Wafer dicing solution composite nanoparticle composition, composite nanoparticle, and preparation method and use thereof

Abstract

This invention provides a composite nanoparticle composition for wafer dicing solution, the composite nanoparticles, their preparation method, and their applications. The composite nanoparticle composition comprises multi-component nanoparticles, a surfactant, an initiator, a hydrophilic polymer, and a first solvent; wherein the multi-component nanoparticles include a combination of nano-sized Al₂O₃, nano-sized SiO₂, and nano-sized TiO₂. The composite nanoparticles prepared by the composite nanoparticle composition of this invention can form microscopic cutting edges and grinding areas on the wafer surface when the wafer is diced by a dicing wheel, increasing cutting and grinding forces, and improving cutting efficiency and precision; simultaneously, it reduces the coefficient of friction on the wafer surface, reducing heat and stress generated during cutting, further reducing wafer surface damage and fragmentation.

Description

Technical Field

[0001] This invention relates to a composite nanoparticle composition, composite nanoparticles, preparation method and application thereof, specifically to a wafer dicing solution composite nanoparticle composition, composite nanoparticles, preparation method and application thereof, belonging to the field of semiconductor device manufacturing. Background Technology

[0002] With the continuous development of semiconductor technology, low-k materials are increasingly widely used in semiconductor processes. However, due to their unique material properties, low-k layers are prone to melting during die cutting, leading to adhesion to the die surface, wafer fragmentation, and die breakage. In low-k layers, an air porosity mechanism is typically used to reduce the dielectric constant. This is achieved by introducing tiny air pores into the material to reduce the interaction of charges, thereby lowering the dielectric constant. However, these tiny voids and cracks also reduce the strength, stability, and surface smoothness of the low-k layer, increase its coefficient of thermal expansion, and easily cause problems such as cracking, peeling, and die adhesion during cutting and processing. Solving the problem of die cutting low-k layers has become a pressing issue in the current semiconductor manufacturing field.

[0003] Currently, there are two technical approaches to solving this problem. The first is to first use a laser to remove the low-k material from the surface of the dicing track, exposing the underlying silicon substrate, and then use a dicing wheel for cutting. This method requires a laser cutting machine, which is expensive and inefficient. The second method is to use a wafer dicing fluid during dicing. The dicing fluid's cleaning, lubrication, and cooling functions can overcome the problems caused by dicing the low-k layer. It is clear that existing wafer dicing fluids still cannot effectively solve the low-k layer problem.

[0004] Therefore, there is an urgent need to study a composite nanoparticle for wafer dicing fluid. This composite nanoparticle can improve the cutting ability of the dicing fluid, solve the adhesion problem when the dicing wheel cuts the low-k layer, and enable the dicing wheel to directly cut wafers with the low-k layer on the surface. Summary of the Invention

[0005] The problem the invention aims to solve

[0006] In view of the technical problems existing in the prior art, the present invention first provides a composite nanoparticle composition and composite nanoparticles. The composite nanoparticle composition of the present invention can form wafer dicing solution composite nanoparticles, which can improve the cutting ability of the dicing solution, solve the adhesion problem when the dicing wheel cuts the low-k layer, and enable the dicing wheel to directly cut wafers with the low-k layer on the surface.

[0007] Furthermore, the present invention also provides a composite nanoparticle composition and a method for preparing the composite nanoparticles. The preparation method is simple and easy to implement, the raw materials are readily available, and it is suitable for mass production.

[0008] Furthermore, the present invention also provides the uses and methods of using composite nanoparticles.

[0009] Solution for solving the problem

[0010] [1]. A composite nanoparticle composition comprising multi-component nanoparticles, a surfactant, an initiator, a hydrophilic polymer, and a first solvent; wherein,

[0011] The multi-component nanoparticles include a combination of nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2.

[0012] Preferably, the mass ratio of nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2 in the multi-component nanoparticles is 1:(1-10):(1-10), and more preferably 1:(1-5):(1-5).

[0013] [2]. According to the composite nanoparticle composition described in [1] above, wherein, by mass parts, the composite nanoparticle composition comprises 0.1-0.5 parts by mass of the multi-element nanoparticles, 10-20 parts by mass of the surfactant, 5-10 parts by mass of the initiator, 5-20 parts by mass of the hydrophilic polymer, and 30-50 parts by mass of the first solvent.

[0014] Preferably, the composite nanoparticle composition comprises 0.2-0.4 parts by weight of the multi-element nanoparticles, 15-20 parts by weight of the surfactant, 6-8 parts by weight of the initiator, 10-15 parts by weight of the hydrophilic polymer, and 40-50 parts by weight of the first solvent.

[0015] [3]. According to the composite nanoparticle composition described in [1] or [2] above, wherein,

[0016] The average particle size of the nano-sized Al2O3 is 0.1-15 nm, preferably 0.5-10 nm, and more preferably 1-5 nm; and / or,

[0017] The average particle size of the nano-sized SiO2 is 0.1-15 nm, preferably 0.5-10 nm, and more preferably 1-5 nm; and / or,

[0018] The average particle size of the nano-sized TiO2 is 0.1-15 nm, preferably 0.5-10 nm, and more preferably 1-5 nm.

