JP5821844B2 - Chemical solution for protective film formation - Google Patents

Description

  The present invention relates to a substrate (wafer) cleaning technique for the purpose of improving the manufacturing yield of a device having a circuit pattern that is fine and has a high aspect ratio, particularly in the manufacture of semiconductor devices. In particular, the present invention relates to a water-repellent protective film-forming chemical solution and the like for the purpose of improving a cleaning process that easily induces a concavo-convex pattern collapse of a wafer having a fine concavo-convex pattern on the surface.

Background of the Invention

  In semiconductor devices for networks and digital home appliances, higher performance, higher functionality, and lower power consumption are required. For this reason, circuit patterns are being miniaturized, and accordingly, the particle size that causes a reduction in manufacturing yield is also miniaturized. As a result, a cleaning process intended to remove contaminants such as micronized particles is frequently used, and as a result, the cleaning process accounts for 30 to 40% of the entire semiconductor manufacturing process.

  On the other hand, in the conventional cleaning with the mixed ammonia cleaning agent, the damage to the wafer due to the basicity becomes a problem as the circuit pattern is miniaturized. For this reason, replacement with, for example, a dilute hydrofluoric acid-based cleaning agent with less damage is in progress.

  Thus, although the problem of damage to the wafer due to cleaning has been improved, the problem due to the increase in the aspect ratio of the pattern accompanying the miniaturization of the semiconductor device has become apparent. That is, after cleaning or rinsing, a phenomenon that the pattern collapses when the gas-liquid interface passes through the pattern causes a significant decrease in yield.

  This pattern collapse occurs when the wafer is pulled up from the cleaning liquid or the rinse liquid. This is said to be caused by a difference in residual liquid height between a portion where the aspect ratio of the pattern is high and a portion where the aspect ratio is low, thereby causing a difference in capillary force acting on the pattern.

  For this reason, if the capillary force is reduced, it can be expected that the difference in capillary force due to the difference in the residual liquid height will be reduced and the pattern collapse will be eliminated. The magnitude of the capillary force is the absolute value of P obtained by the following formula. From this formula, it is expected that the capillary force can be reduced by reducing γ or cos θ.

P = 2 × γ × cos θ / S
(Γ: surface tension, θ: contact angle, S: pattern dimension)
Patent Document 1 discloses a technique for substituting the cleaning liquid from water to 2-propanol before the gas-liquid interface passes through the pattern as a technique for reducing γ and suppressing pattern collapse. However, while this method is effective for preventing pattern collapse, a solvent such as 2-propanol having a small γ tends to have a small normal contact angle and, as a result, tends to increase cos θ. Therefore, it is said that there is a limit, for example, the aspect ratio of the pattern that can be handled is 5 or less.

  Patent Document 2 discloses a technique for resist patterns as a technique for reducing cos θ to suppress pattern collapse. This method is a method of suppressing pattern collapse by setting cos θ close to 0 and reducing the capillary force to the limit by setting the contact angle near 90 °. However, since the disclosed technique is intended for a resist pattern, it modifies the resist itself, and can be finally removed together with the resist. Therefore, it is necessary to assume a method for removing the treatment agent after drying. Is not applicable to this purpose.

  Further, Patent Document 3 discloses that a wafer surface on which a concavo-convex pattern is formed by a film containing silicon is surface-modified by oxidation or the like, and a water-repellent protective film is formed on the surface using a water-soluble surfactant or silane coupling agent. A cleaning method is disclosed that reduces the capillary force and prevents the pattern from collapsing. However, the water repellent used above may have an insufficient water repellency imparting effect.

  In addition, as a technique for preventing pattern collapse of a semiconductor device, use of a critical fluid, use of liquid nitrogen, or the like has been proposed. However, although all have a certain effect, it is difficult to apply to a mass production process because the throughput is worse than the conventional cleaning process.

JP 2008-198958 A Japanese Patent Laid-Open No. 5-299336 Patent No. 4403202

  At the time of manufacturing a semiconductor device, the wafer surface is a surface having a fine uneven pattern. According to the present invention, throughput is impaired in a method of manufacturing a wafer having a fine uneven pattern on the surface and at least a part of the uneven pattern containing silicon element (hereinafter referred to as “silicon wafer” or simply “wafer”). It is an object of the present invention to provide a protective film-forming chemical solution for forming a water-repellent protective film on the surface of a concavo-convex pattern of a wafer for improving a cleaning process that easily induces pattern collapse.

（式［１］中、Ｒ¹は、それぞれ互いに独立して、炭素数が１〜１８の炭化水素基を含む１価の有機基、および、炭素数が１〜８のフルオロアルキル鎖を含む１価の有機基から選ばれる少なくとも１つの基であり、Ｘは、それぞれ互いに独立して、Ｓｉ元素に結合する元素が窒素である１価の有機基であり、ａは１〜３の整数、ｂは０〜２の整数であり、ａとｂの合計は１〜３である。）The chemical liquid for forming a protective film (hereinafter referred to as “chemical liquid for forming a protective film” or simply “chemical liquid”) for forming a water-repellent protective film on the surface of the uneven pattern of the wafer of the present invention has a fine uneven pattern on the surface. At the time of cleaning a wafer in which at least a part of the concavo-convex pattern contains silicon element, a water-repellent protective film (hereinafter referred to as “water-repellent protective film” or simply “protective film”) is formed on at least the concave surface of the concavo-convex pattern. A chemical solution for the above-described purpose, comprising a silicon compound A represented by the following general formula [1] and an acid A, wherein the acid A is trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethane Sulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trif Group consisting of oromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesulfonate It is at least one selected from.

(In the formula [1], R ^{1 s} each independently contain a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl chain having 1 to 8 carbon atoms. X is at least one group selected from a valent organic group, X is each independently a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b Is an integer of 0-2, and the sum of a and b is 1-3.)

R1 in the general formula [1], by reducing the surface energy of the article, the interaction between (interface) with water or other liquid and the article surface, for example, hydrogen bonding, reduces the like intermolecular force . In particular, the effect of reducing the interaction with water is great, but it has the effect of reducing the interaction with a mixed liquid of water and a liquid other than water or a liquid other than water. Thereby, the contact angle of the liquid with respect to the article | item surface can be enlarged.

  The protective film is formed by chemically bonding X in the general formula [1] with the Si element of the silicon wafer. Therefore, when the cleaning liquid is removed from the recess of the silicon wafer, that is, when it is dried, since the protective film is formed on the surface of the recess, the capillary force on the surface of the recess is reduced, and pattern collapse occurs. It becomes difficult. The protective film can be removed in a later step.

  Acid A, namely trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethyl At least one selected from the group consisting of silyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesulfonate is the silicon compound A and Si of silicon wafer To successful to promote the reaction between the elements. When the acid A is present in the chemical solution, the protective film can be formed in a short time. The acid A may form part of the protective film.

  The speed at which the protective film is formed on the substrate surface, that is, the speed at which the water repellency is developed on the substrate surface is determined by the speed at which the component derived from the silicon compound A binds to the reaction site on the substrate surface. Is. When the acid A is present, the component derived from the silicon compound A can quickly react with silanol groups, which are reaction sites on the surface of the concave / convex pattern of the silicon wafer, so that sufficient water repellency is imparted to the substrate surface during the surface treatment. can do.

  When the amount of water in the chemical solution increases, the silicon compound A is hydrolyzed and the reactivity is easily lowered, and as a result, the protective film is hardly formed. For this reason, it is preferable that the total amount of moisture in the starting material is 5000 ppm by mass or less based on the total amount of the starting material. When the water content exceeds 5000 mass ppm, it is difficult to form the protective film in a short time. For this reason, the smaller the total amount of water, the more preferable, particularly 1000 ppm by mass or less, and even more preferable 500 ppm by mass or less. Furthermore, since the storage stability of the said chemical | medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable. In addition, 0.1 mass ppm or more may be sufficient as the moisture content in the raw material of the said chemical | medical solution.

  For example, when a Bronsted acid is used instead of the acid A, the Bronsted acid reacts with the silicon compound A to reduce the silicon compound A or to reduce the reactivity of the silicon compound A. There is. For this reason, the acid A is preferred.

（式［２］中、Ｒ² _c（Ｈ）_dＳｉ−は、（ＣＨ₃）₃Ｓｉ−、（ＣＨ₃）₂（Ｈ）Ｓｉ−、（Ｃ₄Ｈ₉）（ＣＨ₃）₂Ｓｉ−、（Ｃ₆Ｈ₁₃）（ＣＨ₃）₂Ｓｉ−、（Ｃ₈Ｈ₁₇）（ＣＨ₃）₂Ｓｉ−、または、（Ｃ₁₀Ｈ₂₁）（ＣＨ₃）₂Ｓｉ−である。また、Ｙは、それぞれ互いに独立して、Ｓｉ元素と結合する元素が窒素の１価の有機基を示す。）Moreover, the acid A contained in the chemical solution for forming a protective film of the present invention may be obtained by a reaction. For example, at least one selected from the group consisting of silicon compound B represented by the following general formula [2] and trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride (hereinafter referred to as “acid B”). May be obtained by reacting.

(Wherein _{^{[2], R 2 c (}} H) d Si- _{is, (CH 3) 3 Si -} , (CH 3) 2 (H) Si -, (C 4 H 9) (CH 3) 2 Si- , (C ₆ H ₁₃ ) (CH ₃ ) ₂ Si—, (C ₈ H ₁₇ ) (CH ₃ ) ₂ Si—, or (C ₁₀ H ₂₁ ) (CH ₃ ) ₂ Si—. Each independently represents a monovalent organic group in which the element bonded to the Si element is nitrogen.)

  The chemical solution for forming a protective film of the present invention is obtained by adding the silicon compound B excessively to the acid B, and the silicon compound B that is not consumed in the reaction is converted to the protective film using the acid A generated by the reaction as a catalyst. May be formed. That is, the surplus of the silicon compound B that has not been consumed in the reaction may contribute to the formation of the protective film as the silicon compound A. The silicon compound B is preferably 0.2 to 100000 mol times, preferably 0.5 to 50000 mol times, and more preferably 1 to 10000 mol times with respect to the acid B. .

The acid A accepts electrons from the silicon compound A to promote a reaction between the silicon compound A and a silanol group which is a reaction site on the surface of the silicon wafer, and the silicon compound A is converted into Si of the silicon wafer through a siloxane bond. Acts as a catalyst to chemically bond with elements. The acid A is considered to act like the mechanism of the upper stage of the following figure. In the figure, acid A is expressed as “L”. When the acid is present in the chemical solution, the protective film can be formed in a short time. When the amount of water in the chemical solution increases, the silicon compound A is hydrolyzed and the reactivity is easily lowered, and as a result, the protective film is hardly formed. For this reason, it is preferable that the total amount of moisture in the starting material is 5000 ppm by mass or less based on the total amount of the starting material. When the water content exceeds 5000 mass ppm, it is difficult to form the protective film in a short time. For this reason, the smaller the total amount of water, the more preferable, particularly 1000 ppm by mass or less, and even more preferable 500 ppm by mass or less. Furthermore, since the storage stability of the said chemical | medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable. In addition, 0.1 mass ppm or more may be sufficient as the moisture content in the raw material of the said chemical | medical solution. When a Bronsted acid is used instead of the acid A, the Bronsted acid acts like the lower mechanism in the figure below, and the silanol group which is a reaction site on the substrate surface partially reacts to form the silicon compound A. It is considered that the silicon element is chemically bonded to the Si element of the silicon wafer through the siloxane bond, but the Bronsted acid in the chemical solution reacts with the silicon compound A to reduce the silicon compound A or the reactivity of the silicon compound A. Therefore, there is a tendency that sufficient water repellency cannot be expressed on the substrate surface.

