WO2012157507A1 - Agent de traitement de surface et procédé de traitement de surface - Google Patents

Agent de traitement de surface et procédé de traitement de surface Download PDF

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Publication number
WO2012157507A1
WO2012157507A1 PCT/JP2012/061972 JP2012061972W WO2012157507A1 WO 2012157507 A1 WO2012157507 A1 WO 2012157507A1 JP 2012061972 W JP2012061972 W JP 2012061972W WO 2012157507 A1 WO2012157507 A1 WO 2012157507A1
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Prior art keywords
group
surface treatment
compound
acid
substrate
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PCT/JP2012/061972
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English (en)
Japanese (ja)
Inventor
尚正 古田
鈴木　浩
勝可 原田
柱賢 鄭
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東亞合成株式会社
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Priority to JP2013515097A priority Critical patent/JPWO2012157507A1/ja
Publication of WO2012157507A1 publication Critical patent/WO2012157507A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a surface treatment agent and a surface treatment method for improving the water repellency of a surface of an object to be treated, and more specifically, a surface treatment agent for making a substrate surface of a liquid crystal, a semiconductor or the like to which a lithography technique is applied to be water repellent.
  • the present invention also relates to a surface treatment method for making a substrate surface water repellent using the surface treatment agent.
  • lithography technology is used when processing such as etching on a substrate.
  • a photosensitive resin layer is provided on a substrate using a photosensitive resin composition, and then exposed to selective irradiation with actinic radiation for exposure and development, and then a photosensitive resin layer. Is selectively dissolved and removed, a resin pattern is formed on the substrate, and an etching process is performed using the resin pattern as a mask, whereby a pattern to be etched is formed on the substrate.
  • a photosensitive resin layer is formed in order to build a plurality of types of elements and circuits on the substrate.
  • the surface of a semiconductor substrate to which lithography technology is applied can be a mixture of various surface states, such as a previously formed surface or a surface after being removed by etching.
  • a SiO 2 film is usually formed on the surface of a silicon wafer before manufacturing a semiconductor product, and moisture in the atmosphere is bonded to the outermost surface of the SiO 2 film to form Si—OH.
  • Patent Document 1 discloses a method for trimethylsilylation by reacting hexamethyldisilazane with an OH group on an oxidized silicon wafer surface after oxidizing the silicon wafer surface. Is disclosed. It is also known that such a water repellency treatment can improve the adhesion between the substrate surface and the resist resin.
  • Patent Document 2 as a method for preventing pattern collapse, a method for treating a substrate surface using a surface treatment solution obtained by diluting a silylating agent such as N, N-dimethylaminotrimethylsilane or hexamethyldisilazane with an organic solvent. Is disclosed.
  • Patent Document 3 a plurality of convex patterns having a hydroxyl group on the surface formed on a semiconductor substrate, a surface treatment agent containing a silane coupling agent having a hydrolyzable group that reacts with the hydroxyl group, It is disclosed that a water-repellent protective film having low wettability to water can be formed, and that the water repellency is increased by cleaning the substrate surface using sulfuric acid and hydrogen peroxide.
  • Patent Documents 2 and 3 as a method for evaluating the water repellency of the substrate surface, it is described that a contact angle to water is measured, and those having a large contact angle value can suppress pattern collapse. It is known that increasing the contact angle is a solution to pattern collapse.
  • Patent Document 3 describes that surface treatment with a surface treatment agent can be used for a silicon nitride film, but in the case of a silicon-based film, contact with water after forming a water-repellent protective film. In contrast to the angle of 89 degrees, in the case of a silicon nitride film, only about 46 degrees can be obtained, and the contact angle is improved to 59 degrees by converting the silicon nitride film surface to SiO 2 with an oxidizing agent. There is a description.
  • the silicon nitride film is easier to obtain a dense film quality than the oxide film, and also has a characteristic as an antireflection film. Therefore, the silicon nitride film is a material frequently used in recent highly integrated semiconductor devices. A method for providing sufficient water repellency to the surface of the material has been demanded.
  • the subject of this invention is providing the surface treating agent which improves the water repellency of the surface of to-be-processed objects, such as a board
  • Another object of the present invention is to provide a method for making the surface of an object to be treated such as a semiconductor substrate water repellent using the surface treating agent.
  • the present invention is shown below. 1.
  • the surface treating agent characterized by including the compound (A) represented by following General formula (1).
  • R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a cyanoalkyl group,
  • a, w, x, y and z are each independently 0 or a positive number, at least one of w and x is a positive number, 0 ⁇ w / (x + y) ⁇ 5, 0 ⁇ z / (a + w + x + y) ⁇ 1.
  • Compound A may contain only 1 type of each structural unit, and may contain 2 or more types. ] 2.
  • R 3 and R 5 are each independently a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, a cycloaralkyl group or an aryl group, and w, x and y are independently of each other, It is a positive number and z is 0 or a positive number.
  • 3. The surface treating agent according to 1 above, wherein at least one of R 1 , R 2 , R 3 , R 4 and R 5 in the general formula (1) is a cyanoalkyl group. 4). 4. The surface treating agent according to 3 above, wherein the compound (A) is represented by the following general formula (7).
  • B is a cyanoalkyl group
  • b, x, y and z are each independently 0 or a positive number
  • c is a positive number.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, alkyl group, aralkyl group, cycloalkyl group, cycloaralkyl group or aryl group
  • R 14 and R 15 are independently A hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group, and R 14 and R 15 are bonded to each other. Or a saturated or unsaturated heterocycloalkyl group having a nitrogen atom. ] 8).
  • the surface treatment method according to 11 or 12 above, wherein the object to be treated contains silicon nitride on a part of its surface. 14 14. The surface treatment method according to any one of 11 to 13, wherein the object to be treated includes silicon oxide on a part of the surface thereof. 15. The surface treatment method according to any one of the above 11 to 14, wherein the object to be treated contains metallic silicon in a part of its surface. 16. The surface treatment method according to any one of 11 to 15, further comprising an acid contact step in which an acidic liquid containing an acid is brought into contact with the object to be processed before the contact step. 17. 17. The surface treatment method according to 16 above, wherein the acid is an inorganic acid having an acid dissociation constant (pKa) of less than 0. 18.