[0019] [4]. The composite nanoparticle composition according to any one of [1]-[3] above, wherein,

[0020] The surfactant includes anionic surfactants and / or nonionic surfactants; and / or,

[0021] The initiator includes a peroxide initiator; and / or,

[0022] The hydrophilic polymer is selected from one or more combinations of polyvinyl alcohol, polyvinylpyrrolidone, oxidized polyethylene, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide, polyvinyl alcohol-acrylate copolymer, and polyacrylic acid-acrylamide copolymer; and / or,

[0023] The first solvent is water, preferably water with a resistance greater than or equal to 18 MΩ.

[0024] [5]. A method for preparing a composite nanoparticle composition according to any one of [1]-[4] above, comprising the step of mixing the components of the composite nanoparticle composition;

[0025] Preferably, the preparation method includes the following steps:

[0026] By mixing nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2, multi-component nanoparticles are obtained.

[0027] The multi-component nanoparticles, surfactant, hydrophilic polymer, and first solvent are mixed to obtain a premix;

[0028] The premix was mixed with an initiator to obtain a composite nanoparticle composition.

[0029] [6]. A composite nanoparticle comprising the composite nanoparticle composition according to any one of [1]-[4] above;

[0030] Preferably, the average particle size of the composite nanoparticles is 1-30 nm, more preferably 10-20 nm.

[0031] [7]. A method for preparing composite nanoparticles according to [6] above, comprising the following steps:

[0032] The composite nanoparticle composition was heated and stirred to obtain a reaction liquid;

[0033] The reaction liquid is subjected to solid-liquid separation to obtain a precipitate;

[0034] The precipitate was post-treated to obtain composite nanoparticles;

[0035] Preferably, the temperature after heating is 60-80℃; the stirring speed is 300-600 rpm; and the stirring time is 20-40 min.

[0036] [8]. A composite nanoparticle dispersion comprising the step of mixing the composite nanoparticles of [6] above with a second solvent; preferably, the second solvent is water; more preferably, the mass concentration of the composite nanoparticles in the composite nanoparticle dispersion is 0.1-1wt%, preferably 0.3-0.6wt%.

[0037] [9]. Use of a composite nanoparticle according to [6] above or a composite nanoparticle dispersion according to [8] above as a functional additive in the field of wafer dicing.

[0038]

[10] . A method of using the composite nanoparticles according to [6] above or the composite nanoparticle dispersion according to [8] above, comprising the following steps: adding the composite nanoparticles or the composite nanoparticle dispersion to a dicing aid to obtain a wafer dicing solution containing the composite nanoparticles;

[0039] The wafer dicing solution was then used for wafer dicing.

[0040] The effects of the invention

[0041] The composite nanoparticles prepared by the composite nanoparticle composition of the present invention can form microscopic cutting edges and grinding areas on the wafer surface when the cutting wheel cuts the wafer, thereby increasing the cutting force and grinding force, and improving cutting efficiency and accuracy. At the same time, it reduces the coefficient of friction of the wafer surface, reduces the heat and stress generated during cutting, and further reduces the occurrence of damage and fragmentation on the wafer surface.

[0042] Furthermore, the composite nanoparticles of this invention can also fill the tiny pits and cracks on the wafer surface, increase the flatness and smoothness of the wafer surface, reduce the contact points between the low-k layer and the cutting wheel, as well as the thermal expansion and melting of the low-k layer during the cutting process, reduce the wrapping and adhesion of the low-k layer to the cutting wheel, enabling the cutting wheel to directly cut the low-k layer, avoiding the problems of wafer fragments and cutting wheel breakage, and enhancing the density of the low-k material, reducing its expansion coefficient, improving mechanical strength, and effectively avoiding wafer breakage caused by low-k expansion or mechanical stress.

[0043] Furthermore, the composite nanoparticle composition and the preparation method of the composite nanoparticles of the present invention are both simple and easy to implement, the raw materials are readily available, and they are suitable for mass production.

[0044] In addition, the composite nanoparticles of the present invention can be added to wafer dicing agents, and the resulting wafer dicing solution has good cutting ability and stability, which can effectively solve the adhesion problem when the dicing wheel cuts the low-k layer, and improve wafer processing efficiency and quality. Attached Figure Description

[0045] Figure 1 A schematic diagram of the dicing yield after dicing using a wafer dicing solution containing composite nanoparticles from Example 1 is shown, where green represents well-diced wafers and pink represents poorly diced wafers.

[0046] Figure 2 The diagram shows the wafer dicing yield after dicing using a wafer dicing solution containing composite nanoparticles from Comparative Example 4. Green represents well-diced wafers, and pink represents poorly diced wafers.

[0047] Figure 3 The image shown is a SEM image magnified 8000 times after wafer dicing using a wafer dicing solution containing composite nanoparticles from Example 1.

[0048] Figure 4 The image shows an SEM image of the wafer surface magnified 8000 times after dicing using a wafer dicing solution containing composite nanoparticles from Comparative Example 5. Detailed Implementation

[0049] The present invention will now be described in detail. The descriptions of the technical features described below are based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0050] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0051] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0052] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0053] In this specification, the terms "optional" or "optional" are used to indicate the use or omission of certain substances, components, procedures, application conditions, etc.

