Hydrophilic treatment liquid for semiconductor wafer surface

Abstract

The present application provides a semiconductor wafer surface hydrophilization treatment liquid capable of imparting hydrophilicity to the surface of a semiconductor wafer. The semiconductor wafer surface hydrophilization treatment liquid of the present application contains water and a compound represented by the following formula (1), and the total content 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 optionally has a hydroxyl group, or R 2 CO represents a group, the aforementioned R 2 represents a hydrocarbon group having 1 to 24 carbon atoms, and n represents the average polymerization degree of the glycerol unit shown in the parentheses and is 2 to 60).

Description

Technical Field

[0001] The invention of this application relates to a hydrophilic treatment liquid for the surface of semiconductor wafers. This application claims priority to Japanese Patent Application No. 2019-054530, filed on March 22, 2019, the contents of which are incorporated herein by reference. Background Technology

[0002] Generally, in the semiconductor wafer manufacturing process, after the silicon single crystal ingot is diced, it undergoes a polishing process (usually three stages: primary polishing, secondary polishing, and fine polishing) following etching. Maintaining a hydrophilic state is crucial in this polishing process to prevent contamination of the wafer surface. This is because if the wafer surface is dry immediately after polishing, contaminants such as particles, metallic impurities, and organic matter will adhere to the surface and be difficult to remove in subsequent cleaning processes. These contaminants can cause surface defects (LPD: Light point defects) during wafer inspection. Furthermore, an increase in LPD leads to increased surface roughness (haze), resulting in a decrease in wafer surface quality. Therefore, since ancient times, the composition of polishing materials such as pastes has been adjusted to make the surface of the finely polished wafer hydrophilic.

[0003] After fine polishing, the wafer undergoes a cleaning process. This cleaning process involves "water polishing." Water polishing is performed after fine polishing, by supplying cleaning water to the polishing pad while operating the polishing device to rinse the polished surface of the wafer. This removes the abrasive particles adhering to the polishing surface while preventing excessive etching of the wafer surface by the alkaline polishing material.

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

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 10-270492 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, in water polishing using only water, the Si surface of the silicon wafer is exposed through brushing based on the polishing pad. This Si surface is hydrophobic, making it susceptible to contamination by particles, metallic impurities, organic matter, and other foreign matter. Moreover, there is a tendency to be difficult to remove these contaminants adhering to the hydrophobic wafer surface. Therefore, the following problem exists: the wafer surface, which has become hydrophilic after fine polishing, may revert to hydrophobicity due to water polishing, adsorbing the aforementioned contaminants and resulting in a decrease in the cleanliness of the wafer surface.

[0010] Therefore, the purpose of this application is to provide a hydrophilic treatment liquid that can impart hydrophilicity to the surface of a semiconductor wafer.

[0011] In addition, the purpose of this application is to provide a rinsing and polishing solution that can be applied to the surface of a semiconductor wafer that has become hydrophilic after fine polishing, thereby allowing it to remain hydrophilic after rinsing and polishing.

[0012] In addition, another objective of this application is to provide a method for manufacturing a semiconductor device that includes the process of hydrophilicating the surface of a semiconductor wafer using the aforementioned hydrophilicating treatment solution.

[0013] Problem Solving Methods

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that a hydrophilic treatment solution containing water and a compound represented by formula (1) with a total content of water and the compound represented by formula (1) of 95% by weight or more can impart hydrophilicity to the surface of a semiconductor wafer. The invention of this application is based on these insights.

[0015] That is, the present invention provides a hydrophilic treatment solution for the surface of a semiconductor wafer (hereinafter also referred to as "the hydrophilic treatment solution of the present application"), which contains water and a compound represented by the following formula (1), wherein the total content of water and the compound represented by the following formula (1) is 95% by weight or more.

[0016] R 1 O-(C3H6O2) n -H (1)

[0017] (where R is in the formula) 1 Representing a hydrogen atom, an optional hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group, or R 2 The group represented by CO, and the above R 2 The group represents a hydrocarbon group with 1 to 24 carbon atoms, and n represents the average degree of polymerization of the glycerol unit shown in parentheses, which is 2 to 60.

[0018] Preferably, the compound represented by formula (1) is present in a proportion of 0.01 to 1.5% by weight in the above-mentioned hydrophilic treatment solution.

[0019] Preferably, the total content of abrasive particles and alkaline compounds in the above-mentioned hydrophilic treatment solution is 0.1% by weight or less.

[0020] Preferably, the pH of the above-mentioned hydrophilic treatment solution is less than 8.

[0021] Preferably, in the above-mentioned hydrophilic treatment solution, the weight-average molecular weight of the compound represented by formula (1) is 100 to 3000.

[0022] Preferably, in the above-mentioned hydrophilization treatment solution, the compound represented by formula (1) has an HLB value of 14 or higher.

[0023] The hydrophilic treatment solution mentioned above can be a rinsing and grinding solution.

[0024] In addition, the present invention provides a method for manufacturing a semiconductor device, the method comprising: a step of performing a hydrophilic treatment on the surface of a semiconductor wafer using the above-mentioned hydrophilic treatment liquid.

[0025] The effects of the invention

[0026] According to the hydrophilic treatment solution of this application, when applied to a wafer surface, hydrophilicity can be imparted by forming a hydrophilic film. This prevents contamination of the wafer surface by particles, metallic impurities, organic matter, and other foreign substances.

