Hydrophilic treatment liquid for semiconductor wafer surface

Abstract

Provided is a hydrophilic treatment liquid for semiconductor wafer surfaces which is capable of imparting hydrophilicity to a semiconductor wafer surface.　The hydrophilic treatment liquid for semiconductor wafer surfaces comprises water and a compound represented by formula (1), and the total content of the water and the compound represented by formula (1) is 95 weight% or more.　R1O-(C3H6O2)n-H (1) (In the formula, R1 is a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R2CO, R2 is a hydrocarbon group having 1 to 24 carbon atoms, and n is an average degree of polymerization of glycerol units indicated in parentheses and is 2 to 60.)

Description

Technical Field

[0001] The invention according to the present disclosure relates to a hydrophilic treatment liquid for the surface of a semiconductor wafer. This application claims the priority of Japanese Patent Application No. 2019-054530, filed in Japan on March 22, 2019, the content of which is incorporated herein by reference.

Background Art

[0002] Generally, in the manufacturing process of a semiconductor wafer (hereinafter sometimes simply referred to as "wafer"), a cut single-crystal silicon ingot is subjected to a polishing process (usually three steps: primary polishing, secondary polishing, and finish polishing) after an etching process. In this polishing process, it is important to maintain a hydrophilic state in order to prevent contamination of the wafer surface. If the wafer surface dries immediately after polishing, contaminant foreign substances such as particles, metal impurities, and organic substances adhering during that time will adhere firmly to the wafer surface and are difficult to remove even in the subsequent cleaning process. The above-mentioned contaminant foreign substances cause surface defects (LPD: Light point defects) in the wafer inspection process. Also, when LPD increases, the surface roughness (haze) also increases, leading to a deterioration in the quality of the wafer surface. For this reason, conventionally, the surface of the wafer after finish polishing has been hydrophilized by adjusting the composition of a polishing material such as slurry.

[0003] The finish-polished wafer is then subjected to a cleaning process. In this cleaning process, "water polishing" is performed. This water polishing rinses the polished surface of the wafer by operating a polishing apparatus while supplying only cleaning water without a polishing material onto a polishing pad after finish polishing. This prevents the wafer surface from being overly etched by an alkaline polishing material and washes away the abrasive grains adhering to the polished surface.

[0004] For example, Patent Document 1 discloses a surface cleaning method for a semiconductor wafer substrate, which includes a water polishing cleaning step of polishing the surface of the wafer substrate after polishing by supplying only cleaning water without a polishing material.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in water polishing using only water, the Si surface of the silicon wafer is exposed by scrubbing with a polishing pad. Since the Si surface is a hydrophobic surface, it is easily contaminated by contamination foreign matters such as particles, metal impurities, and organic substances. Moreover, these contamination foreign matters attached to the hydrophobic wafer surface tend to be difficult to remove. For this reason, there has been a problem that the wafer surface after finish polishing, which has become hydrophilic, returns to hydrophobicity by water polishing, adsorbs the above-mentioned contamination foreign matters, and the cleanliness of the wafer surface decreases.

[0007] Therefore, an object of the present disclosure is to provide a hydrophilizing treatment liquid capable of imparting hydrophilicity to the surface of a semiconductor wafer. Also, an object is to provide a rinse polishing solution in which hydrophilicity is maintained even after rinse polishing by applying it to the surface of a semiconductor wafer that has become hydrophilic after finish polishing. Another object of the present disclosure is to provide a method for manufacturing a semiconductor device including a step of hydrophilizing the surface of a semiconductor wafer using the above-mentioned hydrophilizing treatment liquid.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventor has found that a hydrophilizing treatment liquid for the surface of a semiconductor wafer containing water and a compound represented by the following formula (1), and having a total content ratio of water and the compound represented by the following formula (1) of 95% by weight or more can impart hydrophilicity to the surface of the semiconductor wafer. The invention according to the present disclosure has been completed based on these findings.

[0009] That is, the invention according to the present disclosure provides a hydrophilic treatment liquid for a semiconductor wafer surface, which contains water and a compound represented by the following formula (1), and the total content ratio of water and the compound represented by the following formula (1) is 95% by weight or more (hereinafter, may be referred to as "the hydrophilic treatment liquid of the present disclosure"). R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R 2 CO, and the above R 2 represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin unit shown in the parentheses and is 2 to 60)

[0010] In the hydrophilic treatment liquid, the content ratio of the compound represented by the formula (1) is preferably 0.01 to 1.5% by weight.

[0011] In the hydrophilic treatment liquid, the total content ratio of abrasive grains and basic compounds is preferably 0.1% by weight or less.

[0012] The pH of the hydrophilic treatment liquid is preferably less than 8.

[0013] In the hydrophilic treatment liquid, the weight average molecular weight of the compound represented by the formula (1) is preferably 100 to 3000.

[0014] In the hydrophilic treatment liquid, the HLB value of the compound represented by the formula (1) is preferably 14 or more.

[0015] The hydrophilic treatment liquid may be a rinse polishing solution.

