CN115895543A - Microwave radiation cured chip-level underfill - Google Patents
Microwave radiation cured chip-level underfill Download PDFInfo
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- CN115895543A CN115895543A CN202211665191.4A CN202211665191A CN115895543A CN 115895543 A CN115895543 A CN 115895543A CN 202211665191 A CN202211665191 A CN 202211665191A CN 115895543 A CN115895543 A CN 115895543A
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Abstract
The invention relates to a microwave radiation cured chip-level underfill adhesive, which comprises the following components in parts by weight: 20-30 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of black paste, 60-70 parts of spherical filler, 8-12 parts of curing agent and 0.5-1 part of accelerator. The underfill material prepared by the invention can be heated and cured in a traditional manner, and is more suitable for microwave curing. The problem of filler sedimentation in the curing process can be effectively solved by curing in a microwave curing mode, and the problem of precipitation on the surfaces of silicon wafers and substrates can be effectively solved. The curing time is shorter, and the physical and chemical properties of the cured body are the same as those of the body cured by the traditional heating method.
Description
Technical Field
The invention relates to a microwave radiation curing chip-level underfill adhesive, belonging to a single-component microwave radiation curing type epoxy electronic adhesive material.
Background
In the chip packaging technology, a joint layer of an IC chip and an organic substrate consists of a large number of tiny welding spots, and the welding spots have poor deformation adaptability and are extremely sensitive to thermal stress, so that the problem of structural reliability is more prominent. The use of polymer underfill to improve the reliability of packaged chips is a new approach developed in recent years. The method is economical and easy, and during the chip packaging process, the underfill (underwfi l) gradually solidifies and forms in the slit between the IC chip and the organic substrate through thermosetting action, and protects the connected welding spots. Meanwhile, the impact load can be effectively reduced, the deformation resistance, the moisture resistance, the chemical corrosion resistance and other performances of the packaged chip can be improved, the fatigue life of the packaged chip can be greatly prolonged, and therefore the method has great development potential.
Chip-level underfill materials are typically filled by capillary flow after the heated viscosity is reduced, and then the glue is cured by heating. Typically, chip-scale underfill cures at relatively high temperatures, typically between 150-170 ℃, for about 2 hours. During the curing period of the chip-level underfill, the viscosity is low due to the high temperature, the internal filler gradually sinks before the glue forms a gel, and sometimes even more serious filler settlement or uneven size distribution occurs. Such sedimentation or maldistribution can cause a certain difference in the properties of the upper and lower layers of the cured glue, especially the difference in the coefficient of thermal expansion. Under the condition, when the packaged chip is tested for reliability, unbalanced stress concentration is easily generated, so that cracks or interface delamination of underfill can be caused, and even the solder ball is cracked seriously, and the chip fails in function. In order to solve the phenomenon of filler settlement or uneven size distribution, the curing speed or the gelling speed is increased, so that the filler is relatively fixed before settlement. Moreover, some precision chip devices are sensitive to temperature, and a higher heating temperature may have an adverse effect on the functions of the chip devices, and it is necessary to lower the curing temperature or shorten the curing time.
In addition, the main principle of microwave curing is that microwave is the vibration of chain segments, side groups or functional groups on the molecular structure or the cooperative vibration of the chain segments, side groups or functional groups and adjacent groups, so that heat energy is generated, and the final curing is realized. The traditional microwave curing material can be realized only by introducing a wave absorbing material in the formula, and aims to effectively increase heat energy or quickly transfer heat between molecules so as to achieve the effect of microwave rapid curing. The wave-absorbing material usually contains metal elements or raw materials with good electric and thermal conductivity. But as a chip-level underfill material, the solder ball is in direct contact with the solder ball in practical application, and if the solder ball contains metal or conductive raw materials, the short circuit of the chip is directly caused. Therefore, the microwave curing material does not use the traditional wave absorbing material and can also achieve the purpose of microwave curing.
Disclosure of Invention
Aiming at the technical problem, the invention provides a microwave radiation curing chip-level underfill and a preparation method thereof. Through combination of different key raw materials in the formula, and combined with a microwave radiation curing mode, the curing time is shortened without higher curing temperature, the possibility of adverse effect on a chip device due to higher temperature is reduced, the filler settlement can be effectively prevented, the precipitation degree is effectively reduced, and the reliability of the packaged chip is improved.