  • pKa acid dissociation constant
  • the object to be processed has a silicon nitride film and a silicon oxide film on the surface thereof, and after the contact step, the contact angle (Can) of water on the surface of the silicon nitride film and the surface of the silicon oxide film 18.
  • a surface treatment method for making a surface of a semiconductor substrate water repellent a first step of bringing an acid liquid containing an acid into contact with the semiconductor substrate, and a surface treatment agent containing a compound represented by the following general formula (11):
  • a surface treatment method comprising sequentially providing a second step of contacting the semiconductor substrate.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, alkyl group, aralkyl group, cycloalkyl group, cycloaralkyl group or aryl group
  • R 14 and R 15 are independently A hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group, and R 14 and R 15 are bonded to each other. Or a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.
  • the semiconductor substrate has a silicon nitride film and a silicon oxide film on its surface, and after the second step, the contact angle (Can) of water on the surface of the silicon nitride film and the surface of the silicon oxide film 24.
  • the surface treating agent of the present invention it is possible to improve the water repellency by forming a film on the surface of an object to be treated such as a substrate used for a liquid crystal or a semiconductor. It is known that the surface of a water-repellent semiconductor substrate or the like has good adhesion to a resist resin, and it is known that the problem of so-called pattern collapse does not occur.
  • the surface treatment agent of the present invention improves the yield of semiconductor manufacturing. Can be expected to do.
  • the surface of the substrate having different surface materials and states can be made water repellent to the same extent, so that the yield is particularly high in a semiconductor substrate or the like in which patterns made of different materials are mixed. The improvement effect can be expected.
  • the contact angle is a value measured using water by a method according to JIS R1257.
  • the surface treating agent of the present invention contains a compound (A) represented by the following general formula (1), and if necessary, contains other silicone compounds, organic solvents, additives and the like.
  • R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a cyanoalkyl group,
  • a, w, x, y and z are each independently 0 or a positive number, at least one of w and x is a positive number, 0 ⁇ w / (x + y) ⁇ 5, 0 ⁇ z / (a + w + x + y) ⁇ 1.
  • Compound A may contain only 1 type of each structural unit, and may contain 2 or more types.
  • the said compound (A) is a silicon compound containing the structural unit shown below as represented by the said General formula (1).
  • the content rate of each structural unit is based on prescription
  • the said compound (A) may not contain all the structural units.
  • the compound (A) represented by the general formula (1) is a kind of polysiloxane in which structural units represented by (SiO 4/2 ) and the like are bonded to each other through a siloxane bond,
  • the bonding form of the structural units may not necessarily be the arrangement order of the general formula (1).
  • a, w, x, y, z represent the composition ratio (molar ratio) of each structural unit.
  • the compound (A) since any one of R 1 , R 2 , R 3 , R 4 and R 5 is a hydrogen atom, the compound (A) has an Si—H bond having chemical reactivity. Will be included. Si—H bonds are sometimes referred to as Si—H groups or hydrosilyl groups.
  • the number average molecular weight (Mn) of the compound (A) represented by the general formula (1) is preferably 120 or more and 20000 or less, more preferably 200 or more and 10,000 or less, and further preferably 240 or more and 10,000 or less.
  • Mn number average molecular weight
  • a surface treating agent containing the compound (A) having Mn in the above range is used, a highly water-repellent film can be formed, and in particular, a water-repellent film can be efficiently formed even on fine uneven surfaces. .
  • a preferred compound (A) is a compound represented by the following general formulas (2) to (6) from the viewpoint of water repellency, and more preferred compounds are represented by the general formulas (3) and (4), and particularly preferred compounds.
  • the compound represented by the general formula (3) has a trifunctional structural unit having both a Si—O bond and a Si—H bond, and the compound represented by the general formula (4) includes two Si— It has a structural unit having both an O bond and a Si—H bond.
  • R 2 , R 4 and R 5 are each independently a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group, and R 6 is a hydrogen atom or a carbon atom number of 1 to 6
  • x and y are positive numbers
  • z is 0 or a positive number
  • the ratio of x / y is preferably 0.5 to 2000, more preferably 1 to 200.
  • R 5 independently of one another represents a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • w and y are positive numbers
  • z is 0 or a positive number
  • the ratio of w / y is preferably 0.3 to 5.0.
  • R 3 and R 5 are each independently a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group
  • R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • w, x and y are positive numbers
  • z is 0 or a positive number.
  • R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, a cycloaralkyl group or an aryl group.
  • x is preferably 0.1 to 0.9, more preferably 0.2 to 0.5 and w are preferably 0.05 to 0.5, more preferably 0.1 to 0.4, and y is preferably 0.05 to 0.5, more preferably 0.1 to 0.00. 4, z is preferably 0.001 to 0.2, more preferably 0.005 to 0.1.
  • the compound (A) in which at least one of R 1 , R 2 , R 3 , R 4 and R 5 in the general formula (1) is a cyanoalkyl group is also a preferred embodiment, and particularly preferably at least R A compound in which 1 is a cyanoalkyl group.
  • a compound in which two or more of R 1 , R 2 , R 3 , R 4 and R 5 are cyanoalkyl groups may be used, and preferred examples in that case include, for example, R 1 and R 5 .
  • the cyanoalkyl group is represented by NC—R 7 —.
  • R 7 is a linear or branched divalent alkyl group having 1 to 5 carbon atoms.
  • R 7 preferably has 1 to 3 carbon atoms.
  • Specific examples of the cyanoalkyl group include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, and the like. In the present invention, a cyanoethyl group or a cyanopropyl group is more preferable, and a cyanoethyl group is particularly preferable.
  • the ratio of x / y is preferably 0.1 to 200, more preferably 0.5 to 20.
  • the ratio of w / y when w and y are not 0 is preferably 0.3 to 5.0.
  • a preferred compound is represented by the following general formula (7).