  Moreover, it is preferable that the number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical solution is 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 μm exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 μm is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. The number of particles larger than 0.5 μm may be 1 or more per 1 mL of the chemical solution. The particle measurement in the liquid phase in the chemical solution in the present invention is performed by using a commercially available measuring device in the light scattering liquid particle measurement method using a laser as a light source. , PSL (polystyrene latex) standard particle-based light scattering equivalent diameter.

  Moreover, it is preferable that the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the said chemical | medical solution is 100 mass ppb or less with respect to this chemical | medical solution total amount. The metal impurities of each element described above are all those that exist in the chemical solution in the form of metal fine particles, ions, colloids, complexes, oxides and nitrides, whether dissolved or undissolved. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may increase, which causes a decrease in device yield and reliability, which is not preferable. Moreover, it is preferable that the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. In addition, 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical | medical solution total amount.

  The chemical solution for forming a protective film of the present invention is used by replacing the cleaning solution with the chemical solution in the step of cleaning the wafer on which the uneven pattern is formed. Further, the replaced chemical liquid may be replaced with another cleaning liquid.

  As described above, the cleaning liquid is replaced with the protective film forming chemical solution, and the protective film is formed on at least the concave surface of the concave / convex pattern while the chemical liquid is held on at least the concave surface of the concave / convex pattern. The protective film of the present invention does not necessarily have to be formed continuously, and does not necessarily have to be formed uniformly. However, since it can impart better water repellency, it can be applied continuously and uniformly. More preferably, it is formed.

  In the present invention, the water-repellent protective film of a wafer refers to a film that is formed on the wafer surface to lower the wettability of the wafer surface, that is, a film that imparts water repellency. In the present invention, the water repellency means that the surface energy of the article surface is reduced and the interaction (for example, hydrogen bond, intermolecular force) between water or other liquid and the article surface is reduced. It is. In particular, the effect of reducing the interaction with water is great, but it has the effect of reducing the interaction with a mixed liquid of water and a liquid other than water or a liquid other than water. By reducing the interaction, the contact angle of the liquid with the article surface can be increased.

  In the present invention, when the cleaning liquid is removed from the recess, that is, when dried, the protective film is formed on at least the recess surface of the recess / protrusion pattern, so that the capillary force on the recess surface is reduced and the pattern collapses. Is less likely to occur. The protective film can be removed by at least one treatment selected from light irradiation of the wafer surface, heating of the wafer, exposure of the wafer to ozone, and irradiation of the wafer surface with plasma.

  Since the protective film formed by the chemical solution for forming a protective film of the present invention is excellent in water repellency, it reduces the capillary force on the surface of the concave / convex pattern of the wafer, and thus exhibits an effect of preventing pattern collapse. When the chemical solution is used, the cleaning step in the method for producing a wafer having a fine uneven pattern on the surface can be improved without lowering the throughput. Therefore, the method for producing a wafer having a fine concavo-convex pattern on the surface, which is carried out using the chemical solution for forming a protective film of the present invention, has high productivity.

  The chemical solution for forming a protective film according to the present invention can cope with a concavo-convex pattern having an aspect ratio of, for example, 7 or more which is expected to become higher in the future, and can reduce the cost of production of higher-density semiconductor devices. . In addition, the conventional apparatus can be applied without significant change, and as a result, can be applied to the manufacture of various semiconductor devices.

1 is a schematic plan view of a wafer 1 whose surface is a surface having a fine concavo-convex pattern 2. FIG. 2 shows a part of the a-a ′ cross section in FIG. 1. The schematic diagram of the state in which the recessed part 4 hold | maintained the chemical | medical solution 8 for protective film formation in the washing | cleaning process is shown. It is a figure which shows the schematic diagram of the state by which the aqueous cleaning liquid was hold | maintained at the recessed part 4 in which the protective film was formed.

A suitable cleaning method for a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element, using the chemical solution for forming a protective film of the present invention,
(Step 1) A step of making the wafer surface a surface having a fine concavo-convex pattern, then subjecting the surface to an aqueous cleaning solution and holding the aqueous cleaning solution on at least the concave surface of the concavo-convex pattern;
(Step 2) A step of replacing the aqueous cleaning liquid held on at least the concave surface of the concavo-convex pattern with a cleaning liquid A different from the aqueous cleaning liquid,
(Step 3) Replacing the cleaning liquid A with a protective film-forming chemical solution, and holding the chemical solution on at least the concave surface of the concave-convex pattern;
(Step 4) A step of removing liquid from the surface of the concavo-convex pattern by drying,
(Step 5) A step of removing the protective film is included.

  Further, after the step (Step 3) of holding the chemical solution for forming the protective film on at least the concave surface of the concavo-convex pattern, the chemical solution held on at least the concave surface of the concavo-convex pattern was replaced with a cleaning liquid B different from the chemical solution. Later, the process may be shifted to a step of removing the liquid from the surface of the concavo-convex pattern by drying (step 4). In addition, after the replacement with the cleaning liquid B, an aqueous cleaning liquid composed of an aqueous solution is held on at least the concave surface of the concave / convex pattern, and then the process may be shifted to a step of removing the liquid from the concave / convex pattern surface by drying (step 4). . In addition, when the protective film forming chemical can be replaced with an aqueous cleaning liquid, the replacement with the cleaning liquid B may be omitted.

  In the present invention, the cleaning method of the wafer is not particularly limited as long as the chemical liquid or the cleaning liquid can be held on at least the concave surface of the concave / convex pattern of the wafer. As a wafer cleaning method, a wafer cleaning method represented by spin cleaning in which a wafer is cleaned one by one by supplying liquid to the vicinity of the rotation center while rotating the wafer while holding the wafer substantially horizontal, or a plurality of cleaning methods in the cleaning tank. One example is a batch system in which a single wafer is immersed and washed. The form of the chemical solution or cleaning liquid when supplying the chemical solution or cleaning liquid to at least the concave surface of the concave / convex pattern of the wafer is not particularly limited as long as it becomes liquid when held on the concave surface, for example, , Liquid, vapor, etc.

（式［１］中、Ｒ¹は、それぞれ互いに独立して、炭素数が１〜１８の炭化水素基を含む１価の有機基、および、炭素数が１〜８のフルオロアルキル鎖を含む１価の有機基から選ばれる少なくとも１つの基であり、Ｘは、それぞれ互いに独立して、Ｓｉ元素に結合する元素が窒素である１価の有機基であり、ａは１〜３の整数、ｂは０〜２の整数であり、ａとｂの合計は１〜３である。）The silicon compound A in the chemical solution is preferably a compound represented by the following general formula [1].

(In the formula [1], R ^{1 s} each independently contain a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl chain having 1 to 8 carbon atoms. X is at least one group selected from a valent organic group, X is each independently a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b Is an integer of 0-2, and the sum of a and b is 1-3.)

In the general formula [1], the monovalent organic group in which the element bonded to the Si element as X is nitrogen includes not only hydrogen, carbon, nitrogen, and oxygen elements but also silicon, sulfur, halogen elements, and the like. May be. Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include isocyanate group, amino group, dialkylamino group, isothiocyanate group, azide group, acetamide group, —N (CH ₃ ) C (O) CH _{3, -N (CH 3) C} (O) CF 3, -N = C (CH 3) OSi (CH 3) 3, -N = C (CF 3) OSi (CH 3) 3, -NHC (O) _{-OSi (CH 3) 3, -NHC} (O) -NH-Si (CH 3) 3, imidazole ring (the following formulas [3]), oxazolidinone ring (the following formulas [4]), morpholine ring (the following formulas [5 ]), - NH-C ( O) -Si (CH 3) 3, -N (H) 2-g (Si (H) h R 3 3-h) g (R 3 , a part or all of the hydrogen A monovalent hydrocarbon group having 1 to 18 carbon atoms in which the element may be replaced by a fluorine element, g is 1 or 2, and h is 0 to 2 Number), and the like. In such a silicon compound A, X, which is a reactive site, reacts quickly with silanol groups, which are reaction sites on the surface of the concave / convex pattern of the silicon wafer, and the silicon compound A reacts with the Si element of the silicon wafer via a siloxane bond. By bonding them together, the wafer surface can be covered with the hydrophobic R ¹ group, so that the capillary force on the concave surface of the wafer can be reduced in a short time.

  Moreover, it is more preferable that the number of X of the silicon compound A represented by 4-ab in the general formula [1] is 1 because the protective film can be formed uniformly.

R ¹ in the general formula [1] is independently of each other C _m H _{2m + 1} (m = 1 to 18) and C _n F _{2n + 1} CH ₂ CH ₂ (n = 1 to 8). When the protective film is formed on the surface of the concavo-convex pattern, at least one group selected from is more preferable because the wettability of the surface can be further reduced, that is, excellent water repellency can be imparted to the surface. Moreover, it is more preferable that m and n are 1 to 8 because a protective film can be formed on the surface of the concavo-convex pattern in a short time.

