution A. When the other treatment liquid can be replaced with the aqueous cleaning solution, the aqueous cleaning solution is maintained on at least the concave surface 157216 of the concave and convex pattern. Doc 8 •40·201216351, the water-based cleaning solution may be replaced by the prior treatment liquid. Further, after (Step 2), the protective film forming chemical solution held on at least the concave portion of the concave-convex pattern may be replaced with The cleaning liquid B having a different protective film forming liquid is transferred to the step (step 3). Further, the water-based cleaning liquid containing the aqueous solution may be held by the replacement of the cleaning liquid B. At least the recess of the pattern After the surface is transferred to the step (step 3), when the protective film forming chemical solution can be replaced with the aqueous cleaning solution, the replacement by the cleaning liquid B may be omitted. In the present invention, the crystal is used as the crystal. The form of the chemical liquid or the cleaning liquid when the chemical liquid (pretreatment liquid or protective film forming chemical liquid) or the cleaning liquid is supplied to at least the concave portion of the circular concave-convex pattern, as long as it is held on the surface of the concave portion The liquid is not particularly limited, and is, for example, liquid, vapor, etc. Further, in the pretreatment step, the surface of the concave-convex pattern is modified at a temperature not reaching the boiling point in the pretreatment step. In the pre-processing step, the form of the chemical liquid when the pretreatment liquid is supplied to at least the concave surface of the concave-convex pattern of the wafer is a liquid. In the present invention, the chemical liquid (pretreatment liquid or protection) may be used. The film forming chemical solution or the cleaning liquid is held on at least the surface of the concave portion of the concave and convex pattern of the wafer, and the cleaning method of the wafer is not particularly limited. As a method of cleaning, a wafer is generally held at a level and rotated, and a single-chip method in which a liquid is supplied to the vicinity of the rotating center and the wafer is washed one by one is used. Or a batch method in which a plurality of wafers are immersed in a cleaning tank and washed. In the case of industrially cleaning wafers, there are cases in which the wafers of the production batches are the same in the same type of 157216.doc -41·201216351, and there are cases in which the wafer types are different for each production batch. A situation. A wafer having a concave-convex pattern on its surface and at least a part of the concave-convex pattern containing a bismuth element includes a film formed on the surface of the wafer containing a cerium or a cerium oxide such as cerium oxide, or the like At least a part of the surface of the concave-convex pattern in the pattern contains ruthenium or a ruthenium element such as ruthenium oxide or nitrite. Furthermore, as Shi Xi, it includes polycrystalline lithox and amorphous germanium. Further, a wafer composed of a plurality of components containing germanium, a carbonized carbide wafer, and various films containing a cut element formed on the wafer may be used as the crystal®. Further, it is also possible to form various films containing germanium elements on wafers of uncut elements such as blue f-stone wafers, various compound semiconductor crystals, and plastic wafers. Further, the wafer having the concave-convex pattern on the surface and at least a part of the concave-convex pattern containing the element may be a wafer composed of at least a plurality of components of the package (four). The wafer constituting the plurality of components includes: forming at least one selected from the group consisting of #, 氧化石, and 氮化石, or at least one of the concave and convex patterns when forming the concave-convex pattern - The portion is at least one selected from the group consisting of #, oxygen cutting, and gas cutting. Hereinafter, each step will be described. First, the following steps are carried out: a step of supplying a liquid to the surface of the wafer (the surface of the concave-convex pattern) having the concave-convex pattern of the bean and holding the liquid on at least the surface of the concave portion of the concave-convex pattern (step 丨). Here, the case where the pretreatment liquid is used as a liquid will be described. In this case, in the step (step), the step of modifying the surface of the concave-convex pattern by supplying the pretreatment liquid to the surface of the concave (four) I57216.doc -42 - 201216351 (hereinafter referred to as "pretreatment" In the pretreatment step, the acid is contained in an amount of 0.001 to 5 mol/L in terms of molar concentration, and the liquid before treatment is used as a treatment liquid of 3 or less, and at 40 C or more, and the liquid for pretreatment is not reached. The surface of the concave-convex pattern is modified at a temperature of the boiling point. This corresponds to the second method. When the pretreatment liquid is supplied to the surface of the concave-convex pattern, the surface of the concave-convex pattern is formed by the acid in the pretreatment liquid. When a reactive site such as a hydroxyl group is present on the surface of the concave-convex pattern, in the following (Step 2), the compound forming the protective film and the reactive site contained in the protective film forming solution are changed. As a result, it is easy to form a water-repellent protective film on the surface of the concave-convex pattern. When at least a part of the concave-convex pattern is formed of tantalum nitride and/or niobium, it is particularly suitable for concave The surface of the convex pattern is supplied with a pretreatment treatment liquid. ^ Corresponding to the above fourth method. When the concave-convex pattern is formed of tantalum nitride or niobium, the surface of the concavo-convex pattern is not modified by the pretreatment treatment liquid. In addition, it is difficult to form a water-repellent protective film on the surface of the uneven pattern even if a protective liquid for forming a protective film is formed on the uneven pattern formed of tantalum nitride or tantalum. However, by modifying the surface of the concavo-convex pattern by the treatment liquid containing the acid, even when the concavo-convex pattern is formed of tantalum nitride or niobium, it is possible to form a sufficient water-repellent protection on the surface of the concavo-convex pattern. Further, the concave-convex pattern formed of tantalum nitride or tantalum can be formed, for example, by etching a film of tantalum nitride or tantalum after forming a film of tantalum nitride or tantalum on the surface of the wafer. The concave-convex pattern formed by tantalum nitride or tantalum may also be formed on the concave-convex pattern by forming a concave-convex pattern on the surface of the wafer after forming a concave-convex pattern on the surface of the wafer. In the pre-treatment step, the surface of the concave-convex pattern is modified at a temperature of 4 (rc or more and less than the sea point of the pretreatment liquid, and as a method of adjusting the temperature at which the surface of the concave-convex pattern is modified, The method of heating the pretreatment liquid, the method of heating a wafer, etc. The organic acid (corresponding to the above-mentioned 3rd method) or an inorganic acid exists as the acid contained in the chemical solution of another process. Examples of the organic acid include hydrochloric acid, an aliphatic monocarboxylic acid such as acetic acid and propionic acid, and an aliphatic polycarboxylate such as cis-butanic acid and anti-succinic acid. An aromatic monocarboxylic acid such as acid or benzoic acid, an aromatic polyacid such as phthalic acid or terephthalic acid, an organic acid such as a sulphuric acid or a benzoic acid, etc. The effect (the effect of forming a reactive site such as a hydroxyl group on the surface of the concave-convex pattern), the molar concentration of the acid in the pretreatment liquid must be 〇1〇〇5 m〇/L, preferably 〇〇〇 5 to 2 mol/L. In order to exhibit the effect of modifying the surface of the concave-convex pattern (the effect of forming a reactive site such as a hydroxyl group on the surface of the concave-convex pattern), the pH of the pretreatment liquid is 3 or less. Further, the pH of the pretreatment liquid is preferably 〇丨 or more. If the pH of the pretreatment liquid is less than 0.1, it is difficult to purify the pretreatment liquid by the ion exchange method before the pretreatment step, and the purification cost is increased. The pH of the pretreatment liquid was determined by the following formula using the proton concentration in the pretreatment liquid. 