CN1946795A - Dual-stage wafer applied underfills - Google Patents

Dual-stage wafer applied underfills Download PDF

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Publication number
CN1946795A
CN1946795A CNA2004800344047A CN200480034404A CN1946795A CN 1946795 A CN1946795 A CN 1946795A CN A2004800344047 A CNA2004800344047 A CN A2004800344047A CN 200480034404 A CN200480034404 A CN 200480034404A CN 1946795 A CN1946795 A CN 1946795A
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Prior art keywords
underfill
acrylate
composition
wafer
epoxy
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Granted
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CN1946795B (en
Inventor
多里安·A·卡内拉斯
凯兰·高希
阿曼达·W·许勒斯
艾德沃德·E·科莱
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Lord Corp
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Lord Corp
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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Abstract

A 100% non-volatile, one-part liquid underfill encapsulant is disclosed for application to the active side of a large wafer or integrated circuit chip. Upon coating, the encapsulant is converted to a liquefiable, tack-free solid by exposure to radiation, particularly in the UV, visible and infrared spectrum. The underfill-coated wafer exhibits outstanding shelf aging of months without advancement of cure. The large wafer can be singulated into smaller wafer sections and stored for months after which during solder reflow assembly, the wafer connects are fixed and the underfill liquefies, flows out to a fillet and transitions to a thermoset state on heat activated crosslinking.

Description

Dual-stage wafer applied underfills
Invention field
The present invention relates to the microelectronic chip assembly, relate in particular to the method and the material that underfill are applied to integrated circuit (IC) wafer.
Background of invention
The surface-mounted of electronic unit obtaining good development in the packaging assembly system automatically.Unicircuit is made up of following: such as the device of transistor and diode, such as the element of resistance and electric capacity, described device is connected by conduction with element and links to each other to form one or more functional circuit.Device is arranged on the wafer or silicon chip with surface, described surface is used for carrying out the identical integrated circuit patterns that a series of manufacturing step separates with the repetition rectangular patterns that forms line by wafer surface or sawline (saw streets), and described line or rectangle region are used as the border between small pieces, chip or the tube core (die).In the later stage of manufacturing processed, link to each other with substrate to form the IC encapsulation from the independent small pieces of wafer.
Conventional flip chip technology (fct) typically refers to the random component that the front of integrated circuit lead links to each other with enclosed chip or printed circuit board (PCB) (being referred to as PCB).Flip-chip assembly can be designed to have or do not have the encapsulation of underfill.For the purposes of flip-chip, have little salient point or solder ball (hereinafter referred to as " salient point " or " solder bump ") on the chip, its be positioned at the corresponding front of the depression of circuit board surface on.Assemble chip by salient point and sleeve-board are closed, make between the corresponding solder joint of solder joint that solder bump is clipped in plate and chip.After using soldering flux, the assembly heating is reached the point of solder reflow.After the cooling, solder hardens, thus flip-chip is installed on the surface of plate.
Conventional underfill is used for a plurality of diverse ways; and be applied in the mounted chip, be used to chip that protection to following situation is provided: chemical attack, moisture, airborne transmission pollution etc. and mechanical shock, vibration and transportation with use in the temperature cycle that meets with change.Conventional capillary flip-chip underfill method must have following steps: the aligning of chip and circuit card, soldering flux distribution, solder reflow, flux cleaning, underfill are used, underfill flows and solidify.
The underfill that is used for Chip Packaging provides following function: protection is avoided interference such as the environmental factors of moisture and pollution with the solder joints of chip and encapsulation or plate interconnection, reallocation mechanical stress, thereby raising device lifetime.Its for chip provide to such as moisture and due to the protection of polluting of metal interconnected corrosive.Yet the wrong choice meeting of tackiness agent causes the Flip-Chip Using failure of multiple mode, for example contraction, layering, hydrolytic instability, corrosion and because the pollution that underfill causes.
Stress between the adhesive that chip bottom filling glue is used to avoid causing owing to different heat expansion coefficient between chip, interconnection, underfill and the substrate.If substrate is organically, and when device size increases, then because the failure mode that stress causes becomes more general.Chip bottom is filled glue must provide the function that adheres to such as the substrate of pottery or organic PCB (for example FR4 epoxy), wherein substrate can by or not by following coated materials: solder mask; Metal alloy or organic interconnection; And integrated circuit lead (chip), described tube core is made of silicon or other inorganics usually, and can by or applied by thin passivation layer.
In the principle method of two kinds of packaged electronic components a kind of, parts are welded on it identical one side are installed onboard.These devices be known as " surface mounting ".The underfill of two kinds of routines is used for the device of surface mounting in practice: capillary flow pattern or " non-current " type.The detailed description of these technology can find in the literature.For example, referring to the book Low Cost Flip Chip Technologies for DCA of John H.Lau, WLCSP and PBGAAssemblies, McGraw-Hill, 2000.For these two kinds of technology, apply heat usually and be used to solidify liquid thermoset formulation or solid film is laminated to assembly.Sometimes adopt vacuum from system, to discharge bubble.Underfill is applied in used surface mounting (SMT) fabrication line of chip or chip on board in the encapsulation usually.Conventional flow and the use of non-current underfill on the SMT line needs a plurality of steps, and this method bottleneck on these microelectronics fabrication lines normally.
In U.S. Patent No. 6,180, the non-current underfill of representational routine is disclosed in 696.At first with this underfill material distribution on substrate or semi-conductor chip, solder bump refluxes then, and the underfill sealing agent solidifies simultaneously.In U.S. Patent No. 6,180, in 696 the underfill of instruction comprise Resins, epoxy and/or Resins, epoxy, organic carboxyl acid acid anhydride stiffening agent, curing catalyst, from flux, viscosity control agent, coupler, surfactant mixtures.The cure peak temperature of underfill prescription is 180-240 ℃.This underfill must be stored in the temperature that is lower than zero degree (℃) under promote to solidify avoiding.
But underfill is different with the imaging photo-resist material that is coated on the PC plate as patterning formation thing, yet, in the use of ubiquitous Resins, epoxy, there is certain similarity.The known employing light trigger of coating that is used for photoresist is used to make by mask be exposed to the zone curing of activating radiation and realize the polymeric second thermal activation radically curing composition in non-radiative or shadow region.Usually a kind of second curing mechanism that utilizes depends on the superoxide that adds thermal activation in prescription; Yet therefore the temperature that need surpass 100 ℃ has usually been got rid of and has been related to for example use of thermo-sensitivity electronic unit to cause the polymerization of peroxide-induced.
U.S. Patent No. 5,077,376 disclose the epoxy adhesive that contains potentiality thermofixation composition.' 376 disclosed contents have been instructed the problem of the known package stability of liquid epoxy material, its make contain the potentiality stiffening agent for example the composition epoxy resin of Dyhard RU 100, binary acid dihydrazide, boron trifluoride-amine adduct, guanamine, melamine etc. be widely used.Yet the defective that this patent instruction Dyhard RU 100, binary acid dihydrazide and guanamine have is that their need 150 ℃ or higher high temperature to be cured.
U.S. Patent No. 5,523,443 disclose the conformal coat of regelate, and it contains the polymerizable system and the moisture-curable mechanism of ultraviolet curing.This polymerizable coating system is a single-component system, and it contains at least a alkoxysilyl-polyurethane-acrylate or methacrylic ester, acrylate or methacrylic ester or vinyl ether thinner, positively charged ion or free radical photo-initiation class polymerization starter and metal catalyst.
