Chamfer treatment agent composition and wafer manufacturing method

Abstract

The chamfer treatment composition of the present invention is a chamfer treatment composition containing a silylating agent for treating the chamfer of a wafer, and has the property that the surface modification index Y and the surface modification index Z measured according to a prescribed procedure satisfy 0.5≤Y / Z≤1.0.

Description

Technical Field

[0001] The present invention relates to a chamfer treatment agent composition and a method for producing a wafer. Background Art

[0002] Various studies have been conducted so far on the cleaning technology of the chamfered portion of a semiconductor wafer. As such technology, for example, the technology described in Patent Document 1 is known. Patent Document 1 describes the following method: a chemical solution is discharged from a chemical solution nozzle toward the surface of the semiconductor wafer, and the cleaning chemical solution is spread to the outside of the chamfered portion by the centrifugal force of the rotation, thereby cleaning the surface of the chamfered portion (Paragraphs 0025, 0026 of Patent Document 1). Figure 3 ).

[0003] In addition, in each process of semiconductor manufacturing, it is known that metal contamination etc. may occur on the surface of the wafer backside and chamfered portion (wafer edge and peripheral portion) other than the device surface of the semiconductor wafer (Paragraph 0004 of Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-218249

[0007] Patent Document 2: Japanese Patent Application Publication No. 2005-340554 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] The present inventors have conducted studies and have determined that the chemical solution described in Patent Document 1 has room for improvement in terms of foreign matter adhesion prevention performance.

[0010] Solutions for solving problems

[0011] It is known that foreign matter such as metal particles adheres to the chamfered portion located at the end of the semiconductor wafer during the manufacturing process of forming semiconductor elements on the semiconductor wafer. If the foreign matter attached to the surface of the chamfered portion spreads to the element forming area on itself or other semiconductor wafers during various processes such as transportation, storage, and processing of the semiconductor wafer, there is a concern that the device characteristics of the semiconductor chip will be reduced.

[0012] As described above, a method of cleaning foreign matter on the surface of the chamfered portion with a cleaning chemical solution is adopted. However, there is a concern that foreign matter may adhere again to the surface of the chamfered portion after cleaning.

[0013] Therefore, the present inventors believed that the adhesion of foreign matter can be controlled by modifying the chamfered portion surface, and focused on the modification process of the chamfered portion surface and conducted research on a chemical solution suitable for the modification process, that is, a chamfered portion treatment agent composition.

[0014] As a result of intensive studies, it was found that the adhesion of foreign matter to the chamfered portion surface can be appropriately controlled by targeting the critical surface tension after treatment with the chamfered portion treating agent composition.

[0015] In addition, it is known that on the chamfer surface, a plurality of insulating films such as silicon oxide film and silicon nitride film are usually stacked, and a film in a state where different materials are mixed is exposed. In view of such a situation, a study was conducted, and as a result, it was found that by using two critical surface tensions of films of different materials as targets, the foreign matter adhesion of the chamfer surface can be stably evaluated.

[0016] Based on this insight, further in-depth research was conducted and it was found that by modifying the chamfer treatment agent composition using the ratio of the critical surface tension Y for silicon oxide film to the critical surface tension Z for silicon nitride film as an indicator and appropriately controlling the above-mentioned indicator "Y / Z", the adhesion ability of foreign matter such as metal particles on the chamfer surface can be improved, thereby completing the present invention.

[0017] According to the present invention, there is provided a chamfer treatment agent composition,

[0018] The invention discloses a chamfer treatment agent composition containing a silylating agent for treating a chamfer of a wafer.

[0019] The surface modification index Y and surface modification index Z measured according to the following steps (1) to (4) satisfy

[0020] 0.5≤Y / Z≤1.0.

[0021] (step)

[0022] (1) A substrate having a silicon oxide film (SiO2 film) with a thickness of 1 μm on the surface is treated using the chamfer treatment agent composition. The treatment conditions are as follows: the substrate is immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in 2-propanol (iPA) for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of iPA, and air is blown to remove the iPA on the surface of the substrate.

[0023] (2) Using a plurality of measurement liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon oxide film after treatment in (1) was determined by the Zisman Plot method. The obtained critical surface tension value (mN / m) was used as the "surface modification index Y".

[0024] (3) A substrate having a silicon nitride film (SiN film) with a thickness of 50 nm on the surface was treated using the chamfer treatment agent composition. The treatment conditions were as follows: the substrate was immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in iPA for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate was taken out of the iPA, and air was blown to remove the iPA on the surface of the substrate.

[0025] (4) Using a plurality of measurement liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon nitride film after treatment in (3) is determined by the Zisman Plot method. The obtained critical surface tension value (mN / m) is used as the "surface modification index Z".

[0026] Furthermore, according to the present invention, a method for manufacturing a wafer is provided.

[0027] It includes: a wafer surface modification process, and

[0028] Wafer processing steps,

[0029] In the surface modification step, the chamfer treatment agent composition is used.

[0030] Effects of the Invention

[0031] According to the present invention, there are provided a chamfer treatment agent composition having excellent foreign matter adhesion prevention performance and a method for producing a wafer using the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a cross-sectional view schematically showing the structure of the chamfered portion of the wafer according to the present embodiment.

[0033] Figure 2 This is a diagram for explaining the outline of the Zisman Plot method.

[0034] Figure 3 The figure shows the SEM image of Example 1.

[0035] Figure 4 The figure shows the SEM image of Example 2.

[0036] Figure 5 The figure shows the SEM image of Comparative Example 1.

[0037] Figure 6 The figure shows the SEM image of Comparative Example 2.

[0038] Figure 7 The figure shows the SEM image of Example 1.

[0039] Figure 8 The figure shows the SEM image of Example 2.

[0040] Fig. 9 The figure shows the SEM image of Comparative Example 1.

[0041] Fig.10 The figure shows the SEM image of Comparative Example 2. DETAILED DESCRIPTION

[0042] The following is an explanation of the embodiments of the present invention with reference to the accompanying drawings. It should be noted that the same reference numerals are used for the same components in all the accompanying drawings, and the explanation is omitted as appropriate. In addition, the drawings are schematic diagrams and are not consistent with the actual dimensional ratios.

[0043] The outline of the chamfer treatment agent composition according to the present embodiment will be described.

[0044] The chamfer treatment agent composition of the present embodiment is a surface modifier for treating the chamfer of a wafer. The chamfer treatment agent composition has the following characteristics: it contains a silylating agent, and the "Y / Z" shown by the surface modification index Y and the surface modification index Z measured according to the following steps (1) to (4) satisfies the following formula (I).

[0045] 0.5≤Y / Z≤1.0···(I)

[0046] (step)

[0047] (1) A substrate having a silicon oxide film (thermal oxide film) with a thickness of 1 μm on the surface is treated using the chamfer treatment agent composition. The treatment conditions are as follows: the substrate is immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in 2-propanol (iPA) for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of the iPA, and air is blown to remove the iPA on the surface of the substrate.

[0048] (2) Using a plurality of measurement liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon oxide film after treatment in (1) was determined by the Zisman Plot method. The obtained critical surface tension value (mN / m) was used as the "surface modification index Y".