157216.doc •44· 201216351 pH=-Logl0[H+] where L〇glQ represents the logarithm of 1〇 and [H+] represents 25. The proton concentration in the solution is treated as the unit of proton concentration S mol/L. Further, the pretreatment treatment liquid is not limited to an aqueous solution, and when only an organic solvent is used as a solvent for the pretreatment treatment liquid, or when water and an organic solvent are used together, the above formula can also be used. The value is set to the pH of the pretreatment liquid. X is the case in the description #, when the solvent of the pretreatment liquid is only water, or when the mixed water and the organic solvent are mixed, the pretreatment liquid is set by the PH meter. The value obtained by measuring the treatment liquid before 25 t. The pretreatment liquid is preferably a liquid containing an acid and a solvent for dissolving the acid. As a solvent, T lists water, an organic solvent, etc. The type f of the money solvent is not particularly limited, and examples thereof include hydrocarbons, _, _, _, tooth-containing solvents, sub-hard solvents, alcohols, polyols, polyhydric alcohol derivatives, nitrogen-containing compounds (tetra), and the like. q, water and (4) material spray alone can be used in combination of two or more. For example, 'combinable water and organic solvent use' can also be used in combination with a plurality of organic solvents. Examples of the hydrocarbons include toluene, benzene, xylene, hexyl alcohol, heptane, and octane; and examples of the vinegar include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Etc.; as an example of the above-mentioned ethers, there are two examples: the above-mentioned examples of the upper phase, and the presence of acetone, acetylene, and sulfhydryl groups. Ethyl ketone, indyl propyl ketone, f butyl ketone, cyclohexanone, isophora, etc.; as an example of the above-mentioned sulphur-containing agent, there is an all-gas spleen, all-in-one appearance, perfluorocyclopentan Perfluorinated 157216.doc •45- 201216351 Perfluorocarbon, hexafluorobenzene and other perfluorocarbons, 1,1,1,3,3_pentafluorobutane, octafluorocyclopentane, 2,3-dihydro-deca Hydrogen oxycarbon such as fluoropentane, zeorora ΖΕΟΝ (manufactured by 曰本ΖΕΟΝ), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, AsahikUn ΑΕ- Hydrogen fluoride such as 3000 (made by Asahi Glass), N〇vec HFE-7100, Novec HFE-7200, Novec 7300, N〇vec 7600 (all manufactured by 3M), chlorocarbon such as four-gas methane, hydrogen chloride such as gas, Dichlorodifluoromethane And other chlorofluorocarbons,! , dichloro-2,2,3,3,3_pentafluoropropane, 1,3-diox_1,1,2,2,3_pentafluoropropane, 1_gas_3,3,3_ a hydrochlorofluorocarbon such as trifluoropropene or 1,2-one gas-3,3,3-trifluoropropene, a perfluoroether, a perfluoropolyether or the like, and as an example of the above sulfoxide-based solvent, a dimercaptopurine is present. Examples of the alcohols include methanol, ethanol, propanol, butanol, and the like; as examples of the polyols, ethylene glycol, H-propylene diol, and the like; and examples of the derivatives of the above polyols exist. Diethylene glycol monoethyl ether, ethylene glycol mono(tetra), ethylene glycol single-butyl test, propylene glycol mono-methyl bond, propylene glycol mono-ethyl scale, diethylene glycol single-ethyl shunt B (four), ethylene glycol monomethyl acetate, Ethylene glycol monobutyl vinegar acetate, propylene glycol monomethyl ether acetate vinegar, propylene glycol monoethyl ether acetate vinegar, diethylene glycol dimethyl sulphate, diethyl sulphate 7 | alcohol ethyl oxime ether, diethylene glycol diethyl ether, two Alcohol diacetate, triethylene glycol dimethyl scale, ethylene glycol diacetate vinegar, ethylene; diethyl ether, ethyl alcohol dimethyl methoxide, etc.; as an example of a nitrogen-containing compound solvent, 曱醯 曱醯 甲基Amine, dimethyl di-based such as hydrazine, diethylamine, triethylamine " than bite. : Considering the effect of the pretreatment liquid, the better it is. Therefore, the higher the solvent point of the solvent, the better, and the disc is used as a mixed solvent of the solvent. When 吏 water and organic solvent are used, or when 157216.doc -46- 201216351 is used as an organic solvent, 1〇〇〇p. 〇^ is preferably used as an organic solvent with a hysteresis exceeding -ut~ In contrast, the sample was treated with a polyol-based bitten alcohol derivative as a solvent. The second liquid of the cheek is preferably such that the temperature of the pretreatment liquid (4) is not reached: no air bubbles are generated. If air bubbles are generated in the pretreatment liquid, the operability of the pretreatment liquid will become a problem. In consideration of the above-mentioned problem, it is preferable that the treatment liquid does not contain an oxidizing agent such as ozone (〇3) or hydrogen peroxide (Η2〇2) as a solvent. The reason for the combination of the pots is that when the oxidizing agent is present in the pretreatment liquid 3, the oxidizing agent is decomposed to generate oxygen. When the temperature of the liquid to be used becomes high, the above problem is considered. The solvent of the pretreatment liquid is preferably an oxygen-free agent. Further, the organic bathing agent, or only the aqueous solution and the organic solvent, the solvent for the treatment liquid is only water and the organic solvent. The ratio of water to organic solvent (water/organic solvent) is preferably water/organic solvent by mass ratio. Help G ~ 9G / 1G, better for 2 coffee ~ surgery 4G. In the preparation method of the pretreatment liquid, it is preferred to purify at least one of the acid and the solution thereof. (2) The water concentration is adjusted by using at least one of the following removal means, such as an adsorbent or a steaming hall of the Knife 4, etc., and the Na, Mg, K, and _ are removed by ion exchange resin or steaming. And ~ each element, is an impurity; and profit (4) according to the device over the sputum to remove particles and other pollution. In consideration of the activity of the pretreatment liquid or the cleanliness of the wafer, it is preferred to adjust the water concentration to remove metal impurities and to limit the order of removal of the contaminated material. 157216.doc •47-201216351 As described above, in (Step 1), the water-based cleaning liquid is supplied to the surface of the concave-convex pattern, and the aqueous cleaning liquid is held on at least the surface of the concave portion of the concave-convex pattern, and then the water system is replaced with the cleaning liquid A. The cleaning solution can be replaced with the pretreatment drug, and the cleaning solution A can be replaced. In the case where the pretreatment treatment liquid can be replaced with the aqueous cleaning solution, the aqueous cleaning solution can also be held in at least the concave portion of the concave-convex pattern. After the surface, the aqueous solution is replaced with the previous treatment solution. ° When the aqueous cleaning solution or the cleaning solution A is replaced with the previous judgment liquid, it is preferable to maintain the water system at least on the surface of the concave portion of the concave-convex pattern. ^ In the state of the liquid or the cleaning solution A, the cleaning solution may be replaced with the pretreatment drug, or after the step D and before the (step 2), the concave and convex pattern table may be supplied differently from the pretreatment liquid. The washing liquid is a water-based washing liquid or a washing liquid A. In this case, it is preferable to maintain the state of at least the concave portion of the concave-convex pattern until the concave and convex case The surface of the protective film is formed The liquid is used as an example of the aqueous cleaning solution, and the solvent H is a mixture of u + M or water, and the water is mainly composed of water (for example, water mass% or more). As a preferred example of the cleaning liquid A, the chemical liquid, the water, the organic t-forming acid 1 _ or the medium-mixing agent, the surfactant, the oxidizing agent, etc. may be used. Examples of the organic solvent which is a preferred example of the H-purifying liquid A, an agent, an alcohol (IV), a "solvent, a sulfoxide-based decyl alcohol derivative, a nitrogen-containing compound solvent, etc. 1572I6.doc 8 -48 - 201216351 Examples of the above hydrocarbons include toluene, benzene, xylene, hexyl alcohol, heptane, octane, etc.; as an example of the above esters, ethyl acetate, propyl acetate, butyl acetate, acetamidine acetate are present. Ethyl ester or the like; as an example of the above ethers, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc. are present; as an example of the above copper, acetone, acetamidine, methyl ethyl ketone are present. , methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc.; For example, there are perfluorocarbons such as perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, and 'to' is pentafluorobutane, octafluorocyclopentane, Hydrogen fluoride such as 2,3-dihydrodecafluoropentane or Ze〇r〇ra H (manufactured by 〇 〇 〇 〇), methyl perfluoroisobutyl ether, decyl perfluorobutyl ether, ethyl perfluorobutyl Ether, ethyl perfluoroisobutyl ether, Asahiklin AE-3000 (made by Asahi Glass), N〇vec HFE-7100 ^ Novec HFE-7200 ^ Novec 7300 . Novec 7600 (all manufactured by 3M) and other hydrofluoroethers, four gas methane Hydrogen carbon such as isochlorocarbon, gas imitation, chlorofluorocarbon such as dichlorodifluoromethane, 1,1_digas-2,2,3,3,3_pentafluoropropane, dichloro-1,1,2 , 2,3-pentafluoropropane, 1·gas-3,3,3-trifluoropropene, 1'2-dichloro-3'3,3-trifluoropropene, etc. Hydrochlorofluorocarbon, perfluoroether, full a fluoropolyether or the like; as an example of the above-mentioned sub-hard solvent, dimethyl sulfene or the like is present; and as an alcohol, there are methyl alcohol, ethanol, propanol, butanol, ethylene glycol, propane diol, etc.; Examples of the above derivatives of the polyol include diethylene glycol, early diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and propylene Monoterpene ether, propylene glycol monoethyl (tetra), diethylene glycol monoacetic acid S, ethylene glycol monomethyl acetate::, ethylene glycol monobutyl acetate, propylene glycol monoacetic acid acetate, propylene glycol monoethyl ether acetate § [, M m diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, triethylene glycol dimethyl 157216.doc • 49· 201216351 > τ. — ar* ^-Alcoholic acid diacetate, ethylene glycol diethyl ether, ethylene glycol diterpene ether, etc.; as an example of a nitrogen-containing compound solvent, there are decylamine, N,N-didecyl decylamine, N, N- Dimethylacetamide, N-methylpyrrolidone, diethylamine, diethylamine, 〇, and the like. Moreover, as an example of an inorganic acid or an organic hydrazine as an inorganic acid which can be mixed with the acid in the cleaning liquid, examples thereof include dynic acid, buffered gas acid, sulfuric acid, nitronium citrate, phosphoric acid, etc.; Examples thereof include a sulphuric acid, a benzene rSsl sulphuric acid, a trisodium sulphuric acid, an acetic acid, a tri-I acetic acid, a pentafluoropropyl amp; and the like, which can be mixed in the cleaning liquid A. Examples of the oxidizing agent that can be mixed in the cleaning liquid A, such as money and biliary test, include ozone, hydrogen peroxide, and the like. Further, when the cleaning liquid A is an organic solvent, the protective film forming drug solution can be supplied to the concave portion without being in contact with water, which is preferable. Further, in the case where the cleaning liquid A on the right contains an aqueous acid solution, the protective film can be formed in a short time in the following (step 2), which is preferable. Further, a plurality of kinds of cleaning liquids may be used as the cleaning liquid A. For example, the following two types can be used: a washing liquid containing the above aqueous acid solution and a washing liquid of the above organic solvent. Then, a step of replacing the liquid with the protective film forming liquid and holding the ?-hai liquid in at least the concave portion surface of the concave-convex pattern is carried out (step 2). Specifically, s is a step of supplying a protective film forming chemical liquid to the surface of the modified concave-convex pattern and forming a water-repellent protective film on the surface of the concave-convex pattern (hereinafter referred to as "protective film forming step"). In the protective film forming step, the protective film is formed by reacting a compound which forms a money film and a hydroxyl group formed on the surface of the concave-convex pattern by the 157216.doc •50·201216351 The site reacts to chemically bond the compound forming the protective film to the Si element of the wafer. In the protective film forming step, a water-repellent protective film is formed on the surface of the concave portion of the wafer, so in the following (step 3), 'when the liquid is removed from the concave portion of the wafer, even when the wafer is dried, the capillary of the concave portion The force becomes small and it becomes difficult to cause a pattern collapse. In the protective film forming step, the liquid held in the concave portion 4 before the step (step 2) is replaced with the chemical solution forming liquid, and the film forming liquid is held at the surface of the concave-convex pattern and the concave P surface. During this period, the protective film is formed on at least the surface of the concave portion of the concave-convex pattern. In the protective film forming step, the protective film does not have to be formed continuously, and it is not necessary to uniformly form 'but to impart more excellent water repellency, more preferably continuous and uniform. When the temperature is raised, the water-repellent protective film is formed in a shorter period of time. The temperature at which the protective film is easily formed is 10 ° C. The boiling point of the protective film forming solution is not reached, and it is particularly preferably maintained at 15. 〇~ The temperature at which the boiling point of the protective film forming solution is lower than 10 °C. The temperature of the protective film forming chemical solution is preferably maintained at the above temperature even when the chemical liquid is held on at least the concave portion surface of the concave-convex pattern. Furthermore, the other cleaning solution can be kept above 10 ° C and does not reach the temperature of the 'Focus point of the cleaning liquid. For example, when the aqueous solution A contains an acid aqueous solution, particularly preferably a solution containing an aqueous acid solution and an organic solvent having a boiling point of 10 CTC or more, if the temperature of the cleaning liquid is raised to the vicinity of the boiling point of the cleaning liquid, The above protective film is easy to form in a short time, and therefore is preferable. 157216.doc •51 · 201216351 The above-mentioned protective film forming chemical liquid contains a water-repellent protective film forming agent (hereinafter also referred to as "compound A") represented by the following general formula [1], which corresponds to the first method described above. R1aSiX4.a [1] [In the formula [1], R1 is independently of each other, and is an unsubstituted hydrocarbon group of hydrogen or a carbon number of 18 or a hydrocarbon group substituted with a halogen element by a halogen element, and X is independently of each other and is selected from the group consisting of ruthenium and ruthenium. The element bonded to the element is a monovalent functional group of nitrogen, an element bonded to the yttrium element is a monovalent functional group of oxygen, and at least one of a group consisting of a functional group, and a is an integer of 1 to 3] . As an example of the compound A, hexamethyldioxane (HMDS,

Hexamethyl disilazane), trimethyl decyl alkyl diethylamine (tmsdEA,

Trimethylsilyl diethylamine), tetramethyldiazane, trimethyldecyldidecylamine, octyldimethyldecyldidecylamine, trimethyldecyl imidazole, dimethylchlorodecane, propyl a decane coupling agent such as methyl phthalane, octyl dimethyl decane, dimethyl dioxane, methyl trioxane, trimethyl methoxy decane or dimercapto ethoxy decane. The protective film forming chemical solution may also contain acid VIII as a catalyst. The acid A in the protective film forming chemical solution is effective for promoting the reaction of the above-mentioned compound A with the "element of the wafer. If the acid A contains water", the water contained in the protective film forming chemical liquid is increased, and it is difficult to form the above-mentioned protection. Therefore, the content of the water of the acid A is preferably as small as possible, and the water content is preferably 35 mass% or less, more preferably 10 mass% or less, more preferably 5% by mass or less, and more preferably unlimited. The concentration of the acid A in the protective film forming chemical solution is preferably 〇〇1 to 2% by mass based on the total amount of the above compound 157216.doc 8 • 52 - 201216351 A. If the amount of addition is small, the effect of the acid catalyst is lowered, so that the effect is not good, and even if the amount of addition is large until the excess is added, the catalyst effect is not improved, and instead, the surface of the wafer is eroded or remains as an impurity on the wafer. The concentration of the above-mentioned acid A is preferably 〇〇% by mass based on the total amount of the above-mentioned compound A. The inorganic acid or organic acid is present as the acid A. The inorganic substance having a small content of water is used. Examples of acid 'the presence of argon halide, sulfuric acid, Perchloric acid, phosphoric acid, etc., as an example of the organic acid, an alkanesulfonic acid, a carboxylic acid, a benzenesulfonic acid, a p-toluenesulfonic acid, etc., in which some or all of the hydrogen elements may be substituted with a fluorine element or the like. A Lewis acid can also be used. The definition of Lewis acid is described, for example, in the "Chemical Chemistry Dictionary (Fifth Edition)". As the Lewis acid, there are an acid liver, a boron compound, and a cerium compound. Examples of the acid anhydride include a calcined acid needle such as trifluoromethane acid, & acetic anhydride, tri-glycolic anhydride, and penta-propionic acid liver (iv) anhydride. In the case of an acid, part or all of the hydrogen element may be substituted by a fluorine element or the like. Examples of the boron compound include an alkyl boronic acid ester, an aryl boronic acid ester, tris(trifluoroethyloxy)boron, a trialkoxyboroxenehexane, and a difluoroboron. As an example of the telluride, gas rhenane, sickle or whole can be cited. An alkyl sulfonylalkyl sulfonate in which a hydrogen element is replaced by a fluorine element or the like, and a part or all of a hydrogen element may be substituted with a fluorine atom or the like. Further, in the case of using the above-described telluride, at least a part of the above protective film may be formed using the telluride. Further, in the chemical solution for forming a protective film, the compound A and the acid A may be diluted with a solvent. When the total amount of the chemical liquid for forming a protective film (10% by mass) 1 and the total amount of the addition of the compound A and the acid A are 157216.doc -53 - 201216351 0.01 to 100% by mass, it is easy to uniformly form at least the concave surface of the concave-convex pattern. The protective film is formed on the ground, so it is preferable if it does not reach the mass of 0.01. Further, there is a tendency that the collapse prevention effect of the concave-convex pattern is insufficient. More preferably 0 05 to 2% by weight. Negatively, as a solvent which can be used for dilution in the protective film forming liquid, for example, hydrocarbons, esters, ethers, ketones, tooth-containing solvents, sub-grinding solvents, alcohols, and poly-alcohols can be preferably used. An organic solvent such as a substance or a nitrogen-containing compound solvent. If the towel does not have an OH group in a derivative of a hydrocarbon, a S-type, a ketone, a ketone, a tooth-containing solvent, or a sulfoxide-based solvent, the polyol can form a protective layer on the surface of the concave-convex pattern in a short time. The film is therefore better. Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, octane, etc.; as examples of the above esters, ethyl acetate, propidium acetate, butyl acetate, and ethyl acetate An ester or the like; as an example of the ether, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane or the like; and as an example of the above ketone, acetone, acetamidine acetone, mercaptoethyl ketone, hydrazine are present. a propyl ketone, a mercaptobutyl ketone, a cyclohexanone, an isophorone, etc.; as an example of the above halogen-containing solvent, perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane , hexafluorobenzene and other perfluorocarbons, ^^, pentafluorobutane to octafluorocyclopentanthene, 2,3-dihydrodecafluoropentane, Zeorora Η (made in Japan), etc. Perfluoroisobutylation, mercapto perfluorobutyl ether, ethyl perfluorobutyl hydrazine, ethyl perfluoroisobutyl ether, Asahiklin ΑΕ _3000 (made by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 Hydrofluoroethers such as tetrahydrofurane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as difluorodifluoromethane, 1,1_diox, etc. 2,2,3,3,3-pentafluoropropane-54- 157216.doc 8 201216351 alkane, 1,3-dioxin-1,1,2,2,3-pentafluoropropane, 1_gas·3, 3,3_trifluoropropene, 1,2-digas-3,3,3-trifluoropropene, etc., hydrochlorofluorine, perfluorinated, perfluoropolyether 4, as an example of the above-mentioned sub-hard solvent Dimethyl sub-bowl, etc.; as an example of the above-mentioned polyol derivative, which does not have a mercapto group, diethylene glycol monoacetic acid vinegar, ethylene glycol monoacetic acid vinegar, ethylene glycol monobutyl ether Acid ester, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate 'diethylene glycol dimethyl ether, diethylene glycol ethyl oxime ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate Ester, ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol dioxime, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether and the like. When the flame retardant is used in the above organic solvent, the chemical solution forming the protective film becomes a sputum or the ignition point becomes high.

Low, so better. The tooth-containing viscous genus is viscous, and the flammable halogen-containing solvent is preferably used as a flame retardant organic solvent. When the surface of the organic solvent is too low, if the organic solvent is too low, the liquid can be easily wetted and spread to the wafer. It is dry before the surface, so it is not good. Further, if the boiling point is too high, the viscosity of the upper backing liquid tends to be too high, so it is not preferable. Therefore, it is preferable to use an organic solvent of μ, +, and H to use a boiling point of 2 〇C. Right consideration of cost or solubility with other cleaning solutions (easy to replace), then this solvent is preferably diethyl -2- Q-alcohol early ether acetate, saponin acetate, propylene glycol monoterpene bis-acid Stuffing, diethylene glycol dimer, ethyl acetate ethyl hydrazone bond, B- _ _ 7-alcohol monomethyl ether, diethylene glycol diacetate, ethylene glycol monoacetate, cyclohexanone, etc. . 157216.doc •55· 201216351 Further, the water-containing stem in the liquid liquid for forming a film is preferably 5000 mass ppm or less with respect to the total amount of the liquid medicine. When the water content exceeds 5000 mass ppm, the above compound A The activity of the acid A is lowered, and it is difficult to form the above protective film in a short time. Therefore, the compound A, the acid A, or the solvent which may be contained in the protective film forming chemical solution contained in the protective film forming chemical solution is preferably one which does not contain a large amount of water. Further, the water content in the protective film forming chemical solution may be 10 ppm by mass or more. Further, in the measurement of the fine particles in the liquid phase in the protective film forming chemical solution by the light scattering type liquid particle detector, the number of particles larger than 〇5 is preferably one for every 1 mL of the chemical liquid. the following. If every! In the case where the number of particles larger than 0.5 μηι in the liquid solution exceeds ι, the pattern damage caused by the fine particles is caused, and the yield of the element is lowered and the reliability is lowered, which is not preferable. Moreover, if the amount of particles larger than 〇·5 μιη per 丨mL of the drug solution is! In the case of the above-mentioned protective film, it is preferable to omit or reduce the washing with a solvent or water after the formation of the above protective film. Therefore, the number of particles larger than 〇5 μm in the protective film forming solution is preferably as small as the number of particles per 丨mL, and the number of particles larger than 〇5 μηη may be in every 1 mL of the liquid. More than one. In addition, the measurement of the fine particles in the liquid phase in the chemical solution forming liquid is performed by a commercially available measuring device using a light scattering type liquid particle measuring method using laser light as a light source, and the particle diameter of the fine particles is determined. Refers to the light scattering equivalent diameter of the PSL (polystyrene latex) standard particle reference. Further, the content of the metal impurities of the respective elements of Na, Mg, K, Ca., Mn, Fe and Cu in the protective film forming liquid is preferably 157216.doc -56·201216351 for the total amount of the liquid medicine. Quality P - down. The metal impurity f of each of the above elements is in the form of a metal «, an ion, a colloid, a complex, an oxide, or a nitride, and is present in any of the liquids, whether dissolved or undissolved. When the metal impurity-containing content I exceeds 1 (10) by mass based on the total amount of the chemical liquid, the joint leakage of the element increases, which causes a decrease in the yield of the element and a decrease in reliability. 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 the protective film is formed. Further, the metal impurity content may be 0.01 mass ppb or more with respect to the total amount of the chemical liquid, respectively. In the method for preparing a protective film forming solution of the compound A and the acid A, it is preferred to purify at least one of the compound A before the mixing, the acid A, and the mixed liquid after mixing. . Further, when the protective film forming drug solution 3 has a Jf shape of a refrigerant, 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 be mixed. At least one of Compound A or a solution thereof, acid eight or a solution thereof, and a mixed liquid after mixing is targeted. The purification is carried out by at least one of the following means: removing the water molecules by using an adsorbent or a vapor of a molecular sieve, etc., removing Na, Mg, K, Ca, Mn, Fe^u by using an ion exchange resin or a steaming chamber. The metal impurities of each element and the use of 遽m to remove pollutants such as particles. When considering the activity of the film forming solution or the cleaning of the wafer, it is preferable to remove the water molecules and remove the metal impurities and remove the contaminants, and the order of removal is not limited. 1572I6.doc •57· 201216351 As mentioned above, after (Step 2), it will remain in the concave & The protective medium forming drug solution on the P surface is replaced with a washing liquid different from the chemical liquid; the liquid B is then transferred to (step 3). Examples of the cleaning liquid b include an aqueous cleaning solution or an organic solvent containing an aqueous solution, or a mixture of the aqueous cleaning solution and an organic solvent, and at least one of an acid, a test, and a surfactant; In the case of the above-mentioned one, the acid A contained in the chemical solution is added to a lower concentration than the protective liquid for forming a protective film. Further, examples of the organic solvent which is a preferred example of the cleaning liquid B include hydrocarbons, vinegars, tests, ketones, tooth-containing solvents, shale-based solvents, alcohols, and polyols. Derivatives, nitrogen-containing compound solvents, and the like. Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and xylene; and examples of the above-mentioned hydrocarbons include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Examples of the above ethers include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.; as an example of the above ketones, acetone, ethyl acetonide, methyl ethyl ketone, and the like are present. Propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc.; as an example of the above halogen-containing solvent, there are perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane , hexafluorobenzene and other perfluorocarbons, 丨 ^ ^ pentafluorobutane, octafluorocyclopentane, 2,3-dihydro decafluoropentane, Zeorora η (made in Japan) and other hydrofluorocarbons Fluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl full tert-butyl ether, Asahiklin ΑΕ-3000 (made by Asahi Glass), N〇vec HFE-7100, Novec HFE-7200, Novec 7300 , Novec 7600 (all manufactured by 3M) and other hydrofluoroethers, four gas methane and other chlorine carbon, chloroform and other hydrogen J57216.doc • 58· 201216351 chlorocarbon 'difluoroethylene Isochlorofluorocarbon ' 1,1_two gas · 2,2,3,3,3_pentafluoropropane, 1,3-diox-1,1,2,2,3-pentafluoropropane, 1- Hydrogen fluorocarbon such as gas-3,3,3-trifluoropropene, 1,2-one gas-3,3,3-trimethyl propylene, full epoxide, sputum, etc.; as the above sulfoxide solvent Examples of the presence of dimercaptopurine and the like; as an example of an alcohol, there are methanol, ethanol, propanol, butanol, ethylene glycol, 1,3-propanediol, etc.; as an example of the above-mentioned polyol derivative, There are diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl acetate , ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl hydrazine, diethylene glycol diethyl ether, Diethylene glycol diacetate, triethylene glycol dimethyl bond, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol diammine, etc.; as an example of a nitrogen-containing compound solvent, there is a formamide , Ν, Ν_dimethylformamide, hydrazine, hydrazine-dimercaptoacetamide, Ν_ 2_ yl-pyrrolidone, diethylamine, triethylamine, pyridine and the like. Further, after the replacement with the above-mentioned cleaning liquid, the aqueous cleaning liquid containing the aqueous solution may be held in the surface of at least the concave portion of the concave-convex pattern, and then transferred to (step 3). Further, as the cleaning liquid, a plurality of cleaning liquids may be used. Examples of the water-based cleaning liquid include water or a mixture of an organic refrigerant, an acid, and a base in water, and the water-based component (for example, a water content of 50% by mass or more). . In particular, when the water-based cleaning solution is used, the contact angle θ of at least the surface of the concave portion of the concave-convex pattern dialed by the protective medium forming chemical solution and the chemical liquid becomes larger, and the capillary of the surface of the concave portion is I572l6. Doc -59- 201216351 The force p becomes small, and it is difficult to leave dirt on the surface of the wafer after drying. When the liquid is removed from the surface of the concave-convex pattern, the body may be a mixture of the protective film forming member, the cleaning solution B'纟-based cleaning solution, and cough, etc., and the above-mentioned The mixed solution of the chemical liquid may be a mixed liquid in a state in which the above-mentioned drug: liquid is replaced with the cleaning liquid 3, or may be obtained by mixing the above-mentioned chemical liquid in a washing liquid different from the chemical liquid. And after the liquid is removed from the surface of the concave-convex pattern, at least one selected from the group consisting of the cleaning liquid B, the aqueous cleaning liquid, and the mixed liquid is held on the surface of the concave-convex pattern, and thereafter When the protective film 10 is formed on the surface of at least the concave portion of the concave-convex pattern of the wafer by the protective film forming chemical solution, the contact angle is assumed to be 60 to 120 when water is held on the surface. It is difficult to produce a pattern collapse, so it is preferable. Also, the closer the contact angle is to 90. The smaller the capillary force on the surface of the concave portion, the more difficult it is to cause pattern collapse, so it is particularly preferably 70 to 110. . Further, the capillary force is preferably 2.1 MN/m2 or less. When the capillary force is 2_1 MN/m2 or less, pattern collapse is less likely to occur, which is preferable. Further, when the capillary force is small, the pattern collapse is more likely to occur, and therefore the capillary force is preferably 1.6 MN/m2 or less, more preferably M MN/m2 or less. Further, it is preferable to adjust the contact angle with the liquid to 9 〇. Nearby, the capillary force is infinitely close to 〇 MN MN/m2. The detailed description of the step of removing the liquid from the surface of the concave-convex pattern (step 3) and the step of removing the protective film (step 4) in the second feature of the present invention is omitted as in the first feature. 157216.doc 201216351 EXAMPLES Examples of the first and second features of the present invention and comparative examples of the comparative examples were evaluated as follows. In the evaluation of the surface on which the surface of the wafer is a concave-convex pattern, and the cleaning liquid which is held in at least the concave portion of the concave-convex pattern by another cleaning liquid, various studies have been conducted in other literatures and the like, and it has been established. In the present invention, the evaluation of the above-mentioned chemical solution for forming a protective film is emphasized. Further, it can be confirmed from the following formula that the pattern collapse closely depends on the contact angle between the cleaning liquid and the wafer surface, that is, the contact angle between the droplet and the wafer surface, and the surface tension of the cleaning liquid: (wherein γ is The surface tension of the liquid held in the concave portion, β is the contact angle between the surface of the concave portion and the liquid held in the concave portion, and s is the width of the concave portion). In the case of the cleaning liquid held in the concave portion of the concave-convex pattern, the contact angle of the liquid droplet is correlated with the capillary force acting on the concave portion, which is considered to be equivalent to the collapse of the round case, and therefore may be stored. J is derived from the above formula and the contact angle between the protective film and the droplet to derive the capillary force. Further, in the examples, the material was made into the above-mentioned cleaning liquid. According to the above formula, the contact angle is closer to 9 〇. The smaller the capillary force is, the more difficult it is to cause the pattern to collapse. Therefore, it is provided when the surface of the protective film is kept with water 60 to 120. , especially good for 7〇~11〇0. However, in the case of having a fine concave surface on the surface, it is impossible to accurately form the contact angle of the Japanese and Japanese rounds in the case of the surface of the concave-convex pattern, and the protective film 1 itself I57216.doc -61 * 201216351 The contact angle evaluation of water droplets is as follows: jIS R 3257 "Test method for full wetness of substrate glass surface", by adding a few microliters of water/quote to the surface of the sample (substrate) and The angle between the water droplets and the surface of the substrate was measured. However, in the case of a patterned wafer, the contact angle becomes very large. The reason for this is that the contact angle affects the surface shape (roughness) of the substrate due to the effect of the Wenzel effect or the Cassie effect, and the contact angle of the water droplets increases in appearance. Therefore, in the present embodiment, the chemical liquid is supplied to the wafer having a smooth surface and a protective film is formed on the surface of the wafer, and the protective film is regarded as a protective film formed on the surface of the wafer 1 on which the uneven pattern 2 is formed. 