One of the purposes of the invention is to provide a microwave radiation cured chip-level underfill which comprises the following components in parts by weight: 20-30 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of black paste, 60-70 parts of spherical filler, 8-12 parts of curing agent and 0.5-1 part of accelerator.
Further, the epoxy resin comprises bisphenol type epoxy resin and special epoxy resin:
among them, 830S and 830CRP of Japanese DIC, RE-303S-L of Japan chemical, DER354 and DER354 of Dow chemical belong to bisphenol F type epoxy resin; 850-S and 850CRP of Japan DIC, RE-310S of Japan Chemicals, DER383 and DER332 of Dow chemical, which are bisphenol A type epoxy resins. ELM-100H of Sumitomo Japan, SW-0510, SW-70 and SW-80 of Hunan Severe, which belong to multifunctional epoxy resin, wherein ELM-100H and SW-0520 are trifunctional types, and SW-70 and SW-80 are tetrafunctional types; HP-4032D and HP4700 of DIC of Japan, and NC-3000-L and NC-2000-L of Chemicals of Japan, which belong to epoxy resins having a rigid structure, wherein HP-4032D and HP4700 are naphthalene epoxy resins, and NC-3000-L and NC-2000-L are biphenyl epoxy resins. The mass ratio of the bisphenol epoxy resin to the special epoxy resin is (1.5-2): 1, and the compounded and combined resin system has the fluidity and the main structural framework of the bisphenol epoxy resin and the rigidity, the heat resistance and other properties of the special epoxy resin.
In the above resins, bisphenol a epoxy resin and bisphenol F epoxy resin are main resins of the entire adhesive and act as a skeleton, and bisphenol a epoxy resin has a higher strength but a higher viscosity and bisphenol F epoxy resin has a lower viscosity but a lower strength, compared with bisphenol a epoxy resin and bisphenol F epoxy resin. The multi-functional epoxy resin in the resin can improve the curing crosslinking density and the strength of the cured material, and some of the multi-functional epoxy resin contains a rigid structure, can improve the strength of the cured material and reduce the thermal expansion coefficient. Further, the coupling agent is one or two of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane. The coupling agent comprises: KBM-403, KBM4803 and KBM6103 of Japan Xinyue, and one or more of BTSE and VPS7163 created in Japan. Wherein KBM-403 is common gamma-glycidoxypropyltrimethoxysilane with relatively short chain; KBM4803 is a long-chain isolated silane coupling agent; KBM6103 is silane coupling agent containing amino; BTSE and VPS7163 are both polyfunctional silane coupling agents. The preferred ratio range for the two coupling agents in common is different according to the actual application, and the ratio range is (1-2): 1. The various coupling agents are compounded, so that different functions can be mutually considered, for example, the VPS7163 nine-functional coupling agent contains more functional groups, so that more contact points with the resin and the filler in a formula system and interface contact points are provided, and the wetting degree is higher. However, the nine-functional coupling agent has a complex molecular structure and larger steric hindrance, so that on the premise of limited use amount, the effective component of the multi-functional coupling agent is less, and a part which cannot be completely soaked exists, so that if the nine-functional coupling agent is matched with a short-chain coupling agent for use, the part which cannot be completely soaked by the multi-functional coupling agent can be complemented.
Further, the curing agent is maleic anhydride, benzoic anhydride, phthalic anhydride, succinic anhydride, 4 '-diamino-3, 3' -diethyldiphenylmethane, diethyltoluenediamine, diaminodiphenylsulfone, m-aminomethamine, xylylenediamine trimer, dibenzylaminoether, diethyltoluenediamine, or the like. The curing agent comprises: MHHPA in Yari chemical industry of Jiangsu, MCD and A-A in Japan chemical, and T-5000 and 5200 in Hensman. MHHPA and MCD are anhydride curing agents, the reaction rate is higher, but the MHHPA and MCD are not suitable for chip-level underfill materials; A-A, T-5000 and 5200 are modified amine type curing agents, the reaction rate is relatively slow, and the epoxy resin composition is suitable for chip-level underfill materials, wherein A-A is oligomeric mixed type modified amine, T-5000 is trifunctional polyether amine, and 5200 is diethyl toluene diamine.