[0016] The invention according to the present disclosure also provides a method for manufacturing a semiconductor device, which includes a step of hydrophilically treating the surface of a semiconductor wafer using the hydrophilic treatment liquid.

Effects of the Invention

[0017] According to the hydrophilic treatment liquid of the present disclosure, when applied to the wafer surface, a hydrophilic film can be formed to impart hydrophilicity. Thereby, adhesion of contaminant foreign matters such as particles, metal impurities, and organic substances to the wafer surface can be prevented.

[0018] Further, if the hydrophilic treatment liquid of the present disclosure is used as a rinse polishing solution for the wafer surface after finish polishing, hydrophilicity can be imparted to the wafer surface. Thereby, even after rinse polishing, the wafer surface does not return to hydrophobicity. Therefore, the hydrophilicity of the wafer surface is maintained, and adhesion of contaminant foreign matters such as particles, metal impurities, and organic substances can be prevented.

[0019] As described above, according to the hydrophilic treatment liquid of the present disclosure, it is possible to manufacture a high-quality semiconductor wafer in which the cleanliness of the wafer surface is maintained and surface defects (LPD) and surface roughness (haze) are reduced.

Mode for Carrying Out the Invention

[0020] 1. Hydrophilic treatment liquid for semiconductor wafer surface The hydrophilic treatment liquid of the present disclosure is used to impart hydrophilicity to the semiconductor wafer surface. The hydrophilic treatment liquid of the present disclosure contains water as an essential component and a compound represented by the following formula (1) (hereinafter, may be referred to as a "polyglycerin derivative"), and the total content ratio of water and the compound represented by the following formula (1) is 95% by weight or more.

[0021] (Compound represented by formula (1)) R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R 2 CO, and the R 2 represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of glycerin units shown in parentheses and is 2 to 60)

[0022] C3H6O2 within the parentheses of formula (1) may have only the structure represented by the following formula (2), may have only the structure represented by the following formula (3), or may have both structures represented by the following formulas (2) and (3). -CH2-CHOH-CH2O- (2) -CH(CH2OH)CH2O- (3)

[0023] Said R 1 is such that 5 to 75% in one molecule is a hydrogen atom.

[0024] Said R 1 and R 2 The hydrocarbon groups in include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by bonding of two or more of these.

[0025] Examples of the aliphatic hydrocarbon group include linear alkyl groups having 1 to 24 carbon atoms (preferably 5 to 20, more preferably 10 to 20, still more preferably 12 to 18) such as methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group (lauryl group), tetradecyl group, myristyl group, cetyl group, stearyl group; branched-chain alkyl groups having 3 to 24 carbon atoms (preferably 5 to 20, more preferably 10 to 20, still more preferably 12 to 18) such as 2-ethylhexyl group, isooctyl group, isodecyl group, isododecyl group, isomyristyl group, isocetyl group, isostearyl group; linear or branched alkenyl groups having 2 to 24 carbon atoms (preferably 10 to 20, more preferably 8 to 18) such as vinyl group, propenyl group, allyl group, hexenyl group, 2-ethylhexenyl group, oleyl group; linear or branched alkapolyenyl groups having 2 to 24 carbon atoms (preferably 2 to 18) such as alkadienyl group, alkatrienyl group, alkatetraenyl group, linoleyl group, linolenyl group; linear or branched alkynyl groups having 2 to 24 carbon atoms such as ethynyl group, propynyl group, etc.

[0026] Among these, as the alkyl group, a linear or branched alkyl group having 12 to 18 carbon atoms such as a dodecyl group or an isostearyl group is preferable. Further, among these, as the alkenyl group, a linear or branched alkenyl group having 5 to 18 carbon atoms such as a hexenyl group or an oleyl group is preferable.

[0027] Examples of the alicyclic hydrocarbon group include cycloalkyl groups having 3 to 24 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclooctyl group; cycloalkenyl groups having 3 to 24 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group, a norbornyl group, an adamantyl group, tricyclo[5.2.1.0 2,6 decane-8-yl group, tetracyclo[4.4.0.1 2,5 .1 7,10 dodecane-3-yl group and other bridged cyclic hydrocarbon groups.

[0028] Examples of the aromatic hydrocarbon group include aryl groups having 6 to 24 carbon atoms (preferably 6 to 15 carbon atoms) such as a phenyl group and a naphthyl group.

[0029] Examples of the hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include cycloalkyl-substituted alkyl groups such as a cyclopentylmethyl group, a cyclohexylmethyl group, and a 2-cyclohexylethyl group (for example, C 3-20 cycloalkyl-substituted C 1-4 alkyl group, etc.). Further, examples of the hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include an aralkyl group (for example, C 7-18 aralkyl group, etc.), an alkyl-substituted aryl group (for example, a phenyl group or a naphthyl group substituted with about 1 to 4 C 1-4 alkyl groups, etc.).