[0054] In this instruction manual, "room temperature" and "normal temperature" refer to indoor ambient temperature of "15-25℃".

[0055] All unit names used in this manual are international standard unit names, and unless otherwise stated, the "%" used refers to weight or mass percentage content.

[0056] In this specification, the term "substantially" is used to indicate that the standard deviation from the theoretical model or theoretical data is within 5%, preferably 3%, and more preferably 1%.

[0057] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0058] <First Aspect>

[0059] A first aspect of the present invention provides a composite nanoparticle composition comprising multi-component nanoparticles, a surfactant, an initiator, a hydrophilic polymer, and a first solvent; wherein,

[0060] The multi-component nanoparticles include a combination of nanoscale Al2O3, nanoscale SiO2, and nanoscale TiO2.

[0061] The composite nanoparticles prepared by the composite nanoparticle composition of the present invention can form microscopic cutting edges and grinding areas on the wafer surface when the cutting wheel cuts the wafer, thereby increasing the cutting force and grinding force, and improving cutting efficiency and accuracy. At the same time, it reduces the coefficient of friction of the wafer surface, reduces the heat and stress generated during cutting, and further reduces the occurrence of damage and fragmentation on the wafer surface.

[0062] Multi-component nanoparticles

[0063] This invention utilizes a multi-component nanoparticle system, specifically comprising nano-sized Al₂O₃, nano-sized SiO₂, and nano-sized TiO₂. By employing a blend of these three nanoparticles, the grinding performance of the wafer dicing fluid can be improved.

[0064] The present invention does not impose any particular limitation on nano-sized Al2O3, which can exist in any form. Specifically, according to crystal form, nano-sized Al2O3 can be one or a combination of two or more of γ-Al2O3, α-Al2O3, θ-Al2O3, etc.; according to shape, it can be spherical Al2O3 and / or rod-shaped Al2O3, etc.; preferably, according to crystal form, nano-sized Al2O3 is preferably α-Al2O3 or γ-Al2O3; according to shape, nano-sized Al2O3 is preferably spherical Al2O3.

[0065] Specifically, in this invention, the average particle size of the nano-sized Al2O3 is 0.1-15 nm, preferably 0.5-10 nm, and more preferably 1-5 nm, for example: 2 nm, 3 nm, 4 nm, 6 nm, 10 nm, 12 nm, 14 nm, etc. An average particle size of 0.1-15 nm for the nano-sized Al2O3 is advantageous for preparing composite nanoparticles.

[0066] The present invention does not impose any particular limitation on nanoscale SiO2, which can exist in any form. Specifically, according to shape, nanoscale SiO2 can be spherical nanoscale SiO2. According to pore structure, nanoscale SiO2 can be mesoporous nanoscale SiO2, etc.; preferably, it is mesoporous nanoscale SiO2.

[0067] Specifically, the average particle size of the nano-sized SiO2 can be 0.1-15nm, preferably 0.5-10nm, more preferably 1-5nm, for example: 2nm, 3nm, 4nm, 6nm, 10nm, 12nm, 14nm, etc.; when the average particle size of the nano-sized SiO2 is 0.1-15nm, it is beneficial to prepare composite nanoparticles.

[0068] The present invention does not impose any particular limitation on nano-sized TiO2, which can exist in any form. Specifically, nano-sized TiO2 can be one or a combination of two or more of anatase TiO2, brookite TiO2, and rutile TiO2. Preferably, it is anatase TiO2 and / or rutile TiO2, and more preferably anatase TiO2.

[0069] Specifically, the average particle size of the nano-sized TiO2 is 0.1-15 nm, preferably 0.5-10 nm, and more preferably 1-5 nm, for example: 2 nm, 3 nm, 4 nm, 6 nm, 10 nm, 12 nm, 14 nm, etc.; when the average particle size of the nano-sized TiO2 is 0.1-15 nm, it is beneficial to prepare composite nanoparticles.

[0070] In some specific implementations, the mass ratio of nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2 in the multi-component nanoparticles is 1:(1-10):(1-10), preferably 1:(1-5):(1-5, for example: 1:(1-8):(1-8), 1:(2-6):(2-6), 1:(3-5):(3-5), etc. When the mass ratio of nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2 is 1:(1-10):(1-10), there is an excellent synergistic effect among the nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2, which can further improve the grinding performance of the wafer dicing fluid.

[0071] Furthermore, in this invention, the content of the multi-component nanoparticles in the composite nanoparticle composition is 0.1-0.5 parts by mass, preferably 0.2-0.4 parts by mass; for example: 0.15 parts by mass, 0.2 parts by mass, 0.25 parts by mass, 0.3 parts by mass, 0.35 parts by mass, 0.4 parts by mass, 0.45 parts by mass, etc. When the content of the multi-component nanoparticles is 0.1-0.5 parts by mass, the respective functions of nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2 can be effectively exerted, and the desired composite nanoparticles can be prepared.

