CN115322718A - Underfill adhesive and preparation method thereof - Google Patents
Underfill adhesive and preparation method thereof Download PDFInfo
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- CN115322718A CN115322718A CN202211006655.0A CN202211006655A CN115322718A CN 115322718 A CN115322718 A CN 115322718A CN 202211006655 A CN202211006655 A CN 202211006655A CN 115322718 A CN115322718 A CN 115322718A
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
Abstract
The invention belongs to the technical field of adhesives, and provides an underfill adhesive and a preparation method thereof. The underfill comprises epoxy resin, a curing agent, a filler, a silane coupling agent and cage type silsesquioxane. According to the invention, the cage type silsesquioxane compound is added into the formula to improve the cohesive force of the underfill, so that the components of the underfill can be well combined in the curing process, the purpose of inhibiting the underfill from overflowing is achieved, meanwhile, the underfill can keep good flow filling performance and mechanical performance, the underfill can be aged by MSL 4-level Precon when being applied to a Flip chip packaging body, and the reliability problems of cracking, layering and the like do not occur after PCT aging.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to an underfill adhesive and a preparation method thereof.
Background
With the miniaturization and high functionality of electronic devices, there is an increasing demand for high-density packaged semiconductor chips and other electronic components. Flip chips are widely used due to their smaller package size, narrower pitch, and high I/O density. Since a flip chip mounting process uses a mounting method in which a semiconductor chip and a substrate are directly connected to each other, if stress generated due to a difference between the thermal expansion coefficient of the silicon chip and the thermal expansion coefficient of the substrate cannot be absorbed, a problem occurs in that cracks are generated in a connection portion, and the connection reliability between the semiconductor chip and the substrate is lowered. Underfill is used between the die and the substrate to provide a stronger mechanical connection and to reduce the stress on the solder joints due to coefficient of thermal expansion mismatch between the die and the substrate. The commonly used underfill is mainly composed of a cured epoxy resin filled with a large amount of silica filler, and the cured epoxy resin has excellent electrical insulation, high modulus and strength, and good adhesion at different interfaces, and is a good underfill matrix resin. However, the underfill during the packaging process may suffer from flash, and as shown in fig. 1, the underfill separates from the resin matrix, and the resin is separated from the underfill body 1 to form a ring of resin matrix 2 at the edge.
When the underfill is applied to the chip, the underfill wets the substrate to a degree dependent on the balance between the underfill to interfacial adhesion and the underfill cohesion. When the adhesion of some of the components of the underfill to the substrate is greater than the underfill cohesion, i.e., the wettability and bonding of the resin matrix to the filler is less than the wettability and adhesion of the components such as resin to the substrate, flash can occur. And the overflow glue can pollute the components and parts when the glue overflow degree is serious, and the bottom filling glue can crack from the edge in the aging process, so that the packaging reliability is seriously influenced, and the packaging yield is reduced. It is therefore necessary to suppress underfill flash. Based on the above theory, the main methods to suppress the flash are to lower the surface energy of the substrate and to increase the cohesion of the underfill. The first is to control the flash degree of the underfill from the viewpoint of reducing the basic surface energy, i.e. the substrate is surface-treated by chemical or physical methods, usually by depositing a silicon oxide film on the substrate surface to form a mechanical barrier around the chip and the substrate bonding region, thereby effectively controlling the flash, but this method of depositing the silicon oxide film makes the packaging process more complicated. And secondly, adopting an auxiliary agent or adding nano filler to control the glue overflow degree of the bottom underfill from the formulation angle. The commonly used auxiliary agent contains a methacrylate structure, a polyester structure, a phenoxy structure and modified silicone oil containing active groups, wherein the modified silicone oil (linear polysiloxane) containing the active groups is introduced into an underfill system to effectively reduce the problem of glue overflow, but the improvement of the glue overflow effect is generally accompanied with the increase of the viscosity of the underfill and the reduction of the filling effect, and the technological performance and the packaging effect of the underfill are seriously influenced. Often the introduction of nanofillers will also inhibit underfill flow, but will also sacrifice underfill flow properties and fill effectiveness. It is found again that the substrate can effectively reduce the degree of glue overflow after being baked, but the baking can generate oxides on the surface of the substrate, and this method can reduce the reliability of the package, so the method for controlling glue overflow is not suitable for use in the packaging process.