1〇, and carry out various evaluations. Further, in the embodiment exemplifying the feature of the present invention, a titanium nitride film-attached wafer having a titanium nitride layer on a wafer having a smooth surface (hereinafter referred to as "TiN wafer" is used. The case) as a wafer with a smooth surface. In the embodiment exemplifying the second feature of the present invention, a silicon wafer having a surface having a surface of a thermal oxide film (Si〇2 film) or a tantalum nitride film (9) is used as a wafer having a smooth surface. . The details are as follows. Hereinafter, the evaluation method of the wafer to be washed by the cleaning method of the present invention, the preparation of the chemical solution for forming a protective film, and the evaluation result of the wafer to be washed by the cleaning method of the present invention will be described. [Evaluation Method of Wafer Washed by the Cleaning Method of the Present Invention] As the evaluation method of the wafer cleaned by the cleaning method of the present invention, the following evaluations (1) to (3) were carried out. (1) Evaluate the contact angle of the protective film formed on the surface of the wafer by placing about 2 μ1 of pure water on the surface of the wafer on which the protective film is formed, using 157216.doc • 62· 201216351 2 (Concord Interface Science: CA_X Type) Determine the angle (contact angle) between the water droplet and the surface of the wafer. Here, in the case of the embodiment of the first feature, the contact angle of the helmet type protective film is 5 〇 to 13 〇. The range is set to pass, and in the case of the embodiment of the second feature, the contact angle is (2). The enclosing is set to pass. (2) Removal of protective film The UV of the mercury lamp (UltraViolet, ultraviolet light will make the contact angle of the water droplets after irradiation to 1 使 under the conditions of the lower line) light-irradiated for 1 minute. The following was judged to have been removed from the protective film and was set to pass. • Lamp: pL2〇〇3N i〇 manufactured by Sen special light source • Illuminance: 15mW/cm2 (the distance from the light source to the sample is ΙΟηπη) (3) Evaluation of the wafer after removing the protective film “Surface smoothness by atomic force electron microscope (Jingwei Electronics Manufacturing: spi3, scanning 2·5 is called square) for surface observation. In the case of the first feature embodiment, the center line average surface roughness of the surface before and after wafer cleaning is determined. Call the difference △ call (10)). In addition, in the Ra system, the average ten-strand line degree defined by JIS B 〇6〇1 is applied to the measurement surface and is three-dimensionally expanded, and the winner obtains the absolute value of the deviation from the reference surface to the designated surface. The value obtained by the average." [Number 1]

|F(XfY)-Z〇|dXdY Here, Xl, Xr, Υβ γτ represent the measurement range of the χ coordinate and the γ coordinate, respectively, 1572l6.doc -63 * 201216351 The area where the measuring surface is the ideal plane Set to the value of (Xr_Xl)x (Yb-Yt). Further, F(X, Y) represents the height of the measurement point (χ, γ), and 2〇 represents the average height in the measurement surface. The Ra value of the wafer surface before the formation of the protective film and the Ra value of the wafer surface after the removal of the protective film are measured. 'If the difference between the two (ΔRa) g±1 nm or less is not invaded by the cleaning # wafer surface and no residue of the above protective film on the surface of the wafer, so it is qualified. In the case of the second embodiment, when the Ra value of the wafer after removing the protective film is 1 nm or less, the surface of the wafer is not eroded by the cleaning, and the residue of the protective film is not present on the surface of the wafer. Therefore, it is set to pass. The following Examples 1 and 2 illustrate the first feature of the present invention, and the following Comparative Examples 1 and 2 are in contrast to the Examples. [Example 1] (1) Preparation of a liquid-repellent protective film forming liquid to be used as a water-repellent protective film forming agent, nonafluorohexyldifluoride-based gas stone [C4F9(CH2)2(CH3)2SiCl] 10 g, 90 g of hydrofluoroether (HFE-7100 manufactured by 3M) as an organic solvent was mixed and uniformly stirred for about 5 minutes to obtain a concentration of the protective film forming agent relative to the total amount of the protective film forming liquid (hereinafter, "S" is used as a protective film. The forming agent concentration ") is 1 〇 mass. /. The protective film forming solution. (2) The TiN wafer is washed as a pre-washed, smooth wafer with a titanium nitride film (a silicon nitride layer with a thickness of 50 nm on the surface) in i% by mass of hydrofluoric acid. The solution was dipped for 2 minutes and then dipped in pure water for 1 minute. 157216.doc • 64 - 201216351 (3) The oxidation treatment of TiN wafers is carried out by mixing water and ethylene glycol (hereinafter referred to as "EG") in a ratio of mass ratio to the surface. The im 〇i/L square 弋 1 dish wipes to prepare an oxidation treatment solution. The m wafer after the "(2) TiN wafer was washed before" was immersed in the oxidizing treatment liquid having the liquid temperature maintained for 13 minutes for 1 minute to carry out oxidation treatment. (4) Surface treatment of the surface of the wafer by the water-repellent protective film forming solution The (10) wafer after the oxidation treatment of the (3) 1W wafer is immersed in 2 propanol (hereinafter referred to as iPA) 1 minute, and then, in the case of propylene glycol mono-acetic acid (hereinafter referred to as "Cong EA"), the W----after the water-repellent protective film forming step, the (four) wafer is described as "(1) Preparation of Protective Solution Forming Solution" (4) The film forming solution is immersed at 20 C! minute. Thereafter, the (four) wafer is

aie〇hM, 2 propanol) in the dipping] minutes followed by pure in the middle / shell 1 knife bell again, the above pre-washing treatment is based on TiN

The wafer surface and the surface are kept in a liquid state. Finally, the TiN wafer is taken out of pure water and air is blown to remove (4) pure water on the surface of the wafer. According to the points described in the "Method for Evaluating Wafers Washed by the Cleaning Method of the Present Invention", the obtained wafers were evaluated, and as a result, the initial contact angle before formation of the water-repellent protective film was less than 1 Å. The contact angle after the formation of the protective film was 96. ,! The staff showed excellent water repellency. Moreover, the contact angle after uv irradiation is less than 10. And the protective film can be removed. Further, it can be confirmed that the ARa value of the wafer irradiated by UV is within ±5 (10), and the wafer is not invaded at the time of cleaning, and the residue of the protective film is not left after the UV irradiation. Example 2]

PGMEA (Propylene giyC〇im〇n〇methyi ether) as an organic solvent, octyl dimethyl dimethylamine oxime [C8H17(CH3)2SiN(CH3)2] 5 g as a water-repellent protective film forming agent Acetate 'propylene glycol monomethyl acetate> 94.82 g, as a catalyst trifluoroacetic anhydride [(CF3c〇) 2〇J 〇·18 g mixed 'stirring for about 5 minutes, to obtain a protective film former concentration of 5 % of the protective film forming drug solution. The TiN wafer obtained by "(2) TiN wafer pre-cleaning and "(3) TiN wafer oxidation treatment" was immersed in ipA for 1 minute in the same manner as in Example 1, followed by PGMEA After the middle immersion, the water-repellent protective film forming step was immersed in the protective film forming solution prepared in the above manner at 45 C for 1 hour. Thereafter, the TiN wafer was immersed in ipA for 1 minute, and then immersed in pure water for 丨 minute. Further, the above-described pre-cleaning treatment is carried out while the liquid remains on the surface of the TiN wafer. Finally, the TiN wafer is taken out of the pure water and air is blown to remove the pure water on the surface of the TiN wafer. The TiN wafer obtained was evaluated according to the points described in the "Method for Evaluating Wafers Washed by the Cleaning Method of the Present Invention", and as a result, the initial contact angle before formation of the water-repellent protective film was less than 10. The contact angle after the formation of the protective film was 71°, which showed an excellent water-repellent imparting effect. Also, the contact angle after uv irradiation is less than 10. Further, the protective film was removed, and it was confirmed that the ARa value of the wafer irradiated with UV was within ±0.5 nm, and the wafer was not invaded during the cleaning, and the residual film of the protective film remained after the UV irradiation. 157216.doc -66 - 201216351 [Comparative Example 1] n, n-didecylaminotrimethylsulfonium [(CH3)3SiN(CH3)2] 5 g as a water-repellent protective film forming agent, as organic PGMEA 95 g of the solvent was mixed and stirred for about 5 minutes to obtain a protective film forming drug solution having a protective film forming agent concentration of 5% by mass. The TiN wafer obtained by "(2) TiN wafer cleaning" and "(3) TiN wafer oxidation treatment" was immersed in iPA for 1 minute in the same manner as in Example 1, followed by PGMEA After the first impregnation for 1 minute, the protective film forming solution prepared in the above manner was immersed at 20 ° C for 1 hour as a water-repellent protective film forming step. Thereafter, the TiN wafer was immersed in iPA for 1 minute and then impregnated in pure water for 1 minute. Further, the above-described pre-cleaning treatment is performed in a state where the liquid is kept on the surface of the TiN wafer. Finally, the TiN wafer is taken from pure water to blow air to remove pure water from the surface of the TiN wafer. The TiN wafer obtained was evaluated according to the points described in the above "Evaluation method of the wafer cleaned by the cleaning method of the present invention". As a result, the initial contact angle before formation of the water-repellent protective film was less than 10. The contact angle after the formation of the protective film was 23. It is impossible to give sufficient water repellency. [Comparative Example 2] 5 g of N,N-didecylaminotrioxane [(CH3)3SiN(CH3)2] as a water-repellent protective film forming agent, and PGMEA% as an organic solvent were mixed and stirred. In the same manner as the embodiment, the "(2) TiN wafer is washed before" (3) TiN wafer is not performed in about 5 minutes. Oxidation treatment, the TiN wafer was immersed in