CN116144303B - Underfill adhesive, preparation method thereof and chip packaging structure - Google Patents

Underfill adhesive, preparation method thereof and chip packaging structure Download PDF

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Publication number
CN116144303B
CN116144303B CN202211680673.7A CN202211680673A CN116144303B CN 116144303 B CN116144303 B CN 116144303B CN 202211680673 A CN202211680673 A CN 202211680673A CN 116144303 B CN116144303 B CN 116144303B
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epoxy resin
inorganic filler
underfill
latent
dicyandiamide
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CN116144303A (en
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肖德海
喻琴
邓振杰
颜明发
徐玉文
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DONGGUAN U-BOND MATERIAL TECHNOLOGY CO LTD
Huangpu Institute of Materials
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DONGGUAN U-BOND MATERIAL TECHNOLOGY CO LTD
Huangpu Institute of Materials
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/16—Fillings or auxiliary members in containers or encapsulations, e.g. centering rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to the technical field of chip packaging, in particular to underfill, a preparation method thereof and a chip packaging structure. Comprises the following raw materials in percentage by mass: 20 to 36.5 weight percent of bisphenol F epoxy resin; 0.7 to 3 weight percent of naphthalene epoxy resin; 0.7 to 3 weight percent of multifunctional epoxy resin; 0.5 to 3 weight percent of reactive diluent; 1 to 8 weight percent of latent dicyandiamide curing agent; 0.3 to 0.5 weight percent of imidazole accelerator; 55-75wt% of inorganic filler; 0.5 to 2 weight percent of functional auxiliary agent; the inorganic filler comprises a first inorganic filler and a second inorganic filler, and the particle size D50 of the first inorganic filler is smaller than the particle size D50 of the second inorganic filler. The underfill disclosed by the invention has the properties of low viscosity, high glass transition temperature, high heat resistance, high flexural modulus and high elastic modulus, and is excellent in comprehensive performance.

Description

Underfill adhesive, preparation method thereof and chip packaging structure
Technical Field
The invention relates to the technical field of chip packaging, in particular to underfill, a preparation method thereof and a chip packaging structure.
Background
The underfill is a glue for underfill, which is required to have a fast flow property, and can well fill a narrow gap between a chip and a circuit board under a suitable temperature condition, thereby achieving the effect of packaging and protecting the chip. Moreover, since the chip generates a large amount of heat during use, in order to prevent warpage, it is also required that the underfill have a high glass transition temperature and a high modulus, thereby ensuring the reliability of the packaged device against high temperatures without failure.
To meet the above properties, some underfill have Cl incorporated therein - Plasma, but with Cl - The introduction of plasma accelerates the corrosion of aluminum leads in the die under the action of moisture, so that the service life of electronic components is adversely affected. The current universal epoxy resin containing about 600mg/kg of hydrolyzable chlorine in the world can only be suitable for the storage degree of 64k storage units, can not meet the storage degree of 256k storage units, and can not meet the future 1M storage unit age.
In addition, in order to improve the heat resistance and mechanical properties of the underfill, a resin with a larger molecular weight may be added for polymerization. However, the introduction of a resin having a relatively large molecular weight increases the viscosity of the system, thereby severely reducing the fluidity of the system, and adversely affecting the flow and adhesion properties of the underfill.
In summary, various comprehensive indexes of the underfill are required to be improved, otherwise, the requirement of chip packaging is difficult to meet, and the underfill product is difficult to popularize and apply in the packaging process of the semiconductor flip chip.
Disclosure of Invention
Based on the above, the invention provides an underfill, a preparation method thereof and a chip packaging structure.
The first aspect of the invention provides an underfill adhesive, which has the following technical scheme:
the underfill comprises the following raw materials in percentage by weight:
the inorganic filler comprises a first inorganic filler and a second inorganic filler, and the particle size D50 of the first inorganic filler is smaller than the particle size D50 of the second inorganic filler.
In some of these embodiments, the multifunctional epoxy resin meets at least one of the following conditions:
1) Including trifunctional epoxy resins, tetrafunctional epoxy resins, or combinations thereof;
2) The epoxy equivalent weight is 90 g/eq-125 g/eq;
3) The viscosity at 25 ℃ is 300 cp-9000 cp.
In some of these embodiments, the bisphenol F epoxy resin meets at least one of the following conditions:
1) The epoxy equivalent weight is 160 g/eq-180 g/eq;
2) The viscosity at 25 ℃ is 1500-5000 cp.