Based on the problems in the prior art, the invention provides the underfill and the preparation method thereof, which ensure good packaging effect and simultaneously give consideration to the anti-overflow glue performance.
Disclosure of Invention
In order to solve the problem that the underfill in the prior art cannot take the packaging effect and the anti-overflow glue performance into consideration, the invention provides the underfill.
The underfill comprises epoxy resin, a curing agent, a filler and a silane couplingA coupling agent and a cage type silsesquioxane, wherein the structural general formula of the cage type silsesquioxane is [ R (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein y is 6, 8, 10 or 12,
r is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、 -(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
R' is selected from- (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
Further, y =8, the structural formula of the cage-type silsesquioxane is shown as follows:
further, the cage-type silsesquioxane is selected from one or more of trans-cyclohexanediol isobutylated cage-type silsesquioxane, propylene isobutylated cage-type silsesquioxane, 1, 2-propanediol isobutylated cage-type silsesquioxane, aminated cage-type silsesquioxane, aminopropyl isooctylated cage-type silsesquioxane, aminoethyl aminopropyl isobutylated cage-type silsesquioxane, N-methylaminopropyl isobutylated cage-type silsesquioxane, maleic acid isobutylated cage-type silsesquioxane, epoxycyclohexyl isobutylated cage-type silsesquioxane, glycidol isobutylated cage-type silsesquioxane, glycidylated cage-type silsesquioxane, methacrylated cage-type silsesquioxane, acrylated cage-type silsesquioxane, N-octylated cage-type silsesquioxane, octahydroxybutylated cage-type silsesquioxane, N-phenylaminopropylated cage-type silsesquioxane and octaglycidol dimethylsilylated cage-type silsesquioxane.
Further, the cage-type silsesquioxane is selected from one or more of propylene isobutanolated cage-type silsesquioxane, gamma-glycidyl ether cage-type silsesquioxane, trans-cyclohexanediol isobutylated cage-type silsesquioxane, methacrylated cage-type silsesquioxane, aminated cage-type silsesquioxane, aminoethylaminopropyl isobutyl cage-type silsesquioxane, aminopropyl sulfooctyl cage-type silsesquioxane, N-methylaminopropyl isobutylated cage-type silsesquioxane, N-phenylaminopropylated cage-type silsesquioxane, epoxycyclohexyl isobutyl cage-type silsesquioxane, epoxycyclohexyl cage-type silsesquioxane and maleic acid isobutylated cage-type silsesquioxane.
Further, the epoxy resin is selected from one or more of liquid bisphenol type epoxy resin, liquid aminophenol type epoxy resin, silicone modified epoxy resin and naphthalene type epoxy resin, more preferably, the epoxy resin is selected from one or more of liquid bisphenol a type epoxy resin, liquid bisphenol F type epoxy resin, para-aminophenol type liquid epoxy resin, 1, 3-bis (3-glycidoxypropyl) tetramethyldisiloxane and naphthalene type epoxy resin;
the curing agent is an aromatic amine-based curing agent, preferably, the curing agent is selected from one or more of diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, diaminodiphenylmethane, 3' -diethyl-4, 4' -diaminodiphenylmethane, 4' -methylenebis (N-methylaniline), trimethylenebis (4-aminobenzoate), polytetrahydrofuran-bis-p-aminobenzoate, methylenebis (2-ethyl-6-methylaniline), 4' -methylenebis (2, 6-dimethylaniline) and 4,4' -methylenebis (2, 6-diethylaniline), more preferably, the curing agent is selected from one or two of diethyltoluenediamine and 3,3' -diethyl-4, 4' -diaminodiphenylmethane;
the filler is spherical silica, and preferably, the particle size of the filler is 0.1-10 μm. The particle size is in the range, which is beneficial to the dispersion of the filler in the liquid epoxy resin;
the silane coupling agent is selected from one or more of epoxy, amino, vinyl, methacrylic, acrylic and mercapto silane coupling agents, preferably from one or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
Further, the mass of the silane coupling agent accounts for 0.1-3% of the total mass of the epoxy resin and the curing agent, the mass of the cage-type silsesquioxane accounts for 0.1-1.5% of the total mass of the epoxy resin and the curing agent, and the mass of the filler accounts for 45-70% of the total mass of the underfill.