iPA for 1 minute' and then impregnated in pGMEA for 1 minute 157216.doc •67·201216351, as a water-repellent protective film forming step, the protective film prepared in the above manner Form the drug solution at 20. The underarm was immersed for 1 hour. Thereafter, the TiN crystal was immersed in ι 1 for 1 minute, and then immersed in pure water for 〖min. Further, the treatment after the above-described pre-cleaning is performed in a state where the liquid is held on the surface of the TiN wafer. Finally, the TiN wafer is taken out of the pure water, and the air is blown to remove the pure water on the surface of the TiN wafer. The obtained TiN wafer was evaluated based on the points described in the above-mentioned "Method for evaluating wafers cleaned by the cleaning method of the present invention", and as a result, the initial contact angle before formation of the water-repellent protective film was less than 1 Å. The contact angle after the formation of the protective film was 18. ‘Unable to give adequate water repellency. The following Examples 1 to 18 are illustrative of the second feature of the present invention, and the following Comparative Examples 1 to 6 are in contrast to the examples. [Example 1] (1) Preparation of a chemical solution for forming a protective film 3 g of hexamethyldioxane (HMDS) as a compound A and 0.1 g of trifluoroacetic acid (TFA) as an acid a were used. 96.9 g of a solvent of propylene glycol monomethyl ether acetate (pGMEA) was mixed and stirred for about 5 minutes to obtain a protective film forming drug solution. (2) The wafer is cleaned and smoothed with a silicon wafer of si〇2 film (a wafer with a thermal oxide film layer having a thickness of 1 μm on the surface, and the following is only a case of rsi〇2 film) The mixture was immersed in a 1 mass/0 Torr aqueous solution of hydrofluoric acid for 2 minutes, then immersed in pure water for 1 minute and immersed in 2-propanol for 1 minute. In addition, the smooth SiN film-attached ray wafer made of LP-CVD (the surface has a thickness of 5 〇 nm nitride film 157216.doc 8 • 68 · 201216351, the stone wafer, the following exists only bamboo The case of "SiN film" is 1 mass. / 〇 〇 酸 酸 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 2 四 2 2 2 四 四 2 2 2 2 2 Immerse in the clean solution for 1 minute and immerse in pure water! minute. (3) The pretreatment is carried out by using an ion exchange method and (iv) n beforehand to make an aqueous solution of hydrochloric acid (in Table 1, which is referred to as HC1) (the actual measured pH is (Μ) purified and obtained as a pretreatment. The liquid medicine is heated in the manner of the liquid temperature by the addition of ', ', and the plate is heated. The film is removed by the above-mentioned film and the wafer with the hN film is separately used in the pretreatment liquid. Immerse for 1 minute and pre-treat. Then, each wafer is immersed in pure water, and the pH of the hydrazine treatment solution is placed in the pre-treatment solution at 25 〇. After 1 hour, it was measured by a pH meter (manufactured by AS One Co., Ltd., Lacom Tester pH meter, pH 1100). (4) The surface treatment of the wafer surface by the protective film forming liquid solution was pretreated. The 制备 wafer of the Si 〇 2 film and the ruthenium wafer with the SiN film are respectively immersed in 2 -propanol for 1 minute, and then protected by the above "(1) Preparation of protective film forming liquid" The film formation solution was immersed for 1 minute at 20 ° C. Thereafter, each wafer was immersed in 2-propanol for 1 minute, followed by pure water. The wafer was immersed for 1 minute. Finally, each wafer was taken out of pure water and air was blown to remove pure water from the surface. The obtained wafers were evaluated according to the points described in the "Method for Evaluation of Wafer". In the case of the wafer with the Si02 film, it is only referred to as "8丨〇2 film". In the case of the wafer with the SiN film, 157216.doc • 69- 201216351, it is only recorded as "SiN film". The evaluation results are shown in the table. 'Si〇2 film system has an initial contact angle of less than 1 表面 before surface treatment. However, the contact angle after surface treatment is 88. It shows the water repellency imparting effect. After the uv irradiation, the contact angle is less than 10 and the 蒦 film can be removed. It can be confirmed that the Ra value of the wafer after the UV irradiation is less than 0.5 nm, and the wafer is not eroded during the cleaning, and thus the MUV is not irradiated. The residue of the protective film remained. The initial contact angle of the SiN film system before the surface treatment was less than (7), but the contact angle after the surface treatment was 69. The water repellency imparting effect was exhibited. Further, the contact angle after UV irradiation was not Up! 〇. And the protective film can be removed. It can be confirmed that UV irradiation The Ra value of the subsequent wafer is less than nm5 nm, and the wafer is not eroded during cleaning', and the residue of the protective film remains after UV irradiation. 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Ga DH 一一五谋驷-军辑驷-军鸯驷εί#*- H#*^ 71 - 201216351 [Examples 2 to 1 8] Appropriately change the acid and acid of the treatment liquid before use in Example 1. The surface treatment of the wafer is carried out under conditions such as concentration, solvent, pH, temperature, or temperature of the surface treatment of the protective film forming solution, and the like. The results are shown in Table i. Furthermore, 'in Table 1, 'HN〇3 means nitric acid, CH3C00H means acetic acid 'HOOCCHCHCOOH means maleic acid, and water/EG=60/40 means mixing water and ethylene with a mass ratio of 60/40. Solvent made of alcohol, water/EG=20/80 means a solvent obtained by mixing water and ethylene glycol in a mass ratio of 20/80' HMDS/TFA/PGMEA means the same composition ratio protection as in Example i Membrane forming solution. [Comparative Example 1] All were the same as in Example 1 except that the pretreatment was not performed. The evaluation results are shown in Table 1. The Si〇2 film system had an initial contact angle of less than 1 〇° before surface treatment, but the contact angle after surface treatment was 91. , showing the water-repellent effect. Moreover, the contact angle after UV irradiation was less than 1 〇. And the protective film can be removed. Further, it was confirmed that the Ra value of the wafer after the uv irradiation was less than 0 5 nm, the wafer was not eroded during the cleaning, and the residual of the protective film remained after the UV irradiation. On the other hand, the SiN film system had an initial contact angle of less than 10 Å before surface treatment, but the contact angle after surface treatment was 47. The water-repellent effect is not sufficient. It can be considered that the amount of the reactive site such as the hydroxyl group present on the surface is almost no change in the amount of the reactive site such as the hydroxyl group on the surface as compared with the evaluation result of Comparative Example 1. Therefore, the surface of the wafer is originally A silicon wafer with a SiN film having a small hydroxyl group does not sufficiently form a water-repellent protective film. [Comparative Example 2] The same procedure as in Example 丨 was carried out except that a 0.0005 mol/L hydrochloric acid aqueous solution (actually measured as 11 is 3 5) was used as the pretreatment treatment liquid. The evaluation results are shown in Table 1. The Si〇2 system had an initial contact angle of less than 10 before surface treatment, but the contact angle after surface treatment was 88. , showing the water-repellent effect and the contact angle after UV irradiation is less than 1 〇. And the protective film can be removed. Further, it was confirmed that the Ra value of the wafer after the UV irradiation did not reach nm 5 nm, and the wafer was eroded during the cleaning, and the residue of the protective film remained after the UV irradiation. On the other hand, the SiN film system had an initial contact angle of less than 1 Å before surface treatment, but the contact angle after surface treatment was 59. The water-repellent effect is not sufficient. [Comparative Example 3] The same procedure as in the Examples was carried out except that a 0.01 mol/L aqueous acetic acid solution (the actually measured pH was 3 6) was used as the pretreatment treatment liquid. The evaluation results are shown in Table 1. The Si〇2 film system had an initial contact angle of less than 10 before surface treatment, but the contact angle after surface treatment was 89. , showing the water-repellent effect. Moreover, the contact angle after UV irradiation was less than 1 〇. And the protective film can be removed. Further, it was confirmed that the Ra value of the wafer after the uv irradiation was less than 0 5 nm, the wafer was not eroded during the cleaning, and the residue of the protective film remained after the UV irradiation. On the other hand, the SiN film system had an initial contact angle of less than 1 Å before surface treatment, but the contact angle after surface treatment was 58. The water-repellent effect is not sufficient. 