[0072] surfactants

[0073] This invention utilizes surfactants to encapsulate multi-component nanoparticles by forming micelles, thereby further improving their dispersibility and stability. Specifically, the surfactants of this invention may include anionic surfactants and / or nonionic surfactants.

[0074] The present invention does not specifically limit the anionic surfactant, and it can be any anionic surfactant commonly used in the art. Specifically, the anionic surfactant can be one or a combination of two or more of carboxylate surfactants, sulfonate surfactants, sulfate surfactants, and phosphate surfactants.

[0075] For carboxylate surfactants, it can be one or a combination of two or more of the following: sodium stearate, sodium benzoate-lactic acid, sodium isostearyl lactylate, sodium hexyl lactylate, sodium lauryl-5 carboxylate, sodium lauryl-6 carboxylate, sodium lauryl-11 carboxylate, etc.

[0076] For sulfonate surfactants, the surface-active anion generated after ionization in water is sulfonate (R-SO3). - These are called sulfonate-type anionic surfactants, which can include various types such as alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfonates, succinate sulfonates, alkylbenzene naphthalene sulfonates, alkylnaphthalene sulfonates, petroleum sulfonates, lignin sulfonates, and alkyl glycerol ether sulfonates. Specific examples include sodium dodecylbenzene sulfonate and sodium dodecyl sulfonate.

[0077] For sulfate surfactants, such as alkyl sulfates, alkyl ester sulfates, alkyl ether sulfates, alkyl alkoxy ester sulfates, glycerol ester sulfates, especially sulfates of fatty alcohols or sulfates of polyoxyalkyl ethers of fatty alcohols, such as sodium dodecyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, and potassium dodecyl sulfate.

[0078] For phosphate surfactants or phosphate ester surfactants, such as alkyl aryl ether phosphates, alkyl ether phosphates, fatty alcohol phosphates, (alkyl) dibutyl phosphate, (alkyl) dimethyl phosphate, hexadecyl-10-phosphate, and other fatty alcohol polyoxyethylene ethers.

[0079] The present invention does not impose any particular limitation on the nonionic surfactant, which can be any nonionic surfactant commonly used in the art. Specifically, the nonionic surfactant can be of two types: polyoxyethylene type and / or polyol type.

[0080] Polyoxyethylene-type nonionic surfactants, also known as polyethylene glycol-type nonionic surfactants, are products of the addition reaction between ethylene oxide and compounds containing active hydrogen. Specifically, they can be alkylphenol polyoxyethylene ethers (e.g., octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether), higher carbon fatty alcohol polyoxyethylene ethers (e.g., the Pingpingjia series of surfactants), fatty acid polyoxyethylene esters, fatty acid methyl ester ethoxylates, and ethylene oxide adducts of polypropylene glycol, among other commonly used nonionic surfactants.

[0081] Polyol-type nonionic surfactants are esters formed from organic compounds containing multiple hydroxyl groups, such as ethylene glycol, pentaerythritol glycerol, sorbitol, and sucrose, and higher fatty acids. Sorbitol, a polyol derived from glucose by hydrogenation, has six hydroxyl groups in its molecule. Under appropriate conditions, sorbitol can be dehydrated to produce sorbitol di- and di-sorbitol. The products are actually a mixture of monoesters, diesters, and trimers; the fatty acids can be lauric acid, palmitic acid, fatty acids, and oleic acid, with the corresponding monoesters designated by trade codes Span-20, 40, 60, and 80, respectively. Further reaction of Span polyol surfactants with ethylene oxide yields the corresponding Tween-type nonionic surfactants. The introduction of polyoxyethylene chains can improve their water solubility, as seen in Tween-60, obtained by adding one Span-60 molecule to 20 ethylene oxide molecules. For nonionic surfactants, this invention preferably uses polyol-type nonionic surfactants.

[0082] Specifically, in this invention, the surfactant preferably includes one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfonate, Tween20, Tween40, Tween60, Span20, Span40, Span60, etc., and is preferably sodium dodecylbenzenesulfonate.

[0083] Furthermore, in this invention, the surfactant content is 10-20 parts by weight, preferably 15-20 parts by weight, for example: 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 18 parts by weight, etc. When the surfactant content is 10-20 parts by weight, it is sufficient to form micelles, encapsulating the multi-component nanoparticles, further improving their dispersibility and stability.

[0084] Initiator

[0085] The inventors of this invention have discovered that, by using an initiator, a composite nanoparticle composition can undergo a chemical reaction under certain conditions to form composite nanoparticles. Specifically, the initiator includes a peroxide initiator. For peroxide initiators, this can include organic peroxide initiators and / or inorganic peroxide initiators.

[0086] Organic peroxide initiators include acyl peroxides (such as benzoyl peroxide, lauroyl peroxide, etc.); hydroperoxides (such as cumene hydroperoxide, tert-butyl hydroperoxide, etc.); dialkyl peroxides (di-tert-butyl peroxide, diisopropylbenzene peroxide, etc.); ester peroxides (such as tert-butyl peroxide, tert-butyl pervalerate, etc.); ketone peroxides (such as methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.); and dicarbonate peroxides (such as diisopropyl peroxide, dicyclohexyl peroxide, etc.).