[0027] Furthermore, when using the hydrophilic treatment solution of this application as the rinsing and polishing solution for the wafer surface after fine polishing, the wafer surface can be endowed with hydrophilicity. Therefore, even after rinsing and polishing, the wafer surface will not revert to hydrophobicity. Thus, the hydrophilicity of the wafer surface can be maintained, preventing the adhesion of contaminants such as particles, metallic impurities, and organic matter.

[0028] As described above, the hydrophilic treatment solution according to this application can maintain the cleanliness of the wafer surface, thereby enabling the manufacture of high-quality semiconductor wafers with reduced surface defects (LPD) and surface roughness (haze). Detailed Implementation

[0029] 1. Hydrophilic treatment solution for semiconductor wafer surface

[0030] The hydrophilization treatment solution of this application is used to impart hydrophilicity to the surface of a semiconductor wafer. The hydrophilization treatment solution of this application contains water and a compound represented by the following formula (1) (hereinafter also referred to as "polyglycerol derivative") as essential components, and the total content of water and the compound represented by the following formula (1) is 95% by weight or more.

[0031] (The compound represented by formula (1))

[0032] R 1 O-(C3H6O2) n-H (1)

[0033] (where R is in the formula) 1 Representing a hydrogen atom, an optional hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group, or R 2 The group represented by CO, and the above R 2 The group represents a hydrocarbon group with 1 to 24 carbon atoms; n represents the average degree of polymerization of the glycerol unit shown in parentheses, which is 2 to 60.

[0034] The C3H6O2 in parentheses of formula (1) can have only the structure represented by formula (2), or only the structure represented by formula (3), or both of the structures represented by formula (2) and (3).

[0035] -CH2-CHOH-CH2O- (2)

[0036] -CH(CH2OH)CH2O- (3)

[0037] The above R 1 5 to 75% of a molecule is composed of hydrogen atoms.

[0038] In the above R 1 R 2 The hydrocarbon groups in the text can include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by the bonding of two or more of these groups.

[0039] Examples of aliphatic hydrocarbon groups include: methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl (lauryl), tetradecyl, myristyl, hexadecyl, stearyl, and other straight-chain alkyl groups with 1 to 24 carbon atoms (preferably 5 to 20, more preferably 10 to 20, and even more preferably 12 to 18); 2-ethylhexyl, isooctyl, isodecyl, isododecyl, isomearyl, isohearyl, isostearyl, and other alkyl groups with 3 to 24 carbon atoms (preferably 5 to 20, more preferably 10 to 20, and even more preferably 12 to 18). Branched alkyl groups (12-18); straight-chain or branched alkenyl groups with 2-24 carbon atoms (preferably 10-20, more preferably 8-18), such as vinyl, propenyl, allyl, hexenyl, 2-ethylhexenyl, and oleylene; straight-chain or branched polyalkenyl groups with 2-24 carbon atoms (preferably 2-18), such as alkanedienyl, alkanetrienyl, alkanetetraenyl, linoleyl, and linolenyl; and straight-chain or branched alkynyl groups with 2-24 carbon atoms, such as ethynyl and propynyl.

[0040] As the aforementioned alkyl group, linear or branched alkyl groups with 12 to 18 carbon atoms, such as dodecyl or isostearyl, are preferred. As the aforementioned alkenyl group, linear or branched alkenyl groups with 5 to 18 carbon atoms, such as hexenyl or oleenyl, are preferred.

[0041] Examples of alicyclic hydrocarbon groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and other 3- to 24-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkyl groups; cyclopentenyl, cyclohexenyl, and other 3- to 24-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkenyl groups; decahydronaphthyl-1-yl, norbornyl, adamantyl, tricyclic [5.2.1.0] 2,6 ] Decane-8-yl, tetracyclo[4.4.0.1 2,5 .1 7,10 Bridged cyclic hydrocarbon groups such as dodecane-3-yl.

[0042] Examples of aromatic hydrocarbon groups include aryl groups with 6 to 24 carbon atoms (preferably 6 to 15), such as phenyl and naphthyl.

[0043] Among the hydrocarbon groups formed by the bonding of aliphatic hydrocarbon groups and alicyclic hydrocarbon groups, examples include cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl, and other cycloalkyl-substituted alkyl groups (e.g., C14). 3-20 Cycloalkyl-substituted C 1-4 Alkyl groups, etc. Additionally, among hydrocarbon groups formed by the bonding of aliphatic and aromatic hydrocarbon groups, examples include: aralkyl groups (e.g., C14, C2 ... 7-18 Aryl alkyl groups, etc.), alkyl-substituted aryl groups (e.g., those with approximately 1 to 4 C atoms). 1-4 Alkyl groups, phenyl groups, or naphthyl groups, etc.

[0044] The above R 2 Groups represented by CO can include, for example, aliphatic acyl groups such as acetyl, propionyl, butyryl, isobutyryl, stearyl, and oleyl; and aromatic acyl groups such as benzoyl, toluyl, and naphthyl.

[0045] As R 1 Preferably, it is selected from at least one of alkyl, acyl, and hydrogen atoms. Additionally, as R... 1 Preferably, it is selected from at least one of the following: a straight-chain alkyl group (preferably a straight-chain alkyl group with 1 to 24 carbon atoms, such as methyl, ethyl, propyl, decyl, dodecyl (lauryl), stearyl, etc., and particularly preferably a straight-chain alkyl group with 10 to 20 carbon atoms, such as dodecyl), a branched alkyl group (preferably a branched alkyl group with 10 to 20 carbon atoms, such as isostearyl), an aliphatic acyl group (preferably acetyl, butyryl, stearyl, oleyl, and particularly preferably acetyl and oleyl), and hydrogen atoms.