[0049] (3) A substrate having a 50 nm thick silicon nitride film (LP-CVD film) on its surface was treated using the chamfer treatment agent composition. The treatment conditions were as follows: the substrate was immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in iPA for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate was taken out of the iPA, and air was blown to remove the iPA on the surface of the substrate.

[0050] (4) Using a plurality of measurement liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon nitride film after treatment in (3) is determined by the Zisman Plot method. The obtained critical surface tension value (mN / m) is used as the "surface modification index Z".

[0051] Figure 1 It is a cross-sectional view schematically showing the structure of the chamfered portion 30 of the wafer 100 .

[0052] An example of the wafer 100 of the present embodiment may include a chamfered portion 30 formed outside the device forming region 10. The chamfered portion 30 includes an upper chamfered portion 40 and a lower chamfered portion 60 formed of inclined surfaces, and an edge portion 50 formed of an edge end surface.

[0053] like Figure 1 As shown, in the film forming process of the film constituting the semiconductor element in the element forming region 10, an insulating film 110 such as a silicon oxide film and a silicon nitride film may be formed on the surface of the upper chamfered portion 40 of the chamfered portion 30 and on the surface of the edge portion 50. The insulating film 110 becomes a heterogeneous film exposed on the surface of the chamfered portion 30 in a state where a plurality of heterogeneous materials are mixed. In addition, in various processes of the wafer 100, foreign matter (particles) such as metal particles and inorganic particles may adhere to the insulating film 110 of the chamfered portion 30.

[0054] According to the findings of the present inventors, it has been found that the adhesion of foreign matter to the surface of the chamfered portion 30 can be appropriately controlled by targeting the critical surface tension after treatment with the chamfered portion treating agent composition.

[0055] Furthermore, it is found that the foreign matter adhesion of the chamfered portion 30 can be stably evaluated by using as a target the ratio of the critical surface tensions of the silicon oxide film and the silicon nitride film, which are representative examples of foreign films exposed on the surface of the chamfered portion 30 .

[0056] Furthermore, the inventors have conducted research on a method for measuring critical surface tension using the Zisman Plot method, and have determined that the critical surface tension of silicon oxide films and silicon nitride films can be appropriately evaluated by using a plurality of liquids having different mixing ratios of water and iPA as measuring liquids under the conditions of the Zisman Plot method.

[0057] As the above-mentioned measuring liquid, two or more liquids selected from the group consisting of liquids having a mixing ratio of water to iPA of 100:0, 99:1, 95:5, 87:13, 80:20, 66:34, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95, 3:97, and 0:100 can be used. By appropriately selecting two or three or more measuring liquids, the critical surface tension can be calculated by Zisman Plot.

[0058] Based on this insight, further in-depth research was conducted and it was found that when the critical surface tension of the silicon oxide film obtained by the above-mentioned Zisman Plot method is used as the "surface modification index Y", and the critical surface tension of the silicon nitride film obtained by the Zisman Plot method is used as the "surface modification index Z", "Y / Z" is used as an index, and a chamfer treatment agent composition that controls the above-mentioned indexes within an appropriate numerical range is used to modify the surface of the chamfer 30, thereby improving the ability to prevent foreign matter adhesion.

[0059] The detailed mechanism is not clear, but it is believed that: even if there is fluctuation in the material of the film such as the insulating film 110 formed on the surface of the chamfered portion 30, the chamfered portion treatment agent composition that appropriately controls the index "Y / Z" can stably exert the surface modification ability on these heterogeneous mixed films, thereby improving the anti-foreign matter adhesion property of the chamfered portion 30.

[0060] The chamfer treatment agent composition of the present embodiment can suppress the adhesion of foreign matter on the surface of the chamfer 30, and therefore can be suitably used in the surface modification process of the chamfer 30. By treating the chamfer 30 with the chamfer treatment agent composition of the present embodiment, contamination caused by foreign matter from the chamfer can be suppressed in the semiconductor manufacturing process, thereby improving the manufacturing stability and manufacturing yield of the semiconductor element. In addition, a semiconductor element with excellent device characteristics can be realized.

[0061] The characteristics of the chamfer treatment agent composition according to the present embodiment will be described.

[0062] The chamfer treatment composition has a property that "Y / Z" represented by the surface modification index Y and the surface modification index Z measured in steps (1) to (4) satisfies the following formula (I).

[0063] 0.5≤Y / Z≤1.0···(I)

[0064] The lower limit of the Y / Z is, for example, 0.50 or more, preferably 0.60 or more, and more preferably 0.70 or more. Thus, the surface modification ability can be stably exerted. On the other hand, the upper limit of the Y / Z is, for example, 1.00 or less, preferably 0.98 or less, and more preferably 0.95 or less. Thus, the ability to prevent foreign matter adhesion can be improved.

[0065] The chamfer treatment agent composition may have a property satisfying 15 mN / m≤Y≤26 mN / m.

[0066] The surface modification index Y is, for example, 15 mN / m to 26 mN / m, preferably 20 mN / m to 25 mN / m, and more preferably 20 mN / m to 24 mN / m. By setting the surface modification index Y within the above numerical range, when a silicon wafer is used as the wafer 100, for example, on the chamfered surface where a natural oxide film is formed, the ability to prevent foreign matter from adhering can be improved.

[0067] In the present embodiment, the above Y / Z and Y can be controlled by, for example, appropriately selecting the type and blending amount of each component contained in the chamfer portion treatment agent composition, the preparation method of the chamfer portion treatment agent composition, etc. Among them, for example, the elements for setting the above Y / Z and Y to the desired numerical range include quickly using the chamfer portion treatment agent composition after mixing the raw materials to prepare the chamfer portion treatment agent composition, and appropriately adjusting the concentration of the silylating agent in the chamfer portion treatment agent composition, the liquid temperature, etc.

[0068] A method for producing a wafer using the chamfer treatment agent composition according to the present embodiment will be described.

[0069] The wafer manufacturing method of the present embodiment includes: a wafer surface modification step and a wafer processing step. In the surface modification step, the chamfer treatment agent composition of the present embodiment is used.

[0070] The chamfer treatment agent composition of this embodiment is as follows Figure 1 As shown, the ability to prevent foreign matter from adhering to the surface of the chamfered portion 30 of the wafer 100 can be improved. By modifying the surface of the chamfered portion 30 in this way, foreign matter contamination of the chamfered portion 30 can be suppressed during the semiconductor manufacturing process, and secondary contamination from foreign matter adhering to the chamfered portion 30 can be suppressed. Therefore, the manufacturing stability and manufacturing yield of the semiconductor element can be improved.

[0071] Examples of the wafer 100 include a silicon wafer, a SiC wafer, a sapphire wafer, and a compound semiconductor wafer.

[0072] The wafer 100 may include an element forming region 10 in which a semiconductor element is formed, a peripheral cutting region 20 for dicing provided outside the element forming region 10 , and a chamfered portion 30 provided outside the peripheral cutting region 20 .

[0073] As processing steps of the wafer 100, the following steps can be cited: a step of forming a fine pattern of a concave-convex shape in the element forming area 10, a step of cutting or grinding the wafer 100, a step of forming various films such as an insulating film 110 and a metal film 120, a step of cleaning the wafer 100, and other steps of forming various semiconductor elements.