[0030] The R 2The group represented by CO includes, for example, aliphatic acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, stearoyl group, oleoyl group; aromatic acyl groups such as benzoyl group, toluoyl group, naphthoyl group, and the like.

[0031] R 1 Among them, it is preferably at least one selected from the group consisting of an alkyl group, an acyl group, and a hydrogen atom. Also, R 1 Among them, it is particularly preferably at least one selected from the group consisting of a linear alkyl group (especially a linear alkyl group having 1 to 24 carbon atoms such as methyl group, ethyl group, propyl group, decyl group, dodecyl group (lauryl group), stearyl group, particularly a linear alkyl group having 10 to 20 carbon atoms such as dodecyl group), a branched alkyl group (especially a branched alkyl group having 10 to 20 carbon atoms such as isostearyl group), an aliphatic acyl group (especially acetyl group, butyl group, stearoyl group, oleoyl group, particularly acetyl group, oleoyl group), and a hydrogen atom.

[0032] In formula (1), n represents the average degree of polymerization of glycerin. The value of n can be easily changed, for example, in the production method of the compound represented by formula (1) described later, by adjusting the molar ratio of the alcohol to be reacted and 2,3-epoxy-1-propanol (trade name "glycidol", manufactured by Daicel Corporation).

[0033] The average degree of polymerization n in formula (1) is, for example, from 2 to 60, preferably from 2 to 40, more preferably from 4 to 20, and even more preferably from 4 to 10. When n is 2 or more, the water solubility is further improved, so the detergency is also excellent. In addition, the adsorptivity to the semiconductor wafer surface is good, and it is even more excellent in forming a hydrophilic film. When n is 60 or less, it shows good hydrophilicity and the water dispersibility is further improved. Unnecessary foaming is suppressed and the workability is further improved. In the present specification, the method for calculating the average degree of polymerization of glycerin constituting polyglycerin is not particularly limited. For example, a method of calculating from the hydroxyl value, gas chromatography, liquid chromatography, thin layer chromatography, gas chromatography-mass spectrometry or liquid chromatography-mass spectrometry, etc. to determine the composition of polyglycerin and calculate the average degree of polymerization, etc. can be mentioned.

[0034] Also, R in formula (1) 1 When is an alkyl group (among others, a linear or branched alkyl group such as a lauryl group, a stearyl group, an isostearyl group, etc.), n is from 2 to 60. Among others, from the viewpoint of good adsorptivity to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in formula (1) 1 When is an alkyl group, n is preferably from 2 to 30, more preferably from 4 to 20, even more preferably from 4 to 15, and most preferably from 4 to 10.

[0035] Also, R in formula (1) 1 When is a hydrogen atom, n is from 2 to 60. Among others, from the viewpoint of good adsorptivity to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in formula (1) 1 When is a hydrogen atom, n is preferably from 2 to 30, more preferably from 4 to 20, even more preferably from 4 to 15, and most preferably from 4 to 10.

[0036] On the other hand, when R in formula (1) 1 is an acyl group, n is from 2 to 60, and among others, from the viewpoint of good adsorptivity to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in formula (1) 1When it is an acyl group, n is preferably from 2 to 30, more preferably from 4 to 20, still more preferably from 4 to 15, and most preferably from 4 to 10.

[0037] When the value of n is outside the above range, the adsorptivity to the semiconductor wafer surface tends to decrease. Also, when the value of n is below the above range, the hydrophilicity decreases, and it becomes difficult to form a hydrophilic film on the semiconductor wafer surface and impart hydrophilicity.

[0038] The weight average molecular weight of the compound represented by formula (1) is, for example, from 100 to 3000. Among them, from the viewpoint of good adsorptivity to the semiconductor wafer surface and excellent formation of a hydrophilic film, it is preferably from 200 to 3000, more preferably from 200 to 2000, still more preferably from 300 to 2000, and most preferably from 400 to 1500. In addition, from the viewpoint of excellent workability in addition to the above viewpoints, it is more preferably from 400 to 1000, and most preferably from 400 to 800. In this specification, the measurement of the weight average molecular weight is by gel permeation chromatography (GPC).

[0039] The HLB value (Hydrophile-Lipophile Balance) of the compound represented by formula (1) is, for example, 14 or more, preferably from 14 to 20, and more preferably from 14 to 18, from the viewpoint of excellent dispersion stability. The above HLB value can be calculated by the Griffin method.