The invention also provides a preparation method of the underfill, which comprises the following steps:
firstly, mixing epoxy resin, a silane coupling agent, cage-type silsesquioxane and a filler, and finally adding a curing agent for mixing to obtain the underfill, wherein the structural general formula of the cage-type silsesquioxane is [ R ] (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein y is 6, 8, 10 or 12.
R is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、 -(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
Further, y =8, the structural formula of the cage type silsesquioxane is as follows:
further, the method comprises the following steps:
s1: uniformly mixing the epoxy resin, the silane coupling agent and the cage type silsesquioxane, and stirring at 1500rpm or 2000rpm for 2min;
s2: adding the filler into the mixture formed by the S1 for three times, and stirring at 1500rpm or 2000rpm for 2min after adding the filler into each batch;
and S3, adding the curing agent into the mixture formed in the S2, and stirring at 1500rpm or 2000rpm for 2min to obtain the underfill.
According to the invention, the cohesion of the underfill is improved by the cage type silsesquioxane compound in the formula, so that the components of the underfill can be well combined in the curing process, the purpose of inhibiting the underfill from overflowing is achieved, meanwhile, the underfill can keep good flow filling performance and mechanical performance, the underfill can be aged by MSL 4-level Precon when applied to Flip chip packaging bodies, and the reliability problems of cracking, layering and the like do not occur after PCT aging.
Drawings
FIG. 1 is a schematic diagram of an overflow effect provided in the background art;
FIG. 2 is a flow chart of a method for preparing the underfill according to the present invention;
FIG. 3 is a graph of the flash effect of underfill provided in comparative example 1 and examples 1-6 of the present invention;
fig. 4 is a graph of the bleed effect of the underfill provided in comparative examples 1-4, in accordance with the present invention.
Fig. 5 is a graph showing the effect of applying underfill according to the present invention to a Flip chip package after PCT aging.
The reference numbers illustrate:
1-underfill body, 2-resin matrix overflowing the underfill body.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below, but are not to be construed as limiting the implementable range of the present invention.
The invention relates to a bottom filling adhesive with an obvious anti-overflow adhesive effect, wherein cage-type silsesquioxane is introduced into a formula to improve the anti-overflow adhesive performance of the bottom filling adhesive, the cage-type silsesquioxane and epoxy resin are blended, have good compatibility and can be well dispersed in matrix resin, and can be tightly combined with epoxy resin chain segments through van der Waals force, hydrogen bond action and dipole action. The cage structure of the cage type silsesquioxane nano particle can also stop the development of the micro crack tip of the resin, initiate silver streaks or shear bands or rearrange molecular chains, and improve the toughness of an epoxy resin system. The introduction of the heat-resistant Si-O bond, the increase of the crosslinking density and the limitation of the movement of the macromolecular chain of the resin can effectively improve the heat resistance of the system. In addition, the introduction of the cage type silsesquioxane can reduce the viscosity of a system, so that the underfill can keep good fluidity. The underfill not only can obviously improve the problem of glue overflow of the underfill, but also can improve the mechanical property of the underfill, reduce the viscosity and flow time of the underfill and reduce the failure probability of the underfill in a packaging body.
The underfill comprises epoxy resin, a curing agent, a filler, a silane coupling agent and cage-type silsesquioxane, wherein the structural general formula of the cage-type silsesquioxane is [ R (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein y is 6, 8, 10 or 12,
r is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、 -(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
R' is selected from- (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
Wherein m and n are integers of 0-18, preferably m and n are integers of 0-4, x is more than or equal to 1 and less than or equal to 4, and x is an integer.