[0087] Furthermore, inorganic peroxides, being soluble in water, are often used in emulsion and aqueous solution polymerization reactions. They are mainly persulfates, such as potassium persulfate, sodium persulfate, and ammonium persulfate, and of course, hydrogen peroxide can also be used.

[0088] Preferably, in this invention, since the first solvent used is preferably water, an inorganic peroxide initiator is also preferred. Specifically, the initiator may include one or more combinations selected from ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, etc., with ammonium persulfate being preferred.

[0089] In this invention, the initiator content is 5-10 parts by weight, preferably 6-8 parts by weight, for example, 7 parts by weight, 9 parts by weight, etc. When the initiator content is 5-10 parts by weight, it is sufficient to cause a chemical reaction in the composite nanoparticle composition.

[0090] This invention utilizes an initiator to initiate a reaction between hydroxyl groups on the surface of multi-component nanoparticles and active functional groups (e.g., hydroxyl, carboxyl, amide, etc.) in hydrophilic polymers.

[0091] hydrophilic polymers

[0092] The hydrophilic polymer of the present invention can coat multi-component nanoparticles on its surface through mechanisms such as adsorption and coating, forming a protective layer to prevent it from being affected by the external environment.

[0093] Specifically, in this invention, the hydrophilic polymer includes one or more of polyvinyl alcohol, polyvinylpyrrolidone, oxidized polyethylene, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide, polyvinyl alcohol acrylate copolymer, and polyacrylic acid acrylamide copolymer, preferably including one or more of polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid, and most preferably polyvinyl alcohol.

[0094] Furthermore, in this invention, the number-average molecular weight Mn of the hydrophilic polymer is 10,000-80,000, preferably 10,000-50,000, and more preferably 20,000-30,000.

[0095] Furthermore, in this invention, the content of the hydrophilic polymer, by weight, is 5-20 parts by weight, preferably 10-15 parts by weight, for example: 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, etc. When the content of the hydrophilic polymer is 5-20 parts by weight, through mechanisms such as adsorption and coating, the multi-component nanoparticles can be effectively coated on its surface, forming a protective layer to prevent it from being affected by the external environment.

[0096] In addition, the hydrophilic polymer and surfactant of the present invention have a synergistic effect, thereby protecting the multi-component nanoparticles.

[0097] First solvent

[0098] The first solvent of this invention is water, preferably water with a resistivity of 18 MΩ or higher, such as deionized water with a resistivity of 18 MΩ or higher, i.e., ultrapure water. In this invention, the content of the first solvent is 30-50 parts by mass, preferably 40-50 parts by mass, for example: 32 parts by mass, 35 parts by mass, 38 parts by mass, 40 parts by mass, 42 parts by mass, 45 parts by mass, 48 ​​parts by mass, etc.

[0099] Preparation method

[0100] The present invention also provides a method for preparing the above-mentioned composite nanoparticle composition, which includes the step of mixing the components of the composite nanoparticle composition.

[0101] Specifically, the preparation method of the composite nanoparticle composition includes the following steps:

[0102] By mixing nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2, multi-component nanoparticles are obtained.

[0103] The multi-component nanoparticles, surfactant, hydrophilic polymer, and first solvent are mixed to obtain a premix;

[0104] The premixed material is mixed with an initiator to obtain a composite nanoparticle composition.

[0105] Specifically, the present invention mixes nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2 to obtain multi-component nanoparticles; the present invention does not particularly limit the mixing method, and nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2 can be mixed directly.

[0106] Furthermore, the multi-component nanoparticles, surfactant, hydrophilic polymer, and first solvent are mixed to obtain a premix; the present invention can perform preliminary surface modification on the multi-component nanoparticles by using surfactant and hydrophilic polymer, so that they have good dispersion stability in the first solvent.

[0107] Specifically, regarding the mixing method, the present invention can first mix the multi-component nanoparticles with a first solvent, then add a surfactant for secondary mixing, and finally mix with a hydrophilic polymer for tertiary mixing to obtain a premix, which is in the form of a microemulsion.

[0108] Specifically, when mixing the multi-component nanoparticles with the first solvent, the mixing can be assisted by ultrasound or stirring, with ultrasound being preferred. Specifically, the mixing can be performed at 30-50MHz, for example, 35MHz, 40MHz, 45MHz, etc., for 20-40 minutes, for example, 25 minutes, 30 minutes, 35 minutes, etc.

[0109] When mixing with surfactants, ultrasonication or stirring can be used to assist mixing, with stirring being preferred, and magnetic stirring being more preferred. Specifically, the stirring speed is 100-200 rpm, for example: 120 rpm, 140 rpm, 160 rpm, 180 rpm, etc.; the stirring temperature is 30-50℃, for example: 35℃, 40℃, 45℃, etc.; and the stirring time is 20-40 min, for example: 25 min, 30 min, 35 min, etc.

[0110] When mixing with hydrophilic polymers three times, ultrasonic or stirring methods can be used to assist mixing, with stirring being preferred, and magnetic stirring being more preferred. Specifically, the stirring speed is 300-600 rpm, for example: 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, etc.; the stirring temperature is 30-50℃, for example: 35℃, 40℃, 45℃, etc.; and the stirring time is 20-40 min, for example: 25 min, 30 min, 35 min, etc.