Examples of the silicon compound A represented by the general formula [1] include CH ₃ Si (NH ₂ ) ₃ , C ₂ H ₅ Si (NH ₂ ) ₃ , C ₃ H ₇ Si (NH ₂ ) ₃ , C ₄ H ₉ Si (NH ₂ ) ₃ , C ₅ H ₁₁ Si (NH ₂ ) ₃ , C ₆ H ₁₃ Si (NH ₂ ) ₃ , C ₇ H ₁₅ Si (NH ₂ ) ₃ , C ₈ H ₁₇ Si (NH ₂ ) ₃ , C ₉ H ₁₉ Si (NH ₂ ) ₃ , C ₁₀ H ₂₁ Si (NH ₂ ) ₃ , C ₁₁ H ₂₃ Si (NH ₂ ) ₃ , C ₁₂ H ₂₅ Si (NH ₂ ) ₃ , C _{13 H 27 Si (NH 2) 3} , C 14 H 29 Si (NH 2) 3, C 15 H 31 Si (NH 2) 3, C 16 H 33 Si (NH 2) 3, C 17 H 35 Si (NH 2 ) ₃ , C ₁₈ H ₃₇ Si (NH ₂ ) ₃ , (CH ₃ ) ₂ Si (NH ₂ ) ₂ , C ₂ H ₅ Si (CH ₃ ) (NH ₂ ) ₂ , (C ₂ H ₅ ) ₂ Si ( NH ₂ ) ₂ , C ₃ H ₇ Si (CH ₃ ) (NH ₂ ) ₂ , (C ₃ H ₇ ) ₂ Si (NH ₂ ) ₂ , C ₄ H ₉ Si (CH ₃ ) (NH ₂ ) ₂ , (C ₄ H ₉ ) ₂ Si (NH ₂ ) ₂ , C ₅ H ₁₁ Si (CH ₃ ) (NH ₂ ) ₂ , C ₆ H ₁₃ Si (CH ₃ ) (NH ₂ ) ₂ , C ₇ H ₁₅ Si (CH ₃ ) (NH ₂ ) ₂ , C ₈ H ₁₇ Si (CH ₃ ) (NH ₂ ) ₂ , C ₉ H ₁₉ Si (CH ₃ ) (NH ₂ ) ₂ , C ₁₀ H ₂₁ Si (CH ₃ ) (NH ₂ ) ₂ , C ₁₁ H ₂₃ Si (CH ₃ ) (NH ₂ ) _{2 , C 12 H 25 Si (CH} 3) (NH 2) 2, C 13 H 27 Si (CH 3) (NH 2) 2, C 14 H 29 Si (CH 3) (NH 2) 2, C 15 H 31 Si (CH ₃ ) (NH ₂ ) ₂ , C ₁₆ H ₃₃ Si (CH ₃ ) (NH ₂ ) ₂ , C ₁₇ H ₃₅ Si (CH ₃ ) (NH ₂ ) ₂ , C ₁₈ H ₃₇ Si (CH ₃ ) _{(NH 2) 2, (CH} 3) 3 SiNH 2, C 2 H 5 Si (C _{3) 2 NH 2, (C} 2 H 5) 2 Si (CH 3) NH 2, (C 2 H 5) 3 SiNH 2, C 3 H 7 Si (CH 3) 2 NH 2, (C 3 H 7) ₂ Si (CH ₃ ) NH ₂ , (C ₃ H ₇ ) ₃ SiNH ₂ , C ₄ H ₉ Si (CH ₃ ) ₂ NH ₂ , (C ₄ H ₉ ) ₃ SiNH ₂ , C ₅ H ₁₁ Si (CH ₃ ) ₂ NH ₂ , C ₆ H ₁₃ Si (CH ₃ ) ₂ NH ₂ , C ₇ H ₁₅ Si (CH ₃ ) ₂ NH ₂ , C ₈ H ₁₇ Si (CH ₃ ) ₂ NH ₂ , C ₉ H ₁₉ Si ( CH ₃ ) ₂ NH ₂ , C ₁₀ H ₂₁ Si (CH ₃ ) ₂ NH ₂ , C ₁₁ H ₂₃ Si (CH ₃ ) ₂ NH ₂ , C ₁₂ H ₂₅ Si (CH ₃ ) ₂ NH ₂ , C ₁₃ H ₂₇ Si (CH ₃ ) ₂ NH ₂ , C ₁₄ H ₂₉ Si (CH ₃ ) ₂ NH ₂ , C ₁₅ H ₃₁ Si (CH ₃ ) ₂ NH ₂ , C ₁₆ H ₃₃ Si (CH ₃ ) ₂ NH ₂ , C ₁₇ H ₃₅ Si (CH ₃ ) ₂ NH ₂ , C ₁₈ H ₃₇ Si (CH ₃ ) ₂ NH ₂ , (CH ₃ ) ₂ Si (H) NH ₂ , CH ₃ Si (H) ₂ NH ₂ , (C ₂ H ₅ ) ₂ Si (H) NH ₂ , C ₂ H ₅ Si (H) ₂ NH ₂ , C ₂ H ₅ Si (CH ₃ ) (H) NH ₂ , (C ₃ H ₇ ) ₂ Si (H) NH ₂ , C ₃ H ₇ Si (H) ₂ NH ₂ , CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si (NH ₂ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si (NH ₂ ) ₃ , CF ₃ CH ₂ CH ₂ Si (CH ₃ ) (NH ₂ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si (CH ₃ ) (NH ₂ ) ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si (CH _{3) (NH 2) 2,} C 4 F 9 CH 2 CH 2 Si (CH 3) (NH 2) 2, C 5 F 11 CH 2 CH 2 Si (CH 3) (NH 2) 2, C 6 F 13 _{CH 2 CH 2 Si (CH 3} ) (NH 2) 2, C 7 F 15 CH 2 CH 2 Si (CH 3) (NH 2) 2, C 8 F 17 CH 2 CH 2 Si (CH 3) (NH 2 _{) 2, CF 3 CH 2 CH} 2 Si (CH 3) 2 NH 2, C 2 F 5 CH 2 CH 2 Si (CH 3) 2 NH 2, C 3 F 7 CH 2 CH 2 Si (CH 3) 2 NH ₂ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) ₂ NH ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si (CH ₃ ) ₂ NH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si (CH ₃ ) _{2 NH 2, C 7 F 15 CH} 2 CH 2 Si (CH 3) 2 NH 2, C 8 F 17 CH 2 CH 2 Si (CH 3) 2 NH 2, CF 3 CH 2 CH 2 Si (CH 3) (H ) Amino such as NH ₂ Silane or the amino group (—NH ₂ group) of the aminosilane is represented by —N═C═O, —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —N═C═S, — _{N 3, -NHC (O) CH} 3, -N (CH 3) C (O) CH 3, -N (CH 3) C (O) CF 3, -N = C (CH 3) OSi (CH 3) ₃ , —N═C (CF ₃ ) OSi (CH ₃ ) ₃ , —NHC (O) —OSi (CH ₃ ) ₃ , —NHC (O) —NH—Si (CH ₃ ) ₃ , imidazole ring, oxazolidinone ring , morpholine ring, -NH-C (O) -Si (CH 3) 3, -N (H) 2-g (Si (H) h R 3 3-h) g (R 3 are, of some or all And a monovalent hydrocarbon group having 1 to 18 carbon atoms in which hydrogen element may be replaced by fluorine element, g is 1 or 2, and h is an integer of 0 to 2). .

Among these, X of the silicon compound A of the formula [1] is —N (CH ₃ ) ₂ , —NH ₂ , —N (C ₂ H ₅ ) ₂ , —N (CH ₃ ) C (O) CH _3. , —N (CH ₃ ) C (O) CF ₃ , —NHC (O) —NH—Si (CH ₃ ) ₃ , imidazole ring, —N═C═O, —NH—C (O) —Si (CH _{3) 3, -N (H)} 2-i (Si (H) j R 4 3-j) i (R 4 , a part or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element A monovalent hydrocarbon group of 1 to 8, i is 1 or 2, and j is an integer of 0 to 2).

  In the chemical solution, the concentration of acid A is preferably 0.01 to 50% by mass with respect to 100% by mass of the total amount of silicon compound A. If the addition amount is small, the effect of the acid is lowered, which is not preferable. Even if the amount is excessively large, the effect of the acid as a catalyst is not improved. is there. For this reason, the concentration of the acid A is particularly preferably 0.05 to 25% by mass with respect to 100% by mass of the total amount of the silicon compound A.

  In the chemical solution, the silicon compound A and the acid A may be diluted with a solvent. When the total amount of silicon compound A and acid A added is 0.01 to 100% by mass with respect to 100% by mass of the total amount of the chemical solution, it is easy to form a protective film uniformly on at least the concave surface of the irregular pattern. Therefore, it is preferable. If it is less than 0.01% by mass, the protective effect of the uneven pattern tends to be insufficient. In addition, if the total amount of silicon compound A and acid A added is large, the cost increases. Further, the silicon compound A and the acid A may come into contact with a protic solvent such as water or alcohol, or the silicon compound A and the acid A may react as a by-product, which is generated when the sum is large. The amount of solid matter to be increased also increases. In many cases, the solid matter can be dissolved in the chemical solution, but the risk of remaining on the wafer as particles after drying increases, so that the chemical solution becomes difficult to handle. From such a viewpoint, the total is more preferably 0.05 to 50% by mass, and more preferably 0.1 to 30% by mass. Further, if the total amount of silicon compound A and acid A added is large, the storage stability of the chemical solution is easily increased. For this reason, 0.5-30 mass%, Furthermore, 1-30 mass% is preferable.

  Examples of the solvent that may be used for dilution in the chemical solution include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohol derivatives, and nitrogen element-containing solvents. An organic solvent such as a solvent is preferably used. Of these, hydrocarbons, esters, ethers, halogen element-containing solvents, sulfoxide solvents, polyhydric alcohol derivatives having no OH group can be used to form a protective film on the surface of the concavo-convex pattern in a short time. Since it can form, it is more preferable.

Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether. Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexane non, isophorone, and the like. There are, as examples of the halogen-containing solvent, perfluorooctane, perfluoro nonane, perfluoro cyclopentane, perfluorocyclohexane, perfluorocarbons such as hexafluorobenzene, 1, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora H (manufactured by Nippon Zeon), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl Hydrofluoroethers such as perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all from 3M), tetrachloromethane, etc. Chlorocarbons, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3 3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3 There are hydrochlorofluorocarbons such as 3-trifluoropropene, perfluoroethers, perfluoropolyethers, etc. Examples of the sulfoxide solvents include dimethyl sulfoxide, which is a derivative of the polyhydric alcohol and has no OH group. Examples of such materials include diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, polyethylene Glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, and the like ethylene glycol dimethyl ether.

  Further, it is preferable to use a nonflammable organic solvent because the chemical liquid for forming the protective film becomes nonflammable, or the flash point becomes high and the risk of the chemical liquid decreases. Many halogen element-containing solvents are nonflammable, and the nonflammable halogen element-containing solvent can be suitably used as a nonflammable organic solvent.

  In addition, when the chemical solution is supplied to the wafer while rotating the wafer, if the boiling point of the organic solvent is too low, the chemical solution is liable to dry before the chemical solution wets and spreads over the entire surface of the wafer. Moreover, when the boiling point is too high, the viscosity of the chemical solution tends to be too high, which is not preferable. For this reason, it is preferable to use the organic solvent having a boiling point of 70 to 220 ° C. As such a solvent, in consideration of cost and solubility with other cleaning liquids (ease of replacement), diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, and ethylene glycol dimethyl ether are preferred.

  Moreover, it is preferable that the total amount of water in the starting material of the chemical solution for forming a protective film is 5000 ppm by mass or less with respect to the total amount of the material. When the total amount of moisture exceeds 5000 mass ppm, the effects of the silicon compound A and acid A represented by the general formula [1] are reduced, and it is difficult to form the protective film in a short time. For this reason, the total amount of the water content is preferably as small as possible, particularly 1000 ppm by mass or less, and more preferably 500 ppm by mass or less. Therefore, it is preferable that the silicon compound A and acid A contained in the chemical solution and the solvent that may be contained in the chemical solution do not contain much water.

  Moreover, it is preferable that the number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical solution is 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 μm exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 μm is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. For this reason, the number of particles larger than 0.5 μm in the chemical solution per 1 mL of the chemical solution is preferably as small as possible, particularly 10 or less, and more preferably 2 or less. The number of particles larger than 0.5 μm may be 1 or more per 1 mL of the chemical solution.

  Moreover, it is preferable that the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical solution. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may be increased, which causes a decrease in device yield and reliability. Moreover, it is preferable that the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. For this reason, the content of the metal impurities is preferably as small as possible, and particularly preferably 1 mass ppb or less, and further preferably 0.1 mass ppb or less. Moreover, 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical | medical solution total amount.

  In the method for preparing a chemical solution for forming a protective film in which the silicon compound A represented by the general formula [1] and the acid A are mixed and contained, the silicon compound A before mixing, the acid A, and the mixed solution after mixing It is preferable to purify at least one of them. When the protective film-forming chemical solution contains a solvent, the silicon compound A and the acid A before mixing may be in a solution state containing a solvent. In this case, the purification is performed before the silicon before mixing. The target may be at least one of compound A or a solution thereof, acid A or a solution thereof, and a mixed solution after mixing.

  The purification includes removal of moisture by adsorbents such as molecular sieves and distillation, removal of metal impurities of each element of Na, Mg, K, Ca, Mn, Fe and Cu by ion exchange resin or distillation, and filter. This is performed using at least one removing means among removing contaminants such as particles by filtration. In consideration of the reactivity of the chemical solution for forming the protective film and the cleanliness of the wafer, it is preferable to remove moisture, remove metal impurities, and remove contaminants, and the removal order is not limited.