Further, y =8, the structural formula of the cage type silsesquioxane is as follows:
further, the cage type silsesquioxane is selected from one or more of trans-cyclohexanediol isobutylated cage type silsesquioxane, propylene isobutylated cage type silsesquioxane, 1, 2-propylene glycol isobutylated cage type silsesquioxane, aminated cage type silsesquioxane, aminopropyl isooctylated cage type silsesquioxane, aminoethyl aminopropyl isobutylated cage type silsesquioxane, N-methylaminopropyl isobutylated cage type silsesquioxane, maleic acid isobutylated cage type silsesquioxane, epoxycyclohexyl isobutylated cage type silsesquioxane, glycidyl isobutylated cage type silsesquioxane, glycidylated cage type silsesquioxane, methylacrylated cage type silsesquioxane, allylated cage type silsesquioxane, N-octylated cage type silsesquioxane, octahydroxybutyl cage type silsesquioxane, N-phenylaminopropylated cage type silsesquioxane and octaglycidyldimethylsilylated cage type silsesquioxane.
Further, the cage-type silsesquioxane is selected from one or more of propylene isobutanolated cage-type silsesquioxane, gamma-glycidyl ether cage-type silsesquioxane, trans-cyclohexanediol isobutylated cage-type silsesquioxane, methacrylated cage-type silsesquioxane, aminated cage-type silsesquioxane, aminoethyl aminopropyl isobutyl cage-type silsesquioxane, aminopropyl sulfooctyl cage-type silsesquioxane, N-methylaminopropyl isobutylated cage-type silsesquioxane, N-phenylaminopropylated cage-type silsesquioxane, epoxycyclohexyl isobutyl cage-type silsesquioxane, epoxycyclohexyl cage-type silsesquioxane and maleic acid isobutylated cage-type silsesquioxane.
Further, the epoxy resin is selected from one or more of liquid bisphenol type epoxy resin, liquid aminophenol type epoxy resin, silicone-modified epoxy resin and naphthalene type epoxy resin, more preferably, the epoxy resin is selected from one or more of liquid bisphenol a type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, 1, 3-bis (3-glycidoxypropyl) tetramethyldisiloxane and naphthalene type epoxy resin;
the curing agent is an aromatic amine-based curing agent, preferably, the curing agent is selected from one or more of diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, diaminodiphenylmethane, 3' -diethyl-4, 4' -diaminodiphenylmethane, 4' -methylenebis (N-methylaniline), trimethylenebis (4-aminobenzoate), polytetrahydrofuran-bis-p-aminobenzoate, methylenebis (2-ethyl-6-methylaniline), 4' -methylenebis (2, 6-dimethylaniline) and 4,4' -methylenebis (2, 6-diethylaniline), more preferably, the curing agent is selected from one or two of diethyltoluenediamine and 3,3' -diethyl-4, 4' -diaminodiphenylmethane;
the filler is spherical silica, preferably, the filler has a particle size of 0.1 to 10 μm. The particle size is in the range, which is beneficial to the dispersion of the filler in the liquid epoxy resin;
the silane coupling agent is selected from one or more of epoxy, amino, vinyl, methacrylic, acrylic and mercapto silane coupling agents, preferably from one or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
Further, the mass of the silane coupling agent accounts for 0.1-3% of the total mass of the epoxy resin and the curing agent, the mass of the cage-type silsesquioxane accounts for 0.1-1.5% of the total mass of the epoxy resin and the curing agent, and the mass of the filler accounts for 45-70% of the total mass of the underfill.
The invention also provides a preparation method of the underfill, which comprises the following steps:
firstly, mixing epoxy resin, silane coupling agent, cage type silsesquioxane and filler, and finally adding curing agent for mixing to obtain the underfill, wherein the structural general formula of the cage type silsesquioxane is [ R ] (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein y is 6, 8, 10 or 12,
r is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、 -(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
One or more of (A), R' is selected from- (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
M and n are integers of 0 to 18, preferably, m and n are integers of 0 to 4, wherein x is more than or equal to 1 and less than or equal to 4, and x is an integer.