In some of these embodiments, the naphthalene based epoxy resin meets at least one of the following conditions:
1) The epoxy equivalent is 130 g/eq-160 g/eq;
2) The viscosity at 30 ℃ is 20000cp to 30000cp.
In some of these embodiments, the inorganic filler satisfies at least one of the following conditions:
1) The first inorganic filler and the second inorganic filler are respectively and independently silicon micropowder;
2) The particle diameter D50 of the first inorganic filler is 0.3-0.7 mu m, and the particle diameter D50 of the second inorganic filler is 1.7-2.1 mu m;
3) The first inorganic filler accounts for 5-25 wt% of the total inorganic filler, and the second inorganic filler accounts for 75-95 wt% of the total inorganic filler.
In some of these embodiments, the reactive diluent is selected from 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate, 1, 2-cyclohexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, or a combination thereof.
In some of these embodiments, the latent dicyandiamide-based curative is selected from the group consisting of latent powder dicyandiamide, latent liquid dicyandiamide, or a combination thereof.
In some of these embodiments, the functional aid comprises a coupling agent, a dispersant, a defoamer, or a combination thereof.
In some embodiments, the underfill comprises the following raw materials in mass percent:
the second aspect of the invention provides a preparation method of underfill, which has the following technical scheme:
mixing the bisphenol F epoxy resin, naphthalene epoxy resin, multifunctional epoxy resin, reactive diluent, latent dicyandiamide curing agent and functional auxiliary agent, stirring, adding the inorganic filler, stirring, adding the imidazole accelerator when the temperature of the obtained mixture is less than or equal to 10 ℃, and stirring.
The third aspect of the present invention provides a chip packaging structure, which has the following technical scheme:
the chip packaging structure comprises a substrate, a chip arranged on the substrate and a plurality of welding convex points arranged at intervals between the substrate and the chip, wherein an underfill material is filled in gaps between the welding convex points between the substrate and the chip, and the underfill material is formed after the underfill is solidified.
Compared with the traditional scheme, the invention has the following beneficial effects:
the invention takes bisphenol F epoxy resin, naphthalene epoxy resin and multifunctional epoxy resin as main resin, can form a three-dimensional network with high crosslinking density on the basis of ensuring that the underfill has lower viscosity to meet the requirement of rapid flow, is beneficial to improving the heat resistance and glass transition temperature of the underfill, has no halogen in the main resin, can meet the storage degree of 256k storage units of a chip, and can even meet the requirement of 1M storage units in the future. Meanwhile, the reactive diluent is added, and the reactive diluent can participate in copolymerization, so that the design of a rigid-flexible molecular chain in a three-dimensional network is realized, the elastic modulus of the underfill is improved, the toughness is improved, the interface and the body of the underfill are prevented from cracking, and the warping resistance and the reliability of the underfill are improved. Meanwhile, the latent dicyandiamide curing agent is added, so that the compatibility of the latent dicyandiamide curing agent and the main resin is good, the curing temperature is reduced, and the medium-temperature rapid curing is realized. Meanwhile, two inorganic fillers with different particle sizes D50 are added, so that the effect of 'large ball boosting' and 'small ball boosting' can be exerted in the flowing process of the underfill, the rapid flowing of products is promoted, in a three-dimensional network of a cured product, the reduction of the thermal expansion coefficient of the products can be promoted through the close accumulation of large and small microspheres, and the improvement of the elastic modulus is facilitated. In conclusion, through the mutual matching of the components, the underfill disclosed by the invention has the performances of low viscosity, high glass transition temperature, high heat resistance, high flexural modulus and high elastic modulus, and has excellent comprehensive performance.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, a selection range in reference to "and/or", "and/or" includes any one of two or more of the items listed in relation to each other, as well as any and all combinations of the items listed in relation to each other, including any two of the items listed in relation to each other, any more of the items listed in relation to each other, or all combinations of the items listed in relation to each other. It should be noted that when at least three items are connected by a combination of at least two conjunctions selected from the group consisting of "and/or", "and/or", it is to be understood that the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly also includes technical solutions that are all connected by "logical or". For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, the terms "plurality", "plural", "multiple", and the like are used in terms of the number of the terms "plurality", "multiple", and the like, and are not particularly limited, but are greater than 2 or equal to 2 in number. For example, "one or more" means one kind or two or more kinds.
In the present invention, reference to "a combination thereof", "any combination thereof", and the like includes all suitable combinations of any two or more of the listed items.