[0074] In the above-mentioned surface modification step of the wafer 100 , the coating method is not particularly limited as long as the chamfered portion treating agent composition of the present embodiment can be coated on the chamfered portion 30 .

[0075] The surface modification process of the wafer 100 can be performed before or after the processing process or between multiple processes in the processing process. The surface modification process can be performed once or twice or more. It can be expected that by performing the surface modification process in the middle of the processing process, contamination of the chamfered portion 30 and secondary contamination from the chamfered portion 30 can be suppressed in subsequent processing processes.

[0076] Next, the components of the chamfered portion treating agent composition according to the present embodiment will be described.

[0077] The chamfered portion treating agent composition of the present embodiment contains a silylation agent.

[0078] The silylating agent may be a known silylating agent. As the silylating agent, for example, a silicon compound represented by the following general formula [1] is used.

[0079] These may be used alone or in combination of two or more.

[0080] R 1 a Si(H) b X 4-a-b [1]

[0081] In the above general formula [1], R 1 Each of them is independently an organic group containing a hydrocarbon group with a carbon number of 1 to 18, in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and each of X is independently a monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen, carbon, or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3.

[0082] In the above general formula [1], R 1It contains not only hydrogen, carbon, nitrogen, oxygen, and fluorine elements, but also silicon, sulfur, and halogen elements (other than fluorine).

[0083] As R in the above general formula [1] 1 , each independently selected from C e H 2e+1 (e = 1 to 18), and C f F 2f+1 At least one group of CH2CH2 (f = 1 to 8). Among them, a silicon compound having a trialkylsilyl group can be used. 1 It may contain unsaturated bonds and aromatic rings.

[0084] It should be noted that R in the above general formula [1] 1 When silicon element is contained, the structure of the general formula [1-1] shown below can be taken.

[0085] R 1 m X 3-m-n (H) n Si-(CH2) p -Si(H) n X 3-m-n R 1 m [1-1]

[0086] It should be noted that in the above general formula [1-1], R 1 (where R 1 does not contain silicon) and X are the same as in the above general formula [1], m is an integer of 1 to 2, n is an integer of 0 to 1, the sum of m and n is 1 to 2, p is an integer of 1 to 18, -(CH2) p -The methylene chain shown may also be substituted by halogen.

[0087] In the above general formula [1], the monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen or carbon may contain not only hydrogen, carbon, nitrogen and oxygen elements but also silicon, sulfur and halogen elements.

[0088] Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azido group, an acetamide group, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3, an imidazole ring, a triazole ring, a tetrazole ring, an oxazolidinone ring, a morpholine ring, -NH-C(=O)-Si(CH3)3, -N(H) 2-g (Si(H) h R 3 3-h ) g (R 3 is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, g is 1 or 2, and h is an integer of 0 to 2), -N(S(=O)2R 4 )2(Here, R 4 Each independently is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements. ) In addition, a substituent having a structure of the following general formula [1-2]

[0089]

[0090] (In the above general formula [1-2], R 5 Each is independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements. ), -N=C(NR 6 2) 2, -N=C(NR 6 2) R 6 (Here, R 6 Each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group optionally has oxygen atoms and / or nitrogen atoms. ), -N(R a1 )R a2 (Here, the above R a1 represents a hydrogen atom, or a saturated or unsaturated alkyl group, R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 are bonded to each other to form a saturated or unsaturated heterocyclic alkyl group optionally having a nitrogen atom. ), -N(R a3 )-Si(R a4 )(R a5 )(Ra6 )(Here, the above R a3 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and the above R a4 , R a5 and R a6 Each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6 The total number of carbon atoms contained in is 1 or more. ), -N(R a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group, or a trialkylsilylamino group. ) and the like.

[0091] Examples of silylating agents in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is nitrogen include CH3Si(NH2)3, C2H5Si(NH2)3, C3H7Si(NH2)3, C4H9Si(NH2)3, C5H 11 Si(NH2)3、C6H 13 Si(NH2)3、C7H 15 Si(NH2)3、C8H 17 Si(NH2)3、C9H 19 Si(NH2)3、C 10 H 21 Si(NH2)3、C 11 H 23 Si(NH2)3、C 12 H 25 Si(NH2)3、C 13 H 27 Si(NH2)3、C 14 H 29 Si(NH2)3、C 15 H 31 Si(NH2)3、C 16 H 33 Si(NH2)3、C 17 H 35 Si(NH2)3、C 18 H 37<h2 style=";text-align:left;direction:ltr">Si(NH2)3, (CH3)2Si(NH2)2, C2H5Si(CH3)(NH2)2, (C2H5)2Si(NH2)2, C3H7Si(CH3)(NH2)2, (C3H7)2Si(NH2)2, C4H9Si(CH3)(NH2)2, (C4H9)2Si(NH2)2, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 27 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 29 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 31 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 35 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, (CH3)3SiNH2, C2H5Si(CH3)2NH2, (C2H5)2Si(CH3)NH2, (C2H5)3SiNH2, C3H7Si(CH3)2NH2, (C3H7)2Si(CH3)NH2, (C3H7)3SiNH2, C4H9Si(CH3)2NH2, (C4H9)3SiNH2, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 23<h2 style=";text-align:left;direction:ltr">Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 27 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 29 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 31 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 35 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、(CH3)2Si(H)NH2、CH3Si(H)2NH2、(C2H5)2Si(H)NH2、C2H5Si(H)2NH2、C2H5Si(CH3)(H)NH2、(C3H7)2Si( H)NH2、C3H7Si(H)2NH2、CF3CH2CH2Si(NH2)3、C2F5CH2CH2Si(NH2)3、C3F7CH2CH2CH2Si(NH2)3、C4F9CH2CH2Si(NH2)3、C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C6F<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C7F<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C8F<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, CF3CH2CH2Si(CH3)(NH2)2, C2F5CH2CH2Si(CH3)(NH2)2, C3F7CH2CH2Si(CH3)(NH2)2, C4F9CH2CH2Si(CH3)(NH2)2, C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C6F<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C7F<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C8F<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, CF3CH2CH2Si(CH3)2NH2, C2F5CH2CH2Si(CH3)2NH2, C3F7CH2CH2Si(CH3)2NH2, C4F9CH2CH2Si(CH3)2NH2, C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)2NH2, C6F<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)2NH2, C7F15 CH2CH2Si(CH3)2NH2、C8F 17 Aminosilanes such as CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2, aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminodimethyl-tert-butylsilane, etc.; or, the amino group (-NH2 group) of the above-mentioned aminosilane is substituted by the following groups: -N=C=O, dialkylamino (-N(CH3)2, -N(C2H5)2, etc.), tert-butylamino, allylamino, -N=C=S, -N3, -NHC(=O)CH3, -NHC(=O)CF3、-N(CH3)C(=O)CH3、-N(CH3)C(=O)CF3、-N=C(CH3)OSi(CH3)3、-N=C(CF3)OSi(CH3)3、-NHC(=O)-OSi(CH3)3、-NHC(=O)-NH-Si(CH3)3(e.g. N,N'-bis(trimethylsilyl)urea, etc.), imidazole ring, triazole ring, tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH3)3、-N(H) 2-g (Si(H) h R 3 3-h ) g (R 3 It is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen atoms are optionally replaced by fluorine atoms, g is 1 or 2, and h is an integer from 0 to 2. Examples include tris(dimethylsilyl)amine and tris(trimethylsilyl)amine. ), -N(S(=O)2R 4 )2(Here, R 4 Each independently is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc.), and a substituent having the structure of the following general formula [1-2]