U.S. Patent No. 5,249,101 (IBM, 1993) instruction has Young's modulus and can cause breaking and layering greater than the brittleness of the protectiveness epoxy coat of Circuits System on the circuitized surface that is used for chip carrier of about 10000psi (69MPa).U.S. ' 101 coatings that proposed to contain acrylated urethane oligomers, acroleic acid esterification monomer and light trigger are used to provide Young's modulus to be equal to or less than the coating that 10000psi and chlorine ion concentration are lower than 10ppm.Wafer does not need solder reflow with the Acrylated urethanes underfill, and this is because it lacks enough thermal insulations.
U.S. Patent No. 5,494,981 disclose cycloaliphatic epoxy resin, cyanate ester resin, optional polyvalent alcohol and as the curing combination of the Bronsted acid (Br  nsted acid) of initiator.When solidifying, said composition provides the polymer network that interpenetrates (IPNs).This IPNs is suitable for and makes high-temperature stability damping material, tackiness agent, abrasive tackiness agent and protective coating.
U.S. Patent No. 5,672,393 disclose acrylate sealing prescription, when it is exposed to wavelength for the radiation in ultraviolet ray and the visual range, it is with high speed response, thereby the epidermis after beginning to generate relatively, and finally be solidified into the settling of relative low-stress with good physical sharpness and surface properties.This method must make the prescription on the object be exposed under the radiation causing photopolymerization and thermopolymerization, and this device comprises actinic radiation tightly arranged side by side and thermal energy source.Catalyst system comprises the light trigger composition and the temperature that is lower than 120 ℃ is had the thermal initiator composition of response.
U.S. Patent No. 5,706,579 disclose the method for assembling unicircuit encapsulation, and described encapsulation is made by tube core, printed wiring board and crown cap, but this method adopts the β-stage resin that is applied to lid in advance and contains the heat conductivity packing material.By the lid of on tube core and substrate boards, suitably placing, with the encapsulation heating to cause resin flows and to form and being connected of tube core.Further heating make resin solidification and form tube core and lid between permanent heat bridge connect.
U.S. Patent No. 6,194,788 disclose the integrated thermoplasticity that is used for flip-chip, molten certainly two-pack underfill.This underfill comprises Resins, epoxy and has from the acetic ester thinner that melts the acid epoxy hardener of type.
U.S. Patent No. 6,323,062 (Alpha Metals, on September 14th, 1999 submitted to) discloses the method that glue is used for flip-chip filled by solvent substrate portion.This method comprises that the wafer that will be with salient point is bonded to the step on the extending carrier substrate, at first, cut wafer to form independent chip, carrier substrate is extended in a bi-directional way forming path between each single chip, then the underfill material is applied to the bump surface of chip and is looped around the edge of chip.This underfill material and unexposed, but it has instructed underfill applying after drying, then cutting underfill material in the passage between chip, and each single chip that will apply underfill removes from carrier.
U.S. Patent No. 6,383,659 disclose the b-stage film of low Tg epoxy group(ing) underfill, and it contains molecular weight is 5,000-200,000 thermoplastic polymer.Should ' 659 patents also instruct autohemagglutination mould assembly composition epoxy resin or the phenol solidified type epoxy resin combination that contains imidazoles usually, it demonstrates the high-temperature behavior of limited stability in storage, moisture-proof gas and curing composition, and is difficult to control the progress of B-elementary reaction.
Above-mentioned prior art illustration form the regelate method of coating, but do not relate to the storage of the b-stage coating that on fragility substrate, contains the regelate chemicals such as silicon wafer.Remove under controlled environment, transportation or store in wafer distortion may take place, break and long-range circumstances store under the about 50 ℃ temperature reaching easily.
After underfill is applied and solidifies, then place the several months until the solder reflow step that is used for two stage solidification underfills, the problem that runs in underfill at wafer is: the initial wetting of liquid coating and adhesion; Coating curing and not from the wafer layering at ambient temperature; The long-range circumstances temperature of coated wafers stores, and not because of solidifying or gel content increases and causes the backflow ability to reduce; In subregion or line, avoid from the wafer layering; Can stencil finishing in the wafer sawline; In initial heating, begin retrogradation lentamente by solder reflow; Do not using around when ring, underfill flow out and around chip to form the ability of fillet (fillet); In underfill, there be not the space after the solder reflow step; And in its acceptable life, its long-term reliability (zero defect) in device.
The wafer of standing storage is not solved by the underfill material of prior art by its all these technical problems of differentiating for underfill before assembling.Therefore, purpose is to be provided for primer is used the material and the method for separating with flip-chip assembly, liquid bottom filling glue directly is coated on the front of wafer by the coating method of routine, and described wafer for example surface-area is 100-500mm 2And bigger wafer, then be cured, and the chip of coated wafers or cutting is stored for a long time, for example the several months.In this case, wafer method of attachment thereafter must be avoided the problem relevant with the character of aging underfill.
Summary of the invention
The method that the present invention relates to wafer-underfill assembly and single component, solvent-free, non-certainly molten underfill are applied directly to front wafer surface with the coat-thickness of common about 0.003 inch-0.070 inch (0.076-1.77mm).Underfill is initially the liquid coating that partially or completely covers the wafer solder bump.Underfill comprises liquid coating filling, 100% solid (non-volatile basically).Underfill passes through at about 50-2400mJ/cm 2Thereby optical radiation reveal down and put that to be frozen into heat on wafer liquable solid-state.Underfill can be applied to outside the wafer sawline with lattice, perhaps can form and can be cut into the continuous coated of individual region or tube core through subject wafer.The individual region of coated wafers or coating can in assembling or welding flux interconnected before around environment store down uncertain time of lag of several months long.Adopting in the assembling chip around sealing agent that wafer is used on every side with underfill, the thermofixation starting point of the liquable solid-state underfill of heat can be 150 ℃ or higher.Be heated liquefaction and flow out to Waffer edge of underfill therein, and upwards flow to a certain extent and form in the embodiment of fillet, the thermofixation activation temperature of underfill must be higher than 170 ℃.Being used for heat that reflux solder applies is enough to start the melt flow of underfill before heat of activation curing system, it is heat cured solid-state that it makes that the underfill gelling changes into.Under the thermoset solid state, underfill demonstrates the modulus in flexure that is lower than 10Gpa.
The single component liquid underfill comprises following mixture: as the filler of one or more ethylenically unsaturated monomers, one or more curable epoxy materials, one or more light triggers, potentiality thermal curing agents, heat conduction and the electrical isolation of photocuring composition, it is characterized in that the photocuring composition accounts for the 5%-30% of underfill gross weight, and the Resins, epoxy composition accounts for the 10%-45% of underfill gross weight.Preferably be light-cured into branch and comprise 100% unsaturated acrylate of simple function ethylenic or methacrylate monomer.Preferred photopolymerization composition is acrylic acid simple function cyclic ethers and/or cyclic acetal.
The accompanying drawing summary
Fig. 1 represents the DSC curve of embodiment 6, and it demonstrates the peak temperature of fusing point, thermofixation starting point and reaction.
Fig. 2 represents the DSC curve of embodiment 7, and it demonstrates the peak temperature of fusing point, thermofixation starting point and reaction.
The detailed description of preferred implementation
Aspect method, underfill according to the present invention is suitable for for example by revolving the conventional coating method that mold forming, stencil finishing, printing etc. are applied to front wafer surface.The rheology that liquid bottom is filled glue material easily is suitable for selected coating method.Liquid bottom is filled glue and is administered on the salient point or front that is carried on on-chip large-scale wafer, and carries out photoinduced radical polymerization, and formation keeps adhering solid-state self-supporting layer to wafer fast.Photocuring solidifies and has obtained the solid underfill surface of not being clamminess, and does not have the distortion of wafer.Show under the surrounding environment that solid-state underfill coating still keeps hot liquefiable state under long-time surrounding environment stores, it can expose the several months and wafer not produced stress under 50 ℃.