[0111] <Second aspect>

[0112] A second aspect of the present invention provides composite nanoparticles comprising the composite nanoparticle composition according to the first aspect of the present invention. The composite nanoparticles of the present invention can be surface-modified nanoscale particles, which can improve the grinding performance of wafer dicing fluids.

[0113] When the cutting wheel cuts the wafer, the composite nanoparticles of the present invention can form microscopic cutting edges and grinding areas on the wafer surface, increasing cutting force and grinding force, and improving cutting efficiency and accuracy; at the same time, they reduce the coefficient of friction of the wafer surface, reduce the heat and stress generated during cutting, and further reduce the occurrence of damage and fragmentation on the wafer surface.

[0114] Furthermore, the composite nanoparticles of this invention can also fill the tiny pits and cracks on the wafer surface, increase the flatness and smoothness of the wafer surface, reduce the contact points between the low-k layer and the cutting wheel, as well as the thermal expansion and melting of the low-k layer during the cutting process, reduce the wrapping and adhesion of the low-k layer to the cutting wheel, enabling the cutting wheel to directly cut the low-k layer, avoiding the problems of wafer fragments and cutting wheel breakage, and enhancing the density of the low-k material, reducing its expansion coefficient, improving mechanical strength, and effectively avoiding wafer breakage caused by low-k expansion or mechanical stress.

[0115] Furthermore, in this invention, if the average particle size of the composite nanoparticles is too large, their dispersion stability in water will be poor due to gravity; if the average particle size of the composite nanoparticles is too small, the specific surface area will be too large, making them prone to aggregation. Specifically, in this invention, the particle size of the composite nanoparticles can be 1-30 nm, preferably 10-20 nm, for example: 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, etc.

[0116] Furthermore, the present invention also provides a method for preparing composite nanoparticles, which includes the following steps:

[0117] The composite nanoparticle composition was heated and stirred to obtain a reaction liquid;

[0118] The reaction liquid is subjected to solid-liquid separation to obtain a precipitate;

[0119] The precipitate was post-treated to obtain composite nanoparticles.

[0120] This invention involves heating and stirring a composite nanoparticle composition to obtain a reaction liquid. The surface of the composite nanoparticle composition is modified by a chemical reaction through heating and stirring to obtain the reaction liquid, thereby enabling the preparation of the desired composite nanoparticles. Surface modification improves the dispersion stability of nanoscale particles in wafer dicing solution.

[0121] Preferably, the temperature after heating is 60-80℃; the stirring speed is 300-600 rpm, for example: 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, etc.; the stirring time is 20-40 min, for example: 25 min, 30 min, 35 min, etc.

[0122] Furthermore, by performing solid-liquid separation on the reaction liquid, a precipitate is obtained; the main component of the precipitate is composite nanoparticles.

[0123] For solid-liquid separation, this invention does not impose any particular limitations and can employ filtration or centrifugation. To obtain the desired precipitate, centrifugation is preferred. The centrifugation speed is not particularly limited and is generally 10,000-20,000 rpm, such as 12,000 rpm, 14,000 rpm, 16,000 rpm, or 18,000 rpm. The centrifugation time can be set as needed, such as 5-20 min, 8-18 min, 10-15 min, or 12-14 min.

[0124] Specifically, the solid-liquid separation of the present invention may include the following steps: the reaction liquid is placed in a centrifuge and centrifuged at a speed of 10,000-20,000 rpm for 5-20 minutes; at this time, the reaction liquid becomes a clear liquid on the upper layer and a precipitate on the lower layer; the clear liquid on the upper layer is aspirated with a dropper to obtain the precipitate on the lower layer.

[0125] Finally, the precipitate is post-treated to obtain composite nanoparticles. The post-treatment is not particularly limited in this invention and can include washing, drying, or other methods commonly used in the art. Washing is not limited in this invention and can be performed using commonly used polar solvents in the art, such as water or alcohol solvents, including methanol and ethanol. Drying is generally carried out at temperatures below 100°C, for example, 40-60°C. The drying time is not particularly limited in this invention and can be 20-40 minutes.

[0126] Specifically, the post-treatment includes transferring the precipitate to a Buchner funnel for filtration and washing. Specifically, the precipitate in the Buchner funnel is washed with methanol 5-20 times. After washing, the solid in the Buchner funnel is transferred to a vacuum oven and dried at 40-60°C for 20-40 minutes.

[0127] Furthermore, the present invention also provides a composite nanoparticle dispersion, which includes the step of mixing composite nanoparticles with a second solvent; preferably, the second solvent is water, such as deionized water or any feasible type of water.

[0128] Specifically, in the composite nanoparticle dispersion, the mass concentration of the composite nanoparticles can be 0.1-1 wt%, preferably 0.3-0.6 wt%, for example: 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, etc.

[0129] <Third aspect>

[0130] A third aspect of the present invention provides the use of the aforementioned composite nanoparticles as a functional additive in the field of wafer dicing, particularly in the field of dicing wheel cutting, which can significantly improve the cutting ability of wafer dicing fluid, prevent the low-k layer from adhering to the surface of the dicing wheel during the cutting process, and effectively solve the problem of dicing wheel cutting low-k layers.