[0046] In formula (1), n ​​represents the average degree of polymerization of glycerol. For the value of n, as shown in the manufacturing method of the compound represented by formula (1) described later, for example in the case of manufacturing polyglycerol ether from alcohol and glycidol, the value of n can be easily changed by adjusting the molar ratio of the alcohol to 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Co., Ltd.) in the reaction.

[0047] The average degree of polymerization n in formula (1) is, for example, 2 to 60, preferably 2 to 40, more preferably 4 to 20, and even more preferably 4 to 10. When n is 2 or more, the water solubility is further improved, and therefore the cleaning performance is also excellent. In addition, the adsorption to the surface of semiconductor wafers is good, and the formation of hydrophilic films is also better. When n is 60 or less, good hydrophilicity is exhibited, and the water dispersibility is further improved. Unwanted foaming is suppressed, and the operability is further improved. In this specification, there is no particular limitation on the method for calculating the average degree of polymerization of glycerol constituting polyglycerol. Examples include: methods calculated based on hydroxyl value; methods for determining the composition of polyglycerol and calculating the average degree of polymerization by gas chromatography, liquid chromatography, thin-layer chromatography, gas chromatography-mass spectrometry, or liquid chromatography-mass spectrometry.

[0048] Additionally, R in equation (1) 1 When the alkyl group is an alkyl group (including straight-chain or branched alkyl groups such as lauryl, stearyl, and isostearyl), n is 2 to 60. From the viewpoint of good adsorption to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in formula (1) is considered... 1 When n is an alkyl group, it is preferably 2 to 30, more preferably 4 to 20, even more preferably 4 to 15, and most preferably 4 to 10.

[0049] Additionally, R in equation (1) 1 In the case of hydrogen atoms, n is 2 to 60. From the viewpoint of good adsorption to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in equation (1) is... 1 When n is a hydrogen atom, it is preferably 2 to 30, more preferably 4 to 20, even more preferably 4 to 15, and most preferably 4 to 10.

[0050] On the other hand, R in equation (1) 1 In the case of an acyl group, n is 2 to 60, wherein, from the viewpoint of good adsorption to the semiconductor wafer surface and excellent formation of a hydrophilic film, R in formula (1) is... 1 When n is an acyl group, it is preferably 2 to 30, more preferably 4 to 20, even more preferably 4 to 15, and most preferably 4 to 10.

[0051] When the value of n is outside the above range, there is a tendency for reduced adsorption to the semiconductor wafer surface. Furthermore, when the value of n is below the above range, there is a tendency for reduced hydrophilicity, failure to form a hydrophilic film on the semiconductor wafer surface, and difficulty in imparting hydrophilicity.

[0052] The weight-average molecular weight of the compound represented by formula (1) is, for example, 100 to 3000. From the viewpoint of good adsorption to semiconductor wafer surfaces and excellent formation of a hydrophilic film, a weight-average molecular weight of 200 to 3000 is preferred, more preferably 200 to 2000, further preferably 300 to 2000, and most preferably 400 to 1500. Furthermore, from the viewpoint of excellent operability, a weight-average molecular weight of 400 to 1000 is further preferred, and most preferably 400 to 800. It should be noted that in this specification, the weight-average molecular weight is determined based on gel permeation chromatography (GPC).

[0053] From the viewpoint of excellent dispersion stability, the HLB value (Hydrophile-Lipophile Balance) of the compound represented by formula (1) is, for example, 14 or more, preferably 14 to 20, and more preferably 14 to 18. It should be noted that the above HLB value can be calculated by the Griffin method.

[0054] As the compound represented by formula (1) in this application, it is preferably selected from at least one of the compounds represented by formulas (1-1) to (1-8) below, and particularly preferably selected from at least one of the compounds represented by formulas (1-1) to (1-4) and (1-6) to (1-8) below.

[0055] C 12 H 25 O-(C3H6O2)4-H (1-1)

[0056] C 12 H 25 O-(C3H6O2) 10 -H (1-2)

[0057] C 18 H 37 -O-(C3H6O2)4-H (1-3)

[0058] C 18 H 37 -O-(C3H6O2) 10 -H (1-4)

[0059] CH2=CH-CH2-O-(C3H6O2)6-H (1-5)

[0060] HO-(C3H6O2)10 -H (1-6)

[0061] HO-(C3H6O2) 20 -H (1-7)

[0062] C 12 H 25 O-(C3H6O2)6-H (1-8)

[0063] As a method for manufacturing the compound represented by formula (1) in this application, examples include: [1] reacting 2,3-epoxy-1-propanol with R in the presence of a base catalyst. 1 Compounds represented by OH (the R) 1 The same as the above) method of addition polymerization; [2] to make R 1 The compound represented by X (where X represents a halogen atom, R) 1 Same as the above meaning. For example, a method for reacting alkyl halides (or acyl halides) with polyglycerol; [3] a method for reacting reactive derivatives of carboxylic acids such as anhydrides with polyglycerol; [4] a method for reacting polyols such as glycidyl ether compounds represented by formula (4) with polyglycerol, etc.

[0064] [Chemical Formula 1]

[0065]

[0066] (where R is in the formula) 1 (Same meaning as above).

[0067] Examples of alkaline catalysts used in the method described above [1] include sodium hydroxide, potassium hydroxide, lithium hydroxide, metallic sodium, and sodium hydride. These alkaline catalysts can be used individually or in combination of two or more.

[0068] Examples of haloalkanes used in the method described above[2] include chloroalkanes, bromoalkanes, iodoalkanes, etc.