Not limiting the time of lag that the wafer that applies with photocuring, the liquable solid-state underfill of heat or individual region is stored before welding flux interconnected forming, for example is several weeks, several months until 1 year etc.Condition of storage in delay can comprise with underfill be exposed to need not under the envrionment temperature refrigeration.Wafer is different with conventional thermoplasticity or thermosetting material with underfill, and wherein said thermoplasticity or thermosetting material are from solvent casting (cast) or use heat and/or vacuum to carry out melt-processed.Yet, according to the present invention, underfill is 100% solid material, it is set on the front wafer surface to photoinduction by addition polymerization, and remain the thermoplasticity state and the curing that always significantly is delayed to second thermal initiation begins all less than at room temperature further solidifying, and thermoplastic filler has following specific key property: no layering, tight form, fully reflux under solder reflow conditions, and have secular adhesivity under the multiple thermal cycle conditions and can not make component failure or breakage in the thermoset state.Heat cured curing underfill is 25 ℃ of modulus in flexurees with 1000-5000MPa, and is being lower than the thermal expansivity (CTE) that has the about 60ppm/ of 15-℃ under the temperature of second-order transition temperature, is more typically ppm/ ℃ of about 25 (+/-10).
The underfill of wafer scale comprises 100% solid mixture.The volatile component that can cause weight loss in long ambient storage for example solvent is non-existent.Do not contain volatile component and exempted solvent removal step, and improved the layering of the control of shrinking and photoinduction gel coating from the front wafer surface surface.The release of volatile organic component has prevented unacceptable contraction and stress, and the waste gas that produces in solder reflow step, has avoided the space that forms between wafer or its zone and PCB.The underfill right and wrong melt certainly.In other words, the composition that is adopted does not provide the fusing effect, and is non-acid.
Aspect usual method, the present invention includes and liquid bottom is filled viscose binder be applied on the integrated circuit (IC) wafer, use the luminous energy (ultraviolet ray, visible light, infrared rays etc.) of manipulated variable, make underfill be frozen into hot liquefiable or melt-flowable state, choose wantonly by line or sawing wafer is cut apart, and in timing period, preserve wafer or the small pieces that apply.After timing period, form to be electrically connected, and the liquefaction of being heated of the solid-state underfill of the photocuring of being used, and in solder reflow process, to flow to the edge of device, thereby change into heat cured solid-state through curing from heated liquid.In time of lag in storage, it is liquable solid-state that coating of the present invention keeps, and gel content does not increase.Therefore an aspect of of the present present invention provides integrated circuit (IC) wafer stable under the envrionment temperature, and its front adheres to the underfill composition, and described composition comprises the single-component composition of photocuring, and this single-component composition comprises following composition with weight basis:
The light-cured acrylate composition,
Polyfunctional epoxy resin,
At least a light trigger,
Non-conductive filler and
Non-melt activation epoxy hardener hot in nature, wherein said underfill in 25 ℃ of modulus in flexurees with 1000-5000MPa, and has 15-50ppm/ ℃ thermal expansivity under the temperature that is lower than described underfill composition second-order transition temperature under the thermoset state.
In yet another aspect, the present invention relates to two stage methods that wafer is cured with the underfill composition.This method comprises the front that the underfill composition is applied to semiconductor wafer with liquid form.The method of using comprises liquid state non-volatile (100% solid) coating directly is coated to the front of chip by revolving mold forming, printing or stencil finishing.Thereby with the UV radiation of selected consumption coated wafers is solidified and to form solid-state coating.Randomly can be with solid-state coated wafers line subregion.Wafer or all zones can store under envrionment temperature, then for subordinate phase, set up the electrical connection of solder bump to PCB in solder reflow step, then solid-state underfill thermosetting are changed into the thermoset state.
100% solid underfill composition consists essentially of light-cured acrylate composition, polyfunctional epoxy resin, light trigger, potentiality epoxy thermal initiator and the inorganic CTE-dilution filler that contains simple function ethylenically unsaturated monomers and/or oligopolymer.Underfill is alkali-soluble in solid-state following right and wrong, and does not contain acidic group in liquid photocuring unsaturated monomer, oligopolymer and/or polymkeric substance, for example free carboxyl, phosphate radical or sulfate radical.The weight percent of used composition adds up to 100% by weight in the wafer set compound, and as follows:
Composition weight %
The light-cured acrylate composition ... 5-30%
Liquid polyfunctional epoxy resin ... 10-45%
Light trigger ... 0.3-3%
Low CTE filler ... 40-70%
The potentiality curing catalyst ... 1-3%
Before being converted into the thermoset state, the liquable solid-state underfill composition of heat is self-supporting, stable storing and can still keeps and the positive adhesivity of wafer or all zones through very long time of lag at ambient temperature, thereby using with solder reflow chip installation steps of underfill can be separated.The present invention can store wafer under envrionment conditions, supply the usefulness of the installation on PCB thereafter.
The branch that is light-cured into of underfill composition is included in ethylenically unsaturated monomers or the monomer combination that has at least 6 carbon atoms in its structure.Introducing has the monomer that is less than 6 carbon atoms and can cause producing unacceptable volatility problem when solid-state being light-cured into, and cause when solid-state contraction problem, this contraction to tend to the chip that adheres to composition is increased stress changing into hot liquable photocuring.Contain the underfill that is higher than the liquid multifunctional ethylenic unsaturated comonomer of 10 weight % based on photocuring composition gross weight, can cause in the chip installation process melt-flow deficiency of hot liquefiable underfill in solder reflow step.Therefore, preferred aspect is not contain many unsaturated monomers in underfill, or is limited in the 10 weight % that are no more than underfill photocuring composition weight.
The unification of term photocuring composition is meant ethylenically unsaturated monomers and/or the oligopolymer that no matter adopts in which way.More preferably, the unsaturated material of ethylenic comprises vinyl ester, vinyl ether and/or α, β-unsaturated acrylate.Preferred photocuring composition is the unsaturated acrylate of ethylenic as monomer, unsaturated oligomer or side chain unsaturated oligomer and combination thereof.Term oligomer is meant at 25 ℃ descends the unsaturated compound that for liquid state, maybe can be dissolved in the optical solidified liquid carrier.Can use non-sense or saturated thermoplastic polymer thinner, for example polyacrylic ester, polyvinyl ether, polyvinyl ester, polyester, polymeric amide, polyolefine and functional derivative etc., its condition is that the softening temperature of thinner can significantly not hinder the melt-flow of hot liquefiable underfill under solder reflow temperature.Such thinner can be used for different features, for example accurately controls or raising melt fluidity and/or cohesive strength.
When the wafer that contains the light-cured acrylate composition with underfill under the influence of UV radiating during polymerization, underfill promptly changes into solid-state at ambient temperature from liquid state.Solid remains thermoplasticity, and promptly it keeps hot liquefiable attitude until thermofixation.The specified amount of photocuring composition is the 5-30 weight % of underfill gross weight.For the weight of photocuring composition, the consumption of multi-functional epoxy's material provides that to solidify fully and keep melt fluidity in solder reflow step be critical during for photocuring.At multi-functional epoxy's material is when being higher than the scope of 10-45 weight %, and then underfill damages wafer trend behind photocuring also can increase.Be lower than this scope, then in hot liquefiable solid, do not have enough cohesive strengths, and creep increase in envrionment temperature stores before solder reflow.The section thickness that imposes on the underfill coating on the front most preferably is the size that a part of solder bump is exposed.Exposure is meant metal exposed in air, or on the outermost outburst area of solder bump, may exist the thin bottom part that is lower than about 0.01 μ m to fill the glue resistates.In preferred embodiment, the thickness of underfill coating is the 50-90% of solder bump section (profile) behind the photocuring.Section is the degree of depth of extending the table planar solder bump part of front wafer surface.