[0040] As the compound represented by formula (1) in the present disclosure, at least one selected from the compounds represented by the following formulas (1-1) to (1-8) is preferable, and in particular, at least one selected from the compounds represented by the following formulas (1-1) to (1-4), (1-6) to (1-8) is preferable. C 12 H 25 O-(C3H6O2)4-H (1-1) C 12 H 25 O-(C3H6O2) 10 -H (1-2) C18 H 37 -O-(C3H6O2)4-H (1-3) C 18 H 37 -O-(C3H6O2) 10 -H (1-4) CH2=CH-CH2-O-(C3H6O2)6-H (1-5) HO-(C3H6O2) 10 -H (1-6) HO-(C3H6O2) 20 -H (1-7) C 12 H 25 O-(C3H6O2)6-H (1-8)

[0041] As a method for producing the compound represented by formula (1) in the present disclosure, for example, [1] a method of addition polymerization of 2,3-epoxy-1-propanol to a compound represented by R 1 OH (wherein R 1 is the same as above), [2] a method of reacting polyglycerin with a compound represented by R 1 X (wherein X represents a halogen atom. R 1 is the same as above. For example, an alkyl halide, an acid halide), [3] a method of reacting polyglycerin with a reactive derivative of a carboxylic acid such as an acid anhydride, [4] a method of reacting polyglycerin with a polyol such as a glycidyl ether compound represented by the following formula (4)

Chemical formula

[0042] Examples of the alkali catalyst used in the method [1] above include sodium hydroxide, potassium hydroxide, lithium hydroxide, metallic sodium, sodium hydride and the like. These can be used alone or in combination of two or more.

[0043] Examples of the alkyl halide used in the method of [2] above include alkyl chloride, alkyl bromide, alkyl iodide, and the like.

[0044] Examples of the polyglycerin used in the methods of [2] to [4] above include commercially available products such as the trade names "PGL 03P (polyglycerin trimer)", "PGL 06 (polyglycerin hexamer)", "PGL 10PSW (polyglycerin decamer)", and "PGL XPW (polyglycerin tetramer)" (manufactured by Daicel Corporation), and the like can be preferably used.

[0045] Examples of the polyol used in the method of [4] above include 2,3-epoxy-1-propanol, ethylene glycol, propylene glycol, 1,3-propanediol (trimethylene glycol), glycerin, xylitol, sorbitol, and the like.

[0046] The hydrophilic treatment liquid of the present disclosure contains at least one kind of the compound represented by the above formula (1). As described above, the compound represented by the above formula (1) includes polyglycerin, polyglycerin monoether, and polyglycerin monoester. Therefore, the hydrophilic treatment liquid of the present disclosure contains at least one kind of polyglycerin derivative selected from polyglycerin, polyglycerin monoether, and polyglycerin monoester.

[0047] The hydrophilic treatment liquid of the present disclosure may contain, as polyglycerol derivatives, in addition to polyglycerol, polyglycerol monoether, and polyglycerol monoester, for example, polyglycerol diether or polyglycerol diester corresponding to the above compounds. In the hydrophilic treatment liquid of the present disclosure, the total content ratio of polyglycerol, polyglycerol monoether, and polyglycerol monoester is preferably 75% by weight or more, more preferably 90% by weight or more, of the total amount of polyglycerol derivatives contained in the hydrophilic treatment liquid of the present disclosure from the viewpoint of imparting good hydrophilicity. Further, the total content ratio of polyglycerol diether and polyglycerol diester is preferably 5% by weight or less, particularly preferably 1% by weight or less, of the total amount of polyglycerol derivatives contained in the hydrophilic treatment liquid of the present disclosure. The content ratio of each component contained in the polyglycerol derivative is determined by separating each component by high performance liquid chromatography, calculating the peak area with a differential refractive index detector, and calculating the area ratio.

[0048] The hydrophilic treatment liquid of the present disclosure contains the compound represented by the above formula (1) as a non-volatile component. The hydrophilic treatment liquid of the present disclosure may further contain other components (for example, water-soluble polymer compounds such as cellulose derivatives) as non-volatile components. However, in the total amount of non-volatile components contained in the hydrophilic treatment liquid of the present disclosure, the content ratio of the compound represented by the formula (1) (= the ratio occupied by the content ratio of the compound represented by the formula (1)) is, for example, preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, most preferably 90% by weight or more (for example, 95% by weight, preferably 97% by weight, more preferably 99.9% by weight, still more preferably 99.99% by weight) in terms of excellent adsorptivity to the semiconductor wafer and excellent effect of adsorbing to the semiconductor wafer and protecting the surface. The upper limit is 100% by weight. That is, the hydrophilic treatment liquid of the present disclosure may contain substantially only the compound represented by the formula (1) as a non-volatile component.

[0049] In the hydrophilic treatment liquid of the present disclosure, the content ratio of the compound represented by the above formula (1) is not particularly limited. However, in 100% by weight of the hydrophilic treatment liquid of the present disclosure, it is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, still more preferably 0.05% by weight or more, particularly preferably 0.1% by weight or more, and most preferably 0.2% by weight or more. Also, the above content ratio is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, still more preferably 0.7% by weight or less, and particularly preferably 0.5% by weight or less. When the content ratio of the compound represented by the above formula (1) is within the above range, it has excellent adsorptivity to the surface of the semiconductor wafer, adsorbs to the semiconductor wafer to form a hydrophilic film, and has an even better effect of protecting the surface. In particular, when it is at least the above lower limit value, it has excellent detergency and can impart better hydrophilicity to the surface of the polished semiconductor wafer. Also, when it is at most the above upper limit value, foaming due to the compound represented by the above formula (1) remaining on the wafer surface is suppressed, and problems such as surface contamination (for example, acting like an adhesive to fix contaminant foreign substances to the surface) do not occur. The content ratio of the compound represented by the above formula (1) is the total of the content ratios of all the compounds represented by the above formula (1) in the hydrophilic treatment liquid of the present disclosure.