Further, y =8, the structural formula of the cage type silsesquioxane is as follows:
further, as shown in fig. 2 of the specification, the preparation method of the underfill comprises the following steps:
s1: uniformly mixing the epoxy resin, the silane coupling agent and the cage-type silsesquioxane, and stirring at 1500rpm or 2000rpm for 2min;
s2: adding the filler into the mixture formed in the step S1 for three times, and stirring at 1500rpm or 2000rpm for 2min after adding the filler into each batch;
and S3, adding a curing agent into the mixture formed in the S2, and stirring at 1500rpm or 2000rpm for 2min to obtain the underfill.
The underfill of examples 1-6 was prepared according to the underfill preparation method described above, with the different examples of examples 1-6 containing different types of cage-type silsesquioxanes, and specifically, the ratios of the components in the underfill of examples 1-6 are shown in Table 1.
The present invention also provides comparative examples 1 to 4, in which, in place of the cage-type silsesquioxane, no cage-type silsesquioxane or hydroxyl group-containing modified silicone oil, carboxyl group-containing modified silicone oil, epoxy group-containing modified silicone oil was added as compared with examples 1 to 6, specifically, the formulation of each component in the underfill of comparative examples 1 to 4 is as shown in table 1 or table 2.
SEM electron microscopy scanning of the underfill prepared in examples 1-6 and comparative example 1 see FIG. 3 of the specification, wherein a represents the underfill prepared in comparative example 1, b represents the underfill prepared in example 1, c represents the underfill prepared in example 2, and d represents the underfill prepared in example 3. SEM scanning electron micrographs of the underfill prepared in comparative examples 1-4 see FIG. 4, a for the underfill prepared in comparative example 1, b for the underfill prepared in comparative example 2, c for the underfill prepared in comparative example 3, and d for the underfill prepared in comparative example 4. The bottom fill margin line length in fig. 3 and 4 indicates the degree of flash, and longer lines indicate more severe flash.
The underfill prepared in examples 1 to 6 and comparative examples 1 to 4 were used as samples for evaluation to carry out the following evaluations.
Testing the overflow length: 5mg of the freshly prepared evaluation sample was dropped onto the organic substrate, and the substrate with the sample was placed in an oven and cured, and then the flash length was photographed and measured with a microscope.
And (3) viscosity testing: the viscosity of the freshly prepared evaluation sample was measured at a liquid temperature of 25 ℃ and 50rpm using a rotational rheometer MCR 302.
And (3) testing the flowing time: the test piece was placed on a hot plate set at 110 ℃, a liquid underfill was applied to one end side of a glass plate, and the time until the injection distance reached 30mm was measured. This sequence was performed 2 times, and the average of the measurement values was used as the measurement value of the flow time.
Measurement of K1 c: the prepared liquid underfill was poured into a mold to prepare a sample of 35mm in length, 7mm in width and 3mm in thickness, and K1c was measured using an electronic universal tester using this sample.
The test results are shown in table 1 or table 2.
TABLE 1
TABLE 2
Wherein, the epoxy resin A: bisphenol F type epoxy resin, epoxy equivalent 158
Curing agent B: diethyl toluene diamine
And (3) filler C: spherical silica Filler (average particle diameter: 0.5 μm)
Silane coupling agent D: 3-glycidoxypropyltrimethoxysilane
(E01) Modified silicone oil: modified silicone oil containing hydroxyl (Xinyue chemical; KF-6000)
(E02) Modified silicone oil: modified silicone oil containing carboxyl (Xinyue chemical; X-22-162C)
(E03) Modified silicone oil: modified silicone oils containing epoxy groups (Xinyue chemistry; X-22-163)
Cage-type silsesquioxane E:
the cage type silsesquioxane E-1 aminated cage type silsesquioxane has the following structural formula:
the cage type silsesquioxane E-2 gamma-glycidyl ether oxygen silicon propyl silsesquioxane has the following structural formula:
the cage type silsesquioxane E-3 epoxy cyclohexyl isobutyl POSS has the following structural formula:
cage-type silsesquioxane E-4: the propylene isobutyl alcoholization cage-shaped silsesquioxane has the following structural formula:
cage-type silsesquioxane E-5: the maleic acid isobutyl esterification cage-shaped silsesquioxane has the following structural formula:
cage-type silsesquioxane E-6: the N-phenylaminopropylated cage-like silsesquioxane has the following structural formula:
and (4) conclusion:
as can be seen from table 1 and the description of fig. 3 (the line length in fig. 3 indicates the length of the flash), the advantages of the underfill provided by the embodiment of the present invention in terms of performance are mainly shown in the following aspects:
1: and (3) glue overflow resistance: the underfill containing the cage-type silsesquioxane provided by the invention can be prepared by the following steps of: the cage-type silsesquioxane with functional groups such as carboxyl, hydroxyl, amino, epoxy and the like reacts with the epoxy resin curing system, so that the cohesive force of the underfill system is improved, and the adhesive overflow phenomenon of the underfill during the curing process is reduced.
