CN101595553A - Be coated with the method for the semiconductor wafer of salient point - Google Patents

Be coated with the method for the semiconductor wafer of salient point Download PDF

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Publication number
CN101595553A
CN101595553A CNA2006800565443A CN200680056544A CN101595553A CN 101595553 A CN101595553 A CN 101595553A CN A2006800565443 A CNA2006800565443 A CN A2006800565443A CN 200680056544 A CN200680056544 A CN 200680056544A CN 101595553 A CN101595553 A CN 101595553A
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CN
China
Prior art keywords
coating
protective materials
wafer
solder bump
salient point
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Pending
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CNA2006800565443A
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Chinese (zh)
Inventor
D·怀亚特
G·达特
A·P·珀瑞兹
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of CN101595553A publication Critical patent/CN101595553A/en
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Abstract

Described active face coating front protecting (FSP) material or the wafer scale bottom filler (WLUF) of the wafer that salient point will be arranged, and solder bump has been polluted coat and/or the method for filler.In the method, protective materials is applied to the top of solder bump on the wafer active face, with the front of coating coating wafer, coating is hardened, and randomly protective materials is removed from solder bump then.

Description

Be coated with the method for the semiconductor wafer of salient point
Technical field
[0001] the present invention relates to be coated with the method for the semiconductor wafer of salient point, its can be used for flip-chip devices wafer-class encapsulation (wafer level packages, WLP) or the wafer scale bottom fill (wafer level underfill, front protecting WLUF).
Background technology
[0002] immediate development of semiconductor device packaging technique comprises step as much as possible at wafer scale.Making totally reduce process time for singulated dies (die) applies material before wafer cutting and simple grainization (singulation), and reducing production costs thus.Usually, have deposition solder bump thereon on the active surface of wafer, these solder bumps are used for the bonding welding pad of single die attachment to the substrate formed the electrical interconnection between the two subsequently.Occurred multiple method for packing, they need be applied to cream or liquid coating on the face that salient point is arranged of wafer.Two examples of these methods comprise the WLP that is used for memory device and are used for the WLUF of microprocessor and application-specific integrated circuit (ASIC) (ASIC) device.
[0003] memory package of producing with the WLP technology needs front protecting (frontside protection, FSP) coating further.This normally was applied to active (salient point is arranged) face of wafer and adhesive or the sealant that solidifies before cutting and simple grainization.Shown in its title, the FSP coating is for example cut in procedure of processing subsequently, simple grainization and be attached to the active face of protection wafer in the process of circuit board.Though not all memory device with WLP encapsulation all needs the FSP coating, thisly need become more general with the development of this technology.Performance requirement for example to the needs of thinner encapsulation, signal transmission faster and the storage capacity that increases, is just causing having the bigger tube core of small salient point height.These variations individually and in combination, cause the encapsulation stress that increases, use the FSP coating to alleviate this encapsulation stress usually.
[0004] flip-chip devices, for example microprocessor or ASIC of those flip-chip devices with big tube core particularly, usually use bottom filler or sealant to encapsulate around solder bump, these solder bumps are used for the active face of tube core is attached to substrate or circuit board.The early stage technology of this encapsulated type is utilized capillary type bottom filler, its be applied to liquid form the tube core that is attached to substrate around.Recently, carried out many work, the bottom filler can be applied on wafer scale, so that can eliminate capillary type bottom filling step consuming time.
[0005] have the coating of the semiconductor wafer of salient point can use various technology well known in the art to carry out, these technology comprise spin coating, stencilization and spraying.Spin coating method has advantage very fast, and can obtain coating layer thickness very uniformly by the suitable selection of coating.And, owing to do not have scraper plate or other physical mediums on salient point, to swipe, thus can apply coating with thickness less than solder bump height, and can use or not use solvent in the formulation for coating material.
[0006] still, when this method was used to have on the surface of salient point, coating not only was coated with the top of tube core but also coating solder bump.Then, must use thermocompression bonding to make die attachment, wherein in the tube core put procedure, form welding by applying heat and pressure.Heat and pressure are driven away coating from the top of solder bump, make can form clean welding between tube core and substrate.This method is very consuming time, and therefore very expensive, and the hot pressing welding equipment is very not general in industry.In addition, if there is filler on solder bump, then thermocompression bonding is insufficient effectively, so it can not use the formulation for coating material that contains the significant quantity filler.Alternatively, to the substrate, can remove the coating on the solder bump top,, obtain and effective interconnection in abutting connection with substrate so that solder bump can form clean welding in die attachment.When coating contained filler, this was very important, and reason is that the filler particles on the salient point is harmful especially to the formation of welding.