Further, the spherical filler is prepared by compounding one or more of SE6050-STE, SO-E2/24C, AC5250 and AC2050 of the Japan Admatechs company. Wherein the average particle size of SE6050-STE and SO-E2/24C is larger than that of the latter, and both are surface modified spherical SiO 2 The filler is filled in the chip-level underfill, and can play a role in comparison with the traditional SiO 2 The filler has better mechanical and thermodynamic properties and better flow property, and can realize capillary flow filling at high temperature. And AC5250 and AC2050, the average particle size of the former is larger than that of the latter, and the two are surface modified Al 2 O 3 A filler consisting essentially of SiO 2 Excellent performance of the filler, and simultaneously better thermal conductivity. In the formula design, the addition ratio of the two fillers with large and small average particle sizes is in the range of (3-4): 1, so that the combination is more favorable for the material to have better high-temperature fluidity without obviously influencing other properties.
Furthermore, JLD 6909 with new holy material is selected as black paste, and MY-25 with ajinomotoxin is selected as accelerator. Wherein MY-25 is used as an accelerator to accelerate the reaction between the resin and the curing agent.
Another object of the present invention is to provide a method for preparing the chip-scale underfill adhesive, which comprises the following steps:
and (2) blending the epoxy resin, the coupling agent and the black paste, stirring for 2 hours in a high-speed planetary stirrer, adding the spherical filler in batches, heating and stirring for 4 hours at 70-90 ℃, cooling to normal temperature, adding the curing agent, controlling the temperature to be 25-30 ℃, and stirring for 2 hours to obtain the final underfill material. Further, the whole preparation process is carried out under vacuum condition, preferably, the whole process is maintained at vacuum degree of not less than-0.08 MPa.
The invention has the beneficial effects that: through the combination of formula design, the prepared underfill material can be heated and cured in a traditional manner and is more suitable for microwave curing. The microwave curing method is used for curing, so that the problem of sedimentation of the filler in the curing process can be effectively solved, and the problem of precipitation on the surfaces of the silicon wafer and the substrate can be effectively solved. The curing time is shorter, and the physical and chemical properties of the cured body are the same as those of the body cured by the traditional heating method.
Drawings
FIG. 1 shows the settling and distribution of filler after slicing after curing in example 1 and comparative example 6, with comparative example 6 on the left and example 1 on the right.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
According to the above preparation process, the formulations of the specific examples and comparative examples are shown in table 1 below:
TABLE 1 examples and comparative example preparation formulations
Testing of
The products obtained in examples 1 and 2 and comparative examples 1 to 5 were cured by microwave curing, and the apparatus used was a RWBZ-08S microwave vacuum drying oven from Sorberry drying apparatus, inc. of Nanjing, and 800W of microwave power was selected for curing. The formulation of comparative example 6 was cured using a conventional electric heating and forced air oven curing method at 165 ℃.
And (3) testing the curing degree: the products obtained in examples 1 and 2 and comparative examples 1 to 5 were cured in a microwave oven at a microwave power of 800W for various times, and the cured samples were tested using a Differential Scanning Calorimeter (DSC) to determine whether 100% cure was achieved by zero peak exotherm, which determines how long the formulation was fully cured at this curing energy. Comparative example 6 was also tested using the same method to determine how long it took to fully cure at 165 ℃. The data in table 2, examples 1 and 2 and comparative examples 1-6, the time required for complete cure.
The silicon surface grease overflowing length measuring method comprises the following steps: after the prepared simulation sample wafer is solidified, observing under a microscope, wherein the edge of the silicon wafer is provided with similar oily foreign matters and is in a rainbow ripple shape, namely the silicon surface grease overflow, and because the silicon wafer is not in a regular shape, 6 points are taken to test the distance from the silicon wafer to the edge, and the average value is the final silicon surface grease overflow length.
Method for measuring length of deposition on substrate: and observing and measuring the prepared simulation sample wafer before and after curing respectively under a high power microscope, measuring the edge of a substance which is obviously whitened or has a color character different from that of the substrate from the outermost side of the curing of the chip-level underfill adhesive until the edge of the substance is measured, and measuring the distance from the edge at 6 points, wherein the average value is the glue precipitation length on the final substrate. The data in table 3 lists the silicon surface flash length and on-substrate bleed length data for examples 1, 2 and comparative examples 1-6.
And (3) measuring the sedimentation condition of the filler: and cutting the solidified simulation sample at a fixed position, grinding and polishing the cross section, and observing the sedimentation and distribution conditions of the filler under a scanning electron microscope. The settling of the filler is illustrated in figure 1 for example 1 and comparative example 6.