157216.doc -73-201216351 It is considered that when the acid concentration in the pretreatment liquid is too low or the value of the pretreatment liquid is too large, compared with the evaluation results of Comparative Examples 2 and 3, The effect of modifying the surface of the wafer is weakened, and the wafer wafer with the SiN film with a small number of warp on the surface of the wafer is sufficiently formed to form a water-repellent protective film. [Comparative Example 4] A hydrochloric acid aqueous solution of 7 m〇1/L (actually measured as yttrium) was used as a pretreatment treatment liquid. However, since the acid concentration of the pretreatment liquid is too high, the purification of the pretreatment liquid cannot be performed by the ion exchange method. [Comparative Example 5] A hydrochloric acid aqueous solution of 90 § and 3 % by weight of hydrogen peroxide (hereinafter referred to as 2 g of liquid mixture and 10 g of the mixture was stirred and mixed for 5 minutes to form a pretreatment liquid (the actual measured enthalpy was 0.0). The concentration of hydrochloric acid in the pretreatment liquid is 〇.9 m hunger, and the composition of the solvent is water/Η2〇2=97/3 (mass ratio). The heating treatment is performed by heating the plate at a liquid temperature of 9 〇C. After the chemical solution is used, air bubbles are generated. It is considered that the hydrogen peroxide is decomposed to generate oxygen. The above-mentioned bubble generation causes the pretreatment to be impossible. [Comparative Example 6] Except for the pretreatment liquid at 3 °C The results are the same as in the examples. The # valence results are shown in Table 1. The Si接触2 film system had an initial contact angle of less than 10 before surface treatment, but the contact angle after surface treatment was 87. The effect is also given. The contact angle after UV irradiation is less than 1 G. The protective film can be removed. It can be confirmed that the value of the wafer after the UV irradiation is less than 5 nm, and the wafer is not (four) at the time of cleaning. No residue of 157216.doc 201216351 film remained after UV irradiation. On the other hand, the surface of SiN film system The initial contact angle before the treatment was less than 10. However, the contact angle after the surface treatment was 51. The water-repellent imparting effect was insufficient. It can be tolerated, compared with the evaluation result of Comparative Example 2, the pretreatment liquid. When the temperature is too low, the effect of modifying the surface of the wafer is weakened. Therefore, the silicon wafer with the SiN film having a small number of hydroxyl groups on the surface of the wafer is not sufficiently formed with the water-repellent protective film. The wafer with the SiN film is used as the wafer with less hydroxyl groups on the surface of the wafer. However, when using a wafer with a germanium film such as polysilicon or the like, it is also conceivable to obtain and use the attached S. Fig. 1 is a schematic plan view of a wafer 1 having a surface having a surface having a concave-convex pattern 2, Fig. 1 showing a_a in Fig. i, a cross section of Fig. 1 Fig. 3 is a view showing a state in which the protective film forming chemical solution 8 is held by the concave portion 4. Fig. 4 is a view showing a state in which the concave portion 4 in which the protective film is formed is in a state in which a liquid is held. 1 wafer 2 wafer surface Concave-convex pattern 3 Pattern convex portion 157216.doc -75- 201216351 4 Pattern concave portion 5 Width of concave portion 6 Height of convex portion 7 Width of convex portion 8 The liquid-repellent protective film forming chemical solution 9 held in the concave portion 4 is held in the concave portion 4 liquid 10 water-repellent protective film 157216.doc -76- 8

Claims (1)

201216351 VII. Patent application scope: 1. A method for cleaning a wafer, characterized in that: a surface of the surface is formed with a concave-convex pattern, and at least a part of the surface of the concave portion of the concave-convex pattern is selected from the group consisting of titanium, titanium nitride, tungsten, aluminum a method for cleaning a wafer of at least one of a group of copper, tin, nitride, niobium, and niobium-containing materials, and comprising: a processing step prior to modifying the surface of the wafer; The water-repellent film forming solution containing the water-repellent (four) (four) agent for forming the water-repellent protective film on the surface of the modified wafer is held in at least the concave portion of the BB circle, and water-repellent is formed on the surface of the concave portion. a water-repellent protective film forming step of the protective film; and the water-repellent protective film forming agent is a ceramsite represented by the following general formula [1]: - LAJ [In the formula [1], R1 is independent of each other and is hydrogen, Or a hydrocarbon group in which the unsubstituted nicotyl or hydrogen element of the carbon number H8 is substituted by a picture element, and the hydrazines are each independently selected from the group consisting of a monovalent functional group in which the element bonded to the 7 element is nitrogen, and a bond with the lithium element. At least one recorded soil of the group consisting of a monovalent functional group of oxygen and a ii group is an integer of 1 to 3; and, in the above-mentioned wafer, 'excluding the 辛元辛仫I The total number of carbons contained in R1 of the formula [1] is 6 or more]. 2. The at least concave portion of the method of cleaning the wafer of the claim 1 and the method for cleaning the embossed wafer at least comprises: 'The surface of the surface of which is formed with a embossed surface containing a portion of the 157216. Doc 201216351 a step of forming an epitaxial protective film on a concave-convex pattern by modifying a surface of the concave-convex pattern by modifying the surface of the concave-convex pattern by modifying the surface of the concave-convex pattern before the surface of the concave-convex pattern is modified by the chemical liquid; The water-repellent protective film is formed to form a water-repellent protective film, and in the above pre-treatment step, 'the treatment liquid containing the acid containing the molar concentration, 5 to 5 mol/L, and the pH is 3 or less, = 4 The surface of the case is modified at a temperature above 〇C and not at the boiling point of the pretreatment treatment liquid. Fig. 3 is a method of cleaning a wafer according to claim 2, wherein the acid contained in the pretreatment liquid is an organic acid. The method of cleaning a wafer according to any one of the preceding claims, wherein the parent portion of the concave pattern is formed by nitriding stone and/or stone eve. 5. The method for cleaning a wafer according to a request, wherein the surface is formed with a concave-convex pattern and at least a portion of the surface of the concave portion of the concave-convex pattern is selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, and nitride. A method for cleaning a wafer of at least one of a group consisting of a group of giant and bismuth, and the water-repellent protective film forming agent is a deuterated R^SiX represented by the following general formula [2] [2] Ri is independent of each other and is a hydrocarbon group substituted with hydrogen or a carbon number or an unsubstituted nicotine or a hydrogen 7C element (4) element, and the formula [takes Rl to contain a total of 6 carbon atoms, X-type and oxime bond The element of the knot is hydrogen. The element bonded to the stone element is a monovalent functional group of oxygen, or 1572I6.doc 201216351 halo]. 6. The method of cleaning a wafer according to claim 5, wherein the water-repellent protective film forming agent is a telluride represented by the following formula [3]: R2(CH3)2SiX [3] [in the formula [3] R2 is an unsubstituted hydrocarbon group having a carbon number of 4 to 18, or a hydrocarbon group in which a hydrogen element is substituted with 2 =, and an element in which the X system is bonded to a ruthenium element is nitrogen (a) the element bonded to the element is an oxygen functional group]. [7] The method for cleaning a wafer according to claim 5 or 6, wherein the above-mentioned water-repellent protective film forming agent is a telluride represented by the following formula [4]: R3(CH3)2SiX [4] 8. ^ In the formula [4], R, a carbon number of 4 to 18, at least a part of the hydrogen element is substituted by a fluorine element, and the element of the X system bonded to the sand element is an valence functional group bonded to the Shixi 70 element. The element is an Hf functional group of oxygen, or a south group]. 9. The method of cleaning a wafer of item 5 or 6, wherein said pre-processing step is to maintain an oxidizing treatment liquid on said wafer surface. The method of cleaning a wafer, wherein the pre-processing step is to maintain an oxidizing treatment liquid on the surface of the wafer. 10. In the method for cleaning a wafer according to claim 8, the method of using the β ^ + 八中中的处理处理处理的反应处理液 is selected from the group consisting of a treatment liquid containing ozone, a treatment liquid containing at least = treatment liquid, and an acid-containing treatment liquid. The main component of the group consisting of a treatment liquid. The oxidizing treatment liquid used in the above pretreatment (4) is at least one treatment liquid selected from the group consisting of a treatment liquid containing ozone, a treatment liquid containing 157216.doc 201216351 hydrogen peroxide, and a treatment liquid containing acid. 157216.doc -4- 8