[0007] removal of unnecessary coating and/or filler particles can be carried out after paint solidification and/or sclerosis, and can comprise by physics or chemical method polish, polishing or chemical etching finish.Unfortunately, these treatment steps are consuming time, may damage solder bump or wafer, and may cause polluting.Therefore, what expect is such coating process---it can be coated with the thickness of wafer to regulation, this thickness is less than solder bump height, and there is not significant coating residual on the solder bump, it is unnecessary to make follow-up coating remove step, and can use " pick up and put (pick and place) " die attachment equipment (this equipment has high-throughput and uses always in industry) of standard.
[0008] stencilization is finished by the solvent based coating prescription that applies the thickness that is enough to cover solder bump usually.Coating is handled by the B-rank then, and this processing is the process of evaporating solvent and partly solidified and/or cured coating.The evaporation of solvent makes coating significantly shrink, so that the thickness of the coating that is produced is less than the height of solder bump.But, still have significant residual coating at the top of salient point, and if coating contain filler, on salient point, also may have filler particles.In order to put die bonding and substrate forms clean welding, must remove coating and/or filler with physics or chemical method by picking up.
[0009] alternatively, after cutting and simple grainization (cutting back tube core separates), use the thermocompression bonding can be with die attachment to substrate, hot like this and pressure forces residual coating to be removed from solder joint, makes it possible to form good bonding and electrical connection.As previously discussed, the hot pressing welding equipment is not very general at present in industry, and this method is an adherence method consuming time, and if on salient point, have filler particles, it is invalid.Therefore, expectation is such coating process---it can be applied to wafer with the thickness of regulation with coating, and this thickness is less than solder bump height, and do not produce coating residue or filler particles on the top of solder bump.This method can be used traditional picking up to put die attachment equipment to come assembled package, and (Packed) formulation for coating material of filling can be easier to use.
[0010] Fig. 1 and Fig. 2 have illustrated the conventional method of two kinds of wafer coating.
Summary of the invention
[0011] the present invention is the method for the active face of coating semiconductor chip, and the active face of wherein said semiconductor wafer has deposition solder bump thereon, and described method comprises:
(a) provide semiconductor wafer, its have the front and with described positive opposing backside surface, described front is active and has deposition solder bump thereon,
(b) protective materials (repellent material) is put on the top of described solder bump,
(c) be coated with the described front of described wafer with coating,
(d) the described coating that hardens, and
(e) randomly, described protective materials is removed from described solder bump.
[0012] this method makes it possible to the thickness of filling or unfilled (Packed or packless) coating will have the wafer coating of salient point extremely to stipulate, described thickness can be lower than solder bump height, and need not from salient point to remove residual coating and need not to use thermocompression bonding, to realize clean welding.
[0013] in another embodiment, the present invention is the semiconductor wafer according to method for preparing.
[0014] description of drawings
[0015] the present invention is understood more fully and can also carry out with reference to the accompanying drawings by reading following detailed description, wherein:
[0016] Fig. 1 (prior art) has illustrated the step and the corresponding wafer cross-section figure of conventional wafer spin coating method.
[0017] Fig. 2 (prior art) has illustrated the step and the corresponding wafer cross-section figure of traditional stencilization coating process.
[0018] Fig. 3 has illustrated an execution mode of the inventive method, and wherein initial coating thickness is lower than the top of solder bump.
[0019] Fig. 4 has illustrated an execution mode of the inventive method, and wherein initial coating thickness is higher than the top of solder bump.
Definition
[0020] as used herein, term " alkyl " is meant the saturated hydrocarbons group of 1 to 24 carbon atom side chain or unbranched, for example methyl (" Me "), ethyl (" Et "), n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, octyl group, decyl and similar group.The preferred alkyl of this paper contains 1 to 12 carbon atom.