[0092]

[0093] (In the above general formula [1-2], R 5 Each is independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements. For example, N-(trimethylsilyl)N,N-difluoromethane-1,3-bis(sulfonyl)imide, etc.), -N=C(NR 6 2) 2, -N=C(NR 6 2) R 6 (Here, R 6Each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group optionally has oxygen atoms and / or nitrogen atoms. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, etc.), -N(R a1 )R a2 (Here, the above R a1 represents a hydrogen atom, or a saturated or unsaturated alkyl group, R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 are bonded to each other to form a saturated or unsaturated heterocyclic alkyl group optionally having a nitrogen atom. ), -N(R a3 )-Si(R a4 )(R a5 )(R a6 )(Here, the above R a3 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and the above R a4 , R a5 and R a6 Each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6 The total number of carbon atoms contained in is 1 or more. For example, hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldisilazane, 1,2-di-N-octyltetramethyldisilazane, 1,2-divinyltetramethyldisilazane, heptamethyldisilazane, nonamethyltrisilazane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyl-tert-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc. ), -N(R a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group, or a trialkylsilylamino group, such as N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc. ) and the like.

[0094] As the silylating agent in the general formula [1], X is a monovalent organic group in which the element bonded to Si is oxygen, for example: the amino group (-NH2 group) of the aminosilane is substituted by the following group: -OC(=A)R a9 (Here, the above A represents O, CHR a10 , CHOR a10 , CR a10 R a10 , or NR a11 , R a9 , R a10 Each independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorinated alkyl group, a trialkylsilyl group, a trialkylsilyloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group, and the above R a11 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. For example, trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl propionate, trimethylsilyl butyrate, etc. ), -OC(R a12 )=N(R a13 )(Here, the above R a12 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group, or a trialkylsilylamino group, R a13 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. ), -OC(R a14 )=CH-C(=O)R a15 (Here, the above R a14 and R a15 Each independently represents a hydrogen atom or an organic group. For example, trimethylsilyloxy-3-penten-2-one, 2-trimethylsilyloxypent-2-en-4-one, etc. ), -OR a16 (Here, the above R a16 It represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a fluorinated alkyl group. For example, CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, C5H 11 Si(OCH3)3、C6H 13 Si(OCH3)3、C7H 15 Si(OCH3)3、C8H 17 Si(OCH3)3、C9H 19 Si(OCH3)3、C 10 H 21 Si(OCH3)3、C 11 H 23Si(OCH3)3、C 12 H 25 Si(OCH3)3、C 13 H 27 Si(OCH3)3、C 14 H 29 Si(OCH3)3、C 15 H 31 Si(OCH3)3、C 16 H 33 Si(OCH3)3、C 17 H 35 Si(OCH3)3、C 18 H 37 Si(OCH3)3、(CH3)2Si(OCH3)2、C2H5Si(CH3)(OCH3)2、(C2H5)2Si(OCH3)2、C3H7Si (CH3)(OCH3)2、(C3H7)2Si(OCH3)2、C4H9Si(CH3)(OCH3)2、(C4H9)2Si(OCH3)2、C5H 11 Si(CH3)(OCH3)2、C6H 13 Si(CH3)(OCH3)2、C7H 15 Si(CH3)(OCH3)2、C8H 17 Si(CH3)(OCH3)2、C9H 19 Si(CH3)(OCH3)2、C 10 H 21 Si(CH3)(OCH3)2、C 11 H 23 Si(CH3)(OCH3)2、C 12 H 25 Si(CH3)(OCH3)2、C 13 H 27 Si(CH3)(OCH3)2、C 14 H 29 Si(CH3)(OCH3)2、C 15 H 31 Si(CH3)(OCH3)2、C 16 H 33 Si(CH3)(OCH3)2、C 17 H 35 Si(CH3)(OCH3)2、C 18 H 37Si(CH3)(OCH3)2, (CH3)3SiOCH3, C2H5Si(CH3)2OCH3, (C2H5)2Si(CH3)OCH3, (C2H5)3SiOCH3, C3H7Si(CH3)2OCH3, (C3H7)2Si(CH3)OCH3, (C3H7)3SiOCH3, C4H9Si(CH3)2OCH3, (C4H9)3SiOCH3, C5H 11 Si(CH3)2OCH3, C6H 13 Si(CH3)2OCH3, C7H 15 Si(CH3)2OCH3, C8H 17 Si(CH3)2OCH3, C9H19Si(CH3)2OCH3, C 10 H 21 Si(CH3)2OCH3, C 11 H 23 Si(CH3)2OCH3, C 12 H 25 Si(CH3)2OCH3, C 13 H 27 Si(CH3)2OCH3, C 14 H 29 Si(CH3)2OCH3, C 15 H 31 Si(CH3)2OCH3, C 16 H 33 Si(CH3)2OCH3, C 17 H 35 Si(CH3)2OCH3, C 18 H 37 Si(CH3)2OCH3, (CH3)2Si(H)OCH3, CH3Si(H)2OCH3, (C2H5)2Si(H)OCH3, C2H5Si(H)2OCH3, C2H5Si(CH3)(H)OCH3, (C3H7)2Si(H)OCH3 and other alkylmethoxysilanes, or CF3CH2CH2Si(OCH3)3, C2F5CH2CH2Si(OCH3)3, C3F7CH2CH2Si(OCH3)3, C4F9CH2CH2Si(OCH3)3, C5F 11 CH2CH2Si(OCH3)3, C6F 13 CH2CH2Si(OCH3)3, C7F 15 CH2CH2Si(OCH3)3, C8F 17CH2CH2Si(OCH3)3, CF3CH2CH2Si(CH3)(OCH3)2, C2F5CH2CH2Si(CH3)(OCH3)2, C3F7CH2CH2Si(CH3)(OCH3)2, C4F9CH2CH2Si(CH3)(OCH3)2, C5F 11 CH2CH2Si(CH3)(OCH3)2、C6F 13 CH2CH2Si(CH3)(OCH3)2、C7F 15 CH2CH2Si(CH3)(OCH3)2、C8F 17 CH2CH2Si(CH3)(OCH3)2, CF3CH2CH2Si(CH3)2OCH3, C2F5CH2CH2Si(CH3)2OCH3, C3F7CH2CH2Si(CH3)2OCH3, C4F9CH2CH2Si(CH3)2OCH3, C5F 11 CH2CH2Si(CH3)2OCH3、C6F 13 CH2CH2Si(CH3)2OCH3、C7F 15 CH2CH2Si(CH3)2OCH3、C8F 17 Fluoroalkylmethoxysilanes such as CH2CH2, Si(CH3)2OCH3, CF3CH2CH2Si(CH3)(H)OCH3, or compounds in which the methyl part of the methoxy group of the above methoxysilane is substituted by a monovalent hydrocarbon group having 2 to 18 carbon atoms, wherein a part or all of the hydrogen elements are optionally substituted by fluorine elements. ) etc.