[0050] (Water) The hydrophilic treatment liquid of the present disclosure contains water as an essential component. In the present disclosure, water serves as, for example, a medium for cleaning the surface of a semiconductor wafer. Usually, pure water is used, and among them, ultrapure water is preferred. Ultrapure water refers to water with an impurity content ratio of 0.01 μg / L or less. Note that "pure water" in this specification also includes ultrapure water.

[0051] The content ratio of the above water in the hydrophilic treatment liquid of the present disclosure is not particularly limited. However, with respect to 100% by weight of the hydrophilic treatment liquid of the present disclosure, it is preferably 93.5% by weight or more, more preferably 95% by weight or more (for example, 98.5% by weight or more, 99% by weight or more, 99.5% by weight or more, 99.95% by weight or more, 99.98% by weight or more). When the content ratio of the above water is at least the above lower limit value, it has excellent cleaning effect on the surface of the semiconductor wafer and is even better at imparting hydrophilicity.

[0052] The hydrophilic treatment liquid of the present disclosure contains water and the compound represented by the above formula (1), and the total content ratio of water and the compound represented by the above formula (1) is, for example, 95% by weight or more (for example, 98% by weight or more, 99% by weight or more), more preferably 99.5% by weight or more, still more preferably 99.95% by weight or more, particularly preferably 99.98% by weight or more, and most preferably 100% by weight.

[0053] (Other components) The hydrophilic treatment liquid of the present disclosure may further contain other components as long as the effects of the present disclosure are not hindered. Examples of the other components include pH adjusters, alcohols, chelates, and the like.

[0054] From the viewpoint of maintaining a high cleanliness of the semiconductor wafer surface and suppressing excessive etching, it is preferable that the hydrophilic treatment liquid of the present disclosure does not substantially contain abrasive grains and basic compounds (for example, alkali metal hydroxides, amines, ammonia, ammonium hydroxide salts, etc.). That is, the total content ratio of abrasive grains and basic compounds in the hydrophilic treatment liquid of the present disclosure is, for example, 0.1% by weight or less (0 to 0.1% by weight), preferably 0.001% by weight or less (0 to 0.001% by weight), and most preferably no formulation (0%).

[0055] From the viewpoint of maintaining a high cleanliness of the semiconductor wafer surface and forming a good hydrophilic film, it is preferable that the hydrophilic treatment liquid of the present disclosure does not substantially contain other components other than water and the compound represented by the above formula (1). That is, the content ratio of the other components with respect to 100% by weight of the hydrophilic treatment liquid of the present disclosure is preferably less than 5% by weight (0 to 5% by weight), more preferably less than 3% by weight (0 to 3% by weight), still more preferably less than 1% by weight (0 to 1% by weight), and particularly preferably less than 0.01% by weight (0 to 0.01% by weight), and most preferably no formulation (0% by weight). When the other components are not substantially contained (that is, less than 0 to 5% by weight), the cleaning and hydrophilic treatment of the semiconductor wafer surface can be performed most effectively without being interfered by the other components.

[0056] The pH of the hydrophilic treatment liquid of the present disclosure at 25°C is, for example, less than 8.0, preferably 7.8 or less, more preferably 7.5 or less, and even more preferably 7.3 or less. When the pH is less than 8, the surface of the semiconductor wafer after finish polishing can be cleaned and the alkalinity can be reduced, and excessive etching can be suppressed. Here, the pH at 25°C can be measured using a commercially available pH meter, and refers to the value after immersing the electrode in the hydrophilic treatment liquid of the present disclosure for 1 minute.

[0057] Next, an example of a method for producing the hydrophilic treatment liquid of the present disclosure will be described.

[0058] The hydrophilic treatment liquid of the present disclosure can be produced according to a known liquid preparation method, except that it includes a step of adding the compound represented by the above formula (1) to the above water.

[0059] The content ratio of each component of the hydrophilic treatment liquid of the present disclosure described as above is the content ratio at the time of use. Therefore, the hydrophilic treatment liquid of the present disclosure may be supplied in a form that can be prepared at the time of use (hereinafter, may be referred to as "materials for preparing the hydrophilic treatment liquid of the present disclosure").

[0060] The materials for preparing the hydrophilic treatment liquid of the present disclosure are materials that can prepare the hydrophilic treatment liquid of the present disclosure, for example, by diluting with water. The materials for preparing the hydrophilic treatment liquid of the present disclosure can be in various liquid forms such as solution form, emulsion form, suspension form, etc., and can also be in various forms such as solidified, semi-solidified, encapsulated, gel form, capsule form, powder form, particle form, granular form, etc.