The optional photocuring oligopolymer that uses is liquid at ambient temperature among the application, or can be dissolved in the solid in the unsaturated acrylate monomer of liquid ethylenic.Oligopolymer contains one or more side groups or terminal olefinic link formula unsaturated group.Typical oligopolymer contains 2 terminal unsaturation groups.Molecular weight is that unsaturated group mean number can be 1-2 in the oligomeric light-cured acrylate composition of 500-3000.The light-cured acrylate composition only gets rid of two, three or four and higher ethylenically unsaturated monomers, dimer or tripolymer.
The embodiment of underfill of the present invention demonstrates enough melt-flow under solder reflow conditions, thereby outwards flows out to the edge of chip, and the space between completely filled chip downside and the PCB.In some cases, outflow can comprise along the edge of tube core upwards flows to form fillet, the solid underfill of photocuring is bonded on the wafer well, and has for standing storage and/or line and can not twist or destroy the necessary enough cohesive strengths of wafer.After the timing period that stores, when the weight ratio of light-cured acrylate composition and epoxy functional composition is 1: 10-1: 2, and when the photocuring composition contains the simple function of designated ratio and polyfunctional monomer and/or oligopolymer, fully flow under being heated that hot liquefiable solid runs in solder reflow step.Be lower than in photocuring composition and epoxy functional components in proportions under 1: 10 the situation, underfill lacks enough cohesive strengths usually and/or demonstrates unacceptable surface viscosity.Be higher than in this ratio under 1: 2 the situation, wafer demonstrates distortion, destruction and/or underfill and trends towards layering or be used to form the mobile insufficient of fillet.
Spendable exemplary single ethylenically unsaturated monomers is the monomer with at least 6 carbon atoms among the application, comprises vinylformic acid or C 1-C 4Acrylic acid alkyl C that alkyl replaces 3-C 12Alkyl ester, it is referred to as (alkyl) acrylate.The object lesson of suitable monofunctional monomer comprises butyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic tert-butyl acrylate, cyclohexyl methacrylate, methacrylic acid 3-methyl cyclohexanol ester, cyclic ether acrylate and monocycle shape acetal acrylate.Monocycle shape shape acetal acrylate is known, and in U.S. Patent No. 4,076, and is open in 727.The acetal acrylate obtains through following deriving: with polyvalent alcohol for example TriMethylolPropane(TMP), trimethylolethane, glycerine, 1,2,4-trihydroxybutane, 1,2,5-penta 3 pure and mild 1,2,6-hexanetriol and aldehyde reaction, and and α, β-unsaturated carboxylate for example vinylformic acid or ester carries out transesterify and obtains.Exemplary photocuring composition is the combination that contains acrylate such as the tetrahydrofurfuryl acrylate (THFA) and the ring-type hydroxyalkyl methylal acrylate of cyclic ethers.Preferred monofunctional acrylate is tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, monomethyl vinylformic acid pentaerythritol ester, single vinylformic acid pentaerythritol ester, TriMethylolPropane(TMP) monomethacrylates, TriMethylolPropane(TMP) mono acrylic ester, ring-type hydroxyalkyl methylal acrylate and ketal acrylate.Acetal acrylate and ketal acrylate can comprise isomer mixture.Ring-type hydroxyalkyl methylal acrylate and ring-type hydroxyalkyl ketal acrylate can be easily by using the monohydroxy acetal derived from trivalent alcohol that acrylate or methacrylic ester esterification are made, and described trivalent alcohol is TriMethylolPropane(TMP) and triethylol propane for example.Can react with aldehydes or ketones, and the structure of using acrylate or methacrylic ester to carry out the suitable trivalent alcohol raw material of acroleic acid esterification comprises following formula:
Preferred ring-type hydroxyalkyl methylal acrylate has following structure (A-C)
Wherein, R 1Be C 1-C 4Alkylidene group, for example-CH 2-,-CH 2CH 2-etc., R 2, R 3And R 4Be H or C 1-C 4Alkyl, for example-CH 3,-CH 2CH 3Deng.
Most preferred ring-type hydroxyalkyl methylal acrylate is TriMethylolPropane(TMP) methylal acrylate (structure B ').
Use separately or comprise acetoacetoxyethyl methacrylate with other photo-curing monomer that above-mentioned combination of monomers is arbitrarily used; vinylformic acid-2-acetoacetoxy groups ethyl ester; methacrylic acid-2-acetoacetoxy groups propyl ester; vinylformic acid-2-acetoacetoxy groups propyl ester; methacrylic acid-2-acetyl acetamide ethyl ester; vinylformic acid-2-acetyl acetamide ethyl ester; methacrylic acid-2-cyano-acetoxy ethyl ester; vinylformic acid-2-cyano-acetoxy ethyl ester; N-(2-cyano-acetoxy ethyl) acrylamide; vinylformic acid-2-propionyl acetoxyl group ethyl ester; N-(2-propionyl acetoxyl group ethyl) Methacrylamide; N-4-(acetoacetoxy groups benzyl) Phenyl Acrylamide; acetate ethyl propylene acyl ester; acetate acryl methyl esters; N-ethyl propylene acyloxy methyl aceto-acetamide; etheric acid ethyl-methyl acryloyl ester; N-allyl cyanide yl acetamide; etheric acid methacryloyl ester; N-(2-methacryloxy methyl) malonamide nitrile; methacrylic acid-ethyl-α-acetoacetyl oxygen ester; N-butyl-N-acryloxy ethyl aceto-acetamide; the polyvalent alcohol of mono acrylic esterization, and the reaction product of the acrylate of hydroxyl and acid anhydrides such as phthalic acid monomethyl acryloxy ethyl ester.Can with the comonomer of (alkyl) acrylate monomer copolymerization, prerequisite is to compare with acrylate monomer, this rate of polymerization does not slow to tangible degree.
The quick photocuring of Acrylic Acid Monomer is the feature of expectation.Photocurable ethylenically unsaturated monomers except that acrylate and alkyl acrylate is limited to about 6 carbon atoms or more senior, its example includes, but are not limited to butyl vinyl ether, IVE, cyclohexyl vinyl ether right-(2-acetoacetyl) ethyl styrene and 4-acetoacetyl-1-methacryloxy piperazine.Contain the ethylenically unsaturated monomers of epoxide-reactive groups and be not used in and be light-cured in the branch, described epoxide-reactive groups for example contains the group of active hydrogen.
The representative of known multifunctional ethylenically unsaturated compounds is alkene two unsaturated monomers, for example ethylene glycol diacrylate, poly-ethylene glycol diacrylate, Ethylene glycol dimethacrylate, hexanediol diacrylate and diacrylate triethyleneglycol ester.Representational three unsaturated monomers comprise Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate, three vinylformic acid glyceryl ester, pentaerythritol triacrylate and trimethylammonium vinylformic acid pentaerythritol ester.The unsaturated photo-curing material of representational vinylformic acid is from Sartomer, Exton, the SR205 of PA, SR306, CD401, SR508, SR603, SR9036.
Other appropriate light polyreactive oligomers material that can be included in the photocuring composition has, for example based on the polyethers of the reaction product of the end capped oligopolymer of polyether acrylate, vinyl ether, hydroxyl functional acrylate and the methacrylic ester and the epoxide of bis-phenol, acroleic acid esterification, ethylenic unsaturated polyester alkyl oxide, above-mentioned cyclic ether acrylate and cyclic ethers acetal acrylate.