[0095] Examples of silylating agents in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is carbon include: 7 )3(Here, R 7 Each is independently selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, for example, (trimethylsilyl) tris(trifluoromethanesulfonyl) methyl substituted.

[0096] In addition, as a silylating agent in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is a halogen, examples thereof include: aminosilanes in which the amino group (-NH2 group) is substituted with a chloro group, a bromo group, or an iodo group (for example, chlorotrimethylsilane, bromotrimethylsilane, etc.).

[0097] The silylating agent may contain a cyclic silazane compound.

[0098] Examples of the cyclic silazane compound include cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disilazane-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disilazane-1-azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane; and the like.

[0099] The chamfer treatment composition may contain, in addition to the silylating agent, one or more selected from the group consisting of compound A, imide compounds, nitrogen-containing compounds, nitrogen-containing heterocyclic compounds, and silylated heterocyclic compounds described below as accelerators (catalysts) of the silylating agent.

[0100] The concentration of the accelerator may be, for example, 0.01 to 50% by mass, or 0.05 to 25% by mass, relative to 100% by mass of the entire silylating agent.

[0101] The chamfer treatment composition may further contain compound A as an accelerator.

[0102] As the specific example of the above-mentioned compound A, for example, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate and decyldimethylsilyl trifluoromethanesulfonate can be enumerated, and one or more selected from them can be included. They can be used alone or in combination of two or more.

[0103] It should be noted that the compound A is equivalent to the silylating agent, but when used as an accelerator, it means that it is used in combination with a silylating agent other than the compound A.

[0104] The compound A as the accelerator may be obtained by reacting a silicon compound represented by the following general formula [2] with one or more acetic acids or sulfonic acids selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride.

[0105] The remaining silicon compound represented by the following general formula [2] which is not consumed in the reaction and remains can be used as the above-mentioned silylating agent together with the compound A obtained in the reaction. The silicon compound represented by the following general formula [2] can be reacted in an amount of, for example, 0.2 to 100,000 mole times, preferably 0.5 to 50,000 mole times, and more preferably 1 to 10,000 mole times, relative to the above-mentioned acetic acid or sulfonic acid in terms of molar ratio.

[0106] R 2 c (H) d Si-X [2]

[0107] In the above general formula [2], R 2 c (H) d Si-, (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3)2Si-, (C6H 13 )(CH3)2Si-,(C8H 17 )(CH3)2Si-、(C 10 H 21 )(CH3)2Si-, etc. In addition, X is the same as in the above general formula [1].

[0108] The compound A as the accelerator may be at least one selected from the group consisting of a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, and a sulfonic acid derivative represented by the following general formula [4].

[0109] R 8 -S(=O)2OH [3]

[0110] [In the above general formula [3], R 8 It is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a hydroxyl group.]

[0111] R 8 -S(=O)2O-Si(H) 3-r (R 9 ) r [4]

[0112] [In the above general formula [4], R 8 is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 9 Each is independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine elements, and r is an integer of 1 to 3.]

[0113] The accelerator compound A may be at least one selected from the group consisting of a sulfonate ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfomethylated product represented by the following general formula

[10] , and a sulfomethylated derivative represented by the following general formula

[11] .

[0114] R 10 -S(=O)2OR 11 [5]

[0115] [In the above general formula [5], R 10 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 11 It is a monovalent alkyl group having 1 to 18 carbon atoms.]

[0116] (R 12 -S(=O)2)2NH [6]

[0117] [In the above general formula [6], R 12 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements.]

[0118]

[0119] [In the above general formula [7], R 13 It is a divalent hydrocarbon group with 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements.]

[0120] ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8]

[0121] [In the above general formula [8], R 14 Each independently represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 15 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, s is an integer of 1 to 3, t is an integer of 0 to 2, and the total of s and t is 3 or less.]

[0122]

[0123] [In the above general formula [9], R 16Each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 17 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, u is an integer of 1 to 3, v is an integer of 0 to 2, and the total of u and v is 3 or less.]

[0124] (R 18 -S(=O)2)3CH

[10]

[0125] [In the above general formula

[10] , R 18 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements.]

[0126] ((R 19 -S(=O)2)3C) w Si(H) x (R 20 ) 4-w-x

[11]

[0127] [In the above general formula

[11] , R 19 Each independently represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 20 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, w is an integer of 1 to 3, x is an integer of 0 to 2, and the total of w and x is 3 or less.]

[0128] The chamfer treatment composition may further contain an imide compound such as a carboxyimidide or a phosphorimidide, as necessary.

[0129] Examples of the imidized product include compounds having a chemical structure obtained by imidizing an acid such as carboxylic acid or phosphoric acid.

[0130] The chamfer treatment composition may further contain at least one nitrogen-containing compound selected from the group consisting of compounds represented by the following general formulas

[12] and

[13] , if necessary.

[0131] R 21 -N=C(NR 22 2)2

[12]

[0132] R 21 -N=C(NR 22 2) R 22

[13]

[0133] [In the above general formulas

[12] and

[13] , R 21 Selected from hydrogen, -C≡N, -NO2, alkylsilyl, and hydrocarbon groups in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, wherein the hydrocarbon groups optionally contain oxygen atoms and / or nitrogen atoms, and when nitrogen atoms are contained, the hydrocarbon groups have a non-cyclic structure. 22 Each is independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group optionally contains oxygen atoms and / or nitrogen atoms, and when containing nitrogen atoms, it takes a non-cyclic structure.]

[0134] Examples of the nitrogen-containing compound include guanidine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,3-diphenylguanidine, 1,2,3-triphenylguanidine, N,N′-diphenylformamidine, and 2,2,3,3,3-pentafluoropropylamidine.

[0135] The chamfer treatment composition may further contain at least one nitrogen-containing compound selected from the group consisting of compounds represented by the following general formulas

[14] and

[15] , if necessary.

[0136]

[0137] [In the above general formula

[14] , R 23 and R 24 Each is independently a divalent organic group formed of a carbon element and / or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen atoms is 1 to 9. When there are 2 or more carbon atoms, the carbon element that does not constitute a ring may not exist.]

[0138]

[0139] [In the above general formula

[15] , R 25 is an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, a trialkylsilyl group having an alkyl group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, an alkenyl group having 2 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, an alkoxy group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, an amino group, an alkylamino group having an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, an aminoalkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted by fluorine, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group, and R 26 , R 27 and R 28Each is independently an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, or a hydrogen group.]

[0140] The chamfer treatment composition may further contain a nitrogen-containing heterocyclic compound containing no silicon atom, if necessary.

[0141] The nitrogen-containing heterocyclic compound may contain a heteroatom other than a nitrogen atom such as an oxygen atom or a sulfur atom in the ring, may have aromaticity, and may be a compound in which two or more rings are bonded by a single bond or a divalent or more polyvalent linking group.