[0131] Furthermore, the present invention also provides a method of using the composite nanoparticles or the composite nanoparticle dispersion according to the second aspect of the present invention, which includes the following steps: adding the composite nanoparticles or the composite nanoparticle dispersion to a dicing aid to obtain a wafer dicing solution containing the composite nanoparticles.

[0132] The wafer dicing solution was then used for wafer dicing with a wafer cutting wheel.

[0133] Preferably, when the composite nanoparticle dispersion is added to the scrambling agent, the content of the composite nanoparticle dispersion is 0.1-5 wt%, preferably 2-3 wt%, for example: 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, etc., based on the total mass of the scrambling agent being 100%.

[0134] Of course, the composite nanoparticles can also be directly added to the scribing agent in this application, but attention should be paid to controlling the amount used.

[0135] Example

[0136] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0137] Examples 1-12

[0138] The composite nanoparticles of Examples 1-12 were prepared according to the compositions in Table 1-2 below and the following preparation methods.

[0139] The specific preparation method is as follows:

[0140] Step 1: Mix nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2 evenly to obtain multi-component nanoparticles;

[0141] Step 2: Add multi-component nanoparticles to ultrapure water and sonicate at 40℃ using 40MHz ultrasound for 30 minutes; add surfactant and stir magnetically at 100rpm and 40℃ for 30 minutes; add hydrophilic polymer and stir magnetically at 500rpm and 40℃ for 30 minutes to form a reaction solution; add initiator, heat to 70℃, and continue stirring at 500rpm for 30 minutes to obtain a composite nanoparticle composition.

[0142] Step 3: Place the composite nanoparticle composition from Step 2 into a centrifuge and centrifuge at 15,000 rpm for 10 minutes. At this point, the composite nanoparticle composition becomes a clear liquid on the upper layer and a solid precipitate on the lower layer. Use a dropper to remove the clear liquid from the upper layer and transfer the lower precipitate to a Buchner funnel for filtration and washing. Rinse the precipitate in the Buchner funnel with methanol 10 times. After rinsing, transfer the solid in the Buchner funnel to a vacuum oven and dry it at 50°C for 30 minutes to obtain composite nanoparticles.

[0143] Step 4: Add the above composite nanoparticles to deionized water at 0.5 wt%, and sonicate with 40 MHz ultrasound for 30 min to obtain a composite nanoparticle dispersion.

[0144] Table 1

[0145]

[0146] Table 2

[0147]

[0148] Comparative Examples 1-5

[0149] According to the composition in Table 3 below, the composite nanoparticle dispersions of Comparative Examples 1-5 were prepared using the preparation methods of Examples 1-12.

[0150] Table 3

[0151]

[0152] Performance testing

[0153] The composite nanoparticle dispersions of Examples 1-12 and Comparative Examples 1-5 were added to the dicing aid ACE210X (Zhejiang Aoshou Materials Technology Co., Ltd.) at a ratio of 2.5 wt% to obtain a wafer dicing solution containing composite nanoparticles. The following tests were then performed, and the test data are shown in Table 4 below.

[0154] 1. Chip scratch ratio test:

[0155] 12-inch wafers with low-k surface material were diced using wafer dicing solutions containing the composite nanoparticles of the examples and comparative examples. After dicing, the dicing ratio of the chip area was inspected using an automated optical inspection device. An 8000x SEM image of the wafer surface after dicing using the wafer dicing solution containing the composite nanoparticles of Example 1 is shown below. Figure 3 As shown; 8000x magnified SEM image of the wafer surface after dicing using a wafer dicing solution containing composite nanoparticles (Comparative Example 4). Figure 4 As shown.

[0156] 2. Slicing yield test:

[0157] 12-inch wafers with low-k material on their surfaces were diced using a wafer dicing solution containing composite nanoparticles from the examples and comparative examples. The dicing yield was then assessed using an automated optical inspection system. Figure 1 A schematic diagram of the dicing yield after dicing using a wafer dicing solution containing composite nanoparticles from Example 1 is shown. Figure 2 The diagram shows the wafer dicing yield after dicing using a wafer dicing solution containing composite nanoparticles (Comparative Example 5); green represents well-diced wafers, and pink represents poorly diced wafers.

[0158] Table 4. Test data for the streaking solution

[0159]

[0160] As can be seen from Table 4, the embodiments of the present invention are superior to comparative examples 1-5 in terms of chip area scratch ratio and dicing yield.

[0161] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the invention. Furthermore, it should be understood that after reading the technical description of this invention, those skilled in the art can make various alterations, modifications, and / or variations to the invention, and all such equivalent forms also fall within the scope of protection defined by the appended claims.