（式［２］中、Ｒ² _c（Ｈ）_dＳｉ−は、（ＣＨ₃）₃Ｓｉ−、（ＣＨ₃）₂（Ｈ）Ｓｉ−、（Ｃ₄Ｈ₉）（ＣＨ₃）₂Ｓｉ−、（Ｃ₆Ｈ₁₃）（ＣＨ₃）₂Ｓｉ−、（Ｃ₈Ｈ₁₇）（ＣＨ₃）₂Ｓｉ−、または、（Ｃ₁₀Ｈ₂₁）（ＣＨ₃）₂Ｓｉ−である。また、Ｙは、それぞれ互いに独立して、Ｓｉ元素と結合する元素が窒素の１価の有機基を示す。）The acid A contained in the protective film-forming chemical solution of the present invention may be obtained by a reaction. For example, it may be obtained by reacting the silicon compound B represented by the following general formula [2] with the acid B.

(Wherein _{^{[2], R 2 c (}} H) d Si- _{is, (CH 3) 3 Si -} , (CH 3) 2 (H) Si -, (C 4 H 9) (CH 3) 2 Si- , (C ₆ H ₁₃ ) (CH ₃ ) ₂ Si—, (C ₈ H ₁₇ ) (CH ₃ ) ₂ Si—, or (C ₁₀ H ₂₁ ) (CH ₃ ) ₂ Si—. Each independently represents a monovalent organic group in which the element bonded to the Si element is nitrogen.)

  In addition, the chemical | medical solution prepared by making it react with the said silicon compound B and using the at least 1 chosen from the trifluoroacetic anhydride and the trifluoromethanesulfonic anhydride for the acid B, or the said silicon compound A And a chemical prepared using acid A as a starting material are more preferable because of their excellent stability.

  In the chemical solution for forming a protective film of the present invention, the silicon compound B is excessively added to the acid B, and the surplus of the silicon compound B not consumed in the reaction contributes to the formation of the protective film as the silicon compound A. It may be a thing. The silicon compound B is preferably 0.2 to 100000 mol times, preferably 0.5 to 50000 mol times, and more preferably 1 to 10000 mol times with respect to the acid B. .

  In addition, as long as the acid A is obtained, reactions other than the reaction of the silicon compound B and the acid B may be used.

The monovalent organic group in which the element bonded to the Si element as Y of the silicon compound B of the general formula [2] is nitrogen includes not only hydrogen, carbon, nitrogen, and oxygen elements but also silicon, sulfur, halogen elements, and the like May be included. Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include isocyanate group, amino group, dialkylamino group, isothiocyanate group, azide group, acetamide group, —N (CH ₃ ) C (O) CH _{3, -N (CH 3) C} (O) CF 3, -N = C (CH 3) OSi (CH 3) 3, -N = C (CF 3) OSi (CH 3) 3, -NHC (O) _{-OSi (CH 3) 3, -NHC} (O) -NH-Si (CH 3) 3, an imidazole ring, an oxazolidinone ring, morpholine ring, -NH-C (O) -Si (CH 3) 3, -N ( H) _2-p (Si (H) _q R ⁵ _3-q ) _p (R ⁵ is a monovalent valence having 1 to 18 carbon atoms in which some or all of the hydrogen elements may be replaced by fluorine elements. Hydrocarbon group, p is 1 or 2, and q is an integer of 0 to 2.

Examples of the silicon compound B of the formula [2] include (CH ₃ ) ₃ SiNH ₂ , C ₄ H ₉ Si (CH ₃ ) ₂ NH ₂ , C ₆ H ₁₃ Si (CH ₃ ) ₂ NH ₂ , C _8. H ₁₇ Si (CH ₃ ) ₂ NH ₂ , C ₁₀ H ₂₁ Si (CH ₃ ) ₂ NH ₂ , (CH ₃ ) ₂ Si (H) NH ₂ aminosilane or the aminosilane amino group (—NH ₂ group) ) and, -N = C = O, -N (CH 3) 2, -N (C 2 H 5) 2, -N = C = S, -N 3, -NHC (O) CH 3, -N ( _{CH 3) C (O) CH} 3, -N (CH 3) C (O) CF 3, -N = C (CH 3) OSi (CH 3) 3, -N = C (CF 3) OSi (CH 3 _{) 3, -NHC (O) -OSi} (CH 3) 3, -NHC (O) -NH-Si (CH 3) 3, an imidazole ring, an oxazolidinone ring, morpholine ring, -NH-C _{O) -Si (CH 3) 3} , -NH-Si (CH 3) 3, -NH-Si (H) (CH 3) 2, -NH-Si (CH 3) 2 (C 4 H 9), - NH—Si (CH ₃ ) ₂ (C ₆ H ₁₃ ), —NH—Si (CH ₃ ) ₂ (C ₈ H ₁₇ ), —NH—Si (CH ₃ ) ₂ (C ₁₀ H ₂₁ ), —N— And the like replaced with {Si (CH ₃ ) ₃ } ₂ .

Among these, Y of the silicon compound B of the formula [2] represents —N (CH ₃ ) ₂ , —NH ₂ , —N (C ₂ H ₅ ) ₂ , —N (CH ₃ ) C (O) CH _3. , —N (CH ₃ ) C (O) CF ₃ , —NHC (O) —NH—Si (CH ₃ ) ₃ , imidazole ring, —NH—C (O) —Si (CH ₃ ) ₃ , —NH— _{Si (CH 3) 3, -NH} -Si (H) (CH 3) 2, -NH-Si (CH 3) 2 (C 4 H 9), - NH-Si (CH 3) 2 (C 6 H 13 ), —NH—Si (CH ₃ ) ₂ (C ₈ H ₁₇ ), —NH—Si (CH ₃ ) ₂ (C ₁₀ H ₂₁ ) are preferred.

  For example, when hexamethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately to obtain trimethylsilyl trifluoroacetate as the acid A.

  For example, when hexamethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride immediately reacts to obtain trimethylsilyl trifluoromethanesulfonate as the acid A. .

  For example, when tetramethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately to obtain dimethylsilyl trifluoroacetate as the acid A.

  For example, when tetramethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately to obtain dimethylsilyl trifluoromethanesulfonate as the acid A. It is done.

  In addition, for example, when 1,3-dibutyltetramethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately and butyldimethylsilyl trimethyl as the acid A is reacted. Fluoroacetate is obtained.

  Further, for example, when 1,3-dibutyltetramethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately and butyldimethyl as the acid A is reacted. Silyl trifluoromethanesulfonate is obtained.

  In addition, for example, when 1,3-dihexyltetramethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately and hexyldimethylsilyltrimethyl as the acid A is reacted. Fluoroacetate is obtained.

  Further, for example, when 1,3-dihexyltetramethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately to form hexyldimethyl as the acid A. Silyl trifluoromethanesulfonate is obtained.

  Further, for example, when 1,3-dioctyltetramethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately and octyldimethylsilyltrimethyl as the acid A is reacted. Fluoroacetate is obtained.

  Further, for example, when 1,3-dioctyltetramethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately and octyldimethyl as the acid A is reacted. Silyl trifluoromethanesulfonate is obtained.

  Further, for example, when octyldimethyl (dimethylamino) silane as the silicon compound B and trifluoroacetic anhydride as the acid B are mixed, the trifluoroacetic anhydride reacts immediately and octyldimethylsilyl trifluoroacetate as the acid A Is obtained.

  Further, for example, when octyldimethyl (dimethylamino) silane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately, and octyldimethylsilyltrifluoromethane as the acid A is reacted. Lomethanesulfonate is obtained.

  Further, for example, when 1,3-didecyltetramethyldisilazane is mixed as the silicon compound B and trifluoroacetic anhydride is mixed as the acid B, the trifluoroacetic anhydride reacts immediately to form decyldimethylsilyl as the acid A. Trifluoroacetate is obtained.

  Further, for example, when 1,3-didecyltetramethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride reacts immediately and decyl as the acid A Dimethylsilyl trifluoromethanesulfonate is obtained.

  Moreover, also when obtaining acid A by reaction as mentioned above, it is preferable that the total amount of the water content in the starting raw material of the chemical | medical solution for protective film formation is 5000 mass ppm or less with respect to the total amount of this raw material. Also in this case, the amount of water in the raw material is preferably as small as possible, particularly preferably 1000 ppm by mass or less, and more preferably 500 ppm by mass or less. Furthermore, since the storage stability of the said chemical | medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable. The total amount of water in the raw material may be 0.1 mass ppm or more.

  In addition, even when the acid A is obtained by reaction as described above, the number of particles larger than 0.5 μm in the particle measurement by the light scattering liquid particle detector in the liquid phase in the protective film forming chemical solution is The number is preferably 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 μm exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 μm is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. For this reason, the number of particles larger than 0.5 μm in the chemical solution per 1 mL of the chemical solution is preferably as small as possible, particularly 10 or less, and more preferably 2 or less. The number of particles larger than 0.5 μm may be 1 or more per 1 mL of the chemical solution.

  Further, even when the acid A is obtained by reaction as described above, the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the protective film forming chemical solution is the total amount of the chemical solution. It is preferable that each is 100 mass ppb or less. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may be increased, which causes a decrease in device yield and reliability, which is not preferable. . Moreover, it is preferable that the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. For this reason, the content of the metal impurities is preferably as small as possible, and particularly preferably 1 mass ppb or less, and further preferably 0.1 mass ppb or less. Moreover, 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical | medical solution total amount.

  In the method for preparing a chemical solution for forming a protective film in which the silicon compound B and the acid B are mixed and reacted to be contained, at least one of the silicon compound B before mixing, the acid B, and the mixed solution after mixing Is preferably purified. When the protective film forming chemical solution contains a solvent, the silicon compound B and the acid B before mixing may be in a solution state containing a solvent. In this case, the purification is performed before mixing. The target may be at least one of silicon compound B or a solution thereof, acid B or a solution thereof, and a mixed solution after mixing. Moreover, when preparing the chemical | medical solution for protective film formation by mixing the said silicon compound A or its solution with the acid A obtained by the said reaction, the silicon compound A before mixing or its solution, the acid A obtained by reaction Alternatively, the target solution may be at least one of the solution and the mixed solution after mixing.

  The purification includes removal of moisture by adsorbents such as molecular sieves and distillation, removal of metal impurities of each element of Na, Mg, K, Ca, Mn, Fe and Cu by ion exchange resin or distillation, and filter. This is performed using at least one removing means among removing contaminants such as particles by filtration. In consideration of the activity and cleanliness of the chemical solution for forming the protective film, it is preferable to remove moisture, remove metal impurities, and remove contaminants, and the removal order is not limited.

  The protective film-forming chemical solution of the present invention includes, in addition to the silicon compound A, acid A, and solvent represented by the general formula [1], other additives and the like as long as the object of the present invention is not impaired. It may contain. Examples of the additive include oxidizing agents such as hydrogen peroxide and ozone, and surfactants. In addition, when there is a material that cannot form a protective film with the silicon compound A in a part of the uneven pattern of the wafer, a material that can form a protective film may be added to the material. Further, other acids may be added for purposes other than the catalyst.

  Moreover, the chemical | medical solution for protective film formation of this invention can be stored in the state which divided the raw material into two or more, and can also be mixed and used before use. For example, when silicon compound A and acid A are used as a part of the raw material of the protective film forming chemical solution, silicon compound A and acid A can be stored separately and mixed before use. When using the silicon compound B and the acid B, the silicon compound B and the acid B can be stored separately and mixed before use. The silicon compound and the acid before mixing may be in a solution state. In addition, the above silicon compound and acid can be stored in the same solution and mixed with another raw material before use.