In the present invention, the "suitable" is referred to in "suitable combination means", "suitable means", "any suitable means", etc., so as to enable implementation of the technical solution of the present invention, solve the technical problem of the present invention, and achieve the technical effects expected by the present invention.
In the present invention, references to "preferred", "better", "preferred" are merely to describe embodiments or examples of better results, and it should be understood that they do not limit the scope of the present invention.
In the present invention, references to "further", "still further", "particularly" and the like are used for descriptive purposes and indicate that the invention is not to be interpreted as limiting the scope of the invention.
In the present invention, reference to "optional", "optional" refers to the presence or absence of the "optional" or "optional" means either of the "with" or "without" side-by-side arrangements. If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the present invention, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. Where a numerical range merely refers to integers within the numerical range, including both end integers of the numerical range, and each integer between the two ends, unless otherwise indicated, each integer is recited herein as directly, such as where t is an integer selected from 1 to 10, and where t is any integer selected from the group of integers consisting of 1,2, 3,4, 5, 6, 7, 8, 9, and 10. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present invention, the content of the components is referred to as mass percent for solid-liquid mixing and solid-solid mixing, and volume percent for liquid-liquid mixing unless otherwise specified.
In the present invention, the term "percent concentration" refers to the final concentration unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
In the present invention,% (w/w) and wt% each represent weight percent,% (v/v) represents volume percent, and% (w/v) represents mass volume percent.
An embodiment of the invention provides an underfill adhesive, which comprises the following raw materials in percentage by mass:
the inorganic filler comprises a first inorganic filler and a second inorganic filler, and the particle size D50 of the first inorganic filler is smaller than the particle size D50 of the second inorganic filler.
According to the embodiment, bisphenol F type epoxy resin, naphthalene epoxy resin and multifunctional epoxy resin are matched to serve as main resin, so that a three-dimensional network with high crosslinking density can be formed on the basis that the underfill has low viscosity to meet the requirement of rapid flow, the heat resistance and the glass transition temperature of the underfill are improved, the main resin is free of halogen, the storage degree of 256k storage units of a chip can be met, and even the requirement of 1M storage units in the future can be met. Meanwhile, the reactive diluent is added, and the reactive diluent can participate in copolymerization, so that the design of a rigid-flexible molecular chain in a three-dimensional network is realized, the elastic modulus of the underfill is improved, the toughness is improved, the interface and the body of the underfill are prevented from cracking, and the warping resistance and the reliability of the underfill are improved. Meanwhile, the latent dicyandiamide curing agent is added, so that the compatibility of the latent dicyandiamide curing agent and the main resin is good, the curing temperature is reduced, and the medium-temperature rapid curing is realized. Meanwhile, two inorganic fillers with different particle sizes D50 are added, so that the effect of 'large ball boosting' and 'small ball boosting' can be exerted in the flowing process of the underfill, the rapid flowing of products is promoted, in a three-dimensional network of a cured product, the reduction of the thermal expansion coefficient of the products can be promoted through the close accumulation of large and small microspheres, and the improvement of the elastic modulus is facilitated. In conclusion, through the mutual matching of the components, the underfill disclosed by the invention has the performances of low viscosity, high glass transition temperature, high heat resistance, high flexural modulus and high elastic modulus, and has excellent comprehensive performance.
Alternatively, the bisphenol F type epoxy resin has an epoxy equivalent of 160g/eq to 180g/eq.
Optionally, the bisphenol F type epoxy resin has a viscosity of 1500cp to 5000cp at 25 ℃.
For example, the bisphenol F type epoxy resin is NPEF-170.
Optionally, the naphthalene based epoxy resin has an epoxy equivalent weight of 130g/eq to 160g/eq.
Optionally, the naphthalene-based epoxy resin has a viscosity of 20000cp to 30000cp at 30 ℃.
For example, the naphthalene based epoxy resin is EBA-65.
Optionally, the multi-functional epoxy resin comprises a tri-functional epoxy resin, a tetra-functional epoxy resin, or a combination thereof. For example, the triglycidyl amine-type epoxy resin, tetraglycidyl amine-type epoxy resin, or a combination thereof is included.
The structure of the triglycidyl para-aminophenol is shown in a formula I, and the structure of the tetraglycidyl amine type phenol is shown in a formula II:
optionally, the epoxy equivalent of the multifunctional epoxy resin is 90g/eq to 125g/eq.
Alternatively, the multifunctional epoxy resin has a viscosity of 300cp to 9000cp at 25 ℃.