[0021] be q.s as " effective dose " of term compound provided herein, product or composition meaning in order to compound, product or the composition that desired result is provided.As hereinafter pointed, the required accurate amount of different encapsulation will change to some extent, and it depends on employed particular compound, product or composition, its method of application or the like.Therefore, can not the total energy regulation accurately measure; But effective dose can only use normal experiment to determine by those of ordinary skills.
[0022] as used herein, term " suitable " be used in reference to be provided for as this paper as described in the compatible part of compound, product or composition of purpose.Adaptability to described purpose can only use normal experiment to determine by those of ordinary skills.
[0023] as used herein, " replacement " is generally used for having referred to remove hydrogen or other atoms and the carbon that replaces with other parts or suitable hetero-atom.And " replacement " intention is meant basic purposes and the replacement of purposes newly that does not change following compound of the present invention, product or composition.
[0024] as used herein, " B rank (B-staging) " (and modification) is used in reference to heat or the radiation processing to material, so that if material dissolves in solvent or disperses, solvent evaporates and material is partly solidified or not partly solidified then, if perhaps material be pure, do not contain solvent, then material is partially cured to the adhesion or the state of sclerosis more.If material is runny adhesive, the processing of B rank can provide extremely low mobile and insufficient curing, so that after adhesive is used for an object is connected to another object, can carry out other curing.The reduction of flowing can be handled ahead of time or solidifies or the two has concurrently and realizes by the part of solvent evaporates, resin or polymer.
Embodiment
[0025] is suitable for semiconductor wafer of the present invention and can has any diameter and any thickness, and can comprise for example silicon, GaAs, indium phosphide or any other semi-conducting material.Semiconductor wafer is prepared into has surface, top (just), and it is active, wherein is formed with electronic component and circuit; And have at the end (back of the body) surface, and it is with respect to active surface, and it is passive.
[0026] front of wafer is electric active and is raised with solder bump, is used to form the electrical connection between integrated circuit and the substrate after the solder bump.Solder bump can have any composition, size and arrange.
[0027] protective materials is by protecting or dry work to coating.Dry or protective action can be applied in wafer and/or the coating hardening process at coating and takes place.Protective materials can be that so any material---it will stick to solder bump, and, and therefore in applying coating or coating hardening process subsequently, coating is dried from the cover part of solder bump with the coating physics that will be applied in or chemically incompatible.Incompatibility or protection feature can obtain by chemistry or physical method.A kind of method that obtains incompatibility is to use surface energy to have material than big difference (5mN/m at least).
[0028] in addition, must not have polar interaction between protective materials and the coating.For example, if a kind of in the material is alkalescence and other are acid, will have polar attraction between them, it is invalid to cause drying.Even there are big surface energy difference in protective materials and coating, this also may be real.
[0029] physical incompatibility can obtain by the protective materials that sclerosis the time has a very smooth surface, so that coating can not physically adhere to protective materials.
[0030] fusing point of protective materials or softening point can be selected being suitable for the method for concrete coating, curing scheme and application by the technical staff, and normally in-40 ℃ to 300 ℃ scope.Protective materials can be solid or liquid in room temperature, as long as its fusing point is lower than the temperature of using in the Reflow Soldering method.In some cases, fusing point or softening point can be chosen to be the B-rank treatment temperature that is lower than coating, and solvent partly evaporates and/or resin partially hardened or curing before protective materials fusing and/or evaporation as long as it is high enough to allow.In other cases; what can expect is to have such protective materials; fusing that it has or softening point are between the B-rank treatment temperature and curing temperature of coating; so that protective materials keeps the location with the protection solder bump in the processing procedure of B-rank fully, maybe may volatilize and in the curing process of coating, melt.Alternatively, if coating is solidified by UV-, then protective materials can have low or high fusion temperature, and it depends on the downstream processes that will use.
[0031] in one embodiment, protective materials is a wax.The wax that is fit to can be natural or synthetic.The example of the wax that is fit to includes but not limited to paraffin, parowax, microwax, pertroleum wax admixture, amorphous wax, polyester wax, soya wax (soy wax), beeswax and their admixture thereof.
[0032] in another embodiment, protective materials is a low surface energy compounds, for example silane, polysiloxanes or polyfluoro compound.