  The protective film-forming chemical solution of the present invention includes, for example, hydrofluoroether, hydrochlorofluorocarbon, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether. At least one organic solvent selected from the group consisting of 76-99.8999 mass%, hexamethyldisilazane, tetramethyldisilazane, 1,3-dioctyltetramethyldisilazane, octyldimethyl (dimethylamino) silane 0.1 to 20% by mass of at least one compound selected from the group, trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethane A mixture comprising at least one acid selected from the group consisting of sulfonic acid, anhydrous trifluoromethanesulfonic acid, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, and dimethylsilyl trifluoroacetate, comprising 0.0001 to 4% by mass. You may use what consists only of the thing or the said mixture.

  In the pattern forming process in which the wafer surface is a surface having a fine concavo-convex pattern, first, after applying a resist to the wafer surface, the resist is exposed through a resist mask, and the exposed resist is not exposed. A resist having a desired concavo-convex pattern is produced by etching away the resist. Moreover, the resist which has an uneven | corrugated pattern can be obtained also by pressing the mold which has a pattern to a resist. Next, the wafer is etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is removed, a wafer having a fine uneven pattern is obtained.

  As a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element, a wafer containing a film containing silicon element such as silicon, silicon oxide, or silicon nitride, or When the concavo-convex pattern is formed, those in which at least a part of the surface of the concavo-convex pattern contains a silicon element such as silicon, silicon oxide, or silicon nitride are included.

  In addition, a wafer composed of a plurality of components including at least one selected from silicon, silicon oxide, and silicon nitride is also protected on at least one surface selected from silicon, silicon oxide, and silicon nitride. A film can be formed. As the wafer composed of the plurality of components, at least one selected from silicon, silicon oxide, and silicon nitride is formed on the wafer surface, or when a concavo-convex pattern is formed, at least one of the concavo-convex pattern is formed. A part whose part is at least one selected from silicon, silicon oxide, and silicon nitride is also included. In addition, it is the surface of the part containing the silicon element in the said uneven | corrugated pattern that can form a protective film with the chemical | medical solution of this invention.

  After making the wafer surface a surface having a fine uneven pattern, cleaning the surface with an aqueous cleaning liquid and removing the aqueous cleaning liquid by drying or the like, the pattern collapses when the width of the concave portion is small and the aspect ratio of the convex portion is large. Is likely to occur. The concavo-convex pattern is defined as shown in FIGS. FIG. 1 is a schematic plan view of a wafer 1 whose surface is a surface having a fine concavo-convex pattern 2, and FIG. 2 shows a part of an a-a ′ cross section in FIG. 1. As shown in FIG. 2, the width 5 of the concave portion is indicated by the interval between the convex portion 3 and the convex portion 3, and the aspect ratio of the convex portion is expressed by dividing the height 6 of the convex portion by the width 7 of the convex portion. Is done. Pattern collapse in the cleaning process tends to occur when the width of the recess is 70 nm or less, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more.

  In a preferred embodiment of the present invention, as described in the above (Step 1), after making the wafer surface a surface having a fine concavo-convex pattern, an aqueous cleaning solution is applied to the surface, and the aqueous cleaning solution is applied to at least the concave surface of the concavo-convex pattern. Hold. Then, as described in the above (Step 2), the aqueous cleaning liquid held on at least the concave surface of the concavo-convex pattern is replaced with a cleaning liquid A different from the aqueous cleaning liquid. Preferred examples of the cleaning liquid A include at least one of a chemical solution for forming a protective film specified in the present invention, water, an organic solvent, or a mixture thereof, or an acid, an alkali, a surfactant, and an oxidizing agent. Are mixed. Further, when a liquid other than the chemical liquid is used as the cleaning liquid A, it is preferable to replace the cleaning liquid A with the protective film-forming chemical liquid in a state where the cleaning liquid A is held on at least the concave surface of the concavo-convex pattern.

  Examples of the organic solvent that is one of the preferred examples of the cleaning liquid A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, and polyhydric alcohol derivatives. And nitrogen element-containing solvents.

  Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether. Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, and the like. Examples of the halogen element-containing solvent include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, and the like. Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluoro Hydrofluoroethers such as fluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all from 3M), chloro such as tetrachloromethane Carbon, hydrochlorocarbon such as chloroform, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3 -Pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3 -Hydrochlorofluorocarbons such as trifluoropropene, perfluoroethers, perfluoropolyethers, etc., examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of alcohols include methanol, ethanol, propanol, Examples of the derivatives of the polyhydric alcohol include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl, and the like. Ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. Examples of the medium include formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, triethylamine, pyridine and the like.

  Examples of acids that can be mixed with the cleaning liquid A include inorganic acids and organic acids. Examples of inorganic acids include hydrofluoric acid, buffered hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc. Examples of organic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid , Acetic acid, trifluoroacetic acid, pentafluoropropionic acid and the like. Examples of the alkali that may be mixed in the cleaning liquid A include ammonia and choline. Examples of the oxidizing agent that may be mixed with the cleaning liquid A include ozone and hydrogen peroxide.

  In addition, it is preferable that the cleaning liquid A is an organic solvent because the chemical liquid for forming a protective film can be provided to the recess without being brought into contact with water. Among these, it is preferable that the organic solvent contains a water-soluble organic solvent (a solubility of 5 parts by mass or more with respect to 100 parts by mass of water) because the cleaning liquid A can be easily replaced from the aqueous cleaning liquid. Further, it is preferable that the cleaning liquid A contains an acid aqueous solution because the protective film can be formed in a short time.

  A plurality of cleaning liquids may be used as the cleaning liquid A. For example, a cleaning solution containing an acid aqueous solution or an alkaline aqueous solution and the organic solvent (preferably containing a water-soluble organic solvent) are used as the cleaning solution A, and the cleaning is performed in the order of the cleaning solution containing the acid aqueous solution or the alkaline aqueous solution → the organic solvent. be able to. Further, an aqueous cleaning solution may be further added, and cleaning may be performed in the order of a cleaning solution containing an aqueous acid solution or an aqueous alkaline solution → an aqueous cleaning solution → the organic solvent.

  FIG. 3 is a schematic view showing a state in which the recess 4 holds the protective film forming chemical 8 in the cleaning process. The wafer in the schematic diagram of FIG. 3 shows a part of the a-a ′ cross section of FIG. 1. In the cleaning process, the protective film forming chemical is supplied to the wafer 1 on which the concave / convex pattern 2 is formed. At this time, the chemical solution is held in the recess 4 as shown in FIG. 3, and a protective film is formed on the surface of the recess 4 to make the surface water repellent.

  When the temperature of the protective film-forming chemical is increased, the protective film can be easily formed in a shorter time. The temperature at which a homogeneous protective film is easily formed is preferably 10 ° C. or higher and lower than the boiling point of the chemical solution, and more preferably 15 ° C. or higher and lower than 10 ° C. lower than the boiling point of the chemical solution. The temperature of the chemical solution is preferably maintained at the temperature even when held on at least the concave surface of the concave / convex pattern.

  Other cleaning liquids may also be held at a temperature of 10 ° C. or higher and lower than the boiling point of the cleaning liquid. For example, when the cleaning liquid A contains an acid aqueous solution, particularly preferably a solution containing an acid aqueous solution and an organic solvent having a boiling point of 100 ° C. or higher, the protective film can be shortened for a short time if the temperature of the cleaning liquid is raised near the boiling point of the cleaning liquid It is preferable because it is easy to form.

  After the step (Step 3) of holding the protective film-forming chemical solution on at least the concave surface of the concave / convex pattern, after replacing the chemical solution held on at least the concave surface of the concave / convex pattern with a cleaning liquid B different from the chemical solution The step of removing the liquid from the surface of the concavo-convex pattern by drying (step 4) may be performed. Examples of the cleaning liquid B include an aqueous cleaning liquid composed of an aqueous solution, an organic solvent, or the aqueous cleaning liquid and the organic solvent. A mixture of at least one of acid, alkali, and surfactant, or silicon compound A and acid A contained in the chemical solution for forming a protective film, and the acid A at a lower concentration than the chemical solution. And so on.

  Examples of the organic solvent that is one of the preferred examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, and derivatives of polyhydric alcohols. And nitrogen element-containing solvents.

  Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether. Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, and the like. Examples of the halogen element-containing solvent include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, and the like. Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluoro Hydrofluoroethers such as fluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all from 3M), chloro such as tetrachloromethane Carbon, hydrochlorocarbon such as chloroform, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3 -Pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3 -Hydrochlorofluorocarbons such as trifluoropropene, perfluoroethers, perfluoropolyethers, etc., examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of alcohols include methanol, ethanol, propanol, Examples of the derivatives of the polyhydric alcohol include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl, and the like. Ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. Examples of the medium include formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, triethylamine, pyridine and the like.

  In addition, after the replacement with the cleaning liquid B, an aqueous cleaning liquid composed of an aqueous solution is held on at least the concave surface of the concave / convex pattern, and then the process may be shifted to a step of removing the liquid from the concave / convex pattern surface by drying (step 4). .

  A plurality of cleaning liquids may be used as the cleaning liquid B. For example, an organic solvent (preferably containing a water-soluble organic solvent) and an aqueous cleaning solution can be used.

  Examples of the aqueous cleaning liquid include water or water mainly containing water mixed with at least one organic solvent, acid or alkali in water (for example, the water content is 50% by mass or more). It is done. In particular, when water is used as the aqueous cleaning liquid, the contact angle θ with the liquid on at least the concave surface of the concave / convex pattern made water repellent by the chemical solution increases, and the capillary force P on the concave surface decreases, and further after drying. This is preferable because dirt on the wafer surface is less likely to remain.

  FIG. 4 shows a schematic diagram when the aqueous cleaning liquid is held in the recess 4 made water repellent by the protective film forming chemical. The wafer in the schematic diagram of FIG. 4 shows a part of the a-a ′ cross section of FIG. 1. The surface of the concavo-convex pattern is water repellent by forming a protective film 10 with the chemical solution. The protective film 10 is held on the wafer surface even when the aqueous cleaning liquid 9 is removed from the uneven pattern surface.

When the protective film 10 is formed on at least the concave surface of the concave / convex pattern of the wafer with the chemical solution for forming the protective film, the contact angle is 70 to 110 ° when it is assumed that water is retained on the surface. It is preferable because it does not easily fall over. Further, the closer the contact angle is to 90 °, the smaller the capillary force on the surface of the recess and the more difficult the pattern collapse occurs, so 75 to 105 ° is more preferable. The capillary force is preferably 1.1 MN / m ² or less. A capillary force of 1.1 MN / m ² or less is preferable because pattern collapse hardly occurs. Further, when the capillary force is reduced, pattern collapse is less likely to occur. Therefore, the capillary force is more preferably 0.8 MN / m ² or less. Furthermore, it is ideal to adjust the contact angle with the cleaning liquid to around 90 ° so that the capillary force is as close as possible to 0.0 MN / m ² .

  Next, as described in the above (Step 4), a step of removing the liquid from the surface of the concavo-convex pattern by drying is performed. In this step, the liquid held on the uneven pattern surface is removed by drying. The drying is preferably performed by a known drying method such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, or vacuum drying.

  When the liquid is removed from the surface of the concavo-convex pattern, the liquid held on the surface may be the chemical liquid, the cleaning liquid B, the aqueous cleaning liquid, and a mixture thereof. The liquid mixture containing the chemical liquid may be a liquid in the middle of replacing the chemical liquid with the cleaning liquid B, or may be a liquid mixture obtained by previously mixing the chemical liquid with a cleaning liquid different from the chemical liquid. Further, after the liquid is once removed from the uneven pattern surface, the uneven pattern surface is held with at least one selected from the cleaning liquid B, the aqueous cleaning liquid, and a mixture thereof, and then dried. Also good.