For example, the multifunctional epoxy may be AG80, AFG90H, 310P, TT310, TT410.
In this embodiment, the copolycondensation of the bisphenol F-type epoxy resin, the naphthalene-based epoxy resin, and the polyfunctional epoxy resin results in a cured product having a high glass transition temperature and a high elastic modulus.
Alternatively, the reactive diluent is selected from 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate, 1, 2-cyclohexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, or a combination thereof.
Wherein the structure of the 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate is shown in a formula III, and the structure of the 1, 2-cyclohexanediol diglycidyl ether is shown in a formula IV:
optionally, the latent dicyandiamide curing agent is selected from latent powder dicyandiamide, latent liquid dicyandiamide, or a combination thereof. The latent dicyandiamide curing agent has good compatibility with an epoxy resin system, is favorable for reducing the curing temperature, and can reduce the curing temperature from 180 ℃ to 130 ℃.
Further alternatively, the particle diameter D50 of the latent powder dicyandiamide is less than or equal to 5 mu m.
Preferably, the latent dicyandiamide curing agent is selected from latent liquid dicyandiamide, and the addition of the latent liquid dicyandiamide is more beneficial to improving the fluidity of the underfill compared with the latent powder dicyandiamide.
Alternatively, the imidazole-based accelerator may be 2-ethylcyano-4-methylimidazole, PN23, PN40J, PN, or combinations thereof.
Optionally, the first inorganic filler and the second inorganic filler are each independently a silica micropowder. The flowability of the bottom filling glue is improved by compounding the large-particle-size silicon micro powder and the small-particle-size silicon micro powder.
Alternatively, the particle diameter D50 of the first inorganic filler is 0.3 μm to 0.7 μm, and the particle diameter D50 of the second inorganic filler is 1.7 μm to 2.1 μm.
Alternatively, the particle diameter D50 of the first inorganic filler is 0.3 μm to 0.7 μm, and the particle diameter D50 of the second inorganic filler is 1.7 μm to 2.1 μm.
Optionally, the functional aid comprises a coupling agent, a dispersant, a defoamer, or a combination thereof.
Optionally, the coupling agent is selected from KH560.
Optionally, the mass percentage of the coupling agent in the total raw materials is 0.3-1 wt%.
Optionally, the dispersant is selected from BKY9010, BKY110, BKY111, BYK306, or a combination thereof.
Optionally, the mass percent of the dispersing agent in the total raw materials is 0.1-0.4 wt%.
Optionally, the defoamer is selected from BKY506, BKY525, BKY530, BYK535, or a combination thereof.
Optionally, the mass percent of the defoamer in the total raw materials is 0.1-0.4 wt%.
Preferably, the underfill comprises the following raw materials in percentage by mass:
the underfill of the embodiment has low adhesiveness, good fluidity, good heat resistance, good mechanical properties and lower curing temperature, and provides powerful guarantee for improving the packaging reliability of the semiconductor chip device.
One embodiment of the present invention provides a method for preparing an underfill comprising the steps of:
mixing the bisphenol F epoxy resin, naphthalene epoxy resin, multifunctional epoxy resin, reactive diluent, latent dicyandiamide curing agent and functional auxiliary agent, stirring, adding the inorganic filler, stirring, adding the imidazole accelerator when the temperature of the obtained mixture is less than or equal to 10 ℃, and stirring.
Optionally, the preparation method of the underfill comprises the following steps:
mixing the bisphenol F epoxy resin, naphthalene epoxy resin, multifunctional epoxy resin, reactive diluent, latent dicyandiamide curing agent and functional auxiliary agent, stirring for 0.5-1 h, adding the inorganic filler, stirring for 1-2 h, adding the imidazole accelerator when the temperature of the obtained mixture is less than or equal to 10 ℃, and stirring for 0.5-1 h.
An embodiment of the invention provides a chip packaging structure, which comprises a substrate, a chip arranged on the substrate and a plurality of welding convex points arranged at intervals between the substrate and the chip, wherein an underfill material is filled in gaps between the welding convex points between the substrate and the chip, and the underfill material is formed by curing the underfill adhesive.
The following examples and comparative examples are further illustrated by the fact that the materials used, unless otherwise indicated, are commercially available and that the equipment used, unless otherwise indicated, are commercially available and that the processes involved, unless otherwise indicated, are routine selections by those skilled in the art.
Wherein NPEF-170 is bisphenol F type epoxy resin, which is sourced from Nanya resin Co., ltd, has an epoxy equivalent of 162g/eq and a viscosity of 1750cp at 25 ℃.