[0061] When the materials for preparing the hydrophilic treatment liquid of the present disclosure are in solution form (concentrate), the dilution ratio is not particularly limited, but from the viewpoint of reducing distribution costs and storage space, 2 times or more is preferable, 10 times or more is more preferable, and 50 times or more is even more preferable.

[0062] When the material for preparing the hydrophilic treatment liquid of the present disclosure is in a solution state (concentrate), with respect to 100% by weight of the material for preparing the hydrophilic treatment liquid of the present disclosure, the content ratio of the compound represented by the above formula (1) is preferably, for example, 3% by weight or more, more preferably 15% by weight or more. Also, the upper limit value of the above content ratio is preferably 75% by weight, more preferably 50% by weight. When it is above the above lower limit value, it is excellent in reducing distribution costs and storage space. Also, when it is below the above upper limit value, it is excellent in handleability (ease of preparation).

[0063] The material for preparing the hydrophilic treatment liquid of the present disclosure can be produced according to the production methods of known liquid agents, solid agents, semi-solid agents, gel agents, capsule agents, powders, granules, etc., except that it includes the step of containing the compound represented by the above formula (1) in the above water.

[0064] In the hydrophilic treatment liquid of the present disclosure, the compound represented by formula (1) can adsorb on the surface of the semiconductor wafer with excellent adsorption force, form a good hydrophilic film, and maintain a high cleanliness of the surface of the semiconductor wafer. Thereby, it becomes possible to manufacture a high-quality semiconductor wafer with reduced surface defects (LPD) and surface roughness (haze).

[0065] The hydrophilic treatment liquid of the present disclosure can be used, for example, in the step of subjecting the surface of a semiconductor wafer to a hydrophilic treatment in the manufacturing process of the semiconductor wafer. Such a step is not particularly limited, but examples include a cutting step of cutting a silicon single crystal ingot into a predetermined silicon wafer, a polishing step of polishing the silicon wafer (usually, there are three steps of primary polishing, secondary polishing, and finish polishing), a cleaning step of cleaning the silicon wafer, etc. Among them, the hydrophilic treatment liquid of the present disclosure is preferably used as a rinse polishing solution in the cleaning step that follows the finish polishing step in the above polishing step.

[0066] An example of using the hydrophilic treatment liquid of the present disclosure as a rinse polishing solution will be described below.

[0067] The polished semiconductor wafer is placed in a polishing apparatus (not shown) comprising a holder for holding the semiconductor wafer and a polishing platen with a polishing pad attached thereto.

[0068] Next, rinse polishing is performed while supplying the hydrophilization treatment liquid of the present disclosure onto the polishing pad. The supply at this time is continuously supplied by a pump or the like. The supply amount of the hydrophilization treatment liquid of the present disclosure may be in a state where the surface of the polishing pad is always covered with the treatment liquid, and is not particularly limited. For example, it is 100 ml / min or more, preferably 150 ml / min or more.

[0069] The polishing pressure during rinse polishing is not particularly limited, but it is preferable to apply a pressure in the range of 50 to 300 gf / cm 2 and more preferably in the range of 80 to 250 gf / cm 2 of the range.

[0070] The rotational speed of the polishing platen during rinse polishing is not particularly limited, but for example, a range of 50 to 200 rpm is preferable, and more preferably 60 to 150 rpm.

[0071] The rinse time during rinse polishing is not particularly limited, but for example, it can be appropriately set in the range of 1 to 10 minutes, and preferably 2 to 7 minutes.

[0072] In addition, after the above rinse polishing, water polishing (water polish) may be separately added. Even when water polishing is further performed after rinse polishing with the hydrophilization treatment liquid of the present disclosure, the state of the surface of the hydrophilized semiconductor wafer is maintained well.

[0073] Each configuration and their combinations etc. in the above embodiments are examples, and within the range not departing from the gist of the invention according to the present disclosure, addition, omission, substitution, and other changes of the configuration can be made as appropriate. The invention according to the present disclosure is not limited by the embodiments, but is limited only by the scope of the claims.

[0074] Each aspect disclosed in this specification can be combined with any other features disclosed in this specification.

Example

[0075] Hereinafter, the invention according to the present disclosure will be described more specifically by way of examples, but the invention according to the present disclosure is not limited to these examples. (Examples 2 to 6, 8 to 12, 14 to 18, 20 to 24, 26 to 36 shall be Reference Examples 1 to 31) 。

[0076] (Production Example 1) To 1 mol of lauryl alcohol, 4 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation) was added to obtain compound (A1) (C 12 H 25 O-(C3H6O2)4-H, weight average molecular weight: 482).

[0077] (Production Example 2) Compound (A2) (C 12 H 25 O-(C3H6O2) 10 -H, weight average molecular weight: 926) was obtained in the same manner as in Example 1 except that the amount of 2,3-epoxy-1-propanol used was changed to 10 mol.

[0078] (Production Example 3) Compound (A3) (C 12 H 25 O-(C3H6O2)6-H, weight average molecular weight: 630) was obtained in the same manner as in Example 1 except that the amount of 2,3-epoxy-1-propanol used was changed to 6 mol.