  Next, as described in the above (Step 5), a step of removing the protective film 10 is performed. When removing the protective film, it is effective to cut the C—C bond and C—F bond in the protective film. The method is not particularly limited as long as it can cut the bond, for example, irradiating the wafer surface with light, heating the wafer, exposing the wafer to ozone, irradiating the wafer surface with plasma, For example, corona discharge on the wafer surface may be mentioned.

When the protective film 10 is removed by light irradiation, it is effective to cut the C—C bond and the C—F bond in the protective film 10, and for this purpose, their binding energy is 83 kcal / mol. It is preferable to irradiate ultraviolet rays including wavelengths shorter than 340 nm and 240 nm, which are energy corresponding to 116 kcal / mol. As this light source, a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an excimer lamp, a carbon arc, or the like is used. If the ultraviolet irradiation intensity is a metal halide lamp, for example, measurement with an illuminometer (irradiance intensity meter UM-10 manufactured by Konica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400 nm]) 100 mW / cm ² or more is preferable in value, 200 mW / cm ² or more is particularly preferable. When the irradiation intensity is less than 100 mW / cm ² , it takes a long time to remove the protective film 10. In addition, a low-pressure mercury lamp is preferable because ultraviolet rays having a shorter wavelength are irradiated, and thus the protective film 10 can be removed in a short time even if the irradiation intensity is low.

  Further, when the protective film 10 is removed by light irradiation, ozone is generated at the same time as the constituent components of the protective film 10 are decomposed by ultraviolet rays, and the constituent components of the protective film 10 are oxidized and volatilized by the ozone. Is particularly preferable. As this light source, a low-pressure mercury lamp or an excimer lamp is used. Further, the wafer may be heated while irradiating light.

  When the wafer is heated, the wafer is heated at 400 to 700 ° C, preferably 500 to 700 ° C. This heating time is preferably 0.5 to 60 minutes, preferably 1 to 30 minutes. In this process, ozone exposure, plasma irradiation, corona discharge, etc. may be used in combination. Further, light irradiation may be performed while heating the wafer.

  When the wafer is exposed to ozone, it is preferable that ozone generated by ultraviolet irradiation with a low-pressure mercury lamp or the like or low-temperature discharge with a high voltage is provided on the wafer surface. The wafer may be irradiated with light while being exposed to ozone, or may be heated.

  In the step of removing the protective film on the wafer surface, the protective film on the wafer surface can be efficiently removed by combining light irradiation treatment, heat treatment, ozone exposure treatment, plasma irradiation treatment, corona discharge treatment, and the like. it can.

  The chemical solution of the present invention may be a one-component type in which the silicon compound A and the acid A are mixed from the beginning, or used as a two-component type of a solution containing the silicon compound A and a solution containing the acid A. When mixing, you may mix. Moreover, it is good also as a 2 liquid type of the liquid containing the said silicon compound B, and the liquid containing the said acid B.

Making the surface of the wafer a surface having a fine concavo-convex pattern and replacing the cleaning liquid held on at least the concave surface of the concavo-convex pattern with other cleaning liquids have already been established through various studies in other literature. Therefore, in the present invention, the evaluation of the chemical solution for forming a protective film was mainly performed. In addition, the formula P = 2 × γ × cos θ / S described in the background of the invention
(Γ: surface tension, θ: contact angle, S: pattern dimension)
As can be seen from the above, the pattern collapse greatly depends on the contact angle of the cleaning liquid to the wafer surface, that is, the contact angle of the droplets and the surface tension of the cleaning liquid. In the case of the cleaning liquid held in the concave portion 4 of the concave-convex pattern 2, the contact angle of the droplet and the capillary force on the concave surface, which can be considered as equivalent to the pattern collapse, have a correlation. Capillary force may be derived from the evaluation of the contact angle of ten droplets. In the examples, water, which is a typical aqueous cleaning solution, was used as the cleaning solution.

  However, in the case of a wafer having a fine concavo-convex pattern on the surface, since the pattern is very fine, the contact angle of the protective film 10 formed on the concavo-convex pattern surface cannot be accurately evaluated.

  The contact angle of water droplets is evaluated by dropping several μl of water droplets on the sample (base material) surface as in JIS R 3257 “Test method for wettability of substrate glass surface”, and the angle between the water droplet and the substrate surface. It is made by measuring. However, in the case of a wafer having a pattern, the contact angle becomes very large. This is because a Wenzel effect and a Cassie effect occur, and the contact angle is affected by the surface shape (roughness) of the substrate, and the apparent contact angle of water droplets increases.

  Therefore, in the present invention, the chemical solution is applied to a wafer having a smooth surface, a protective film is formed on the wafer surface, and the protective film is formed on the surface of the wafer 1 on which the fine uneven pattern 2 is formed. Various evaluations were made considering the protective film 10. In the present invention, as a wafer having a smooth surface, a silicon wafer having a surface having a thermal oxide film layer, a silicon nitride layer or a silicon layer and having a smooth surface is used.

  Details are described below. In the following, a method for evaluating a wafer provided with a chemical solution for forming a protective film, preparation of the chemical solution for forming the protective film, and an evaluation result after providing the chemical solution for forming a protective film on the wafer are described.

[Evaluation method of wafer provided with chemical solution for forming protective film]
The following evaluations (1) to (4) were performed as methods for evaluating a wafer provided with a chemical solution for forming a protective film.

(1) Contact angle evaluation of the protective film formed on the wafer surface About 2 μl of pure water is placed on the surface of the wafer on which the protective film is formed, and the angle (contact angle) formed between the water droplet and the wafer surface is measured by a contact angle meter (Kyowa). It was measured by Interface Science: CA-X type).

(2) Evaluation of capillary force P was calculated using the following equation, and the capillary force (absolute value of P) was determined.

P = 2 × γ × cos θ / S
Here, γ is the surface tension, θ is the contact angle, and S is the pattern dimension.
In this example, as an example of the pattern shape, a line-and-space pattern wafer having a line width (recess width) corresponding to the pattern dimension of 45 nm was assumed. In the pattern with a line width of 45 nm, the pattern tends to collapse when the cleaning liquid when the gas-liquid interface passes through the wafer is water, and the pattern does not easily collapse when 2-propanol is used. When the pattern size is 45 nm and the wafer surface is silicon oxide, the capillary force is 0.98 MN / m ² when the cleaning liquid is 2-propanol (surface tension: 22 mN / m, contact angle with silicon oxide: 1 °). On the other hand, the capillary force is 3.2 MN / m ^{2 in} water (surface tension: 72 mN / m, contact angle with silicon oxide: 2.5 °) having the largest surface tension among liquids excluding mercury. Capillary force is preferably 1.1 MN / m ² or less, particularly preferably 0.8Mn / m ² or less.

(3) Removability of protective film The sample was irradiated with UV light from a metal halide lamp for 2 hours under the following conditions. A sample having a water droplet contact angle of 30 ° or less after irradiation was regarded as acceptable (denoted as “◯” in the table).
・ Lamp: M0155-L312 made by Eye Graphics
(Strength: 1.5 kW)
Illuminance: The measured value under the following conditions is 128 mW / cm ²
・ Measurement device: UV intensity meter (Konica Minolta Sensing, UM-10)
-Light receiving part: UM-360
(Receiving wavelength: 310 to 400 nm, peak wavelength: 365 nm)
・ Measurement mode: Irradiance measurement

(4) Evaluation of surface smoothness of wafer after removal of protective film Surface observation is performed with an atomic force electron microscope (Seiko Electronics: SPI3700, 2.5 μm square scan) to obtain centerline average surface roughness: Ra (nm). It was. Ra is a three-dimensional extension of the centerline average roughness defined in JIS B 0601 applied to the measurement surface. “The absolute value of the difference from the reference surface to the specified surface is averaged. The value was calculated by the following formula. If the Ra value of the wafer after removal of the protective film is 1 nm or less, the wafer surface is not eroded by cleaning, and the residue of the protective film is not present on the wafer surface. ).

ここで、Ｘ_L、Ｘ_R、Ｙ_B、Ｙ_Tは、それぞれ、Ｘ座標、Ｙ座標の測定範囲を示す。Ｓ₀は、測定面が理想的にフラットであるとした時の面積であり、（Ｘ_R−Ｘ_L）×（Ｙ_B−Ｙ_T）の値とした。また、Ｆ（Ｘ，Ｙ）は、測定点（Ｘ，Ｙ）における高さ、Ｚ₀は、測定面内の平均高さを表す。

Here, X _L , X _R , Y _B , and Y _T indicate measurement ranges of the X coordinate and the Y coordinate, respectively. S ₀ is an area when the measurement surface is ideally flat, and is a value of (X _R −X _L ) × (Y _B −Y _T ). F (X, Y) represents the height at the measurement point (X, Y), and Z ₀ represents the average height in the measurement plane.

[Example 1]
(1) Preparation of chemical solution for forming protective film Hexamethyldisilazane [(H3C) 3Si-NH-Si (CH3) 3] as silicon compound A; 1 g, trimethylsilyl trifluoroacetate [(CH3) 3Si-OC ( O) CF3]; 0.1 g and propylene glycol monomethyl ether acetate (PGMEA); 98.9 g as an organic solvent were mixed to obtain a chemical solution for forming a protective film. In addition, it confirmed that the total amount of the water | moisture content in the starting raw material of the said chemical | medical solution was 5000 mass ppm or less with respect to the total amount of this raw material. Moisture is removed from the chemical solution using molecular sieve 4A (made by Union Showa), then metal impurities are removed from the chemical solution using ion exchange resin (Nippon Pole's Ion Clean SL), and then filtered (Nippon Integris Optimizer) ) To remove particles from the chemical solution for purification. When the water content in the chemical solution after purification was measured with a Karl Fischer moisture meter (ADP-511, manufactured by Kyoto Electronics Co., Ltd.), the water content in the chemical solution after purification was 6 mass relative to the total amount of the chemical solution. ppm. Further, when the metal impurity content in the chemical solution after purification was measured by an inductively coupled plasma mass spectrometer (Yokogawa Analytical Systems, Agilent 7500cs type), Na, Mg, K, The metal impurity content of each element of Ca, Mn, Fe, and Cu is Na = 2 mass ppb, Mg = 0.04 mass ppb, K = 0.2 mass ppb, Ca = 1 mass with respect to the total amount of the chemical solution, respectively. It was ppb, Mn = 0.005 mass ppb, Fe = 0.08 mass ppb, Cu = 0.06 mass ppb. Further, when the number of particles larger than 0.5 μm in the particle measurement by the light scattering liquid particle detector in the liquid phase was measured with a light scattering liquid particle measuring device (Lion Co., Ltd., KS-42AF type), The number of particles larger than 0.5 μm was 2 per 1 mL of the drug solution. In addition, also in the examples after this example, the same purification was performed, the water content was 5000 ppm by mass or less with respect to the total amount of the chemical solution, and the metal of each element of Na, Mg, K, Ca, Mn, Fe and Cu Impurity content was 100 mass ppb or less with respect to the total amount of the chemical solution, and a chemical solution was confirmed that the number of particles larger than 0.5 μm was 100 or less per mL of the chemical solution.