The photopolymerization composition can be that single unsaturated acrylate monomer and number-average molecular weight are 500-5000, is preferably the mixture of the ethylenic unsaturated oligomer of 1000-4000.Liquid photocuring oligopolymer can comprise the urethane acrylate oligomer with isocyanate reactive group.Urethane acrylate oligomer also can make up with the unsaturated acrylate monomer of ethylenic.The urethane of acroleic acid esterification can be aliphatic series or aromatics.The example of commercially available Acrylated urethanes comprises the known products of following trade(brand)name: from Henkel Corp.Hoboken, and the PHOTOMER of N.J. (as PHOTOMER 6010); From UCB Radcure Inc.Smyrna, Ga. EBECRYL 220 (molecular weight is 1000 six functional aromatic urethane acrylates), EBECRYL 284 (be with the molecular weight of 1,6 hexanediol diacrylate dilution 1200 aliphatic urethane diacrylate), EBECRYL 4827 (molecular weight is 1600 aromatic polyurethane diacrylate), EBECRYL 4830 (molecular weight by tetraethylene glycol diacrylate dilution is 1600 aromatic polyurethane diacrylate), EBECRYL 6602 (be with the molecular weight of TriMethylolPropane(TMP) oxyethyl group triacrylate dilution 1300 trifunctional aromatic polyurethane acrylate), with EBECRYL 840 (molecular weight is 1000 aliphatic urethane diacrylate); Come from Sartomer Co., Exton, the SARTOMER of Pa. (for example SARTOMER 9635,9645,9655,963-B80,966-A80 etc.) and come from Morton International, Chicago, the UVITHANE of III (for example UVITHANE 782).
Optional can be contained in the light-cured acrylate composition be have one or more than a unsaturated acrylate group of photocuring, with acrylate modified epoxy material, the diacrylate of bisphenol A epoxide resin for example, the mixture of even now is not preferred.Representational acrylate modified epoxy obtains by hydroxyl on the acrylate and ethylene oxide group reaction.There is not unreacted curable epoxy functional group residual.The commercial examples of the epoxide of acroleic acid esterification comprises the product from the commodity CMD by name of Radcure Specialties.Unsaturated epoxy oligomer of other suitable vinylformic acid or urethane acrylate oligomer have commercially available, for example from CN929, CN136, CN970, CN104, the CN120C60 of Sartomer.Distinctive acrylate modified epoxy liquid can be prepared by other list or polyfunctional acrylic ester.List or the monomeric content of polyfunctional acrylic ester are in total compositing range of photocuring composition in addition arbitrarily.
The functional photo-curing material of representational diacrylate comprises SR205, SR306, CD401, SR508, SR603, SR9036.Representational trifunctional material comprises SR350, SR444, CD501, SR9021.Four functional acrylate comprise SR295, SR355, SR399, SR9041.
The thermoset polyfunctional epoxy resin composition of underfill comprises at least a liquid resin, described liquid resin contains at least two epoxy group(ing), under 25 ℃, have and be lower than about 10, the viscosity of 000 pool, the weight in average of every epoxide (WPE) scope is about 1000 for about 100-, and average molecular weight range is about 500-about 3500.Can easy-to-use epoxide be known, comprise the diglycidylether, 2 of dihydroxyphenyl propane, 2-pair-4-(2, the 3-glycidoxy)-phenyl) propane.Commercially available suitable epoxy compounds is sold with following trade(brand)name: from EPON 828, the EPON1004 of Shell Chemical Co. and EPON1001F with from DER-331, DER-332 and the DER-334 of Dow Chemical Co.Other suitable Resins, epoxy comprises the glycidyl ether (for example from Dow Chemical Co DEN-431 and DEN-428) of cycloaliphatic epoxide, phenol formaldehyde (PF) phenolic varnish.The blend of radically curing resin and Resins, epoxy further describes in 138 (Tumey etc.) and the U.S. Patent No. 5,256,170 (Harmer etc.) in U.S. Patent No. 4,751.In preferred embodiment, adopt the combination of three kinds of Resins, epoxy, it is that to be the biphenyl epoxy resin, WPE of about 192g/eq. be the mixture of the triglycidyl ether of the diglycidylether of the Bisphenol F of about 172g/eq., p-aminophenol that WPE is about 101g/eq. to WPE.The commercial goods name of these three kinds of Resins, epoxy is respectively RSS, EPICLON and ARALDITE.
Liquid wafer coating contains at least a light trigger of the 1-3 weight % that has an appointment, and it can make liquid bottom fill glue and effectively be frozen into the surface of not being clamminess when being exposed to conventional grade of other actinic radiation.Selected light trigger type depends on the curing depth of expectation, the contrast medium type that is adopted and the preferred radiation wavelength that adopts.Be applicable to that commercially available light trigger the application's purposes, that produce radical comprises; but be not limited to benzophenone, benzoin ether and acylphosphine oxide photoinitiator; the product of selling with following trade(brand)name for example: from Ciba Specialty Chemicals; Basel, the IRGACURE  of Switzerland and DAROCUR .
Preferred photoinitiator system is monoacyl phosphine, the bisacylphosphine oxide of the ketone-functionality light trigger of following mixture: 25%-50% and 50%-75% or the light trigger that contains phosphonic acid ester.The example of ketone photoinitiator comprises the 1-hydroxycyclohexylphenylketone; the hydroxymethyl phenyl-acetone; the dimethoxy benzene benzoylformaldoxime; 2-methyl isophthalic acid-[4 (methylthio group)-phenyl]-2-morpholine acetone-1; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone; 1-(4-dodecyl-phenyl)-2-hydroxy-2-methyl third-1-ketone; 4-(2-hydroxyl-oxethyl) phenyl-2-(2-hydroxyl-2-propyl group)-ketone; the diethoxybenzene benzoylformaldoxime; 2; 4,6-trimethylbenzoyl diphenyl phosphine; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl third-1-ketone; 2-hydroxyl thioxanthene-9-one.Representational acylphosphine oxide light trigger comprises ethyl-2,4,6-trimethylbenzoyl diphenyl phosphine oxide compound, 2,4,6-triethylbenzene formyl radical diphenyl phosphine oxide, 2,4,6-triphenylbenzene formyl radical diphenyl phosphine oxide.The specific examples of filling the light trigger composition that the glue deeply-curing uses with liquid bottom for wafer is based on the underfill gross weight and is the phenyl of 0.5-0.7 weight % pairs (2 as the 1-hydroxycyclohexylphenylketone of 0.2-0.5 weight % and based on the underfill gross weight; 4, the 6-trimethylbenzoyl) phosphine oxide.
The coating temperature can not risen to any actinic light dosage source that is higher than 120 ℃ all can be used for the underfill photocuring is solidified as liquable solid gel state.The easiest employing is UV-light, also can be other form, for example Type RS fluorescent lamp, carbon arc lamp, xenon arc lamp, mercury discharge lamp, tungsten halide lamp etc.Radiating capacity can send from point source, or sends with the infinite ray form.Yet the light beam of dispersing also can be used as photochemical light source.At 100-2400mJ/cm 2UV amount in the scope can effectively provide the curing depth of about 1.2-1.8mm for underfill, and can be lower than under 100 ℃ in the underfill temperature and finish radio polymerization.The underfill composition is light-cured into the surface of not being clamminess.Can adjust set time by selecting suitable ultraviolet source, underfill photocuring composition concentration and contrast medium.
In package assembling, the automatic visual inspection of product need be used pigment, in order to provide contrast between plate, underfill and chip.Suitable has such as the sooty contrast medium with such as the pigment of buying with the Sandorin  board of Clariant AG.In one embodiment, with having disperseed 15 weight % sooty Resins, epoxy to be used for mixing the carbon black of 0.1-0.2 weight %, be used as automatic visual inspection effective contrast is provided at underfill.