[0033] in another embodiment, protective materials is dissolved in the solvent and solvent/protective materials formulation is applied to solder bump.In this embodiment, in room temperature or be lower than under the elevated temperature of solvent boiling point and use protective materials.In treatment step subsequently, solvent volatilizees by applying heat, stays protective materials and is coated with salient point.
[0034] protective materials is applied to the top of solder bump, and it is deposited on the controlled part of solder bump by the material with controlled variable and any method of not damaging solder bump or wafer is carried out.In one embodiment, salient point is pressed in the liner (pad) in the protective coating that is immersed in fusing.This liner can be that non-weaving or textile material, fabric, sponge or any protective materials that similarly will absorb are to be transferred to the material of salient point.In another embodiment, salient point is immersed in the pond of the protective materials that melts.In these two execution modes, wafer is advanced protective materials pond or liner, so that the top of salient point is capped the controlled part to they whole height.
[0035] in another embodiment, protective materials, is laminated on the salient point on carriers such as paper, polyester film (mylar), polyethylene, polypropylene, metal forming for example then as film coated, obtains the controlled thickness and the coating degree of depth.In another embodiment, protective materials is melted, and is imprinted on then on the top of salient point.In this embodiment, can use have with wafer on the masterplate or the mask of the pattern that is complementary of salient point pattern, on the salient point top, be deposited into controlled height to guarantee wax.
[0036] meeting of the part of the salient point that will be capped encapsulates the needs and the variation of creating conditions according to concrete, and can be in the scope of whole bump height 5% to 100%.Normally, when using the bottom filling, only the salient point of minimum is covered by protective materials.The salable solder bump as much as possible of filler bottom this makes, and still expose enough solder bump surfaces to form good the connection with substrate.On the contrary, in front protecting was used, the amount of the salient point that covers with protective materials can be minimum, and to realize the front protecting material of thick coating, if need extremely thin front protecting material layer in perhaps using, then the major part of salient point can be capped.
[0037] application of protective materials can be carried out under any temperature of selected concrete material being suitable for, and can need not too much experiment by those of ordinary skills and determine.For example, if protective materials is flowable in room temperature, it can be in room-temperature applications.If protective materials is hard in room temperature, it need be heated, so that it can be softened or melt, does not damage them so that be applied to solder bump.Protective materials also can be heated above room temperature but be lower than the temperature of material melts temperature, so that material is in soft state, can be by embrocating or light contact method is applied to salient point and does not damage salient point, and can make coating not need significantly cooling with sclerosis.This method allows well coating of control, can not drip or flows, and may run into for the protective materials of liquefaction fully and drip or flow.And wafer itself can be in room temperature, and perhaps it can be heated with auxiliary coating process, and is desired as creating conditions of selected concrete material group and use.
[0038] thickness of protective materials or the degree of depth also can be at several microns to 100 micrometer ranges with the requirement of satisfying concrete manufacture method by technical staff's selection on the salient point.Minimum if desired wax is residual, and thinner layer of protective material is normally desired.But thicker layer of protective material is desired under the situation about having, for example in case the protection zone so as not to solder bump expand and collapse.This may take place when coating is front wafer protection material.If protective materials is coated on the whole salient point as thick-layer, after the protective materials volatilization, may generate clear area around salient point, salient point may expand in the clear area and collapse.
[0039] degree of depth of layer of protective material or thickness can partly be controlled by the viscosity under the application of temperature.Have under application of temperature that full-bodied material will tend to produce thicker layer and have low viscous material at application of temperature and will tend to produce thin layer, less protective materials is employed.The technical staff can comprise that the compressibility of protective materials prescription, application of temperature, applying pressure or applicating medium changes the amount that protective materials is used by changing many variablees.
[0040] but depend on whether protective materials is in flow regime when using, can have additional treatment step, and wherein before coating was applied to wafer, protective materials was hardened.Under the situation that protective materials is used as liquid, may need the sclerosis of protective materials to prevent the top that coating is physically removed protective materials and polluted salient point.And the sclerosis of protective materials can prevent that it from dripping to the active face of wafer from the surface of salient point, and this may prevent that coating from suitably sealing the bottom of salient point.Normally, can finish sclerosis by the protective materials of cooling on wafer.