Claims

1. A composite nanoparticle for wafer dicing liquid, characterized by, The composite nanoparticles are prepared from a composite nanoparticle composition; the composite nanoparticle composition includes multi-component nanoparticles, a surfactant, an initiator, a hydrophilic polymer, and a first solvent; wherein... The multi-component nanoparticles are composed of nano-sized Al2O3, nano-sized SiO2, and nano-sized TiO2. The mass ratio of nanoscale Al2O3, nanoscale SiO2 and nanoscale TiO2 in the multi-component nanoparticles is 1:(1-10):(1-10); The average particle size of the nano-sized Al2O3 is 0.1-15 nm, the average particle size of the nano-sized SiO2 is 0.1-15 nm, and the average particle size of the nano-sized TiO2 is 0.1-15 nm. The hydrophilic polymer coats the multi-component nanoparticles onto its surface through adsorption and coating mechanisms. The surfactants include anionic surfactants and / or nonionic surfactants; The hydrophilic polymer is selected from one or more combinations of polyvinyl alcohol, polyvinylpyrrolidone, oxidized polyethylene, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide, polyvinyl alcohol-acrylate copolymer, and polyacrylic acid-acrylamide copolymer.

2. The composite nanoparticle of claim 1, wherein, The mass ratio of nanoscale Al2O3, nanoscale SiO2 and nanoscale TiO2 in the multi-component nanoparticles is 1:(1-5):(1-5).

3. The composite nanoparticle of claim 1, wherein, Based on parts by weight, the composite nanoparticle composition comprises 0.1-0.5 parts by weight of the multi-element nanoparticles, 10-20 parts by weight of the surfactant, 5-10 parts by weight of the initiator, 5-20 parts by weight of the hydrophilic polymer, and 30-50 parts by weight of the first solvent.

4. The composite nanoparticle of claim 3, wherein, The composite nanoparticle composition comprises 0.2-0.4 parts by weight of the multi-element nanoparticles, 15-20 parts by weight of the surfactant, 6-8 parts by weight of the initiator, 10-15 parts by weight of the hydrophilic polymer, and 40-50 parts by weight of the first solvent.

5. The composite nanoparticles according to any one of claims 1-4, characterized in that, The average particle size of the nano-sized Al2O3 is 0.5-10 nm; and / or, The average particle size of the nanoscale SiO2 is 0.5-10 nm; and / or, The average particle size of the nano-sized TiO2 is 0.5-10 nm.

6. The composite nanoparticles according to claim 5, characterized in that, The average particle size of the nano-sized Al2O3 is 1-5 nm; and / or, The average particle size of the nano-sized SiO2 is 1-5 nm; and / or, The average particle size of the nano-sized TiO2 is 1-5 nm.

7. The composite nanoparticle according to any one of claims 1-4, wherein, The initiator includes a peroxide initiator; and / or, The first solvent is water.

8. The composite nanoparticle of claim 7, wherein, The first solvent is water with a resistance greater than or equal to 18 MΩ.

9. The composite nanoparticle according to any one of claims 1-4, wherein, The method for preparing the composite nanoparticle composition includes the step of mixing the components of the composite nanoparticle composition.

10. The composite nanoparticle of claim 9, wherein, The preparation method of the composite nanoparticle composition includes the following steps: By mixing nano-sized Al2O3, nano-sized SiO2 and nano-sized TiO2, multi-component nanoparticles are obtained. The multi-component nanoparticles, surfactant, hydrophilic polymer, and first solvent are mixed to obtain a premix; The premixed material is mixed with an initiator to obtain a composite nanoparticle composition.

11. The composite nanoparticle according to any one of claims 1-4, wherein, The average particle size of the composite nanoparticles is 1-30 nm.

12. The composite nanoparticle of claim 11, wherein, The average particle size of the composite nanoparticles is 10-20 nm.

13. A method for preparing composite nanoparticles according to any one of claims 1-12, characterized in that, Includes the following steps: The composite nanoparticle composition was heated and stirred to obtain a reaction liquid; The reaction liquid is subjected to solid-liquid separation to obtain a precipitate; The precipitate was post-treated to obtain composite nanoparticles.

14. The method for preparing composite nanoparticles according to claim 13, characterized in that, The temperature after heating is 60-80℃; the stirring speed is 300-600 rpm; and the stirring time is 20-40 min.

15. A composite nanoparticle dispersion, characterized in that, The composite nanoparticles of any one of claims 1-12 and the second solvent.

16. The composite nanoparticle dispersion of claim 15, wherein, The second solvent is water.

17. The composite nanoparticle dispersion of claim 15 or 16, wherein, In the composite nanoparticle dispersion, the mass concentration of the composite nanoparticles is 0.1-1 wt%.

18. The composite nanoparticle dispersion of claim 17, wherein, In the composite nanoparticle dispersion, the mass concentration of the composite nanoparticles is 0.3-0.6 wt%.

19. The use of a composite nanoparticle according to any one of claims 1-12 or a composite nanoparticle dispersion according to any one of claims 15-18 as a functional additive in the field of wafer dicing.

20. A method of using the composite nanoparticle according to any one of claims 1 to 12 or the composite nanoparticle dispersion liquid according to any one of claims 15 to 18, characterized by, The process includes the following steps: adding the composite nanoparticles or composite nanoparticle dispersion to a dicing aid to obtain a wafer dicing solution containing composite nanoparticles; The wafer dicing solution was then used for wafer dicing.

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