  • B is cyanoalkyl group, R 2, R 3, R 4 and R 5, independently of one another, a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group
  • R 6 Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • b, x, y and z are each independently 0 or a positive number
  • c is a positive number.
  • a more preferable compound can be represented by the following general formula (8).
  • B is a cyanoalkyl group
  • R 3 and R 5 are each independently an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group
  • R 6 is a hydrogen atom or a carbon atom of 1 -6 alkyl groups
  • b, x, y and z are independently of each other 0 or a positive number
  • c is a positive number.
  • the compound represented by the general formula (8) is also a kind of polysiloxane.
  • R 2 , R 4 and R 5 are each independently a hydrogen atom, a cyanoalkyl group, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group, and R 2 , R 4 and R 5 are At least one of them is a cyanoalkyl group, R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x and y are positive numbers, and z is 0 or a positive number.
  • X / y ratio is preferably 0.1 to 200, more preferably 0.5 to 20.
  • one R 5 is a cyanoalkyl group
  • the other R 5 is independently a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group or an aryl group
  • R 6 is a hydrogen atom.
  • An atom or an alkyl group having 1 to 6 carbon atoms, w and y are positive numbers, z is 0 or a positive number, and the ratio of w / y is preferably 0.3 to 5.0. More preferably, it is 0.8 to 4.0.
  • the manufacturing method of the said compound (A) is not specifically limited, The method of using for the raw material organosilicon compound which forms each structural unit to hydrolytic condensation on acidic conditions is common.
  • the structural unit (i) tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrachlorosilane, or the like can be used as a raw material organic silicon compound.
  • trimethoxysilane, triethoxysilane, tripropoxysilane, trichlorosilane, cyanopropyltrimethoxysilane, cyanoethyltriethoxysilane, or the like can be used as the raw material organic silicon compound.
  • dimethoxymethylsilane, diethoxymethylsilane, dipropoxymethylsilane, dichloromethylsilane, or the like can be used as a raw material organic silicon compound.
  • methoxytrimethylsilane, chlorotrimethylsilane, trimethylsilanol, hexamethyldisiloxane, tetramethyldisiloxane, or the like can be used as a raw material organic silicon compound.
  • methanol, ethanol, propanol, s-butanol, or the like can be used.
  • the surface treating agent of the present invention may contain only one kind of the above compound (A), or may contain two or more kinds. For example, you may combine the compound represented by the said General formula (4), and the compound represented by the said General formula (7).
  • the surface treating agent of the present invention contains the compound (A) represented by the general formula (1) and may be composed only of the compound (A), or the compound (A) and other repellent materials. It may consist of a hydrating agent. As another water repellent, a compound represented by the following general formula (11) (hereinafter referred to as “compound (B)”) is preferable.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, alkyl group, aralkyl group, cycloalkyl group, cycloaralkyl group or aryl group
  • R 14 and R 15 are independently A hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group, and R 14 and R 15 are bonded to each other. Or a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.
  • Examples of the compound (B) include N, N-dimethylaminotrimethylsilane (hereinafter abbreviated as “DMATMS”), N, N-dimethylaminotriethylsilane, N, N-diphenylaminotriethylsilane, N, N-diethylaminotrimethyl.
  • DMATMS N, N-dimethylaminotrimethylsilane
  • N, N-dimethylaminotriethylsilane N, N-diphenylaminotriethylsilane
  • N-diethylaminotrimethyl N, N-diethylaminotrimethyl.
  • the content ratio of the compound (A) and the compound (B) is not limited.
  • the sum total of a compound (A) and a compound (B) is 100 mass%, the ratio of a compound (B) becomes like this.
  • it is less than 60 mass%, More preferably, it is 1 to 40 mass%.
  • the surface treatment agent of the present invention may further contain an organic solvent and additives (pH adjuster, leveling agent, surfactant, silane coupling agent, stabilizer, etc.).
  • an organic solvent a solvent that dissolves the compound (A) or a solvent that does not dissolve the compound (A) but disperses the compound (A) and additives can be used.
  • a compound capable of dissolving the compound (A) is preferable because a surface treatment agent having a more uniform concentration distribution can be obtained.
  • substrate of a semiconductor or the to-be-etched pattern surface can be used.
  • sulfoxides such as dimethylsulfoxide; sulfones such as dimethylsulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone, tetramethylenesulfone; N, N-dimethylformamide, N-methylformamide, N, N Amides such as dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2 -Lactams such as pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidi
  • Non-imidazolidinones such as non-dimethyl ether, die
  • organic solvents those having a relatively small polarity and a small molecular weight are preferred. However, if the molecular weight is too small, the volatility is too high and handling becomes difficult. Accordingly, preferred organic solvents are linear or branched hydrocarbon solvents or terpene solvents having 6 to 12 carbon atoms, and specifically include n-hexane, n-heptane, n-octane. N-nonane, methyloctane, n-decane, n-undecane, n-dodecane and the like.
  • Terpene solvents include p-menthane, o-menthane, m-menthan and other menthane, diphenylmenthane, limonene, ⁇ -terpinene, ⁇ -terpinene, ⁇ -terpinene and other terpinenes, bornane, norbornane, pinane, ⁇ -Pinenes such as pinene and ⁇ -pinene, monoterpenes such as karan and longifolene, diterpenes such as abiethane, and the like.
  • These organic solvents may be used alone or in combination of two or more. More preferred organic solvents are linear hydrocarbon solvents having 7 to 10 carbon atoms, menthane and pinane, particularly preferably hexane and octane.
  • the concentration of the compound (A) or the concentration of the total amount of the compound (A) and other water repellent is relative to the total amount of the surface treatment agent.
  • it is 0.1 to 60%, more preferably 0.5 to 30%, more preferably 1 to 20%.
  • Si As the substrate suitable for water repellency of the surface of the object to be processed using the surface treatment agent of the present invention, Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al , Cu, Al—Si, Si—C, alumina, sapphire, glass, resin, and the like.
  • the substrate is not limited to the above-mentioned material
  • the base surface has Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al, Cu, Al-Si, alumina, Water repellency can be similarly applied to a laminated substrate film having a film made of sapphire, ITO, ZnO, glass or the like.