[0142] Examples of the nitrogen-containing heterocyclic compounds include pyridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrole, pyrazole, imidazole, methylimidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline, isoquinoline, cinnoline, phthalazine, quinoxaline, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, benzoxadiazole, benzothiadiazole, saccharin, pyrrolidine, and piperidine.

[0143] The above-mentioned nitrogen-containing heterocyclic compound may have a substituent.

[0144] The chamfered portion treating agent composition may further contain a silylated heterocyclic compound as necessary.

[0145] Examples of the silylated heterocyclic compound include silylated imidazole compounds and silylated triazole compounds. Examples of the silylated heterocyclic compound include monomethylsilyl imidazole, dimethylsilyl imidazole, trimethylsilyl imidazole, monomethylsilyl triazole, dimethylsilyl triazole, trimethylsilyl triazole, and the like.

[0146] It should be noted that the silylated heterocyclic compound is equivalent to the silylating agent, and when used as an accelerator, it means that it is used in combination with a silylating agent other than the silylated heterocyclic compound.

[0147] The chamfered portion treating agent composition may contain a solvent.

[0148] The solvent is not particularly limited as long as it dissolves the silylating agent. As the solvent, for example, organic solvents such as hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, carbonate-based solvents, polyol derivatives, nitrogen-containing solvents, organosilicon solvents, and thiols can be used. Among them, hydrocarbons, esters, ethers, halogen-containing solvents, sulfoxide-based solvents, and polyol derivatives that do not have an OH group are preferred.

[0149] These may be used alone or in combination of two or more.

[0150] Examples of the above hydrocarbons include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, and branched hydrocarbons corresponding to these carbon numbers (for example, isododecane, isohexadecane, etc.), cyclohexane, methylcyclohexane, decalin, benzene, toluene, xylene, (o-, m-, or p-)diethylbenzene, 1,3,5-trimethylbenzene, naphthalene, etc.

[0151] Furthermore, as the hydrocarbons, from the viewpoint of the storage property of the silylating agent, hydrocarbon non-polar solvents such as linear, branched, or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and terpene solvents can be used. Among them, linear or branched hydrocarbon solvents or terpene solvents having 6 to 12 carbon atoms are preferred. Examples of terpene solvents include p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane.

[0152] Examples of the esters include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and the like.

[0153] In addition, as the above-mentioned esters, cyclic esters such as lactone compounds can be used. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-valerolactone, δ-caprolactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, ε-caprolactone, etc.

[0154] Examples of the above-mentioned ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-pentyl ether, di-n-pentyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, and ethers having branched hydrocarbon groups corresponding to the carbon numbers of these ethers, such as diisopropyl ether and diisopentyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

[0155] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0156] Examples of the halogen-containing solvent include perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and other perfluorocarbons, 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora H (manufactured by Zeon Corporation) and other hydrocarbon fluorocarbons, methyl perfluoropropyl ether, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, methyl perfluorohexyl ether, ethyl perfluorohexyl ether, Asahiklin AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec Hydrocarbon fluoroethers such as HFE-7200, Novec7300, and Novec7600 (all manufactured by 3M), chlorocarbons such as tetrachloromethane, hydrofluorocarbons 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-3,3,3-trifluoropropene, and other hydrocarbon chlorofluorocarbons, perfluoroethers, and perfluoropolyethers.

[0157] Examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like.

[0158] Examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0159] Examples of the above-mentioned polyol derivatives that do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol Dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol Propylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerol triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

[0160] Examples of the nitrogen-containing solvent include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, diethylamine, triethylamine, pyridine, and the like.

[0161] Examples of the organic silicon solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0162] Examples of the above-mentioned thiols include 1-hexanethiol, 2-methyl-1-pentanethiol, 3-methyl-1-pentanethiol, 4-methyl-1-pentanethiol, 2,2-dimethyl-1-butanethiol, 3,3-dimethyl-1-butanethiol, 2-ethyl-1-butanethiol, 1-heptanethiol, benzyl mercaptan, 1-octanethiol, 2-ethyl-1-hexanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, and 1-tridecanethiol.

[0163] From the viewpoint of cost and solubility, 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.

[0164] The chamfered portion treating agent composition may be one in which the silylating agent is diluted with a solvent.

[0165] In the chamfer treatment agent composition, the concentration of the silylating agent, or the total concentration of the silylating agent and the accelerator, relative to 100 mass % of the solvent, can be, for example, 0.01 mass % to 100 mass %, preferably 0.1 mass % to 50 mass %, and more preferably 1 mass % to 30 mass %.

[0166] The chamfer treatment composition may contain other components other than the above components within a range not hindering the purpose of the present invention. Examples of the other components include oxidants such as hydrogen peroxide and ozone, and surfactants.

[0167] The chamfered portion treating agent composition of the present embodiment can be obtained by mixing the above-mentioned components. The obtained mixed solution can be purified using an adsorbent, a filter, etc. as necessary.

[0168] It should be noted that the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.

[0169] As mentioned above, although embodiment of this invention was described, these are an example of this invention, and various structures other than the above-mentioned can also be adopted.

[0170] Example

[0171] <Preparation of treatment agent composition>

[0172] (Test Example 1)

[0173] 10 g of (H3C)3Si-N(CH3)2 and 1 g of CF3C(=O)OH were mixed in 989 g of propylene glycol monomethyl ether acetate (PGMEA) at a liquid temperature of 25°C for 1 minute to react (H3C)3Si-N(CH3)2 with CF3C(=O)OH to prepare a treatment agent composition A containing CF3C(=O)OSi(H3C)3 as compound A and (H3C)3Si-N(CH3)2 as a silicon compound. Use the treatment agent composition A within 30 minutes after preparation. Hereinafter, "within 30 minutes after preparation" will be referred to as "immediately after preparation".

[0174] (Test Example 2)

[0175] Hexamethyldisilazane (HMDS) was mixed with PGMEA at a liquid temperature of 25° C. for 1 minute to prepare a mixed solution having an HMDS concentration of 5% by mass. The mixed solution immediately after the preparation was used as the chamfer treatment agent composition B.

[0176] (Test Example 3)

[0177] HMDS was mixed with PGMEA at a liquid temperature of 25° C. for 1 minute to prepare a mixed solution having an HMDS concentration of 3% by mass. The mixed solution immediately after the preparation was used as the chamfer treatment agent composition C.

[0178] (Test Example 4)

[0179] In the same manner as in Test Example 1, a chamfer treatment agent composition A containing CF3C(=O)OSi(H3C)3 as compound A and (H3C)3Si-N(CH3)2 as a silicon compound was prepared. The obtained treatment agent composition A was stored in a HDPE container at 25°C for 2 weeks and used as treatment agent composition D.

[0180] (Determination of surface modification index)

[0181] In the treatment agent compositions A to D obtained in Test Examples 1 to 4, the "surface modification index Y" indicating the critical surface tension of the silicon oxide film and the "surface modification index Z" indicating the critical surface tension of the silicon nitride film were measured based on the following steps (1) to (4). The measurement results are shown in Table 1.