[0079] (Production Example 4) To 1 mol of isostearyl alcohol, 10 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation) was added to obtain compound (A4) (C 18 H 37 O-(C3H6O2) 10 -H, weight average molecular weight: 1010).

[0080] (Production Example 5) To 1 mol of glycerin, 9 mol of 2,3-epoxy-1-propanol (trade name "glycidol", manufactured by Daicel Corporation) was added to obtain compound (A5) (HO-(C3H6O2) 10 -H, weight average molecular weight: 758).

[0081] (Production Example 6) Compound (A6) (HO-(C3H6O2) 20 -H, weight average molecular weight: 1498) was obtained in the same manner as in Example 5 except that the amount of 2,3-epoxy-1-propanol used was changed to 19 mol.

[0082] Using the compounds (A1) to (A6) obtained in the above Production Examples 1 to 6, test solutions of Examples 1 to 36 were prepared according to the formulations shown in Table 1. Pure water was prepared as the test solution of Comparative Example 1.

[0083] 1. Evaluation of hydrophilicity of semiconductor wafer after rinse polishing A number of wafers after secondary polishing were prepared. Finish polishing was carried out under the following conditions, and then rinse polishing was carried out under the following conditions for each wafer after finish polishing while it was placed in the polishing machine. Each test solution of Examples and Comparative Example 1 was used for rinse polishing. Immediately after rinse polishing and after 1 hour had elapsed, the state of the surface of each wafer was visually observed, and the results were evaluated based on the following evaluation criteria. The results are shown in Table 1.

[0084] (Conditions for finish polishing) · pH: 10 · Slurry: Nanopure NP8020 (manufactured by Nitta Haas Co., Ltd.) high-purity colloidal silica, abrasive grain concentration 9.5% by weight, abrasive grain size 60 - 80 nm · Polishing pad: Whitex-DV18 (manufactured by Nitta Haas Co., Ltd.) · Polishing machine: RN20 (manufactured by Nitta Haas Co., Ltd.) · Rotation speed of polishing platen: 115 rpm · Slurry flow rate: 300 ml / min · Polishing pressure: 100 gf / cm 2

[0085] (Rinse polishing conditions) ·Rinse time: 5 minutes ·Rotational speed of polishing platen: 115 rpm ·Flow rate of rinse polishing solution: 300 ml / min ·Polishing pressure: 100 gf / cm 2 Note that for 1 minute after rinse polishing, water polishing was performed under the same conditions as rinse polishing using pure water instead of the test solution.

[0086] (Evaluation criteria) ○ (Good): The entire surface of the wafer is in a wet state and there is no dried part. × (Bad): There is a dried part on at least a part of the wafer surface.

[0087]

Table 1

[0088] (Evaluation of results) The surface of the wafer immediately after rinse polishing with the test solution of the example showed strong hydrophilicity and was in a state of complete wetting. Furthermore, the wet state of the wafer surface was maintained even after 1 hour had passed. On the other hand, for the wafer surface rinse polished with the test solution of Comparative Example 1, the presence of a partially dried part was recognized even immediately after rinse polishing, water droplets were formed by the moisture, and it was not hydrophilized.

[0089] As a summary above, the configuration of the invention according to the present disclosure and its variations are appended below. [1] A composition containing water and a compound represented by the following formula (1), wherein the total content ratio of water and the compound represented by the following formula (1) is 95% by weight or more. R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R 2 CO, and the above R 2represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of glycerin units shown in parentheses, and is 2 to 60) [2] R in the above formula 1 The composition according to [1], wherein is a hydrocarbon group having 12 to 18 carbon atoms. [3] R in the above formula 1 The composition according to [1], wherein is at least one selected from the group consisting of a dodecyl group, an isostearyl group, and a hydrogen atom. [4] R in the above formula 1 The composition according to [1], wherein is a dodecyl group. [5] R in the above formula 1 The composition according to [1], wherein is an isostearyl group. [6] R in the above formula 1 The composition according to [1], wherein is a hydrogen atom. [7] The composition according to any one of [1] to [6], wherein n in the above formula is 2 to 40. [8] The composition according to any one of [1] to [6], wherein n in the above formula is 2 to 30. [9] The composition according to any one of [1] to [6], wherein n in the above formula is 2 to 20.

[10] The composition according to any one of [1] to [6], wherein n in the above formula is 2 to 15.

[11] The composition according to any one of [1] to [6], wherein n in the above formula is 2 to 10.

[12] The composition according to any one of [1] to [6], wherein n in the above formula is 4 to 40.

[13] The composition according to any one of [1] to [6], wherein n in the above formula is 4 to 30.

[14] The composition according to any one of [1] to [6], wherein n in the above formula is 4 to 20.

[15] The composition according to any one of [1] to [6], wherein n in the above formula is 4 to 15.