  • the above film is formed using a conventionally known technique such as CVD, vacuum vapor deposition, plating, plating, or the like.
  • CVD methods such as plasma CVD, thermal CVD, and photo-CVD are known, but a film formed by any method may be used.
  • various types such as a low temperature film formation technique such as plasma and a method of epitaxial growth at high temperature are known.
  • SiN is not necessarily a composition of Si 3 N 4 which is a stoichiometric value but an intermediate composition expressed as SiN x .
  • any of the compositions has an effect, it is typically referred to as SiN (or silicon nitride).
  • a preferable object to be treated has a material having a contact angle of preferably 0 to 80 degrees, more preferably 5 to 60 degrees, and still more preferably 10 to 50 degrees on the surface.
  • it is a semiconductor substrate using a silicon wafer, and a film or pattern of SiN, SiO 2 , metal silicon (Si) or the like (including the case of having Si—OH) may be placed on the surface thereof, A resist resin film or its pattern may be placed thereon.
  • the effect of the present invention is most remarkable in at least a part of the surface of the substrate on three kinds of materials such as SiN such as Si 3 N 4 and SiON, SiO 2 , and Si such as amorphous silicon and crystalline silicon.
  • a high water-repellent film can be provided regardless of the material of the surface of the object to be treated.
  • the Si—H bond in the compound (A) is such that the H atom is negative and the Si atom is positively polarized.
  • the —H bond since the O atom is negative and the H atom is positively polarized, a hydrogen bond is generated here, and the compound (A) is oriented on the substrate surface to make the substrate surface water repellent. It is thought that the effect is given.
  • the surface treatment agent of the present invention contains a compound (A) in which at least one of R 1 , R 2 , R 3 , R 4 and R 5 in the general formula (1) is a cyanoalkyl group
  • a high water-repellent film can be provided for any of SiO 2 , SiN, and Si.
  • the compound (A) contains a cyanoalkyl group
  • the magnitude of the effect on each surface material can be controlled by the amount of the cyanoalkyl group and the amount of Si—H bond.
  • the ratio of the total amount of structural units having a cyanoalkyl group and the total amount of structural units having a Si—H bond is 1 to 20 mol% when the sum of both is 100 mol% and 99 to 80 mol%.
  • the amount of the structural unit having a cyanoalkyl group focused on the cyanoalkyl group and an Si—H bond focused on the Si—H bond If the calculation is carried out with the total of both as the amount of structural units being 100 mol%, the above control can be made the same. By such control, the values of the contact angles on the surfaces of different materials of SiO 2 , SiN, and Si can be made closer.
  • the latest liquid crystal and semiconductor substrate surfaces have micropatterns of various surface materials such as SiO 2 , SiN, Si, etc., so that not only can the substrate surface be made water-repellent, but the same level on the surface of different materials
  • the ability to impart the water repellency is an extremely advantageous effect in solving the problem of pattern collapse on the substrate surface of a semiconductor or the like having a complicated pattern. Such an effect has not been conventionally known.
  • the surface treatment method of the present invention includes a contact step of bringing the surface treatment agent of the present invention into contact with the surface of an object to be processed.
  • the specific method of a contact process is not specifically limited,
  • coating a surface treating agent is simple.
  • the coating may be any method such as spray coating, spin coating or dipping, but spin coating is preferred from the viewpoint that a thin and uniform water-repellent film can be obtained.
  • what contains an organic solvent is preferably used for a surface treating agent.
  • the surface treatment agent of the present invention contains the compound (A) and the compound (B), it is preferable to use them in a mixed state from the viewpoint of the uniformity of the thickness of the coating film.
  • Either one of the compound (A) and the compound (B) is first brought into contact with the surface of the semiconductor substrate and then brought into contact with the other, or both the compound (A) and the compound (B) are supplied from separate supply ports.
  • a method of supplying the surface of the semiconductor substrate can be used.
  • the object to be processed is preferably a semiconductor substrate having a film made of at least one of SiO 2 , SiN and Si on a part of its surface.
  • pretreatment such as cleaning and drying of the semiconductor substrate may be performed, and after the contacting step, post-processing such as washing and drying may be performed.
  • post-processing such as washing and drying may be performed.
  • the cleaning method in the pretreatment step is not particularly limited, but for example, a method called “SC1 cleaning” using ammonia and hydrogen peroxide is known. Further, acid treatment of the surface (hereinafter referred to as “acid contact step”) may be performed before and after cleaning the semiconductor substrate.
  • the acid contact step is to bring an acidic liquid containing acid into contact with the surface of the semiconductor substrate by a method such as coating, spraying, dipping, or vapor contact.
  • the method of immersing the substrate in an aqueous acid solution is preferable because it can be carried out with a simple apparatus.
  • the concentration of the acid when an aqueous solution is used as the acidic liquid is preferably 0.1% by mass or more and 96% by mass or less, more preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less. is there.
  • the condition for bringing the acidic liquid into contact with the surface of the semiconductor substrate is not particularly limited, but it is preferably about 1 second to 30 minutes, more preferably 10 seconds to 10 minutes at a temperature higher than 0 ° C. and lower than 70 ° C. Thus, effects such as impurity removal can be obtained.
  • the acid used in the acid contact step may be either an organic acid or an inorganic acid.
  • an acid having an acid dissociation constant (pKa) of 2.0 or less such as oxalic acid, trichloroacetic acid, trifluoroacetic acid, or dichloroacetic acid, is preferable, and oxalic acid is more preferable.
  • an inorganic acid having an acid dissociation constant (pKa) of 0.0 or less is preferable.
  • hydrochloric acid, sulfuric acid, nitric acid, hydroiodic acid, hydrobromic acid, chloric acid, bromic acid examples thereof include iodic acid, permanganic acid, thiocyanic acid, perchloric acid, perbromic acid, tetrafluoroboric acid, hexafluorophosphoric acid and the like.
  • hydrochloric acid, sulfuric acid, and nitric acid that are easily obtained industrially are preferable, and hydrochloric acid is particularly preferable because it is safe in that it is not oxidizable and hardly forms a hardly soluble salt.