Heat cured system
The epoxy curing systems that uses among the present invention is the non-melt type that contains the short thermit powder of potentiality, and the curing of wherein said short thermit powder begins temperature greater than 150 ℃, is preferably greater than 160 ℃ ± 5 ℃, more preferably 175 ℃ ± 5 ℃ and higher.Employing is used for the potentiality thermal curing agents of Resins, epoxy, be used to make solidify, the aged underfill causes the thermoset stage that is cured under temperature that the back met with takes place solder reflow.Dyhard RU 100 can not be used alone as thermal curing agents, but can urge the thermit powder coupling with potentiality slightly, but does not preferably contain Dyhard RU 100.Preferred potentiality thermal curing agents comprises amine, amine adduct; It comprises imidazoles and urea derivatives, for example 2,4, and 6-trimethylammonium-1, two (3, the 3-dimethyl urea groups) benzene and 1 of 3-, two (3, the 3-dimethyl urea groups) naphthalenes of 5-.The necessary right and wrong of thermal curing agents are halogenated.The example of solidifying agent can be with following as U.S. Patent No. 5,543,486 currently known methodss of being instructed obtain: epoxy compounds or isocyanate compound are mixed with amine compound, perhaps epoxy compounds or isocyanate compound, amine compound are mixed with active dydrogen compounds.(blocked amine) is all applicable for various end capped amine.Preferred thermal curing agents is the protectiveness amine that has tertiary amine and urea part.The exemplary imidazoles that is applicable to the thermofixation composition is a glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecenyl imidazoles, 1-vinyl-glyoxal ethyline, 2-n-heptadecane base imidazoles, the 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 1-cyano ethyl-2-phenylimidazole, 1-guanidine amino-ethyl-glyoxal ethyline, 2-(to dimethylaminophenyl)-4, the 5-diphenyl-imidazole, 2-(2-hydroxy phenyl)-4, the 5-diphenyl-imidazole, 2-phenyl-4-hydroxymethyl imidazoles, 2-phenyl-4,5-two (hydroxymethyl)-imidazoles, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, the adduct of imidazoles and trimellitic acid, the adduct of imidazoles and 2-n-heptadecane base-4-methylimidazole, phenylimidazole, benzyl imidazole, 1-(dodecylbenzyl)-glyoxal ethyline, 2-(2-hydroxyl-4-tert-butyl-phenyl)-4, the 5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-methyl-4, the 5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 2-(3-hydroxy phenyl)-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole and 2-are to the methoxyl-styrene imidazoles.Preferred thermal curing agents is the product of the Curezol  2-PHZ-S by name that buys from Air Products and Chemicals.
The thermal curing agents of replaceability can comprise end capped Lewis acid, for example can use potentiality etheric acid metal-functionality solidifying agent, as aluminum chelate, comprise that methyl aceto acetate metal diiso propoxide, three (methyl aceto acetate) metal, etheric acid alkane ester metal diiso propoxide, single hexadecyl acetone close aluminium two (methyl aceto acetate), tri acetylacetonato closes aluminium; The example of ring-type aluminium oligopolymer comprises ring-type aluminum oxide isopropoxide.
In order to provide enough backflows to liquable photocuring solid, the heat cured system that stores in the photocuring solid cladding of timing period on wafer or small pieces does not make progress.By the thermal curing agents that is adopted being selected to pre-determine the minimum temperature that thermofixation begins, and begin the back in solder reflow and be greater than or equal to 150 ℃ in temperature thermofixations take place down.Preferably, the minimum temperature scope that begins of underfill thermofixation is 150 ℃-225 ℃.Thermofixation begins temperature and the solidification rate peak value can easily determine that by dsc it is known in the art.Thermofixation begins selection and the amount that temperature depends on promotor, should not be higher than 280 ℃.Can not be when thermofixation begins too near peak temperature, this peak temperature for low eutectic solder is or near 250 ℃ usually, for lead-free solder is or near 300 ℃.The common solder reflow time is 3-4 minute, and the exposure of underfill under peak temperature is less than 30 seconds usually.Cause underfill liquefaction and flow insufficient being lower than the thermofixation that causes under 150 ℃ the temperature.
Non-conducting filler is used to limit the CTE in the underfill.These fillers are known and multiple suitable type are arranged.Based on the attribute and the cost of expectation, can select to use the aluminium of fused quartz, crystal, boron nitride, aluminium and silicon, magnesium oxide, Magnesium Silicate q-agent and the silica coating of microelectronics level.Filling the viscosity that forms in the glue at liquid bottom is the standard of selecting.Owing to do not contain solvent or non-reactive diluent, can easily be suitable for adopting the method for relative low viscosity coating, for example known spin-coating method according to underfill embodiment of the present invention.Rotatablely according to the present invention be coated with the conventional viscosity that the underfill embodiment that exposes to the sun has, lower relatively than the common viscosity of the underfill of using by stencil finishing or printing.
In preferred embodiment, underfill is used by hollowed printing with 70% the pattern that covers each wafer area between sawline at least.The CTE scope of the underfill in the thermoset state is 15-50ppm/ ℃, requires the non-conducting filler of certain level, is preferably the spherical fused quartz particle of amount ranges 40 weight %-70 weight %, is preferably 45 weight %-60 weight %.More preferably adopt the low CTE mineral filler of 45-55 weight %.The mean particle size of preferred low CET mineral filler is at least 10 μ m, and mean particle size is not more than about 75 μ m.The upper limit of used filler diameter must be less than the thickness of above-mentioned underfill coating.
Randomly, underfill can contain the adhesion modifying agent.Common usage quantity is 3-8 weight %.Bonding improver is known, comprises organosilane, organopolysiloxane, organic hydrogen polysiloxanes, prehydrolysis organosilane, siloxanes and silsesquioxane.Exemplary organosilane contains epoxy-functional, for example single (epoxy alkyl) trialkoxy silane, as γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane and β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; Or preferred ethylenic unsaturated group.The ethylenic unsaturated organosilicon compounds comprises list or polyene-based functional organic alkane, for example 3-(methyl) acryloxy propyl trimethoxy silicane, vinyltriethoxysilane, allyltrimethoxysilanis and polyene-based-functionality siloxanes, for example 1,1,3,3-tetramethyl disiloxane and 1,2,4-trivinyl hexanaphthene and/or 1,3, the hydrosilylation thing of 5-trivinyl hexanaphthene.
A kind of method that underfill is applied to wafer must adopt known screen printing technique.Wafer according to the present invention can advantageously print to wafer to cover the mode on the wafer surface region outside the sawline with underfill.Preferably, the filler of using by printing process contains optional rheology control agent.The known type that is fit to is the amorphous smoked silicon of amorphous smoked silicon or silanization, for example can be buied by Cabot Corporation.
Randomly can use known flowing regulator.The thermoplasticity flowing regulator has improved the effusive trend of hot liquable underfill in solder reflow.Representational flow improver comprises that I.V. is generally the polymethacrylate copolymer of 0.2-0.6, for example the commercially available prod of commodity Elvacite  by name.Example is the Elvacite  2013 of ICI Acrylics, and it is defined as the multipolymer that I.V. is 64% butyl methacrylate/36% methyl methacrylate of 0.2.Other flowing regulators known in the art comprise as Lubrizol, Wickliffe, Ohio, the Lanco  Flow P10 of U.S.A. and available from Solutia, St.Louis, the MODAFLOW  Powder of Mo.FLOW IMPROVERS can be based on SAN or alpha-olefinic polymer etc.Preferred FLOW IMPROVERS is that molecular weight is 60,000 thermoplasticity PMMA multipolymer, for example from INEOS Acrylics, and the Elvacite  4026 of Inc..The suggestion amount of optional thermoplasticity FLOW IMPROVERS is divided into 1.0-10.0 weight % with respect to being light-cured into.In order to regulate the flowability of underfill under the liquable photocuring state of heat, can use for example softening agent of carboxyl ester more on a small quantity with what be lower than 10 weight %, or the lubricant of ethylenebisstearamide for example.
Testing method
1. second-order transition temperature (Tg)
Use b stage or thermoset solidify material, use thermodynamic analyzer, use the dynamic mechanical analysis instrument, use differential scanning calorimeter with the heating rate of 5 ℃/min, measure second-order transition temperature with the heating rate of 5 ℃/min with the heating rate of 5 ℃/min.