Silicon surface adhesion test: solidifying the underfill on the surface of the silicon wafer into a pudding shape by customizing a mold, setting the platform temperature to be 260 ℃ by using a DAGE 4000 tester, and pushing the pudding-shaped glue block from the surface of the silicon wafer until the pudding-shaped glue block falls off, wherein the force value at the moment of falling off is the bonding force of the underfill on the surface of the silicon wafer. The data in table 3 lists the silicon surface adhesion data for example 1 and comparative example 6.
Other tests: the Tg (DMA) and storage modulus of the cured material were measured using the method of ASTM D7028, the coefficient of thermal expansion (CTE 1 and CTE 2) of the cured material was measured using the method of GB/T36800.2-2018, and the flexural strength and flexural modulus of the cured material were measured using the method of GB/T9341-2008. The data in Table 3 set forth additional test data for example 1 and comparative example 6
TABLE 2 time required for complete curing
Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
Curing time (min) | 46 | 44 | 68 | 59 | 62 | 57 | 53 | 77 |
Table 3 comparison of main properties of examples 1, 2 and comparative example 6
Test items | Example 1 | Example 2 | Comparative example 6 |
Tg(℃,DMA) | 142 | 140 | 139 |
Storage modulus (Mpa) | 6885 | 6990 | 7021 |
Tg(℃,TMA) | 119 | 121 | 117 |
CTE1(ppm/℃) | 25.3 | 25.1 | 26.1 |
CTE2(ppm/℃) | 97.7 | 98.4 | 95.4 |
Flexural modulus (MPa) | 6933 | 6885 | 6875 |
Flexural strength (Mpa) | 161 | 166 | 166 |
Silicon surface flash length (mum) | 13 | 20 | 77 |
Length of precipitated particles on substrate surface (. Mu.m) | 34 | 39 | 82 |
Pudding die bond strength (Si, 260 ℃, kg) | 2.52 | 3.03 | 1.97 |
As shown in the data in table 1, it can be seen that the trifunctional epoxy resin is more suitable for microwave radiation curing than the epoxy resin containing a biphenyl structure, because the trifunctional epoxy resin has more functional groups and higher reactivity than the epoxy resin containing a biphenyl structure, and is more susceptible to vibrational heat generation under the action of microwaves, while the biphenyl structure has greater steric hindrance and is less susceptible to vibrational heat generation than the biphenyl structure, as compared to comparative examples 1 and 2.
Comparison of comparative examples 2 and 3 shows that the addition of KBE403 and VPS7163 did not significantly affect the curing rate by microwave radiation, and comparative example 2 was slightly faster. As can be seen from comparison of comparative examples 3 and 4, the microwave curing rate increased after doubling the amount of VPS 7163. This is because KBE403 has a relatively short segment and a low molecular weight, while VPS7163 is a nine-functional coupling agent and has a large molecular weight, and therefore, at the same amount, KBE403 has more active ingredient than VPS7163, and thus the microwave curing rate of comparative examples 3 and 4 is not significant. When the dosage of VPS7163 is doubled, the effect of high activity of the nine-functional coupling agent begins to appear, the coupling agent mainly has the effect of infiltrating the surfaces of the epoxy resin and the filler and the surface of the bonded material and forming intermolecular force, and when microwave curing is adopted, the functional groups have more contact points with the interface, so that vibration and heat generation can be fully realized, and the curing is accelerated.
Comparison of comparative examples 4 and 5 shows that microwave radiation curing was also carried out, and that formulations using the AC5250, AC2050 filler combination had faster cure rates than formulations using the SE6050-STE, SO-E2/24C filler combination. This is because SE6050-STE, SO-E2/24C, is SiO 2 While AC5250, AC2050 belong to Al 2 O 3 The latter has a higher thermal conductivity, so that when microwave curing is performed, the latter can more easily transfer heat generated by molecular vibration caused by microwaves to the whole curing system, and thus the microwave curing speed is higher.
Comparison of example 1 with comparative example 5 shows that microwave radiation curing is also carried out, and that formulations using T-5000 curing agent have faster curing speed than formulations using A-A curing agent. This is because T-5000 isbase:Sub>A trifunctional polyetheramine and A-A is an oligomeric modified amine, the former being more reactive and causing more rapid heating of the molecule by vibrational heating under microwave irradiation, and thus exhibitingbase:Sub>A relatively faster cure rate.
Example 1 and comparative example 6 further demonstrate that the curing rate is faster with the microwave radiation curing mode than with the conventional heat curing mode.