[0182] (step)

[0183] (1) A substrate having a silicon oxide film (SiO2 film, thermal oxide film) with a thickness of 1 μm on the surface is treated using the obtained treatment agent composition. The treatment conditions are as follows: the substrate is immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in 2-propanol (iPA) for 1 minute, then immersed in the obtained treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of iPA, and air is blown to remove the iPA on the surface of the substrate.

[0184] (2) Using a plurality of measuring liquids with different mixing ratios of water to iPA (two or more measuring liquids selected from solutions having a mixing ratio of water to iPA of 100:0, 99:1, 95:5, 87:13, 80:20, 66:34, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95, 3:97, 0:100 by mass ratio), the critical surface tension of the silicon oxide film after treatment in (1) is determined by the Zisman Plot method. The value (mN / m) of the critical surface tension of the silicon oxide film obtained is used as the "surface modification index Y".

[0185] (3) A substrate having a silicon nitride film (SiN film, LP-CVD film) with a thickness of 50 nm on the surface was treated using the obtained treatment agent composition. The treatment conditions were as follows: the substrate was immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in iPA for 1 minute, then immersed in the obtained treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate was taken out of the iPA, and air was blown to remove the iPA on the substrate surface.

[0186] (4) Using a plurality of measuring liquids with different mixing ratios of water to iPA (two or more measuring liquids selected from solutions having a mixing ratio of water to iPA of 100:0, 99:1, 95:5, 87:13, 80:20, 66:34, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95, 3:97, and 0:100 by mass ratio), the critical surface tension of the silicon nitride film after treatment in (3) is determined by the Zisman Plot method. The value (mN / m) of the critical surface tension of the silicon nitride film obtained is used as the "surface modification index Z".

[0187] The mixing ratio of water and iPA in the measurement liquid used in each of Test Examples 1 to 4 is as follows.

[0188] <Test Example 1>

[0189] Surface modification index Y (80:20, 66:34, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95)

[0190] Surface modification index Z (80:20, 66:34, 60:40, 50:50)

[0191] <Test Example 2>:

[0192] Surface modification index Y (80:20, 66:34, 60:40)

[0193] Surface modification index Z (87:13, 80:20)

[0194] <Test Example 3>

[0195] Surface modification index Y (99:1, 95:5)

[0196] Surface modification index Z (87:13, 80:20)

[0197] <Test Example 4>

[0198] Surface modification index Y (100:0, 99:1, 95:5, 87:13, 80:20, 66:34, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95, 3:97, 0:100)

[0199] Surface modification index Z (87:13, 80:20)

[0200] The method for calculating the critical surface tension of the substrate based on the above-mentioned Zisman Plot method is as follows. Figure 2 This is a diagram for explaining the outline of the Zisman Plot method.

[0201] For example, when a plurality of measuring liquids 1 to 3 having different surface tensions are used, the contact angle (°) of each liquid with respect to the substrate surface is measured, and the cosine (COS) of the contact angle of each liquid is plotted against the surface tension of each liquid to obtain Figure 2 Next, the surface tension when the cosine on the straight line becomes 1.0 (completely wetted state) is determined as the critical surface tension (mN / m) of the substrate surface to be measured.

[0202] When two or four or more measuring liquids are used, the critical surface tension can be measured in the same manner as in the case of using three liquids.

[0203] In this embodiment, the substrate is a substrate having a silicon oxide film after the above-mentioned (1) treatment or a substrate having a silicon nitride film after the above-mentioned (3) treatment, and the above-mentioned measuring liquid is used. The ambient temperature of the contact angle and the liquid temperature of the measuring liquid are set to 25°C.

[0204] However, when the critical surface tension at which all the droplets of the measurement liquid wet and spread cannot be measured, the critical surface tension is set to 72.0 [mN / m], which is the same as the surface tension of water. The critical surface tension at this time is indicated as "*" in Table 1.

[0205] [Table 1]

[0206]

[0207] In view of the measurement results of "Y / Z" representing the ratio of "surface modification index Y" to the obtained "surface modification index Z", the treatment agent compositions A and B of Test Examples 1 and 2 were used as Examples 1 and 2, and the treatment agent compositions C and D of Test Examples 3 and 4 were used as Comparative Examples 1 and 2.

[0208] The treatment agent compositions of the obtained examples and comparative examples were evaluated based on the following evaluation items. The evaluation results are shown in Table 1.

[0209] (Evaluation of foreign matter adhesion)

[0210] (1) A substrate A having a 1 μm-thick silicon oxide film (SiO 2 film) on its surface and a substrate B having a 50 nm-thick silicon nitride film (SiN film) on its surface are prepared.

[0211] (2) The substrate A and the substrate B in the above (1) were immersed in a 1 mass % hydrofluoric acid aqueous solution at room temperature for 10 minutes, and then immersed in pure water for 1 minute for cleaning.

[0212] (3) The aqueous dispersion of aluminum oxide particles was applied to the surfaces of the substrates A and B cleaned in the above (2), and then the substrates A and B were immersed in iPA for 1 minute.

[0213] (4) The substrate A and substrate B obtained in the above (3) were immersed in each of the treatment agent compositions obtained in Test Examples 1 to 4 at 25° C. for 1 minute, and then immersed in iPA for 1 minute.

[0214] (5) After the above (4), take out the substrate A and substrate B from the iPA, blow air to remove the iPA on the substrate surface.

[0215] The surfaces of the substrates A and B obtained in the above (1) to (5) were observed using a SEM, and the amount of residual aluminum oxide particles was evaluated based on the obtained SEM images.

[0216] The SEM images of the substrate A in Examples 1 and 2 and Comparative Examples 1 and 2 are respectively Figures 3 to 6 , the SEM images of the substrate B in Examples 1, 2 and Comparative Examples 1, 2 are Figures 7-10 . Figures 3 to 10 The white part in the figure represents the aluminum oxide particles remaining on the substrate surface.

[0217] The results of the obtained SEM images showed that, in each of Substrate A and Substrate B, when the treatment agent compositions of Examples 1 and 2 were used, the amount of residual aluminum oxide was reduced compared to Comparative Examples 1 and 2.

[0218] In Table 1, the residual amount of aluminum oxide in Comparative Example 2 was designated as the standard "-", a value lower than the standard was designated as "○", and a value equal to or greater than the standard was designated as "×".

[0219] It should be noted that, when the treatment agent compositions of Examples 1 and 2 were used, almost no aggregation of aluminum oxide particles was observed to adhere to the substrates A and B.

[0220] Based on the above, the treatment compositions of Examples 1 and 2 are superior in preventing metal particles from adhering to the treatment compositions of Comparative Examples 1 and 2. The treatment compositions of Examples 1 and 2 are expected to be suitable for use as chamfer treatment compositions for treating chamfers of semiconductor wafers.

[0221] This application claims the benefit of priority based on Japanese patent application No. 2018-218942, filed on November 22, 2018, the disclosure of which is incorporated herein in its entirety.

Claims

1. A method for using a chamfer treatment composition, which is a method for using a chamfer treatment composition containing a silylation agent for treating a chamfer of a wafer, The surface modification index Y and surface modification index Z measured according to the following steps (1) to (4) satisfy 0.5≤Y / Z≤1.