  • organic acids and inorganic acids inorganic acids are preferred in that high purity products are easily obtained.
  • acids are preferably highly pure to the extent that they are commercially available.
  • EL grade except a particle can also be used preferably similarly.
  • an acid having low water solubility such as oxalic acid
  • a solution using 2-propanol, methyl ethyl ketone or the like as an organic solvent can be used in the same manner as other acid aqueous solutions.
  • the compound (A) contained in the surface treatment agent of the present invention may be hydrolyzed by contact with water, and a preferable solvent in the case where the surface treatment agent contains an organic solvent is one having a relatively small polarity. Therefore, when water is used in the cleaning in the pretreatment process or the acid contact process after cleaning, the water and the surface between the cleaning process and the acid contact process, and between the acid contact process and the contact process. It is preferable to provide a step of replacing the medium remaining on the surface of the semiconductor substrate with an organic solvent such as alcohol having an intermediate polarity of the organic solvent contained in the treatment agent.
  • the substrate is washed by a washing method using deionized water, then washed with water, and alcohol.
  • a contact process with the surface treatment agent the surface treatment agent diluted with a low-polarity solvent is brought into contact with the substrate, then the solvent is replaced with alcohol, washed with deionized water, and dried.
  • the substrate is cleaned by a cleaning method using deionized water, and then the acid is added.
  • the main constituent material of the formed water-repellent film is the compound (A) itself or the compound (A).
  • the contact angle in this water-repellent coating is preferably 80 to 120 degrees, more preferably 85 to 95 degrees.
  • the main constituent material of the formed water-repellent film is the compound (A) and the compound (B) itself.
  • the contact angle in this water-repellent coating is preferably 80 to 120 degrees, more preferably 85 to 95 degrees.
  • the object to be processed is a silicon wafer (semiconductor substrate) having a silicon nitride film and a silicon oxide film on its surface, a contact angle (Can) on the surface of the silicon nitride film after the contact step.
  • the contact angle (Cao) at the surface of the silicon oxide film (Can / Cao) is preferably in the range of 0.7 to 1.3, more preferably 0.9 to 1.1, particularly preferably 0. 97 to 1.03.
  • Another aspect of the present invention is a surface treatment method for imparting water repellency to the surface of a semiconductor substrate, which is represented by a first step in which an acidic liquid containing an acid is brought into contact with the semiconductor substrate, and the following general formula (11):
  • a surface treatment method comprising sequentially providing a second step of bringing a surface treatment agent containing a compound (B) into contact with the semiconductor substrate.
  • the semiconductor substrate means a silicon wafer having a material with a contact angle of preferably 0 to 80 degrees, more preferably 5 to 60 degrees, and still more preferably 10 to 50 degrees on the surface, and SiN, A film or pattern of SiO 2 , (Si) or the like (including the case of having Si—OH) may be placed, or a resist resin film or pattern thereof may be placed.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, alkyl group, aralkyl group, cycloalkyl group, cycloaralkyl group or aryl group
  • R 14 and R 15 are independently A hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group, and R 14 and R 15 are bonded to each other. Or a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.
  • the substrate surface can be cleaned before the step of bringing the acidic liquid into contact with the semiconductor substrate surface, which is the first step.
  • a cleaning method for example, a method called “SC1 cleaning” using ammonia and hydrogen peroxide and a method called “SC2 cleaning” using hydrochloric acid and hydrogen peroxide are known, and any known cleaning method can be used. Can be used. However, for example, a cleaning method using a mixture of hydrofluoric acid and nitric acid obviously erodes the semiconductor substrate surface, and it goes without saying that it is not preferable to apply it to the surface after the pattern is formed. .
  • the SC1 cleaning solution is alkaline, it is preferable to perform a water washing step in the present invention before performing the step of bringing the acidic liquid into contact with the semiconductor substrate surface. Similarly, it is preferable to perform water washing after SC2 washing.
  • the acidic liquid used in the present invention and the cleaning liquid in which hydrochloric acid and hydrogen peroxide used in SC2 cleaning coexist are different in the presence or absence of hydrogen peroxide, and even if SC2 cleaning is performed instead of the step of contacting the acidic liquid, There is no effect.
  • the compound (B) used in the second step may be hydrolyzed, and a preferable solvent when the surface treatment agent is used after being diluted with a solvent is relatively small in polarity. After that, it is preferable to carry out water washing, and further sandwich a step of solvent replacement using a solvent such as alcohol having an intermediate polarity between water and the solvent used in the second step.
  • the method of bringing the surface treatment agent into contact with the substrate is not particularly limited, but the method of applying the surface treatment agent is simple. Coating may be any method such as spray coating, spin coating or dipping, but spin coating is preferred in that a thin and uniform treated film can be obtained. Further, the surface treatment agent is preferably diluted with a solvent.
  • pretreatment such as cleaning and drying of the substrate
  • posttreatment such as washing and drying may be performed, but the surface tension when the cleaning liquid dries.
  • it is not preferable to put a drying step in the pretreatment and it is preferable to perform the surface treatment using the surface treatment agent used in the present invention without drying after washing with the washing liquid.
  • a drying step is usually included, and it is an effect of the present invention that pattern collapse does not occur in the drying step, but an excessive surface treatment agent is present before the drying step. If a large amount remains, it may cause spots on the substrate surface. Therefore, it is preferable that the surface treatment agent diluted with a solvent having a relatively small polarity is brought into contact with the substrate surface, and then the surface treatment with water is performed. It is preferable to wash with water with a step of solvent replacement using a solvent such as alcohol having an intermediate polarity of the solvent used in step 1.
  • the substrate surface that has been subjected to the surface treatment of the present invention can maintain water repellency even after the above-described solvent replacement or cleaning, and pattern collapse can be suppressed even after drying.
  • a process such as dry ashing, ozone oxidation, or wet oxidation can be performed.
  • the substrate is washed by a washing method using deionized water, and then immersed in an aqueous solution containing an acidic liquid (first step) and washed with water.