As shown by the data in table 3, most of the key physicochemical properties of examples 1 and 2 and comparative example 6 are comparable, indicating that conventional heat curing and microwave radiation curing do not affect the main physicochemical properties of the same formulation. However, the length of the silicone surface grease overflowing and the substrate surface precipitation after the formulation of example 1 is cured is smaller than that of comparative example 6, because the same formulation has faster microwave curing speed and faster time for generating gel, so the low molecular substance in the formulation is already fixed before diffusing and precipitating, and the precipitation is less obvious. The grease overflow and the precipitation of example 1 are more slight than those of example 2, mainly because the short-chain coupling agent is partially introduced into example 2, and the precipitation is more easily caused than that of the nine-functional coupling agent.
For the high temperature silicon wafer adhesion, example 1 is higher than comparative example 6 because the resin and coupling agent in the underfill material move more vigorously due to microwave curing, and stronger intermolecular forces are formed with the silicon interface, thereby increasing the high temperature adhesion. Further, the high temperature silicon wafer adhesion of example 2 is higher than that of example 2 because two coupling agents are used in combination, wherein the nine-functional coupling agent is beneficial to generate enough heat during the microwave curing stage to accelerate the coupling. The nine-functional coupling agent has larger molecular volume and larger steric hindrance, so that under limited dosage, KBE403 serving as a short-chain coupling agent can supplement the part which cannot completely perform interface coupling action, and the silicon wafer interface shown in example 2 has higher adhesive force.
As shown in FIG. 1, the same formulation, using microwave curing, is less prone to filler settling or uneven filler distribution than heat curing formulations. This is because the microwave cure rate is faster and the rate of gel formation is faster, so that no time before the filler settles, gel formation has occurred or viscosity begins to increase, and the filler position is relatively fixed and so no sedimentation occurs.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The microwave radiation cured chip-level underfill is characterized by comprising the following components in parts by weight: 20-30 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of black paste, 60-70 parts of spherical filler, 8-12 parts of curing agent and 0.5-1 part of accelerator;
the epoxy resin is bisphenol epoxy resin and special epoxy resin, and the mass ratio of the bisphenol epoxy resin to the special epoxy resin is (1.5-2): 1;
the bisphenol type epoxy resin is bisphenol F type epoxy resin and bisphenol A type epoxy resin; the bisphenol F type epoxy resin is 830S and 830CRP of Japanese DIC, RE-303S-L of Japan chemical, DER354 and DER354 of Dow chemical or a mixture of more than one of the above resins; the bisphenol A type epoxy resin is one or more of 850-S and 850CRP of DIC, RE-310S of Japan chemical, DER383 and DER332 of Dow chemical.
2. The microwave radiation-curable chip-scale underfill according to claim 1, wherein the specific epoxy resin is one or a mixture of ELM-100H of Sumitomo, SW-0510, SW-70, and SW-80 of Severv, HP-4032D and HP4700 of DIC, and NC-3000-L and NC-2000-L of Nippon Chemicals.
3. The microwave radiation-curable chip-scale underfill according to claim 1, wherein the spherical filler is one or more selected from SE6050-STE, SO-E2/24C, AC5250 and AC2050 of Admatechs, japan.
4. The microwave radiation-curable chip-scale underfill according to claim 1, wherein the coupling agent is gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyl-triethoxysilane, gamma-aminopropyl-triethoxysilane, gamma-glycidoxypropyl-trimethoxysilane ― One of aminopropyl trimethoxy silaneOr both.
5. The microwave radiation-curable chip-scale underfill according to claim 1, wherein said curing agent is one or more selected from the group consisting of maleic anhydride, benzoic anhydride, phthalic anhydride, succinic anhydride, 4 '-diamino-3, 3' -diethyldiphenylmethane, diethyltoluenediamine, diaminodiphenylsulfone, m-aminomethane, xylylenediamine trimer, dibenzylaminoether, and diethyltoluenediamine.
6. The microwave radiation-curable chip-scale underfill according to claim 1, wherein the accelerator is MY-25 of ajinomoto.
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KR20150065326A (en) * | 2013-12-05 | 2015-06-15 | 한국생산기술연구원 | Adhesive cured by microwave radiation |
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CN113969126A (en) * | 2021-10-13 | 2022-01-25 | 烟台德邦科技股份有限公司 | Chip-level underfill with low-fat overflow on silicon surface |
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