[0041] coating can be any material that can be applied to the die front side of salient point, includes but not limited to adhesive, sealant or front protecting material.The coating purpose in the semiconductor packages and the method for application are depended in the selection of the coating that is fit to.Coating contains certain type polymer or curable resin usually, and it can comprise thermoplastic resin, thermosetting resin, elastomer, thermoset rubber or these combination.Coating can contain or not contain solvent.Polymer or curable resin be the main component except that the filler of any existence normally.
[0042] other compositions that are generally used for coating composition can be selected to add by the professional; These other compositions include but not limited to curing agent, fusion agent, wetting agent, flow control agent, adhesion promoter and degasser.Curing agent is to cause, transmit or any material of acceleration paint solidification or the combination of material, and comprises promoter, catalyst, initator and curing agent.Coating composition also can contain filler, and in this case, the amount of filler is going up to 95% of total composition.
[0043] viscosity of coating and thixotropic index can be by the protective materials of professional's selection to be suitable for application process, to create conditions and to use, and usually 100 to 60, in the 000cP scope, it is measured under 25 ℃ and 5rpm with Brookfield CP 51 viscosimeters.For example, if coating applies by spin coating, dope viscosity will be quite low.If coating applies with silk screen printing, it has higher viscosity usually.In this case, coating may not dry solder bump after wafer coating at once, and reason is its high viscosity and can not flows.But, when wafer is exposed to be heated to the B-rank or when coating material solidified, the viscosity of coating can descend before it begins to solidify, make coating flow and solder bump dries.In this case, the fusing point of protective materials or softening point will be selected as being higher than the temperature that coating flows, so that it can remain on the appropriate location to realize drying of solder bump.
[0044] resin and the polymer that is used for coating can be solid, liquid or the combination of the two.The resin that is fit to comprises epoxy resin, acrylate or methacrylate, maleimide, bismaleimides, vinethene, polyester, poly-(butadiene), silication alkene, organic siliconresin, siloxanes, styrene resin and cyanate ester resin.In one embodiment, coating contains epoxy resin, bismaleimides and acrylate.
[0045] in one embodiment, solid aromatics bismaleimides (BMI) toner is included in the coating.The solid BMI resin that is fit to has structure:
[0046]
Figure A20068005654400121
Wherein X is an aromatic group; Exemplary aromatic group comprises:
Figure A20068005654400122
Figure A20068005654400131
Figure A20068005654400132
Wherein n is 1-3,
Figure A20068005654400133
And
【0057】
Figure A20068005654400134
[0058] bimaleimide resin with these X bridging groups be can buy and can obtain from for example Sartomer (USA) or HOS-Technic GmbH (Austria).
[0059] in another embodiment, the maleimide resin that is used for coating composition comprises having formula
Figure A20068005654400135
Those resins, wherein n is 1 to 3, and X 1Be aliphat or aromatic group.Exemplary X 1Entity comprises: poly-(butadiene), poly-(carbonic ester), poly-(urethanes), poly-(ether) gather (ester), simple hydrocarbons and contain for example simple hydrocarbons of carbonyl, carboxyl, acid amides, carbamate, urea or ether functional group.The resin of these types can be buied and can be from for example National Starch and Chemical Company and Dainippon Ink and Chemical, and Inc obtains.