[0069] As for the polyglycerol used in the methods described above [2] to [4], commercially available products such as "PGL 03P (polyglycerol 3 polymer)", "PGL 06 (polyglycerol 6 polymer)", "PGL 10PSW (polyglycerol 10 polymer)", and "PGL XPW (polyglycerol 40 polymer)" (made by Daicel Co., Ltd.) may be suitable.

[0070] Examples of polyols used in the method described above[4] include: 2,3-epoxy-1-propanol, ethylene glycol, propylene glycol, 1,3-propanediol (trimethylene glycol), glycerol, xylitol, sorbitol, etc.

[0071] The hydrophilic treatment solution of this application contains at least one compound represented by formula (1) above. As mentioned above, the compound represented by formula (1) includes polyglycerol, polyglycerol monoether, and polyglycerol monoester. Therefore, the hydrophilic treatment solution of this application contains at least one polyglycerol derivative selected from polyglycerol, polyglycerol monoether, and polyglycerol monoester.

[0072] In the hydrophilization treatment solution of this application, in addition to polyglycerol, polyglycerol monoether, and polyglycerol monoester, the polyglycerol derivative may also contain, for example, polyglycerol diether and polyglycerol diester corresponding to the above-mentioned compounds. From the viewpoint of imparting good hydrophilicity, the total content ratio of polyglycerol, polyglycerol monoether, and polyglycerol monoester in the hydrophilization treatment solution of this application is preferably 75% by weight or more, more preferably 90% by weight or more. Furthermore, 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 polyglycerol derivative in the hydrophilization treatment solution of this application. It should be noted that the content ratio of each component in the polyglycerol derivative can be determined by separating each component using high-performance liquid chromatography, calculating the peak area using a differential refractive index detector, and calculating the area ratio.

[0073] The hydrophilic treatment liquid of this application contains the compound represented by formula (1) as a non-volatile component. The hydrophilic treatment liquid of this application may further contain other components (e.g., water-soluble polymers such as cellulose derivatives) as non-volatile components, but considering the excellent adsorption to semiconductor wafers and the excellent effect of adsorbing onto semiconductor wafers and protecting the surface, the proportion of the compound represented by formula (1) in the total amount of non-volatile components contained in the hydrophilic treatment liquid of this application (=the proportion of the compound represented by formula (1)) is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 90% by weight or more (e.g., 95% by weight, preferably 97% by weight, more preferably 99.9% by weight, and further preferably 99.99% by weight). It should be noted that the upper limit is 100% by weight. That is, the hydrophilic treatment liquid of this application may substantially contain only the compound represented by formula (1) as a non-volatile component.

[0074] In the hydrophilization treatment solution of this application, the content ratio of the compound represented by formula (1) above is not particularly limited. In 100% by weight of the hydrophilization treatment solution of this application, it is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, further preferably 0.05% by weight or more, particularly preferably 0.1% by weight or more, and most preferably 0.2% by weight or more. In addition, the above-mentioned content ratio is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, further 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 formula (1) above is within the above range, the adsorption on the surface of the semiconductor wafer is excellent, and the effect of adsorbing onto the semiconductor wafer to form a hydrophilic film and thus protecting the surface is even better. In particular, by making the content ratio at or above the above lower limit value, the cleaning power is excellent, and the surface of the finely polished semiconductor wafer can be imparted with hydrophilicity more effectively. Furthermore, by keeping the content ratio below the aforementioned upper limit, bubbling caused by the compound represented by formula (1) remaining on the wafer surface can be suppressed, and adverse conditions such as surface contamination (e.g., acting like an adhesive, causing contaminants to adhere to the surface) will not occur. The content ratio of the compound represented by formula (1) is the total content ratio of all compounds represented by formula (1) in the hydrophilic treatment liquid of this application.

[0075] (water)

[0076] The hydrophilic treatment solution of this application contains water as an essential component. In this application, water serves, for example, as a medium for cleaning the surface of semiconductor wafers. Pure water is typically used, with ultrapure water being preferred. Ultrapure water refers to water in which the impurity content is less than 0.01 μg / L. It should be noted that "pure water" in this specification also includes ultrapure water.

[0077] The proportion of water in the hydrophilization treatment solution of this application is not particularly limited, but is preferably 93.5% by weight or more, more preferably 95% by weight or more (e.g., 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) relative to 100% by weight of the hydrophilization treatment solution of this application. When the proportion of water is at or above the aforementioned lower limit, the cleaning effect on the semiconductor wafer surface is excellent, and the imparting of hydrophilicity is even better.

[0078] The hydrophilic treatment liquid of this application contains water and the compound represented by the above formula (1). The total content of water and the compound represented by the above formula (1) is preferably 95% by weight or more (e.g., 98% by weight or more, 99% by weight or more), more preferably 99.5% by weight or more, further preferably 99.95% by weight or more, particularly preferably 99.98% by weight or more, and most preferably 100% by weight.

[0079] (Other ingredients)

[0080] To the extent that it does not impair the effectiveness of this application, the hydrophilic treatment solution of this application may further contain other components. Examples of such other components include pH adjusters, alcohols, chelating agents, etc.

[0081] From the viewpoint of maintaining high cleanliness of the semiconductor wafer surface and suppressing excessive etching, it is preferable that the hydrophilic treatment solution of this application is substantially free of abrasive particles and alkaline compounds (e.g., alkali metal hydroxides, amines, ammonia, ammonium hydroxides, etc.). That is, the total content of abrasive particles and alkaline compounds in the hydrophilic treatment solution of this application 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 not mixed (0%).