EBA-65 is naphthalene based epoxy resin, available from Shanghai Hua Yi resin Co., ltd, having an epoxy equivalent of 142g/eq and a viscosity of 26000CP at 30 ℃.
TT310 is a multifunctional epoxy resin, from Tiantai chemical Co., ltd., having an epoxy equivalent of 96g/eq and a viscosity of 380cp at 25 ℃.
AFG90H is a multifunctional epoxy resin derived from Shanghai Hua Yi, has an epoxy equivalent of 114g/eq and a viscosity of 4200cp at 25 ℃.
BE188EL is bisphenol A type epoxy resin, available from vinca resin Co., ltd, having an epoxy equivalent of 187g/eq and a viscosity of 5000CP at 25 ℃.
CD represents 1, 2-cyclohexanediol diglycidyl ether, available from Guangzhou macro distance corporation.
DICY represents superfine powder dicyandiamide, and the particle size D50 is 5 mu m.
2E4MZ-CN is 2-ethylcyano-4-methylimidazole, which is available from Kagaku Kogyo Co., ltd.
PN23 was obtained from Nippon Denshoku Kogyo as an imidazole accelerator.
Example 1
The embodiment provides an underfill and a preparation method thereof, wherein the steps are as follows:
referring to Table 1, 24wt% of NPEF-170 (bisphenol F type epoxy resin), 1.3wt% of EBA-65 (naphthalene type epoxy resin), 1.3wt% of TT310 (polyfunctional epoxy resin), 1wt% of CD (1, 2-cyclohexanediol diglycidyl ether, reactive diluent), 1.9wt% of DICY (superfine powder dicyandiamide, latent dicyandiamide curing agent), 0.5wt% of coupling agent KH560,0.2wt% of dispersing agent BKY9010 and 0.4wt% of defoaming agent BKY are added into a stirred tank, after uniform stirring, 69wt% of silica micropowder (silica micropowder with a particle size D50 of 0.5 μm accounts for 5% of the total mass of the silica micropowder, silica micropowder with a particle size D50 of 1.9 μm accounts for 95% of the total mass of the silica micropowder) are added, stirring is carried out for 1 hour, the temperature of the reactant is reduced to 10 ℃ or lower, 0.4wt% of 2E 4-CN (2-cyano-4-methylimidazole, imidazole accelerator) is added, and the stirred tank is filled in a half-hour under vacuum condition to obtain a foam rubber.
The following performance tests were performed on the resulting underfill, and the results are summarized in table 1:
1) The underfill was found to have a viscosity of 387888 mpa.s at 25 ℃.
2) The flow distance of the underfill was measured at 100℃for 30min at a gap of 100 microns between two 25.4mm by 76.2mm by 1mm glass sheets.
3) The glass transition temperature of the underfill was 148℃and the flexural modulus was 9.8GPa as measured by GB/T40564-2021.
4) And (3) testing by adopting a DMA double-cantilever mode, and measuring the elastic modulus E of the underfill adhesive to be 6.2GPa.
Examples 2 to 7
Referring to table 1 and the underfill of example 1 and the preparation method thereof, the underfill of examples 2 to 7 were prepared.
The properties of the resulting underfill were tested in the same manner as in example 1 and are summarized in Table 1.
Examples 8 to 9, comparative examples 1 to 5
Referring to table 2 and the underfill of example 1 and the preparation method thereof, the underfill of examples 8 to 9 and comparative examples 1 to 5 were prepared.
The properties of the resulting underfill were tested in the same manner as in example 1 and are summarized in Table 2.
TABLE 1
TABLE 2
Among them, the fine silica powder having a particle diameter D50 of 0.5 μm in the fine silica powder of example 8 was 25% by mass of the total mass of the fine silica powder, and the fine silica powder having a particle diameter D50 of 1.9 μm was 75% by mass of the total mass of the fine silica powder.
The fine silica powder having a particle diameter D50 of 1.9 μm in the fine silica powder of comparative example 4 accounted for 100% of the total mass of the fine silica powder.
"-" means that the ingredient was not added.