(2) Cleaning of silicon wafer A silicon wafer with a smooth thermal oxide film (Si wafer having a 1 μm thick thermal oxide film layer on the surface) is immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes at room temperature, and then pure water For 1 minute and then immersed in 2-propanol (iPA) for 1 minute.

(3) Surface treatment of silicon wafer surface with chemical solution for forming protective film A silicon wafer was immersed in the chemical solution for forming a protective film prepared in “(1) Preparation of chemical solution for forming protective film” at 20 ° C. for 10 minutes. . Thereafter, the silicon wafer was immersed in iPA for 1 minute, and then immersed in pure water as an aqueous cleaning solution for 1 minute. Finally, the silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.

When the obtained wafer was evaluated in the manner described in “Method for evaluating wafer provided with protective film forming chemical solution”, as shown in Table 1, the initial contact angle before the surface treatment was less than 10 °. However, the contact angle after the surface treatment was 84 °, which showed the effect of imparting water repellency. Further, when the capillary force when water was held was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 0.3 MN / m ² and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation. The chemical solution used in this example had no change in appearance even after storage at 45 ° C. for 1 week, the contact angle after the surface treatment was 84 °, and no performance degradation was observed.

[Examples 2 to 56]
The silicon compound A used in Example 1, the concentration of the silicon compound A, the acid A, the organic solvent, the conditions such as the treatment procedure after the surface treatment of the protective film forming chemical solution are appropriately changed, and the wafer surface treatment is performed. Furthermore, the evaluation was performed. The results are shown in Tables 1 and 2.

In the table, “(H ₃ C) ₂ Si (H) —NH—Si (H) (CH ₃ ) ₂ ” means tetramethyldisilazane, and “C ₆ H ₅ Si (CH ₃ ) _2”. “—NH—Si (CH ₃ ) ₂ C ₆ H ₅ ” means diphenyltetramethyldisilazane, “CF ₃ C ₂ H ₄ Si (CH ₃ ) ₂ —NH—Si (CH ₃ ) ₂ C ₂ H _4. “CF ₃ ” means 1,3-bis (trifluoropropyl) tetramethyldisilazane, “(CH ₃ ) ₃ Si—N (CH ₃ ) ₂ ” means trimethylsilyldimethylamine, “(CH ₃ ) _“3 Si—N (C ₂ H ₅ ) ₂ ” means trimethylsilyldiethylamine, “(CH ₃ ) ₃ Si—NCO” means trimethylsilyl isocyanate, and “C ₄ H ₉ Si (CH ₃ ) ₂ —N ( CH _{3) 2} "is meaning butyl (dimethylamino) silane And _{"C 8 H 17 Si (CH 3} ) 2 -N (CH 3) 2 " means octyl dimethyl (dimethylamino) silane.

In Examples 45 to 46, trimethylsilylimidazole represented by the following formula was used as silicon compound A in the protective film forming chemical.

In the table, “(CH ₃ ) ₃ Si—OS (O ₂ ) CF ₃ ” means trimethylsilyl trifluoromethanesulfonate.

  In the table, “PGMEA” means propylene glycol monomethyl ether acetate, “HFE-7100” means hydrofluoroether (3M HFE-7100), and “HFE-7100 / PGMEA” is a mass ratio. It means a mixed solution with HFE-7100: PGMEA = 95: 5. “CTFP” means 1-chloro-3,3,3-trifluoropropene, and “CTFP / PGMEA” means a mixed solution having a mass ratio of CTFP: PGMEA = 95: 5. “DCTFP” means cis-1,2-dichloro-3,3,3-trifluoropropene, and “DCTFP / PGMEA” means a mixed solution having a mass ratio of DCTFP: PGMEA = 95: 5.

  In Example 56, 0.05 g each of trimethylsilyl trifluoroacetate and trimethylsilyl trifluoromethanesulfonate was used as the acid A.

  In Examples 17 to 20, after immersing the silicon wafer in the protective film forming chemical solution in “(3) Surface treatment with the protective film forming chemical solution on the surface of the silicon wafer”, the silicon wafer was immersed in pure water for 1 minute. The silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.

  In Examples 21 to 24, after immersing the silicon wafer in the protective film forming chemical solution in the above “(3) Surface treatment with the protective film forming chemical solution on the silicon wafer surface”, the silicon wafer was immersed in iPA for 1 minute, and finally, The silicon wafer was taken out from the iPA and air was blown to remove the surface iPA.

  In Examples 25 to 28, after the silicon wafer was taken out from the chemical solution for forming the protective film in “(3) Surface treatment with the chemical solution for forming the protective film on the surface of the silicon wafer”, air was blown to form the protective film on the surface. The medical solution was removed.

  In Examples 29 to 30, after the silicon wafer was immersed in the chemical solution for forming the protective film in “(3) Surface treatment with the chemical solution for forming the protective film on the surface of the silicon wafer”, air was blown to form the protective film on the surface. The medical solution was removed. Subsequently, it was immersed in pure water for 1 minute. Finally, the silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.

  In Examples 31 to 32, after the silicon wafer was immersed in the protective film forming chemical solution in the above “(3) Surface treatment with the protective film forming chemical solution on the silicon wafer surface”, air was blown to form the protective film on the surface. The medical solution was removed. Subsequently, it was immersed in iPA for 1 minute. Finally, the silicon wafer was taken out from iPA and air was blown to remove iPA on the surface.

  In Examples 33 to 34, after immersing a silicon wafer in a protective film forming chemical solution in the above “(3) Surface treatment with a chemical solution for forming a protective film on the silicon wafer surface”, air was blown to form a protective film on the surface. The medical solution was removed. Next, it was immersed in iPA for 1 minute, and immersed in pure water for 1 minute. Finally, the silicon wafer was taken out from the pure water, and air was blown to remove the pure water on the surface.

  In Example 51, in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 μm on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, it was immersed in a 0.3 mass% hydrochloric acid aqueous solution at 98 ° C. for 1 minute, then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol (iPA) for 1 minute. In Examples 52 and 54, the same treatment as described above was performed using a smooth silicon nitride-coated silicon wafer (Si wafer having a 0.3 μm thick silicon nitride layer on the surface).

  In Example 53 and Example 55, 1% by mass of the silicon wafer with a smooth silicon nitride film (Si wafer having a silicon nitride layer with a thickness of 0.3 μm on the surface) was obtained in the above “(2) Cleaning of silicon wafer”. Was immersed in a hydrofluoric acid aqueous solution at room temperature for 2 minutes and then immersed in pure water for 1 minute. Further, after immersing in a mixture of 0.6 mass% hydrochloric acid aqueous solution and ethylene glycol in a mass ratio of 50:50 at 98 ° C. for 1 minute, and then immersed in pure water for 1 minute at room temperature, 2-propanol (iPA) For 1 minute.

[Example 57]
As silicon compound B, hexamethyldisilazane [(H ₃ C) ₃ Si—NH—Si (CH ₃ ) ₃ ]; 1 g, acid B as trifluoroacetic anhydride [{CF ₃ C (O)} ₂ O]; 0.1 g and 98.9 g of PGMEA as an organic solvent were mixed and reacted to give a protective film forming chemical solution containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent. It was the same as Example 1 except that it was obtained. Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A. As shown in Table 3, the evaluation result showed that the contact angle after the surface treatment was 82 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.4 MN / m ² , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

[Examples 58 to 71]
The conditions of the silicon compound B, acid B, organic solvent, and the like used in Example 57 were changed as appropriate, and the wafer was subjected to a surface treatment and further evaluated. The results are shown in Table 3.

In the table, “C ₄ H ₉ Si (CH ₃ ) ₂ —NH—Si (CH ₃ ) ₂ C ₄ H ₉ ” means 1,3-dibutyltetramethyldisilazane, and “C ₈ H ₁₇ “Si (CH ₃ ) ₂ —NH—Si (CH ₃ ) ₂ C ₈ H ₁₇ ” means 1,3-dioctyltetramethyldisilazane.

In the table, “{CF ₃ S (O ₂ )} ₂ O” means trifluoromethanesulfonic anhydride.

  In Examples 58 to 59, when trifluoroacetic anhydride used as acid B is mixed with hexamethyldisilazane which is silicon compound B, it immediately reacts and changes to trimethylsilyl trifluoroacetate. The examples have the same meaning as when trimethylsilyl trifluoroacetate is used as acid A.

  In Examples 60 to 62, when trifluoromethanesulfonic anhydride used as acid B is mixed with hexamethyldisilazane which is silicon compound B, it immediately reacts and changes to trimethylsilyl trifluoromethanesulfonate. This example has the same meaning as when trimethylsilyl trifluoromethanesulfonate is used as acid A.

  In Examples 63 to 65, when trifluoroacetic anhydride used as acid B is mixed with tetramethyldisilazane which is silicon compound B, it immediately reacts and changes to dimethylsilyl trifluoroacetate. This example has the same meaning as when dimethylsilyl trifluoroacetate is used as acid A.

  In Examples 66 to 67, when trifluoromethanesulfonic anhydride used as acid B is mixed with tetramethyldisilazane which is silicon compound B, it reacts immediately and changes to dimethylsilyltrifluoromethanesulfonate. The examples have the same meaning as when dimethylsilyl trifluoromethanesulfonate is used as the acid A.

  In Example 68, when trifluoroacetic anhydride used as acid B is mixed with 1,3-dibutyltetramethyldisilazane which is silicon compound B, it immediately reacts to form butyldimethylsilyl trifluoroacetate. Since this varies, this example has the same meaning as when butyldimethylsilyl trifluoroacetate is used as acid A.

  In Example 69, when trifluoromethanesulfonic anhydride used as acid B is mixed with 1,3-dibutyltetramethyldisilazane which is silicon compound B, it reacts immediately and butyldimethylsilyl trifluoromethanesulfonate. Therefore, this example has the same meaning as that when butyldimethylsilyl trifluoromethanesulfonate is used as the acid A.

  In Example 70, when trifluoroacetic anhydride used as acid B was mixed with 1,3-dioctyltetramethyldisilazane which is silicon compound B, it immediately reacted to form octyldimethylsilyl trifluoroacetate. This example has the same meaning as when octyldimethylsilyl trifluoroacetate is used as acid A.

  In Example 71, when trifluoromethanesulfonic anhydride used as acid B is mixed with 1,3-dioctyltetramethyldisilazane which is silicon compound B, it reacts immediately and octyldimethylsilyl trifluoromethanesulfonate. Therefore, this example has the same meaning as the case where octyldimethylsilyl trifluoromethanesulfonate is used as the acid A.

[Example 72]
As the silicon compound B, hexamethyldisilazane [(H ₃ C) ₃ Si—NH—Si (CH ₃ ) ₃ ]; 1 g, as the acid B, trifluoroacetic acid [CF ₃ C (O) —OH]; 0.1 g And 98.9 g of PGMEA as an organic solvent are mixed and reacted as shown in the following formula to form a protective film containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent The procedure was the same as Example 1 except that the chemical solution was obtained. Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A. As shown in Table 4, the evaluation results showed that the contact angle after the surface treatment was 84 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.3 MN / m ² , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

[Examples 73 to 103]
The conditions of the silicon compound B, the concentration of the silicon compound B used in Example 72, the acid B, the organic solvent, and the like were appropriately changed, and the wafer was subjected to surface treatment and further evaluated. The results are shown in Table 4.

In the table, “CF ₃ C (O) —OH” means trifluoroacetic acid, and “CF ₃ S (O ₂ ) —OH” means trifluoromethanesulfonic acid.

In Example 78, a chemical solution for forming a protective film containing dimethylsilyl trifluoroacetate as acid A and tetramethyldisilazane as silicon compound A was obtained by the reaction of the following formula. Tetramethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.