[0060] in further execution mode, maleimide resin is selected from
Figure A20068005654400136
C wherein 36Expression has the linear of 36 carbon atoms or the chain (having or do not have annulus) of side chain is arranged;
【0061】
Figure A20068005654400137
[0062]
Figure A20068005654400141
And
【0063】
Figure A20068005654400142
[0064] acrylate of Shi Heing comprises having formula
[0065]
Figure A20068005654400143
Those resins, wherein, n from 1 to 6, R 1Be-H or-CH 3, and X 2Be aromatic group or fat group.Exemplary X 2Entity comprises poly-(butadiene), poly-(carbonic ester), poly-(urethanes), poly-(ether), poly-(ester), simple hydrocarbons and contain for example simple hydrocarbons of carbonyl, carboxyl, acid amides, carbamate, urea, ester or ether of functional group.Can comprise (methyl) butyl acrylate by the commercial material that obtains, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, positive ten diester of (methyl) acrylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid three decyl ester, (methyl) n-stearyla crylate, (methyl) cyclohexyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) isobornyl acrylate, two (methyl) acrylic acid 1, the 4-butanediol ester, two (methyl) acrylic acid 1,6-hexylene glycol ester, two (methyl) acrylic acid 1,9-nonanediol ester, (methyl) acrylic acid perfluoro capryl ethyl ester, two (methyl) acrylic acid 1,10-decanediol ester, nonyl phenol gathers propoxyl group ester (methyl) acrylate (nonylphenol polypropoxylate (meth) acrylate), and poly-amoxy ester tetrahydrofurfuryl acrylate, can be from Kyoeisha Chemical Co., LTD obtains; Polybutadiene two (methyl) urethane acrylate (CN302, NTX6513) and polybutadiene two (methyl) acrylate (CN301, NTX6039, PRO6270) can be from Sartomer Company, and Inc obtains; Merlon diacrylate urethanes (Art Resin UN9200A) can be from Negami Chemical Industries Co., and LTD obtains; Propylene acidifying aliphatic urethane oligomer (Ebecryl 230,264,265,270,284,4830,4833,4834,4835,4866,4881,4883,8402,8800-20R, 8803,8804), can be from RadcureSpecialities, Inc obtains; Polyester acrylic ester oligomer (Ebecryl 657,770,810,830,1657,1810,1830) can be from Radcure Specialities, and Inc obtains; And Epocryl (CN104,111,112,115,116,117,118,119,120,124,136), can be from Sartomer Company, Inc obtains.In one embodiment, acrylate poly-(butadiene) that be selected from isobornyl acrylate, isobornyl methacrylate, dodecyl acrylate, metering system dodecyl gallate, have poly-(butadiene) of acrylate functionalities and have methacrylate functionality.
[0066] vinyl ether resin of Shi Heing comprises having formula
Figure A20068005654400151
Those, wherein n is 1 to 6 and X 3Be aromatics or aliphatic group.Exemplary X 3Entity comprises poly-(butadiene), poly-(carbonic ester), poly-(urethanes), poly-(ether), poly-(ester), simple hydrocarbons and contain for example simple hydrocarbons of carbonyl, carboxyl, acid amides, carbamate, urea or ether functional group.The resin that can buy comprises cyclohexanedimethanol divinyl ether, dodecyl vinethene, cyclohexyl vinethene, 2-ethylhexyl vinethene, dipropylene glycol divinyl ether, hexylene glycol divinyl ether, octadecyl vinethene and butanediol divinyl ether, can be available from International Speciality Products (ISP); Vectomer 4010,4020,4030,4040,4051,4210,4220,4230,4060,5015, can be available from Sigma-Aldrich, and Inc.
[0067] poly-(butadiene) resin that is fit to comprises poly-(butadiene), BS and the hycar of poly-(butadiene), epoxidised poly-(butadiene), maleic acid poly-(butadiene), propylene acidifying.The material that can buy comprises homopolymers butadiene (Ricon130,131,134,142,150,152,153,154,156,157, P30D), can be available from Sartomer Company, Inc; Butadiene and cinnamic random copolymer (Ricon100,181,184) can be available from Sartomer Company Inc.; Poly-(butadiene) (Ricon 130MA8,130MA13,130MA20,131MA5,131MA10,131MA17,131MA20,156MA17) of maleation can be available from Sartomer Company, Inc.; Poly-(butadiene) (CN302, NTX6513, CN301, NTX6039, PRO6270, Ricacryl3100, Ricacryl 3500) of propylene acidifying can be available from Sartomer Inc; Epoxidised poly-(butadiene) (Polybd600,605) can be available from Sartomer Company.Inc and Epolead PB3600, can be available from Daicel Chemical IndusIndustries, Ltd; And acrylonitrile and butadiene copolymer (Hycar CTBN series, ATBN series, VTBN series and ETBN series), can be available from Hanse Chemical.