[0082] From the viewpoint of maintaining a high level of cleanliness on the semiconductor wafer surface and forming a good hydrophilic film, the hydrophilization treatment solution of this application preferably contains substantially no components other than water and the compound represented by formula (1) above. That is, relative to 100% by weight of the hydrophilization treatment solution of this application, the content of the above-mentioned other components is preferably less than 5% by weight (0 to 5% by weight), more preferably less than 3% by weight (0 to 3% by weight), further preferably less than 1% by weight (0 to 1% by weight), particularly preferably less than 0.01% by weight (0 to 0.01% by weight), and most preferably not mixed (0% by weight). When substantially free of the above-mentioned other components (i.e., 0 to less than 5% by weight), there is no interference from other components, and the cleaning and hydrophilization treatment of the semiconductor wafer surface can be performed most effectively.

[0083] The hydrophilic treatment solution of this application has a pH of less than 8.0 at 25°C, preferably less than 7.8, more preferably less than 7.5, and even more preferably less than 7.3. When the pH is less than 8, the alkalinity can be reduced by cleaning the surface of the finely polished semiconductor wafer, which can suppress excessive etching. Here, the pH at 25°C can be measured using a commercially available pH meter, referring to the value after immersing the electrode in the hydrophilic treatment solution of this application for 1 minute.

[0084] Next, an example of the method for manufacturing the hydrophilic treatment liquid of this application will be described.

[0085] The hydrophilic treatment liquid of this application can be manufactured according to known liquid manufacturing methods, except for the above-mentioned step of making water contain the compound represented by formula (1).

[0086] The proportions of each component in the hydrophilic treatment liquid of this application as described above are the proportions for use. Therefore, the hydrophilic treatment liquid of this application can be supplied in a form that can be prepared for use (hereinafter also referred to as "material for preparing the hydrophilic treatment liquid of this application").

[0087] The material for preparing the hydrophilic treatment liquid of this application can be prepared by diluting it, for example, with water. The material for preparing the hydrophilic treatment liquid of this application can be made into various liquid forms such as solutions, emulsions, and suspensions. Furthermore, it can be made into various forms such as gels, capsules, powders, particles, and granules, either solidified, semi-solidified, or encapsulated.

[0088] When the material used to prepare the hydrophilic treatment liquid in this application is in the form of a solution (concentrated liquid), the dilution ratio is not particularly limited. From the viewpoint of reducing distribution costs and storage space, it is preferable to dilute by more than 2 times, more preferably by more than 10 times, and even more preferably by more than 50 times.

[0089] When the material for preparing the hydrophilic treatment liquid of this application is in solution form (concentrated liquid), the content of the compound represented by the above formula (1) is preferably 3% by weight or more, more preferably 15% by weight or more, relative to 100% by weight of the material for preparing the hydrophilic treatment liquid of this application. Furthermore, the upper limit of the above content is preferably 75% by weight, more preferably 50% by weight. When the content is at or above the lower limit, the reduction in distribution costs and storage space is more significant. Furthermore, when the content is below the upper limit, the processability (ease of preparation) is more excellent.

[0090] For the material used in preparing the hydrophilic treatment liquid of this application, apart from the above-mentioned step of making water contain the compound represented by the above formula (1), it can be manufactured by known manufacturing methods of liquids, solids, semi-solids, gels, capsules, powders, granules, etc.

[0091] Regarding the hydrophilic treatment solution of this application, the compound represented by formula (1) adsorbs onto the surface of the semiconductor wafer with excellent adsorption force, forming a good hydrophilic film, which can maintain the high cleanliness of the semiconductor wafer surface. As a result, it is possible to manufacture high-quality semiconductor wafers with reduced surface defects (LPD) and surface roughness (haze).

[0092] The hydrophilic treatment solution of this application can be used, for example, in the process of hydrophilicating the surface of a semiconductor wafer during semiconductor wafer manufacturing. Such processes are not particularly limited, and examples include: a dicing process of cutting a silicon single crystal ingot into a given silicon wafer; a polishing process of grinding the silicon wafer (typically including three stages: primary polishing, secondary polishing, and fine polishing); and a cleaning process of cleaning the silicon wafer. Preferably, the hydrophilic treatment solution of this application is used as a rinsing polishing solution in the cleaning process following the fine polishing stage in the aforementioned polishing processes.

[0093] The following describes an example of using the hydrophilic treatment solution of this application as a rinsing and grinding solution.

[0094] The semiconductor wafer, after fine polishing, is placed in a polishing apparatus (not shown), which includes a holder for holding the semiconductor wafer and a polishing table on which polishing pads are mounted.

[0095] Next, the hydrophilic treatment solution of this application is supplied to the polishing pad while rinsing and polishing are performed. The supply is continuous using a pump or the like. The amount of hydrophilic treatment solution supplied is not particularly limited, as long as the surface of the polishing pad is always covered by the solution; for example, it is 100 ml / min or more, preferably 150 ml / min or more.

[0096] There is no particular limitation on the grinding pressure during rinsing and grinding, but it is preferred to apply 50–300 gf / cm. 2 The pressure range is more preferably 80–250 gf / cm. 2 The range.

[0097] There is no particular limitation on the rotation speed of the grinding table during rinsing and grinding, but it is preferably in the range of 50 to 200 rpm, and more preferably 60 to 150 rpm.

[0098] There is no particular limitation on the rinsing time during the grinding process; for example, it can be appropriately set within the range of 1 to 10 minutes, preferably 2 to 7 minutes.