As can be seen from table 1, in examples 1 to 9, bisphenol F epoxy resin, naphthalene epoxy resin and multifunctional epoxy resin were used as main resins, powder dicyandiamide or liquid dicyandiamide was used as curing agent, silica micropowder with large and small particle size was used as filler, and reactive diluent and imidazole accelerator were added, so that the obtained underfill had a small viscosity at 25 ℃ and a large flow distance at 100 ℃, and had a high glass transition temperature, a high heat resistance, and a high flexural modulus and elastic modulus.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The underfill is characterized by comprising the following raw materials in percentage by weight:
20-36.5 wt% of bisphenol F epoxy resin;
0.7-3 wt% of naphthalene epoxy resin;
0.7-3 wt% of multifunctional epoxy resin;
0.5-3 wt% of 1, 6-hexanediol diglycidyl ether;
1-8 wt% of a latent dicyandiamide curing agent;
0.3-0.5 wt% of imidazole accelerator;
55-75 wt% of inorganic filler;
0.5-2 wt% of functional auxiliary agent;
the inorganic filler comprises a first inorganic filler and a second inorganic filler, the first inorganic filler is silica micropowder, the particle size D50 is 0.3-0.7 mu m, the second inorganic filler is silica micropowder, and the particle size D50 is 1.7-2.1 mu m;
the functional auxiliary agent comprises a coupling agent, a dispersing agent, a defoaming agent or a combination thereof;
the multifunctional epoxy resin includes triglycidyl amine type epoxy resin, tetraglycidyl amine type epoxy resin, or a combination thereof.
2. The underfill according to claim 1 wherein the multifunctional epoxy resin meets at least one of the following conditions:
1) The epoxy equivalent is 90g/eq to 125g/eq;
2) The viscosity at 25 ℃ is 300-9000 cp.
3. The underfill according to claim 1 wherein the bisphenol F type epoxy resin meets at least one of the following conditions:
1) The epoxy equivalent is 160g/eq to 180g/eq;
2) The viscosity at 25 ℃ is 1500-5000 cp.
4. The underfill according to claim 1 wherein the naphthalene based epoxy resin meets at least one of the following conditions:
1) The epoxy equivalent is 130 g/eq-160 g/eq;
2) The viscosity at 30 ℃ is 20000 cp-30000 cp.
5. The underfill according to any one of claims 1 to 4, wherein the first inorganic filler is 5wt% to 25wt% of the total inorganic filler and the second inorganic filler is 75wt% to 95wt% of the total inorganic filler.
6. The underfill according to any one of claims 1 to 4 wherein the latent dicyandiamide curing agent is selected from the group consisting of latent powder dicyandiamide, latent liquid dicyandiamide or combinations thereof.
7. The underfill of claim 1, wherein the imidazole-based accelerator is selected from the group consisting of 2-ethyl cyano-4-methylimidazole, PN23, PN40J, PN, and combinations thereof.
8. The underfill according to any one of claims 1-4, comprising the following raw materials in mass percent:
22-30% of bisphenol F type epoxy resin;
1-2 wt% of naphthalene epoxy resin;
1-2 wt% of multifunctional epoxy resin;
0.5-2 wt% of 1, 6-hexanediol diglycidyl ether;
5-8 wt% of latent liquid dicyandiamide;
0.3-0.5 wt% of imidazole accelerator;
58-66 wt% of inorganic filler;
0.5-2 wt% of functional auxiliary agent.
9. A method of preparing an underfill comprising the steps of:
mixing the bisphenol F epoxy resin, naphthalene epoxy resin, multifunctional epoxy resin, 1, 6-hexanediol diglycidyl ether, a latent dicyandiamide curing agent and a functional additive according to any one of claims 1-8, stirring, adding the inorganic filler, stirring, adding the imidazole accelerator when the temperature of the obtained mixture is less than or equal to 10 ℃, and stirring.
10. A chip packaging structure, characterized in that: the packaging structure comprises a substrate, a chip arranged on the substrate and a plurality of welding convex points arranged at intervals between the substrate and the chip, wherein an underfill material is filled in gaps between the welding convex points between the substrate and the chip, and the underfill material is formed by curing the underfill adhesive according to any one of claims 1-8.
CN202211680673.7A 2022-12-27 2022-12-27 Underfill adhesive, preparation method thereof and chip packaging structure Active CN116144303B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114989761A (en) * 2022-06-29 2022-09-02 东莞市德聚胶接技术有限公司 Underfill adhesive composition for wafer-level chip size packaging and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114989761A (en) * 2022-06-29 2022-09-02 东莞市德聚胶接技术有限公司 Underfill adhesive composition for wafer-level chip size packaging and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
滕翠青等.《聚合物基复合材料》.中国纺织出版社,2021,(第1版),第16-17页. *

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