  • the solvent was replaced with alcohol, and as a contact step (second step) with the surface treatment agent containing compound (B), the surface treatment agent diluted with a low-polar solvent was brought into contact with the substrate, and then the solvent with alcohol was used. Subsequently, a series of steps of washing with deionized water and then drying can be mentioned.
  • the present inventors consider that the reason why the effect does not appear on the silicon nitride surface is that there is a basic functional group on the substrate surface, and in order to change the substrate surface to acidic, hydrogen peroxide is allowed to coexist.
  • the surface treatment was performed with a surface treatment agent containing a specific water repellent, the present invention was completed by finding an excellent effect.
  • the number average molecular weight of the polysiloxane such as the compound (A) according to the present invention was measured by a high-speed GPC system “HLC-8320GPC” (model name) manufactured by Tosoh Corporation as a GPC apparatus.
  • the column used was “TSKgel G4000H XL ” and “TSKgel G2000H XL ” manufactured by Tosoh Corporation.
  • the viscosity of the polysiloxane was measured with an E-type viscometer.
  • HMDS 1,1,1,3,3,3-hexamethyldisilazane manufactured by Kishida Chemical Co., Ltd.
  • TMCT 2,4,6,8-tetramethylcyclotetrasiloxane manufactured by Alpha Eiser.
  • OMCT Octamethylcyclotetrasiloxane manufactured by Tokyo Chemical Industry Co., Ltd., a compound having no Si—H bond.
  • KF-96 This is a dimethyl silicone oil “KF-96-30cs” (trade name) manufactured by Shin-Etsu Silicone Co., which is a compound having no Si—H bond with z of 0 in the general formula (1).
  • KF-99 This is a hydrogen silicone oil “KF-99” (trade name) manufactured by Shin-Etsu Silicone Co., which is a compound in which a, w and z in the general formula (1) are all 0.
  • Synthesis Example 1-1 The manufacturing method of the compound (A) based on this invention is described.
  • a 300 ml four-necked flask was equipped with a magnetic rotor, a liquid feed pump, a reflux condenser and a thermometer, and the system was replaced with nitrogen gas.
  • the temperature in the flask was kept at 25 ° C., and a mixture of 9.30 g of a 3.14% hydrochloric acid aqueous solution and 12.35 g of 2-butanol was gradually added from the dropping funnel while stirring. After completion of dropping, the reaction solution was allowed to stand at 25 ° C. for 22 hours.
  • PCN1 a colorless liquid
  • Mn number average molecular weight
  • PCN1 polysiloxane
  • CN represents a cyano group
  • Me represents a methyl group
  • s-Bu represents a secondary butyl group
  • Et represents an ethyl group.
  • composition was subjected to 1 H-NMR (proton nuclear magnetic resonance) and 29 Si-NMR measurements using polysiloxane (PCN1) as a CDCl 3 (deuterated chloroform) solvent, and analyzed from the obtained chemical shift. That is, a signal having a chemical shift ⁇ (ppm) in the 1 H-NMR spectrum of 2.2 to 2.5 is derived from (CH 2 CH 2 CN), and ⁇ (ppm) is 3.6 to 3.8. signal, (OCH 2 CH 3), the signal [delta] (ppm) is 3.8-4.1, from (OCH (CH 3) CH 2 CH 3).
  • PCN1 polysiloxane
  • the signal with ⁇ (ppm) of ⁇ 10 to 0 is derived from the structure of SiO 1/2
  • the signal with ⁇ (ppm) of ⁇ 40 to ⁇ 35 is SiO 2/2 Derived from the structure.
  • a raw material compound giving a structure having three Si—O— bonds expressed as SiO 1.5 or SiO 3/2 (called T monomer), and Si—O expressed as SiO 1.0 or SiO 2/2 -It has been found that for raw material compounds (called D monomers) that give a structure having two bonds, the raw material compounds charged in the condensation reaction are incorporated into the polysiloxane in a proportion of the amount used.
  • Synthesis Example 1-2 A 300 ml four-necked flask was equipped with a magnetic rotor, a liquid feed pump, a reflux condenser and a thermometer, and the system was replaced with nitrogen gas. To this flask, 12.32 g (75 mmol) of triethoxysilane, 5.43 g (25 mmol) of 2-cyanoethyltriethoxysilane, 10.62 g (100 mmol) of dimethoxymethylsilane, 1,1,3,3-tetramethyldisiloxane 20 .15 g (150 mmol), 2-butanol 24.71 g and xylene 74.12 g were accommodated, and the reaction system was put in a nitrogen gas atmosphere.
  • the temperature in the flask was kept at 25 ° C., and a mixture of 9.30 g of a 3.14% hydrochloric acid aqueous solution and 12.35 g of 2-butanol was gradually added from the dropping funnel while stirring. After completion of dropping, the reaction solution was allowed to stand at 25 ° C. for 22 hours.
  • PCN2 a colorless liquid
  • Mn number average molecular weight
  • PCN2 polysiloxane
  • CN represents a cyano group
  • Me represents a methyl group
  • s-Bu represents a secondary butyl group
  • Et represents an ethyl group.
  • Synthesis Example 1-3 A 300 ml four-necked flask was equipped with a magnetic rotor, a liquid feed pump, a reflux condenser and a thermometer, and the system was replaced with nitrogen gas. This flask was charged with 32.85 g (200 mmol) of triethoxysilane, 20.15 g (150 mmol) of 1,1,3,3-tetramethyldisiloxane, 24.04 g of 2-propanol and 72.12 g of xylene. Was put in a nitrogen gas atmosphere.
  • the temperature in the flask was kept at 25 ° C., and a mixed solution of 2.63% hydrochloric acid aqueous solution (11.10 g) and 2-propanol (12.02 g) was gradually added from the dropping funnel. After completion of dropping, the reaction solution was allowed to stand at 25 ° C. for 22 hours.
  • composition of polysiloxane (P1) is shown in the following structural formula (14) together with the molar ratio of structural units.
  • Me represents a methyl group
  • i-Pr represents an isopropyl group
  • Et represents an ethyl group.