[16] The composition according to any one of [1] to [6], wherein n in the above formula is 4 to 10. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.01 to 1.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.01 to 1.0% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.01 to 0.7% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.01 to 0.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.02 to 1.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.02 to 1.0% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.02 to 0.7% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.02 to 0.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.05 to 1.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.05 to 1.0% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.05 to 0.7% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.05 to 0.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by formula (1) is 0.1 to 1.5% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by the formula (1) is 0.1 to 1.0% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by the formula (1) is 0.1 to 0.7% by weight. The composition according to any one of [1] to

[16] , wherein the content ratio of the compound represented by the formula (1) is 0.1 to 0.5% by weight. The composition according to any one of [1] to

[32] , wherein the total content ratio of the abrasive grains and the basic compound is 0.1% by weight or less. The composition according to any one of [1] to

[32] , wherein the total content ratio of the abrasive grains and the basic compound is 0.001% by weight or less. The composition according to any one of [1] to

[34] , wherein the pH is less than 8.0. The composition according to any one of [1] to

[34] , wherein the pH is 7.8 or less. The composition according to any one of [1] to

[34] , wherein the pH is 7.5 or less. The composition according to any one of [1] to

[34] , wherein the pH is 7.3 or less. The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 3000. The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 2000. The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 1500. The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 1000. The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 800.

[44] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 200 to 3000.

[45] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 200 to 2000.

[46] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 200 to 1500.

[47] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 200 to 1000.

[48] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 200 to 800.

[49] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 300 to 3000.

[50] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 300 to 2000.

[51] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 300 to 1500.

[52] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 300 to 1000.

[53] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 300 to 800.

[54] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 400 to 3000.

[55] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 400 to 2000.

[56] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is from 400 to 1500.

[57] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 400 to 1000.

[58] The composition according to any one of [1] to

[38] , wherein the weight average molecular weight of the compound represented by the formula (1) is 400 to 800.

[59] The composition according to any one of [1] to

[58] , wherein the HLB value of the compound represented by the formula (1) is 14 or more.

[60] The composition according to any one of [1] to

[58] , wherein the HLB value of the compound represented by the formula (1) is 14 to 20.

[61] The composition according to any one of [1] to

[58] , wherein the HLB value of the compound represented by the formula (1) is 14 to 18.

[62] The composition according to any one of [1] to

[61] , which is a hydrophilizing treatment liquid for the surface of a semiconductor wafer.

[63] The composition according to any one of [1] to

[61] , which is a rinse polishing solution.

[64] A method for manufacturing a semiconductor device, comprising a step of hydrophilizing the surface of a semiconductor wafer using the composition according to any one of [1] to

[63] .

[65] A method for manufacturing a composition, comprising a step of containing the compound represented by the above formula (1) in water, for manufacturing the composition according to any one of [1] to

[61] .

[66] A method for manufacturing a hydrophilizing treatment liquid for the surface of a semiconductor wafer, wherein the composition according to

[65] is a hydrophilizing treatment liquid for the surface of a semiconductor wafer.

[67] A method for manufacturing a rinse polishing solution, wherein the composition according to

[65] is a rinse polishing solution.

[68] Use of the composition according to any one of [1] to

[61] as a hydrophilizing treatment liquid for the surface of a semiconductor wafer.

[69] Use of the composition according to any one of [1] to

[61] as a rinse polishing solution.

Industrial Applicability

[0090] According to the hydrophilization treatment liquid of the present invention, by forming a hydrophilic film on the wafer surface, hydrophilicity can be imparted. Thereby, it is possible to prevent the adhesion of contaminant foreign substances such as particles, metal impurities, and organic substances to the wafer surface. Therefore, the present invention has industrial applicability.

Claims

1. A hydrophilizing treatment liquid for a semiconductor wafer surface, comprising water and a compound represented by the following formula (1), wherein the total content ratio of water and the compound represented by the following formula (1) is 95% by weight or more, the content ratio of the compound represented by the following formula (1) is 0.01 to 0.05% by weight, and the total content of abrasive grains and basic compounds is 0.001% by weight or less. R １ O-(C ３ H ６ O ２ ) ｎ -H (1) (wherein, R １ represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R ２ CO, and the above R ２ represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin units shown in parentheses, and is 2 to 10)

2. The hydrophilizing treatment liquid according to claim 1, wherein the total content ratio of abrasive grains and basic substances is 0% by weight.

3. The hydrophilizing treatment liquid according to claim 1 or 2, having a pH of less than 8.

4. The hydrophilizing treatment liquid according to any one of claims 1 to 3, wherein the weight average molecular weight of the compound represented by formula (1) is 100 to 3000.

5. The hydrophilizing treatment liquid according to any one of claims 1 to 4, wherein the HLB value of the compound represented by formula (1) is 14 or more.

6. The hydrophilizing treatment liquid according to any one of claims 1 to 5, which is a rinse polishing solution.

7. A method for manufacturing a semiconductor device, comprising a step of hydrophilizing the surface of a semiconductor wafer using the hydrophilizing treatment liquid according to any one of claims 1 to 6.

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