2: viscosity and fluidity aspects: the addition of the cage type silsesquioxane has little influence on the viscosity and the flow time of the underfill, so that the underfill keeps good flow property.
3: mechanical properties: the addition of the cage-type silsesquioxane improves the mechanical property of the bottom underfill while improving the problem of glue overflow of the bottom underfill.
4: and (3) packaging reliability: the application of this underfill in Flip chip packages enables MSL4 level Precon burn-in and does not suffer from reliability issues such as cracking delamination after PCT burn-in.
In combination with table 2 and fig. 4 (the line length in fig. 4 indicates the length of the flash), it can be seen that the underfill prepared by using the hydroxyl group-containing modified silicone oil, the carboxyl group-containing modified silicone oil, and the epoxy group-containing modified silicone oil in the comparative example is mainly reflected in the following aspects in terms of performance:
1: and (3) glue overflow resistance: it can be seen that the introduction of the hydroxyl-containing modified silicone oil, the carboxyl-containing modified silicone oil and the epoxy-containing modified silicone oil into the underfill can effectively improve the problem of glue overflow.
2: viscosity and fluidity aspects: the introduction of the hydroxyl-containing modified silicone oil, the carboxyl-containing modified silicone oil and the epoxy-containing modified silicone oil can cause the viscosity and the flowing time of the underfill to be obviously increased, and even the addition of the modified silicone oil can cause the underfill not to have fluidity at a narrow interval, so that the underfill cannot be applied to a packaging body and the technological performance of the underfill in the packaging process is influenced.
3: mechanical properties: the addition of the hydroxyl-containing modified silicone oil, the carboxyl-containing modified silicone oil and the epoxy-containing modified silicone oil can improve the mechanical property of the bottom underfill while improving the problem of glue overflow of the bottom underfill.
The left panel of fig. 5 has no cracks, indicating no cracking after PCT aging; the area between two solder balls in the right figure also has no cracks, which shows that the area has no problems of filler sedimentation or unstable solder ball fixation, and the two aspects show that the underfill provided by the invention has better reliability when being applied to a Flip chip package.
Therefore, the underfill provided by the invention not only can obviously improve the problem of glue overflow of the underfill, but also can improve the mechanical property of the underfill, reduce the viscosity and the flowing time of the underfill and reduce the failure probability of the underfill in a package body.
Claims (9)
1. The underfill is characterized by comprising epoxy resin, a curing agent, a filler, a silane coupling agent and cage-type silsesquioxane, wherein the structural general formula of the cage-type silsesquioxane is [ R [ ] (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein y is 6, 8, 10 or 12,
r is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
R' is taken from- (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
2. The underfill of claim 1, wherein y =8, the cage silsesquioxane has the formula:
3. the underfill of claim 1 wherein the cage silsesquioxane is selected from one or more of trans-cyclohexanediol isobutylated cage silsesquioxane, propylene isobutylated cage silsesquioxane, 1, 2-propanediol isobutylated cage silsesquioxane, aminated cage silsesquioxane, aminopropyl isooctylated cage silsesquioxane, aminoethyl aminopropyl isobutylated cage silsesquioxane, N-methylaminopropyl isobutylated cage silsesquioxane, maleic acid isobutylated cage silsesquioxane, epoxycyclohexyl isobutylated cage silsesquioxane, glycidyl isobutylated cage silsesquioxane, glycidated cage silsesquioxane, methacrylated cage silsesquioxane, acrylated cage silsesquioxane, N-octylated cage silsesquioxane, octahydroxybutylated cage silsesquioxane, N-phenylaminopropylated cage silsesquioxane and octaglycidyl dimethylsilylated cage silsesquioxane.