  • composition was subjected to 1 H-NMR (proton nuclear magnetic resonance) measurement using polysiloxane (P1) as a CDCl 3 (deuterated chloroform) solvent and analyzed from the obtained chemical shift. That is, a signal with a chemical shift ⁇ (ppm) of ⁇ 0.2 to 0.6 in the 1 H-NMR spectrum is a signal with a ⁇ (ppm) of 0.9 to 1.5 based on the structure of Si—CH 3. Is (OCH (CH 3 ) 2 and OCH 2 CH 3 ), and a signal with ⁇ (ppm) of 3.5 to 4.1 is OCH 2 CH 3 and ⁇ (ppm) of 4.1 to 5.5.
  • P1 polysiloxane
  • Synthesis Example 1-4 A 300 ml four-necked flask was equipped with a magnetic rotor, a liquid feed pump, a reflux condenser and a thermometer, and the system was replaced with nitrogen gas. To this flask, 16.43 g (100 mmol) of triethoxysilane, 10.62 g (100 mmol) of dimethoxymethylsilane, 20.15 g (150 mmol) of 1,1,3,3-tetramethyldisiloxane, 20.03 g of 2-propanol and 60.10 g of xylene was accommodated, and the reaction system was placed in a nitrogen gas atmosphere.
  • the temperature in the flask was kept at 25 ° C., and a mixture of 9.30 g of a 3.14% hydrochloric acid aqueous solution and 10.02 g of 2-propanol was stirred while gradually being added from the dropping funnel. After completion of dropping, the reaction solution was allowed to stand at 25 ° C. for 22 hours.
  • composition of polysiloxane (P2) is shown in the following structural formula (15) together with the molar ratio of structural units.
  • Me represents a methyl group
  • Et represents an ethyl group
  • i-Pr represents an isopropyl group.
  • composition was subjected to 1 H-NMR (proton nuclear magnetic resonance) measurement using polysiloxane (P2) as a CDCl 3 (deuterated chloroform) solvent and analyzed from the obtained chemical shift. That is, a signal with a chemical shift ⁇ (ppm) of ⁇ 0.2 to 0.6 in the 1 H-NMR spectrum is a signal with a ⁇ (ppm) of 0.9 to 1.5 based on the structure of Si—CH 3. Is (OCH (CH 3 ) 2 and OCH 2 CH 3 ), and a signal with ⁇ (ppm) of 3.5 to 4.1 is OCH 2 CH 3 and ⁇ (ppm) of 4.1 to 5.5.
  • P2 polysiloxane
  • T monomer which gives a structure having three Si—O— bonds represented by SiO 1.5 or SiO 3/2
  • the charged raw material compound is almost in proportion to the amount used. It has been found to be incorporated into polysiloxanes. Therefore, simultaneous equations relating to the side chains were prepared from the integrated values of the signal intensities, and the molar ratio of each structural unit contained in the polysiloxane (P2) was determined from the charged amount of each monomer and the integrated value of NMR. .
  • substrate An object to be processed (hereinafter referred to as “substrate”) is a silicon wafer with a silicon nitride film (hereinafter sometimes referred to as “SiN substrate”) cut into a size of 10 mm ⁇ 50 mm, or a silicon wafer with a silicon oxide film (hereinafter referred to as “SiN substrate”). , “Sometimes referred to as“ SiO 2 substrate ”) and silicon wafer (hereinafter sometimes referred to as“ Si substrate ”). The substrate is designated as No. 2 in Table 2. 1-1 to No.
  • the contact angle on the surface of the substrate after the surface treatment is determined by JIS R1257: 1999 static droplets in air using a dataphysics automatic contact angle measuring device “OCA20 type” for the substrate after drying by nitrogen gas blowing for 20 seconds. It is the average value measured five times by the method.
  • Table 1 shows standard deviations (calculated values) of contact angles on three types of substrate surfaces.
  • the standard deviation is defined according to JIS Z8101-1.
  • the standard deviation is defined as the positive square root of the dispersion of the three contact angle values on the surfaces of the SiN substrate, the SiO 2 substrate and the Si substrate shown in Table 1. The closer this standard deviation value is to 0, the smaller the contact angle deviation due to the type of substrate.
  • Experimental Example 1-13 This experimental example is No. 1 in Table 2. 1-1 to No. This is a blank test in which, in the order of 1-5, each chemical solution (about 5 ml) was immersed in a predetermined temperature at a predetermined temperature for a predetermined time, then nitrogen gas was blown for 20 seconds to remove water, and the contact angle was measured immediately. (See Table 1).
  • Experimental example 2-1 A surface treating agent was prepared by mixing 5 parts by mass of KF-99 and 95 parts by mass of n-octane (see Table 3). Using the chemical solution containing this surface treatment agent, the surface treatment of the object to be treated was performed. The specific method of surface treatment is as shown in Table 2.
  • the object to be processed is a silicon wafer with a SiN film (SiN substrate) having a size of 10 mm ⁇ 50 mm.
  • the contact angle measurement method is also the same as in Experimental Example 1-1 and the like (see Table 3).
  • Experimental Example 2-2 10 parts by mass of KF-99 and 90 parts by mass of n-octane were mixed to prepare a surface treatment agent, and the surface treatment of the SiN substrate surface was performed in the same manner as in Experimental Example 2-1, and the substrate after the treatment The contact angle at the surface was measured. The results are shown in Table 3.
  • Experimental Example 2-3 A surface treating agent was prepared by mixing 5 parts by mass of the polysiloxane (P1) obtained in Synthesis Example 1-3 and 95 parts by mass of n-octane, and the surface of the SiN substrate in the same manner as in Experimental Example 2-1. The contact angle on the substrate surface after the treatment was measured. The results are shown in Table 3.
  • Experimental Example 2-7 The treatment was performed in the same manner as in Experimental Example 2-6 except that a SiO 2 substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 3. In the case of an SiO 2 substrate, No. is used so that the oxide film does not melt. In the treatment in 1-4, the immersion time of the 1% HF aqueous solution was 30 seconds.
  • Experimental Example 2-8 The treatment was performed in the same manner as in Experimental Example 2-6, except that a Si substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 3.