0. Step (1) uses the chamfer treatment agent composition to treat a substrate having a silicon oxide film (SiO2 film) with a thickness of 1 μm on the surface, and the treatment conditions are as follows: the substrate is immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in 2-propanol (iPA) for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of the iPA, and air is blown to remove the iPA on the surface of the substrate. Step (2) Using a plurality of measuring liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon oxide film treated in step (1) is determined according to the Zisman Plot method, and the value of the critical surface tension (mN / m) obtained is used as the "surface modification index Y". Step (3) uses the chamfer treatment agent composition to treat a substrate having a silicon nitride film (SiN film) with a thickness of 50 nm on the surface, and the treatment conditions are as follows: the substrate is immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in iPA for 1 minute, then immersed in the chamfer treatment agent composition at 25°C for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of the iPA, and air is blown to remove the iPA on the surface of the substrate. In step (4), the critical surface tension of the silicon nitride film treated in step (3) is determined by the Zisman Plot method using a plurality of measuring liquids having different mixing ratios of water and iPA, and the obtained critical surface tension value (mN / m) is used as the "surface modification index Z".

2. The method for using the chamfer treatment composition according to claim 1, wherein: The surface modification index Y satisfies 15mN / m≤Y≤26mN / m.

3. The method for using the chamfer treatment agent composition according to claim 1 or 2, wherein: The silylating agent comprises a silicon compound represented by the following general formula [1]: R 1 a Si(H) b X 4-a-b [1] In the general formula [1], R 1 Each of them is independently an organic group containing a hydrocarbon group with a carbon number of 1 to 18 in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and each of X is independently a monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen, carbon, or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3.

4. The method for using the chamfer treatment composition according to claim 1 or 2, wherein: The silylating agent includes a silicon compound having a trialkylsilyl group.

5. The method for using the chamfer treatment composition according to claim 1 or 2, wherein: The chamfer treatment agent composition contains an organic solvent.

6. The method for using the chamfer treatment composition according to claim 3, wherein: The chamfer treatment agent composition comprises an accelerator of the silicon compound, The accelerator comprises a methyl silyl trifluoroacetate, a methyl silyl trifluoromethanesulfonate, a dimethyl silyl trifluoroacetate, a dimethyl silyl trifluoromethanesulfonate, a butyl dimethyl silyl trifluoroacetate, a butyl dimethyl silyl trifluoromethanesulfonate, a hexyl dimethyl silyl trifluoroacetate, a hexyl dimethyl silyl trifluoromethanesulfonate, an octyl dimethyl silyl trifluoroacetate, an octyl dimethyl silyl trifluoromethanesulfonate, a decyl dimethyl silyl trifluoroacet ... at least one selected from the group consisting of trifluoromethanesulfonate, a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by the following general formula [4], a sulfonic acid ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfomethylated product represented by the following general formula [10], a sulfomethylated derivative represented by the following general formula [11], an imide, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound, R 8 -S(=O)2OH[3] In the general formula [3], R 8 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a hydroxyl group, R 8 -S(=O)2O-Si(H) 3-r (R 9 ) r [4] In the general formula [4], R 8 is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 9 Each independently represents at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and r is an integer of 1 to 3, R 10 -S(=O)2OR 11 [5] In the general formula [5], R 10 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 11 is a monovalent alkyl group having 1 to 18 carbon atoms, (R 12 -S(=O)2)2NH[6] In the general formula [6], R 12 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, In the general formula [7], R 13 It is a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8] In the general formula [8], R 14 Each independently represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 15 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, s is an integer of 1 to 3, t is an integer of 0 to 2, and the total of s and t is 3 or less, In the general formula [9], R 16 Each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 17 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, u is an integer of 1 to 3, v is an integer of 0 to 2, and the total of u and v is 3 or less, (R 18 -S(=O)2)3CH[10] In the general formula [10], R 18 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, ((R 19 -S(=O)2)3C) w Yes(H) x (R 20 ) 4-w-x [11] In the general formula [11], R 19 Each independently represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, R 20 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of hydrogen elements are optionally replaced by fluorine elements; w is an integer of 1 to 3; x is an integer of 0 to 2; and the total of w and x is 3 or less.

7. The method for using the chamfer treatment composition according to claim 1, wherein: Satisfies 0.86≤Y / Z≤0.

95.

8. A method for manufacturing a wafer, comprising: Surface modification process of a wafer having a chamfered portion, and Wafer processing steps, In the surface modification step, a chamfer treatment agent composition is applied to the chamfered portion. For the chamfer treatment agent composition, the surface modification index Y and the surface modification index Z measured according to the following steps (1) to (4) satisfy 0.5≤Y / Z≤1.0, Step (1) uses the chamfer treatment agent composition to treat a substrate having a silicon oxide film (SiO2 film) with a thickness of 1 μm on the surface, and the treatment conditions are as follows: the substrate is immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in 2-propanol (iPA) for 1 minute, then immersed in the chamfer treatment agent composition at 25° C. for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of the iPA, and air is blown to remove the iPA on the surface of the substrate. Step (2) Using a plurality of measuring liquids having different mixing ratios of water and iPA, the critical surface tension of the silicon oxide film treated in step (1) is determined according to the Zisman Plot method, and the value of the critical surface tension (mN / m) obtained is used as the "surface modification index Y". Step (3) uses the chamfer treatment agent composition to treat a substrate having a silicon nitride film (SiN film) with a thickness of 50 nm on the surface, and the treatment conditions are as follows: the substrate is immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, immersed in iPA for 1 minute, then immersed in the chamfer treatment agent composition at 25°C for 1 minute, then immersed in iPA for 1 minute, and finally, the substrate is taken out of the iPA, and air is blown to remove the iPA on the surface of the substrate. In step (4), the critical surface tension of the silicon nitride film treated in step (3) is determined by the Zisman Plot method using a plurality of measuring liquids having different mixing ratios of water and iPA, and the obtained critical surface tension value (mN / m) is used as the "surface modification index Z".

9. The method for manufacturing a wafer according to claim 8, wherein: The wafer processing step is selected from the following steps: a step of forming a fine pattern of a concave-convex shape in a component forming area of ​​the wafer, a step of cutting or grinding the wafer, a film forming step of forming an insulating film or a metal film on the chamfered portion, and a step of cleaning the wafer. The wafer surface modification step is performed before or after the wafer processing step, or between a plurality of steps in the wafer processing step.

10. The method for manufacturing a wafer according to claim 9, wherein: The insulating film is a different type film in which a plurality of different types of materials are mixed and exposed on the surface of the chamfered portion.

11. The method for manufacturing a wafer according to claim 9 or 10, wherein: The insulating film includes a silicon oxide film and a silicon nitride film.

12. The method for manufacturing a wafer according to claim 8 or 9, wherein: In the surface modification step, the chamfer treatment composition is used within 30 minutes after preparation.

13. The method for manufacturing a wafer according to claim 8 or 9, wherein: In the surface modification step, the chamfer treatment agent composition prepared at a liquid temperature of 25° C. was used.

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