4. The underfill of claim 3 wherein the cage-type silsesquioxane is selected from one or more of propylene isobutylated cage-type silsesquioxane, γ -glycidyl ether cage-type silsesquioxane, trans-cyclohexanediol isobutylated cage-type silsesquioxane, methacrylated cage-type silsesquioxane, aminated cage-type silsesquioxane, aminoethylaminopropylisobutylcage-type silsesquioxane, aminopropylsulfooctylcage-type silsesquioxane, N-methylaminopropylisobutylated cage-type silsesquioxane, N-phenylaminopropylated cage-type silsesquioxane, epoxycyclohexylisobutylcage-type silsesquioxane, epoxycyclohexylcage-type silsesquioxane and maleic acid isobutylated cage-type silsesquioxane.
5. The underfill of claim 1,
the epoxy resin is selected from one or more of liquid bisphenol epoxy resin, liquid aminophenol epoxy resin, organic silicon modified epoxy resin and naphthalene epoxy resin;
the curing agent is selected from aromatic amine curing agents;
the filler is spherical silicon dioxide;
the silane coupling agent is selected from one or more of epoxy, amino, vinyl, methacrylic, acrylic and mercapto silane coupling agents.
6. The underfill according to claim 1, wherein the mass of the silane coupling agent is 0.1 to 3% of the total mass of the epoxy resin and the curing agent, the mass of the cage type silsesquioxane is 0.1 to 1.5% of the total mass of the epoxy resin and the curing agent, and the mass of the filler is 45 to 70% of the total mass of the underfill.
7. The preparation method of the underfill is characterized by comprising the following steps of:
firstly, mixing epoxy resin, a silane coupling agent, cage-type silsesquioxane and a filler, and finally adding a curing agent for mixing to obtain the underfill, wherein the structural general formula of the cage-type silsesquioxane is [ R ] (y-1)/y R” 1/y (SiO 3/2 )] y ，
Wherein n is 6, 8, 10 or 12,
r is selected from H, C1-18 alkyl, phenyl, vinyl, cyclohexyl, isobutyl, tert-butyl, - (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
R' is selected from- (CH) 2 ) n NH 2 、-(CH 2 ) n COOH、-(CH 2 ) n NH(CH 2 ) m CH 3 、-(CH 2 ) n OH、
8. The method of claim 7, wherein y =8 and the cage silsesquioxane has the formula:
9. the method of preparing an underfill according to claim 7, comprising the steps of:
s1: uniformly mixing the epoxy resin, the silane coupling agent and the cage type silsesquioxane, and stirring at 1500rpm or 2000rpm for 2min;
s2: adding the filler into the mixture formed in the step S1 for three times, and stirring at 1500rpm or 2000rpm for 2min after adding the filler into each batch;
s3: and adding the curing agent into the mixture formed in the step S2, and stirring at 1500rpm or 2000rpm for 2min to obtain the underfill.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851194A (en) * | 2022-12-07 | 2023-03-28 | 东莞市新懿电子材料技术有限公司 | Underfill with anti-overflow grease performance and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009079163A (en) * | 2007-09-27 | 2009-04-16 | Ube Ind Ltd | Curable composition, cured silsesquioxane, and method for producing cured silsesquioxane |
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009079163A (en) * | 2007-09-27 | 2009-04-16 | Ube Ind Ltd | Curable composition, cured silsesquioxane, and method for producing cured silsesquioxane |
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851194A (en) * | 2022-12-07 | 2023-03-28 | 东莞市新懿电子材料技术有限公司 | Underfill with anti-overflow grease performance and preparation method thereof |
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