In Example 86, a chemical solution for forming a protective film containing trimethylsilyl trifluoroacetate as acid A and trimethylsilyldimethylamine as silicon compound A was obtained by the reaction of the following formula. Trimethylsilyldimethylamine contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining the acid A, and the component functions as silicon compound A.

In Example 88, a chemical solution for forming a protective film containing trimethylsilyl trifluoroacetate as acid A and trimethylsilyldiethylamine as silicon compound A was obtained by the reaction of the following formula. Trimethylsilyldiethylamine contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining the acid A, and the component functions as silicon compound A.

In Example 90, a chemical solution for forming a protective film containing butyldimethylsilyl trifluoroacetate as acid A and butyldimethyl (dimethylamino) silane as silicon compound A was obtained by the reaction of the following formula. Butyldimethyl (dimethylamino) silane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.

In Example 92, a chemical solution for forming a protective film containing octyldimethylsilyl trifluoroacetate as acid A and octyldimethyl (dimethylamino) silane as silicon compound A was obtained by the reaction of the following formula. Octyldimethyl (dimethylamino) silane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.

  In Example 97, in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a 1 μm thick thermal oxide film layer on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, it was immersed in a 0.3 mass% hydrochloric acid aqueous solution at 98 ° C. for 1 minute, then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol (iPA) for 1 minute. In Examples 98 and 100, the same treatment as described above was performed using a smooth silicon nitride-coated silicon wafer (Si wafer having a silicon nitride layer having a thickness of 0.3 μm on the surface). In Example 102, the same treatment as described above was performed using a smooth silicon wafer with a polysilicon film (Si wafer having a polysilicon layer with a thickness of 0.3 μm on the surface).

  In Example 99 and Example 101, 1% by mass of the silicon wafer with a smooth silicon nitride film (Si wafer having a silicon nitride layer with a thickness of 0.3 μm on the surface) was obtained in the above “(2) Cleaning of silicon wafer”. Was immersed in a hydrofluoric acid aqueous solution at room temperature for 2 minutes and then immersed in pure water for 1 minute. Further, after immersing in a mixture of 0.6 mass% hydrochloric acid aqueous solution and ethylene glycol in a mass ratio of 50:50 at 98 ° C. for 1 minute, and then immersed in pure water for 1 minute at room temperature, 2-propanol (iPA) For 1 minute. In Example 103, the same treatment as described above was performed using a smooth silicon wafer with a polysilicon film (Si wafer having a polysilicon layer with a thickness of 0.3 μm on the surface).

[Example 104]
1 g of hexamethyldisilazane [(H ₃ C) ₃ Si—NH—Si (CH ₃ ) ₃ ]; 1 g of trifluoroacetic acid [CF ₃ C (O) OH] as acid B; PGMEA as an organic solvent; 98 g The same procedure as in Example 1 was conducted except that a chemical solution for forming a protective film was obtained by mixing. As a result of the evaluation, the contact angle after the surface treatment was 84 °, indicating a water repellency imparting effect. Further, the capillary force when water was held was 0.3 MN / m ² , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

  However, when a chemical solution stored at 45 ° C. for 1 week was used, the contact angle after the surface treatment was 10 °. This is thought to be because hexamethyldisilazane was consumed by the reaction of trifluoroacetic acid with hexamethyldisilazane. The chemical solution of Example 1 using acid A as a starting material had a contact angle of 84 ° after the surface treatment even after storage at 45 ° C. for 1 week, and no performance degradation was observed. Therefore, a chemical solution prepared using silicon compound A and acid A as starting materials is more preferable because the chemical solution is excellent in stability.

[Example 105]
In Example 1, in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 μm on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, in the above “(3) Surface treatment with a chemical solution for forming a protective film on the silicon wafer surface”, a silicon wafer wetted with water is placed on a spin coater and rotated on the wafer surface while rotating at a speed of 1000 rpm. Propanol (iPA) for 1 minute, then protective film-forming chemical solution for 10 minutes, then iPA for 1 minute, then pure water for 1 minute, and finally rotating for 1 minute without supplying anything, Of pure water was removed. As a result of evaluation of the obtained wafer, the contact angle after the surface treatment was 82 °, which showed the effect of imparting water repellency. Further, the capillary force when water was held was 0.4 MN / m ² , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

[Example 106]
Example 2 was the same as Example 2 except that the starting material used had a total amount of moisture of 5500 ppm by mass with respect to the total amount of the starting material. As a result of the evaluation, the contact angle after the surface treatment was 70 °, which showed the effect of imparting water repellency. Further, the capillary force when water was held was 1.1 MN / m ² , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

Comparative Example 1
The same procedure as in Example 1 was performed except that the silicon wafer was not supplied with the chemical solution for forming the protective film. That is, in this comparative example, a wafer having a surface state that is not water-repellent was evaluated. As shown in Table 5, the contact angle of the wafer was as low as 3 °, and the capillary force when water was held was as large as 3.2 MN / m ² .

Comparative Example 2
Hexamethyldisilazane; 1.0 g, PGMEA; 99.0 g were mixed to obtain a protective film-forming chemical solution, which was the same as Example 1. That is, in this comparative example, a chemical solution for forming a protective film containing no acid was used. As shown in Table 5, the contact angle after the surface treatment was as low as 28 °, and the capillary force when water was retained was as large as 2.8 MN / m ² .

[Comparative Examples 3 to 8]
The acid A used in Example 1 was changed, and the wafer was surface-treated and further evaluated. The results are shown in Table 5.

In the table, “CH ₃ S (O ₂ ) —OH” means methanesulfonic acid, “CH ₃ COOH” means acetic acid, and “H ₂ SO ₄ ” means sulfuric acid (water content is 2 mass). “H ₃ PO ₄ ” means phosphoric acid (water content is 15 mass%), “HCl” means hydrochloric acid (water content is 65 mass%), “HNO” “ ₃ ” means nitric acid (water content is 31 mass%).

  In Example 1, acid A was used, and in Comparative Examples 3 to 8, an acid other than acid A was used. Otherwise, the surface treatment was performed under the same conditions. It was confirmed that only Example 1 using trimethylsilyl trifluoroacetate which is acid A can impart excellent water repellency to the wafer surface. On the other hand, it was confirmed that Comparative Examples 3 to 8 could not give sufficient water repellency to the silicon wafer. The chemical solution capable of imparting sufficient water repellency to the surface of the silicon wafer means that the silanol group, which is a reaction site on the surface of the silicon wafer, and the silicon compound A are reacted rapidly to convert the silicon compound A to silicon via a siloxane bond. It is suggested that trimethylsilyl trifluoroacetate, which is acid A, significantly increases the reaction rate of the chemical because it is a chemical that can be chemically bonded to the Si element of the wafer.

In Examples 35 to 38, 47 to 50, 68 to 71, 90 to 93, and 95 to 96, silicon compound A having a relatively bulky hydrocarbon group was used as R ¹ of the general formula [1]. Since such silicon compound A reacts with silanol groups, which are reaction sites on the surface of the silicon wafer, and the Si element of the silicon wafer can be covered with bulky hydrocarbon groups via siloxane bonds, it is efficient. The wafer surface can be made water repellent. Naturally, the silicon surface A having such a relatively bulky hydrocarbon group and the acid A that can remarkably increase the reaction rate of the chemical solution are combined to repel the wafer surface more efficiently. Can do.

[Reference Examples 1 to 4]
The silicon compound A and the organic solvent used in Example 1 were appropriately changed, and the wafer was surface-treated using trimethylchlorosilane [(CH ₃ ) ₃ SiCl] as an acid other than the acid A, and further evaluated. It was. The results are shown in Table 6. The chemical solution used in this reference example had a cloudy appearance at the time of preparation, and a deposited component was observed. However, when the chemical solution was purified and surface-treated, the contact angle was 78 to 84 °, and there was almost no change. The same effects as those of the chemical solutions of the inventive examples were obtained.

DESCRIPTION OF SYMBOLS 1 Wafer 2 Fine uneven | corrugated pattern on the wafer surface 3 Pattern convex part 4 Pattern concave part 5 Concave width 6 Convex height 7 Convex width 8 The protective film forming chemical 9 held in the concave part 4 In the concave part 4 Retained aqueous cleaning solution 10 Protective film

Claims (12)

A chemical solution for forming a water-repellent protective film on at least the concave surface of the concavo-convex pattern when cleaning a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element,
A silicon compound A represented by the following general formula [1] and an acid A,
The acid A is trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl. trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyl butyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and, Ri least 1 Tsudea selected from the group consisting of decyl dimethyl silyl trifluoromethane sulfonate,
The total amount of water starting in the raw material of the chemical, characterized in der Rukoto below 100 ppm by weight relative to the total amount of the raw material, liquid chemical for forming a protective film.

(In the formula [1], R ^{1 s} each independently contain a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl chain having 1 to 8 carbon atoms. X is at least one group selected from a valent organic group, X is each independently a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b Is an integer of 0-2, and the sum of a and b is 1-3.) The protective film-forming chemical solution according to claim 1 , wherein the starting material of the chemical solution is substantially free of moisture . 3. The number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical liquid is 100 or less per 1 mL of the chemical liquid. The chemical | medical solution for protective film formation of description. Na of the liquid chemical, Mg, K, Ca, Mn , metal impurity content of each element of Fe and Cu, characterized in that to the liquid chemical amount or less each 100 mass ppb, claims 1 to 3 The chemical | medical solution for protective film formation in any one of. A process for the preparation of liquid chemical for forming a protective film according to any one of claims 1 to 4, prior to mixing a raw material for chemicals such protective film forming silicon compound A and the acid A, and, after mixing The said preparation method characterized by refine | purifying at least 1 among liquid mixtures.   A silicon compound A represented by the following general formula [1] and an acid A,
The acid A is trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl. It is at least one selected from the group consisting of trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesulfonate
Protective film forming chemical
A fine concavo-convex pattern is formed on the surface, and at least a part of the concavo-convex pattern is held on at least a concave surface of a wafer containing silicon element, and a water-repellent protective film is formed on at least the concave surface of the concavo-convex pattern. A method for cleaning a wafer surface.

(In the formula [1], R ¹ Are each independently selected from a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X is a monovalent organic group in which the element bonded to the Si element is nitrogen independently of each other, a is an integer of 1 to 3, b is an integer of 0 to 2, The sum of a and b is 1 to 3. )   The wafer surface cleaning method according to claim 6, wherein the total amount of moisture in the starting material of the chemical solution is 5000 ppm by mass or less based on the total amount of the material.   The number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical liquid is 100 or less per mL of the chemical liquid, according to claim 6 or 7. 2. A method for cleaning a wafer surface according to 1.   The metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe and Cu in the chemical solution is 100 mass ppb or less for each total amount of the chemical solution. The method for cleaning a wafer surface according to any one of the above.   The silicon compound A and the acid A before mixing, which are raw materials of the protective film forming chemical solution, and at least one of the mixed solution after mixing are purified, according to any one of claims 6 to 9, The wafer surface cleaning method as described.   The method for cleaning a wafer surface according to any one of claims 6 to 10, further comprising a step of removing the protective film from the wafer surface after removing the cleaning liquid from the wafer surface.   The step of removing the protective film from the wafer surface is at least one treatment selected from irradiating the wafer surface with light, heating the wafer, exposing the wafer to ozone, and irradiating the wafer surface with plasma. The wafer surface cleaning method according to claim 11, wherein the wafer surface is cleaned.

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