  • Experimental Example 2-13 The treatment was performed in the same manner as in Experimental Example 2-10 except that a SiO 2 substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 3. In the case of an SiO 2 substrate, No. is used so that the oxide film does not melt. In the treatment in 1-4, the immersion time of the 1% HF aqueous solution was 30 seconds.
  • Experimental Example 2-14 The treatment was performed in the same manner as in Experimental Example 2-10 except that a Si substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 3.
  • Experimental Examples 2-9 to 2-14 are examples using a surface treating agent containing a compound containing no Si—H group, and show a low contact angle of less than 85 degrees. It was.
  • Experimental Examples 2-1 to 2-8 are examples using a surface treating agent containing a compound containing a Si—H group, and the contact angle was 86 degrees or more, indicating good water repellency.
  • Experimental Example 3-1 A surface treating agent was prepared by mixing 1 part by mass of KF-99, 4 parts by mass of DMATMS, and 95 parts by mass of n-octane (see Table 4). Using the chemical solution containing this surface treatment agent, the surface treatment of the object to be treated was performed. The specific method of surface treatment is as shown in Table 2.
  • the object to be processed is a silicon wafer with a SiN film (SiN substrate) having a size of 10 mm ⁇ 50 mm.
  • the contact angle measurement method is also the same as in Experimental Example 1-1 and the like (see Table 4).
  • Experimental Example 3-12 The treatment was performed in the same manner as in Experimental Example 3-4 except that a SiO 2 substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 4. In the case of an SiO 2 substrate, No. is used so that the oxide film does not melt. In the treatment in 1-4, the immersion time of the 1% HF aqueous solution was 30 seconds.
  • Experimental Example 3-13 The treatment was performed in the same manner as in Experimental Example 3-4, except that a Si substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 4.
  • Experimental Example 3-21 The treatment was performed in the same manner as in Experimental Example 3-15 except that a SiO 2 substrate was used instead of the SiN substrate, and the contact angle on the treated substrate surface was measured. The results are shown in Table 4. In the case of an SiO 2 substrate, No. is used so that the oxide film does not melt. In the treatment in 1-4, the immersion time of the 1% HF aqueous solution was 30 seconds.
  • Experimental Example 3-22 The treatment was performed in the same manner as in Experimental Example 3-15 except that a Si substrate was used instead of the SiN substrate, and the contact angle on the substrate surface after the treatment was measured. The results are shown in Table 4.
  • surface treatment agents 4-1 to 4-7 shown in Table 5 were prepared, and surface treatment was performed on the SiN substrate, the SiO 2 substrate, and the Si substrate.
  • Experimental Example 4-1 Surface treatment of the object to be treated was performed using a chemical solution containing the individual surface treatment agents 4-1 to 4-7.
  • Table 6 shows specific methods of surface treatment.
  • the object to be processed is a silicon wafer with a SiN film (SiN substrate), a SiO 2 substrate, and a Si substrate having a size of 10 mm ⁇ 50 mm.
  • the substrate was designated as No. 6 in Table 6. 2-1.
  • 2-14 After immersing each chemical solution (about 5 ml) weighed in a resin cup at a predetermined temperature for a predetermined time, blow off nitrogen gas for 20 seconds to remove water, and quickly contact angle Was measured. No. In the HF process in 2-4, a 1 minute process is performed.
  • Experimental Example 4-2 No. The surface treatment of the SiN substrate was performed in the same manner as in Experimental Example 4-1, except that 16% sulfuric acid aqueous solution was used in the acid treatment in 2-9. The results are shown in Table 7.
  • Experimental Example 4-3 No. Surface treatment of the SiN substrate was performed in the same manner as in Experimental Example 4-1, except that 20% nitric acid aqueous solution was used in the acid treatment in 2-9. The results are shown in Table 7.
  • Experimental Example 4-4 No. A surface treatment of the SiN substrate was performed in the same manner as in Experimental Example 4-1, except that a 14% oxalic acid aqueous solution was used in the acid treatment in 2-9. The results are shown in Table 7.
  • the surface of a semiconductor substrate or the like that has a pattern with a high aspect ratio can be made water repellent uniformly, and the yield during semiconductor manufacturing can be improved. .
  • the surface of the semiconductor substrate having a high aspect ratio pattern can be made water repellent uniformly, and the yield during semiconductor manufacturing can be improved. it can.

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Abstract

Cette invention concerne un agent de traitement de surface approprié pour rendre la surface d'un objet d'intérêt hydrophobe, ledit agent comprenant un composé (A) représenté par la formule générale (1). [Dans la formule, R6 représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 6 atomes de carbone; R1, R2, R3, R4 et R5 représentent indépendamment un atome d'hydrogène, un groupe cyanoalkyle, un groupe alkyle, un groupe aralkyle, un groupe cycloalkyle, un groupe cycloaralkyle ou un groupe aryle, au moins un des R1, R2, R3, R4 et R5 représentant un atome d'hydrogène; et a, w, x, y et z représentent indépendamment 0 ou un nombre positif, w et/ou x représentant un nombre positif et les relations suivantes 0 ≤ w/(x+y) ≤ 5 et 0 ≤ z/(a+w+x+y) ≤ 1 étant satisfaites].
PCT/JP2012/061972 2011-05-17 2012-05-10 Agent de traitement de surface et procédé de traitement de surface WO2012157507A1 (fr)

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JP2015032735A (ja) * 2013-08-05 2015-02-16 株式会社東芝 半導体基板の洗浄方法および半導体基板の洗浄装置
JP2019210476A (ja) * 2018-06-04 2019-12-12 東亞合成株式会社 撥水撥油膜組成物及びその利用
CN111512418A (zh) * 2017-12-22 2020-08-07 中央硝子株式会社 表面处理剂和表面处理体的制造方法
WO2020196563A1 (fr) * 2019-03-28 2020-10-01 日産化学株式会社 Composition filmogène
US11981828B2 (en) 2018-06-04 2024-05-14 Toagosei Co. Ltd. Water repellent and oil repellent film composition and use thereof

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