2. thermal expansivity
In the mensuration of the thermal expansivity under being higher or lower than Tg, determine by using conventional thermodynamic analyzer.
3. viscosity
What be suitable for has Brookfield VDIII+ taper and a plate rheometer, but uses Haake  RheoStress I.
4. (die shear) adhesivity is sheared in test according to ASTM D1002
5. measure heat and oxidative stability by thermogravimetric analysis.Underfill demonstrates under 300 ℃ in air and is lower than 5% weight loss.
The photopolymerization condition
Use the following condition of AETEK UV processing unit to be enough to make liquid bottom filling glue all to realize solidifying at whole profile depth
Lamp 1 (W) Lamp 2 (W) Belt speed (fpm) Solidify energy (mJ/cm 2)
400 200 200 200 200 200 125 125 200 200 200 125 125 400 200 200 200 200 200 125 125 0 0 0 0 0 34 30 45 60 65 70 30 70 45 60 70 70 90 1170 761 515 384 349 327 712 297 274 205 176 149 116
The mode of production
Prepared underfill embodiment 1-4 in 30 seconds by in Hauschild  cup, adding each composition and under 3000rpm, mixing.With preparation be spin-coated to 4 inches (10.1cm) diameter * 400+/-the Umicore  semiconductor wafer of μ m thickness on.With Aetec UV baking oven under the setting of 200W/200W in 30fpm and N 2Under the atm wafer that applies is carried out disposable photocuring.The film of liquefiable gel state is not clamminess.Confirm that by DSC the underfill under the photocuring state stores 8 months can not cause further curing activity.It is 150 ℃ ± 2 ℃ that thermofixation begins temperature, at 166 ℃ of peak values that exotherm occurs.
Embodiment 1
Composition Weight part
1. dihydroxyphenyl propane-Epicholorohydrin-Resins, epoxy ((RSL-1462 of the residual amount of Epicholorohydrin＜1ppm); as available from Shell Resins; Inc. (CAS #25068-38-6)) 2. poly-(acryl) unsaturated polyurethanes origoester acrylate (CN120C60; as available from Sartomer) 3. epoxy acrylate oligomer (CN136; as available from Sartomer) 4. epoxy hardener 1 (Ancamine 2441; as available from Air Products ﹠ Chem) 5. epoxy hardener 2 (Dyhard  100s; as available from SKWCHem.) 6. trifunctional acrylate (SR351; as available from Sartomer) 7. light trigger Irgacure 184 Irgacure819 8. fused quartzs (F5BLDX, as available from Denka) amount to 19.03 18.50 1.14 1.33 7.00 2.00 1.00 50.00 100.00
Embodiment 2
Composition Weight part
1. dihydroxyphenyl propane-Epicholorohydrin-Resins, epoxy ((RSL-1462 of the residual amount of Epicholorohydrin＜1ppm), as available from Shell Resins, lnc. (CAS #25068-38-6)) 2. epoxy hardener 1 (Ancamine 2441, as available from Air Products ﹠ Chem) 3. epoxy hardener 2 (Dyhard  100s, as available from SKWCHem.) 36.28 2.18 2.54
4. trifunctional acrylate (SR351; As available from Sartomer) 5. light trigger Irgacure 184 Irgacure819 6. vitreous silicas (F5BLDX, as available from Denka) amount to 6.00 1.50 1.50 50.00 100.00
Embodiment 3
Composition Weight part
1. dihydroxyphenyl propane-Epicholorohydrin-Resins, epoxy ((RSL-1462 of the residual amount of Epicholorohydrin＜1ppm), as available from Shell Resins, lnc. (CAS #25068-38-6)) 2. the potentiality amine promoter (Ancamine 2441, as available from Air Products ﹠ Chem) 3. Dyhard RU 100 (Dyhard  100s, as available from SKWCHem.) 4. trifunctional acrylate (SR351, as available from Sartomer) 5. light trigger Irgacure 184 Irgacure819 6. fused quartzs (F5BLDX, as available from Denka) amount to 36.29 2.18 2.54 6.00 2.00 1.00 50.00 100.01
Embodiment 4
Composition Weight part
1. dihydroxyphenyl propane-epoxy alcohol-Resins, epoxy ((RSL-1462 of the residual amount of epoxy alcohol＜1ppm), as available from Shell Resins, lnc. (CAS #25068-38-6)) 2. acrylate modified epoxy oligomer (CN136, as available from Sartomer) 3. the potentiality amine promoter (Ancamine 2441, as available from Air Products ﹠ Chem) 4. Dyhard RU 100 (Dyhard  100s, as available from SKWCHem.) 5. trifunctional acrylate (SR351, as available from Sartomer) 6. light trigger Irgacure 184 Irgacure819 7. fused quartzs (F5BLDX, as available from Denka) amount to 18.15 19.50 2.18 2.54 6.00 1.50 1.50 50.00 101.37
Preparation embodiment 5-7 and be spin-coated to 4 inches (10.1cm) diameter * 400+/-the Umicore  semiconductor wafer of μ m thickness on.With Aetec UV baking oven, under the setting of 200W/200W in 30fpm and N 2Under the atm wafer that applies is carried out disposable photocuring.The photocuring film that is in hot liquefiable state among the embodiment 5-7 is not clamminess.
Embodiment 5
In the preparation of embodiment 5, composition 1-4 is mixed in the Hauschild of 40g  cup, and be heated to 60 ℃ and dissolve fully until light trigger.Then on Hauschild  mixing tank, 30 seconds of recombined sample under 3000rpm.Add remaining composition respectively, each time all mixes between adding.The silicon-dioxide that under mixing, adds incremental portion.
Composition Describe Weight part
1.CN136 2.SR203 3.Irgacure  184 4.Irgacure  819 5.RSL-1462 6.RSS-1407 7.Curezol  2PHZ-S 8. fillers amount to The diglycidyl ether biphenyl epoxy resin imidazoles potentiality curing agent vitreous silica of epoxy THFMA light trigger light trigger bisphenol-A epoxy amino modified, acroleic acid esterification 6.70 12.40 0.30 0.50 14.35 14.35 1.43 49.99 100.02
It is 167 ℃ that the thermofixation of embodiment 5 begins temperature.
Embodiment 5
The Tg-UV-B-stage 23.56℃
The Tg-thermofixation 106.25℃
CTE-is lower than Tg 40.37ppm/℃
CTE-is higher than Tg 107.7ppm/℃
@25 ℃ of storage modulus () 2,761Mpa
@175 ℃ of storage modulus () 0.025Gpa
Embodiment 6
Except that 50% fused quartz, in the Hauschild of 40g  cup, add each composition and under 3000rpm, mixed for 30 seconds and prepare embodiment 6.Add the remainder of fused quartz then and under 3000rpm, mixed for 30 seconds.In baking oven in 45 ℃ of following heated mixt 30 minutes with the dissolving light trigger.Under 3000rpm, solution mixture was mixed for 30 seconds once more.
Raw material Describe Weight part
SR203 Irgacure  184 Irgacure  819 RSS-1407 Curezol  2PHZ-S fillers amount to THFMA light trigger light trigger biphenyl epoxy resin imidazoles potentiality curing agent vitreous silica 19.10 0.30 0.50 28.66 1.43 50.01 100.00
With reference to Fig. 1, the DSC scanning curve of its expression embodiment 6.
The condition that is used for differential scanning calorimeter is:
Use is such as Perkin-Elmer, the differential scanning calorimeter of model DSC 7
The heat temperature raising condition is-20 ℃ to 300 ℃, 5 ℃/min of speed
All samples are tested under the photocuring state.The temperature of fusion that scanning illustrates solid epoxy resin is at 95.23 ℃, and solidifying the beginning temperature is 191.65 ℃, and the peak value temperature of reaction of thermofixation is 193.71 ℃.