[0099] It should be noted that water polishing can be performed after the above-mentioned rinsing and polishing. When water polishing is further performed after rinsing and polishing with the hydrophilic treatment solution of this application, the surface condition of the hydrophilicated semiconductor wafer can be well maintained.

[0100] The various solutions and combinations thereof in the above embodiments are examples, and appropriate additions, omissions, substitutions, and other modifications can be made to the solutions without departing from the inventive spirit of this application. The invention of this application is not limited to the embodiments, but only to the scope of the claims.

[0101] The various embodiments disclosed in this specification can be combined with any other features disclosed in this specification.

[0102] Example

[0103] The invention of this application will be described in more detail below with reference to the embodiments, but the invention of this application is not limited to these embodiments.

[0104] (Manufacturing Example 1)

[0105] The addition of 4 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Co., Ltd.) to 1 mol of lauryl alcohol yielded compound (A1)(C). 12 H 25 O-(C3H6O2)4-H, weight-average molecular weight: 482).

[0106] (Manufacturing Example 2)

[0107] By changing the amount of 2,3-epoxy-1-propanol to 10 mol, compound (A2)(C) was obtained in the same manner as in Example 1. 12 H 25 O-(C3H6O2) 10 -H, weight-average molecular weight: 926).

[0108] (Manufacturing Example 3)

[0109] By changing the amount of 2,3-epoxy-1-propanol to 6 mol, the same compound (A3)(C) was obtained as in Example 1. 12 H 25 O-(C3H6O2)6-H, weight-average molecular weight: 630).

[0110] (Manufacturing Example 4)

[0111] The addition reaction of 10 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Co., Ltd.) with 1 mol of isostearyl alcohol yielded compound (A4)(C 18 H 37 O-(C3H6O2) 10 -H, weight-average molecular weight: 1010).

[0112] (Manufacturing Example 5)

[0113] The addition of 9 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Co., Ltd.) to 1 mol of glycerol yielded compound (A5)(HO-(C3H6O2). 10 -H, weight-average molecular weight: 758).

[0114] (Manufacturing Example 6)

[0115] By changing the amount of 2,3-epoxy-1-propanol to 19 mol, the same compound (A6)(HO-(C3H6O2)) was obtained as in Example 5. 20 -H, weight-average molecular weight: 1498).

[0116] Using compounds (A1) to (A6) obtained in Manufacturing Examples 1 to 6 above, the test solutions of Examples 1 to 36 were prepared according to the formulations described in Table 1. Pure water was prepared as the test solution for Comparative Example 1.

[0117] 1. Evaluation of the hydrophilicity of semiconductor wafers after rinsing and polishing

[0118] Multiple wafers that had undergone secondary polishing were prepared. Fine polishing was performed under the following conditions, followed by rinsing polishing under the same conditions while the wafers remained in the polishing machine. The test solutions of Examples 1 and Comparative Example 1 were used in the rinsing polishing. The surface condition of each wafer was visually observed immediately after rinsing polishing and one hour later, and the results were evaluated based on the following evaluation criteria. The results are shown in Table 1.

[0119] (Conditions for fine grinding)

[0120] pH: 10

[0121] • Slurry: Nanopure NP8020 (manufactured by Nitta Haas Co., Ltd.), high-purity colloidal silica, abrasive concentration 9.5% by weight, abrasive size 60-80 nm

[0122] • Grinding pad: Whitex-DV18 (manufactured by Nitta Haas Co., Ltd.)

[0123] ·Grinder: RN20 (made by Nitta Haas Co., Ltd.)

[0124] • Grinding table speed: 115 rpm

[0125] • Slurry flow rate: 300ml / min

[0126] Grinding pressure: 100gf / cm 2

[0127] (Conditions for rinsing and grinding)

[0128] Rinse time: 5 minutes

[0129] • Grinding table speed: 115 rpm

[0130] • Flow rate of rinsing and grinding solution: 300 ml / min

[0131] Grinding pressure: 100gf / cm 2

[0132] It should be noted that, one minute after rinsing and grinding, pure water was used instead of the test solution, and water grinding was performed under the same conditions as rinsing and grinding.

[0133] (Evaluation Criteria)

[0134] ○ (Good): The entire surface of the wafer is wetted, with no dry parts.

[0135] × (Defect): At least a portion of the wafer surface is dry.

[0136] [Table 1]

[0137]

[0138] (Note) In the table, "-" indicates that no cooperation was made.

[0139] (Evaluation of results)

[0140] The wafer surface immediately after rinsing and polishing with the test solution of the example exhibited strong hydrophilicity, remaining completely wetted. Furthermore, this wettability was maintained even after one hour. On the other hand, the wafer surface immediately after rinsing and polishing with the test solution of Comparative Example 1 showed some dry areas, with water droplets forming, indicating that hydrophilicity was not achieved.

[0141] In summary, the structure and variations of the present invention are described below.

[0142] [1] A composition comprising water and a compound represented by formula (1) below, wherein the total content of water and the compound represented by formula (1) below is 95% by weight or more.

[0143] R 1 O-(C3H6O2) n -H (1)

[0144] (where R is in the formula) 1 Representing a hydrogen atom, an optional hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group, or R 2 The group represented by CO, and the above R 2(This indicates a hydrocarbon group with 1 to 24 carbon atoms, and n represents the average degree of polymerization of the glycerol unit shown in parentheses, which is 2 to 60.)

[0145] [2] The composition according to [1], wherein,

[0146] R in the above formula 1 It consists of hydrocarbon groups with 12 to 18 carbon atoms.

[0147] [3] The composition according to [1], wherein,

[0148] R in the above formula 1 It is selected from at least one of dodecyl, isostearyl, and hydrogen atoms.

[0149] [4] The composition according to [1], wherein,

[0150] R in the above formula 1 It is a dodecyl group.

[0151] [5] The composition according to [1], wherein,

[0152] R in the above formula 1 It is isostearyl group.

[0153] [6] The composition according to [1], wherein,

[0154] R in the above formula 1 It is a hydrogen atom.

[0155] [7] The composition according to any one of [1] to [6], wherein,

[0156] In the above formula, n ranges from 2 to 40.

[0157] [8] The composition according to any one of [1] to [6], wherein,

[0158] In the above formula, n ranges from 2 to 30.

[0159] [9] The composition according to any one of [1] to [6], wherein,

[0160] In the above formula, n ranges from 2 to 20.

[0161]

[10] The composition according to any one of [1] to [6], wherein,

[0162] In the above formula, n ranges from 2 to 15.

[0163]

[11] The composition according to any one of [1] to [6], wherein,

[0164] In the above formula, n ranges from 2 to 10.

[0165]

[12] The composition according to any one of [1] to [6], wherein,

[0166] In the above formula, n ranges from 4 to 40.

[0167]

[13] The composition according to any one of [1] to [6], wherein,

[0168] In the above formula, n ranges from 4 to 30.

[0169]

[14] The composition according to any one of [1] to [6], wherein,

[0170] In the above formula, n ranges from 4 to 20.

[0171]

[15] The composition according to any one of [1] to [6], wherein,

[0172] In the above formula, n ranges from 4 to 15.

[0173]

[16] The composition according to any one of [1] to [6], wherein,

[0174] In the above formula, n is 4 to 10.

[0175]

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

[16] , wherein,

[0176] The compound represented by formula (1) is present in a proportion of 0.01 to 1.5% by weight.

[0177]

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

[16] , wherein,

[0178] The compound represented by formula (1) is present in a proportion of 0.01 to 1.0% by weight.

[0179]

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

[16] , wherein,

[0180] The compound represented by formula (1) is present in a proportion of 0.01 to 0.7% by weight.

[0181]

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

[16] , wherein,

[0182] The compound represented by formula (1) is present in a proportion of 0.01 to 0.5% by weight.

[0183]

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

[16] , wherein,

[0184] The compound represented by formula (1) is present in a proportion of 0.02 to 1.5% by weight.

[0185]

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

[16] , wherein,

[0186] The compound represented by formula (1) is present in a proportion of 0.02 to 1.0% by weight.

[0187]

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

[16] , wherein,

[0188] The compound represented by formula (1) is present in a proportion of 0.02–0.7% by weight.

[0189]

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

[16] , wherein,

[0190] The compound represented by formula (1) is present in a proportion of 0.02 to 0.5% by weight.

[0191]

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

[16] , wherein,

[0192] The compound represented by formula (1) is present in a proportion of 0.05 to 1.5% by weight.

[0193]

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

[16] , wherein,

[0194] The compound represented by formula (1) is present in a proportion of 0.05–1.0% by weight.

[0195]

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

[16] , wherein,

[0196] The compound represented by formula (1) is present in a proportion of 0.05–0.7% by weight.

[0197]

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

[16] , wherein,

[0198] The compound represented by formula (1) is present in a proportion of 0.05 to 0.5% by weight.

[0199]

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

[16] , wherein,

[0200] The compound represented by formula (1) is present in a proportion of 0.1 to 1.5% by weight.

[0201]

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

[16] , wherein,

[0202] The compound represented by formula (1) is present in a proportion of 0.1 to 1.0% by weight.

[0203]

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

[16] , wherein,

[0204] The compound represented by formula (1) is present in a proportion of 0.1 to 0.7% by weight.

[0205]

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

[16] , wherein,

[0206] The compound represented by formula (1) is present in a proportion of 0.1 to 0.5% by weight.

[0207]

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

[32] , wherein,

[0208] The total content of abrasive particles and alkaline compounds is less than 0.1% by weight.

[0209]

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

[32] , wherein,

[0210] The total content of abrasive particles and alkaline compounds is less than 0.001% by weight.

[0211]

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

[34] has a pH of less than 8.0.

[0212]

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

[34] has a pH of 7.8 or less.

[0213]

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

[34] has a pH of 7.5 or less.

[0214]

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

[34] has a pH of 7.3 or less.

[0215]

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

[38] , wherein,

[0216] The weight-average molecular weight of the compound represented by the above formula (1) is 100 to 3000.

[0217]

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

[38] , wherein,

[0218] The weight-average molecular weight of the compound represented by formula (1) above is 100 to 2000.

[0219]

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

[38] , wherein,

[0220] The weight-average molecular weight of the compound represented by formula (1) above is 100 to 1500.

[0221]

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

[38] , wherein,

[0222] The weight-average molecular weight of the compound represented by the above formula (1) is 100 to 1000.

[0223]

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

[38] , wherein,

[0224] The weight-average molecular weight of the compound represented by the above formula (1) is 100 to 800.

[0225]

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

[38] , wherein,

[0226] The weight-average molecular weight of the compound represented by formula (1) above is 200 to 3000.

[0227]

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

[38] , wherein,

[0228] The weight-average molecular weight of the compound represented by the above formula (1) is 200 to 2000.

[0229]

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

[38] , wherein,

[0230] The weight-average molecular weight of the compound represented by formula (1) above is 200 to 1500.

[0231]

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

[38] , wherein,

[0232] The weight-average molecular weight of the compound represented by formula (1) above is 200 to 1000.