Embodiment 7
Except 50% fused quartz, in the Hauschild of 40g  cup, add each composition and under 3000rpm, mixed for 30 seconds and prepare embodiment 7.Add the remainder of fused quartz then and under 3000rpm, mixed for 30 seconds.In baking oven in 45 ℃ of following heated mixt 30 minutes with the dissolving light trigger.Under 3000rpm, solution mixture was mixed for 30 seconds once more.
Raw material Describe Weight part
SR285 Irgacure 184 Irgacure 819 RSS-1407 Curezol fillers amount to % THFA light trigger light trigger biphenyl epoxy resin imidazoles fused quartz 19.05 0.30 0.50 28.71 1.44 50.01 100.00
Fig. 2 represents the DCS scanning curve of embodiment 7.
The condition that is used for differential scanning calorimeter is:
Use is such as Perkin-Elmer, the differential scanning calorimeter of model DSC 7
The condition of heat temperature raising is-20 ℃ to 300 ℃, 5 ℃/min of speed
All samples are tested under the photocuring state.The temperature of fusion that scanning illustrates solid epoxy is at 99.5 ℃, and solidifying the beginning temperature is 189.62 ℃, and the peak value temperature of reaction of thermofixation is 192.6 ℃.
Embodiment 8
Except that 50% fused quartz, in the Hauschild of 40g  cup, add each composition and under 3000rpm, mixed for 30 seconds and prepare embodiment 8.Add the remainder of fused quartz then and under 3000rpm, mixed for 30 seconds.In baking oven in 45 ℃ of heated mixt 30 minutes with the dissolving light trigger.Under 3000rpm, solution mixture was mixed for 30 seconds once more.
Raw material Describe Weight part
CN136 SR203 Irgacure  184 Irgacure  819 RSL-1462 RSS-1407 Curezol  2PHZ-S fillers amount to The diglycidyl ether biphenyl epoxy resin imidazoles FB5LDX (vitreous silica) of the epoxy THFMA light trigger light trigger bisphenol-A epoxy amine modification, acroleic acid esterification 6.70 12.40 0.30 0.50 8.61 20.09 1.43 49.99 100.02
Embodiment 8
Tg-light B-stage WAU 31.47℃
The Tg-thermofixation 116.44℃
CTE-is lower than Tg 40.56ppm/℃
CTE-is higher than Tg 120.5ppm/℃
Storage modulus (25 ℃) 3,313Mpa
Storage modulus (175 ℃) 0.0268Gpa
Comparative example A (77-5)
Composition Weight part
1. acrylate modified epoxy oligomer and three (acryloyl group) functional monomer's mixture (CN120C60; As available from Sartomer) 2. three (acryloyl group) functional monomer (SR351; As available from Sartomer) 3. dicyandiamide (Dyhard  100s; As available from SKWCHem.) 4. light trigger Irgacure 184 Irgacure819 5. vitreous silicas (F5BLDX, as available from Denka) amount to 43.00 4.00 1.33 2.00 1.00 50.00 100.00
The comparative example A behind photocuring, in ambient storage after 24 hours from the wafer higher slice, can determine that this is owing to cause by photocuring inductive excess shrinkage.
Comparative Examples B
1. dihydroxyphenyl propane-Epicholorohydrin-Resins, epoxy ((RSL-1462 of the residual amount of Epicholorohydrin＜1ppm); as available from Shell Resins; lnc. (CAS #25068-38-6)) 2. acrylate modified epoxy oligomer and three (acryl) functional monomer's mixture (CN120C60; as available from Sartomer) 3. potentiality amine promoter (Ancamine  2441; as available from Air Products ﹠ Chem) 4. Dyhard RU 100 (Dyhard  100s, as available from SKWCHem.) 18.15 20.5 1.09 1.27
5. light trigger Irgacure 184 Irgacure819 6. fused quartzs (F5BLDX, as available from Denka) amount to 1.50 1.00 50.00 100.00
Layering also takes place in ambient storage in Comparative Examples B after 24 hours.
The present invention has found wafer particular industry practicality of underfill and preparation method thereof, composition of the present invention also can be used for the microelectronic applications except that underfill, for example is used to cover top (glob top), directly chip connects and other is used for the application of thermoset composition.Although described some preferred embodiment, can do many modifications and change according to above-mentioned instruction.Therefore can recognize that under the prerequisite that does not break away from the claims scope, the present invention can implement by the mode outside specifically describing.

Claims (6)

1. stable integrated circuit (IC) wafer under the envrionment temperature, its front adheres to the underfill composition, and described underfill composition comprises the single-component composition of photocuring, and this single-component composition comprises following single-component mixture:
Liquid light-cured acrylate composition,
Polyfunctional epoxy resin,
At least a light trigger,
Non-conductive filler and
Non-melt thermal activation epoxy hardener, wherein said underfill down in 25 ℃ of modulus in flexurees that show 1000-5000MPa, and shows 15-50ppm/ ℃ thermal expansivity solid-state under the temperature below the described underfill composition second-order transition temperature.
2.100% solid is non-from molten single component liquid underfill, and it comprises:
The unsaturated photocuring composition of the simple function of 5%-30%,
The polyfunctional epoxy resin of 10%-45%,
At least a light trigger of 0.3%-3%,
The non-conductive filler of 40%-70%,
Described underfill in 20 ℃ of modulus in flexurees that show 1000-5000MPa, and shows 15-50ppm/ ℃ thermal expansivity under its temperature below second-order transition temperature under the thermoset state.
3. according to the underfill composition of claim 2, the wherein said branch that is light-cured into comprises and is selected from following at least a compound: vinylformic acid C 3-C 12Alkyl ester, C 1-C 4The vinylformic acid C that alkyl replaces 3-C 12Ester.
4. according to the underfill composition of claim 2, wherein said be light-cured into be divided into be selected from following at least a: tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, monomethyl vinylformic acid pentaerythritol ester, single vinylformic acid pentaerythritol ester, TriMethylolPropane(TMP) monomethacrylates, TriMethylolPropane(TMP) mono acrylic ester, ring-type hydroxyalkyl methylal acrylate and ketal acrylate.
5. according to the underfill of claim 2, wherein said photocuring composition is to be selected from following unsaturated oligomer: the bis-phenol polyether acrylate, the end capped oligopolymer of vinyl ether, the Resins, epoxy of acroleic acid esterification, the undersaturated poly alkyl ether of ethylenic, poly-(ring-type) ether acrylate and poly-ring-type (ether) acetal acrylate.
6. according to the underfill of claim 4, it further comprises monounsaturated acrylate monomer, and wherein said oligopolymer has 500-5,000 number-average molecular weight.
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CN104937027A (en) * 2013-01-23 2015-09-23 汉高知识产权控股有限责任公司 Underfill composition and packaging process using the same
CN104937027B (en) * 2013-01-23 2018-10-12 汉高知识产权控股有限责任公司 Underfill composition and the packaging technology for using the composition
TWI649371B (en) * 2013-01-23 2019-02-01 德商漢高智慧財產控股公司 Bottom filling composition and packaging method using the same
CN106995584A (en) * 2016-10-27 2017-08-01 武汉市三选科技有限公司 The preparation of capactive film constituent and capactive film and the capactive film and method for packing
WO2020258621A1 (en) * 2019-06-26 2020-12-30 苏州太湖电工新材料股份有限公司 High thermal conductivity modified epoxy resin and preparation method therefor

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EP1694769A1 (en) 2006-08-30
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JP2007515785A (en) 2007-06-14
WO2005056675A1 (en) 2005-06-23
KR20070000399A (en) 2007-01-02

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