[0233]

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

[38] , wherein,

[0234] The weight-average molecular weight of the compound represented by formula (1) above is 200 to 800.

[0235]

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

[38] , wherein,

[0236] The weight-average molecular weight of the compound represented by the above formula (1) is 300 to 3000.

[0237]

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

[38] , wherein,

[0238] The weight-average molecular weight of the compound represented by the above formula (1) is 300 to 2000.

[0239]

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

[38] , wherein,

[0240] The weight-average molecular weight of the compound represented by formula (1) above is 300 to 1500.

[0241]

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

[38] , wherein,

[0242] The weight-average molecular weight of the compound represented by the above formula (1) is 300 to 1000.

[0243]

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

[38] , wherein,

[0244] The weight-average molecular weight of the compound represented by formula (1) above is 300 to 800.

[0245]

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

[38] , wherein,

[0246] The weight-average molecular weight of the compound represented by the above formula (1) is 400 to 3000.

[0247]

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

[38] , wherein,

[0248] The weight-average molecular weight of the compound represented by formula (1) above is 400 to 2000.

[0249]

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

[38] , wherein,

[0250] The weight-average molecular weight of the compound represented by the above formula (1) is 400 to 1500.

[0251]

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

[38] , wherein,

[0252] The weight-average molecular weight of the compound represented by the above formula (1) is 400 to 1000.

[0253]

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

[38] , wherein,

[0254] The weight-average molecular weight of the compound represented by formula (1) above is 400 to 800.

[0255]

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

[58] , wherein,

[0256] The compound represented by formula (1) has an HLB value of 14 or higher.

[0257]

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

[58] , wherein,

[0258] The HLB values ​​of the compounds represented by formula (1) are 14 to 20.

[0259]

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

[58] , wherein,

[0260] The HLB values ​​of the compounds represented by formula (1) are 14 to 18.

[0261]

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

[61] is a hydrophilic treatment solution for the surface of a semiconductor wafer.

[0262]

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

[61] is a rinsing and grinding solution.

[0263]

[64] A method for manufacturing a semiconductor device, the method comprising:

[0264] The process of hydrophilic treatment of semiconductor wafer surface using any one of the compositions described in [1] to

[63] .

[0265]

[65] A method for manufacturing a composition, which is a method for manufacturing any one of [1] to

[61] , the method comprising:

[0266] A process of making water contain the compound represented by the above formula (1).

[0267]

[66] A method for manufacturing a hydrophilic treatment liquid for the surface of a semiconductor wafer, wherein,

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

[0268]

[67] A method for manufacturing a rinsing and grinding solution, wherein the composition described in

[65] is a rinsing and grinding solution.

[0269]

[68] Use of the composition described in any one of [1] to

[61] above as a hydrophilic treatment solution for the surface of a semiconductor wafer.

[0270]

[69] Use of the composition described in any one of [1] to

[61] above as a rinsing and grinding solution.

[0271] Industrial applicability

[0272] The hydrophilic treatment solution according to the present invention imparts hydrophilicity by forming a hydrophilic film on the wafer surface. This prevents the adhesion of contaminants such as particles, metallic impurities, and organic matter to the wafer surface. Therefore, the present invention has industrial applicability.

Claims

1. A hydrophilic treatment solution for the surface of a semiconductor wafer, comprising water and a compound represented by formula (1) below, wherein the total content of water and the compound represented by formula (1) below is 95% by weight or more, and the content of the compound represented by formula (1) is 0.01% to 0.05% by weight. R 1 O-(C3H6O2) n -H (1) In equation (1), R 1 Represents a hydrogen atom, an optional hydrocarbon group with 1 to 24 carbon atoms having a hydroxyl group, or R 2 The group represented by CO, wherein R 2 Represents hydrocarbon groups with 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerol units shown in parentheses, in R 1 The values ​​are 2 to 60 when representing hydrogen atoms, and in R 1 This indicates an optional hydrocarbon group with 1 to 24 carbon atoms containing a hydroxyl group, or R. 2 In the case of CO groups, the value is 2~10. in, The total content of abrasive particles and alkaline compounds is less than 0.001% by weight.

2. The hydrophilization treatment solution according to claim 1, wherein, The R 1 It can be any hydrocarbon group with 1 to 24 carbon atoms containing a hydroxyl group, or R 2 CO represents a group.

3. The hydrophilization treatment solution according to claim 1, wherein, The average degree of polymerization in R 1 The values ​​are 2 to 15 when representing hydrogen atoms, and in R 1 This indicates an optional hydrocarbon group with 1 to 24 carbon atoms containing a hydroxyl group, or R. 2 In the case of CO groups, the value is 4 to 10.

4. The hydrophilization treatment solution according to claim 1, wherein, The total content of abrasive particles and alkaline compounds is 0 by weight.

5. The hydrophilization treatment solution according to claim 1 has a pH less than 8.

6. The hydrophilization treatment solution according to claim 1, wherein, The weight-average molecular weight of the compound represented by formula (1) is 100~3000.

7. The hydrophilization treatment solution according to claim 1, wherein, The weight-average molecular weight of the compound represented by formula (1) is 100~1000.

8. The hydrophilization treatment solution according to claim 1, wherein, The compound represented by formula (1) has an HLB value of 14 or higher.

9. The hydrophilic treatment solution according to any one of claims 1 to 8, wherein it is a rinsing and grinding solution.

10. A method for manufacturing a semiconductor device, comprising: The process of performing hydrophilic treatment on the surface of a semiconductor wafer using the hydrophilic treatment solution according to any one of claims 1 to 8.

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