[0068] epoxy resin of Shi Heing comprises bis-phenol, naphthalene and aliphat type epoxy resin.The material that can buy comprises bisphenol-type epoxy resin (Epiclon 830LVP, 830CRP, 835LV, 850CRP), can be available from Dainippon Ink ﹠amp; Chemicals, Inc.; Naphthalene type epoxy resin (Epiclon HP4032) can be available from Dainippon Ink ﹠amp; Chemicals, Inc.; Aliphatic epoxy resin (Araldite CY179,184,192,175,179), can be available from Ciba SpecialtyChemicals, (Epoxy 1234,249,206), can be available from Union Carbide Corporation, and (EHPE-3150), can be available from Daicel Chemical Industries, Ltd..Other epoxy resin that is fit to comprises cycloaliphatic epoxy resin, bisphenol-A type epoxy resin, bisphenol-f type epoxy resin, epoxy-Novolak resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bicyclopentadiene-phenol type epoxy resin, reactive epoxy resin dilution and composition thereof.
[0069] the silication olefin resin of Shi Heing obtains by the selective silicon hydrogenation of siloxanes and divinyl material, and it has formula,
[0070]
Figure A20068005654400161
N wherein 1Be 2 or bigger, n 2Be 1 or bigger and n 1＞n 2These materials can be buied and can obtain from for example National Starch andChemical Company.
[0071] organic siliconresin of Shi Heing comprises reactive organic siliconresin, and it has formula
[0072]
Figure A20068005654400162
Wherein n is 0 or arbitrary integer, X 4And X 5Be hydrogen, methyl, amine, epoxy, carboxyl, hydroxyl, acrylate, methacrylate, sulfydryl, phenol or vinyl-functional, R 2And R 3Can be-H ,-CH 3, vinyl, phenyl or any hydrocarbon structure that has greater than two carbon.The material that can buy comprises KF8012, KF8002, KF8003, KF-1001, X-22-3710, KF6001, X-22-164C, KF2001, X-22-170DX, X-22-173DX, X-22-174DX X-22-176DX, KF-857, KF862, KF8001, X-22-3367 and X-22-3939A, can be available from Shin-Etsu SiloconeInternational Trading (Shanghai) Co., Ltd..
[0073] styrene resin of Shi Heing comprises having formula
Figure A20068005654400171
Those resins, wherein n is 1 or bigger, R 4Be-H or-CH 3And X 6It is aliphatic group.Exemplary X 3Entity comprises poly-(butadiene), poly-(carbonic ester), poly-(urethanes), poly-(ether), poly-(ester), simple hydrocarbons and contain for example simple hydrocarbons of carbonyl, carboxyl, acid amides, carbamate, urea or ether functional group.These resins can be buied and can obtain from for example NationalStarchand Chemical Company or Sigma-Aldrich Co..
[0074] cyanate ester resin of Shi Heing comprises having formula
Figure A20068005654400172
Those resins, wherein n is 1 or bigger and X 7It is hydrocarbyl group.Exemplary X 7Entity comprises the linear novolaks of bis-phenol, phenol or cresols, bicyclopentadiene, polybutadiene, Merlon, polyurethane, polyethers or polyester.The material that can buy comprises: AroCy L-10, AroCy XU366, AroCy XU371, AroCy XU378, XU71787.02L and XU 71787.07L, and can be available from Huntsman LLC; Primaset PT30, Primaset PT30 S75, Primaset PT60, Primaset PT60S, Primaset BADCY, Primaset DA230S, Primaset MethylCy and Primaset LECY can be available from Lonza Group Limited; 2-chavicol cyanate, 4-metoxyphenol cyanate, 2, two (the 4-cyanato-phenol)-1,1,1 of 2-, 3,3,3-HFC-236fa, bisphenol-A cyanate, diallyl bisphenol cyanate, 4-phenyl phenol cyanate, 1,1,1-three (4-cyanogen oxygen phenyl) ethane, 4-cumyl phenol cyanate, 1, two (4-cyanato--phenyl) ethane, 2,2 of 1-, 3,4,4,5,5,6,6,7,7-11 fluoro-ethohexadiols, two cyanates and 4,4 '-the bis-phenol cyanate, can be from Oakwood Products, Inc. obtains.
[0075] polymer that is fit to that is used for coating composition further comprises polyamide, phenoxy group, Polybenzoxazine, acrylate, cyanate, bismaleimides, polyether sulfone, polyimides benzoxazine, vinethene, silication alkene, polyolefin, polybenzoxazole (polybenzoxyzole), polyester, polystyrene, Merlon, polypropylene, poly-(vinyl chloride), polyisobutene, polyacrylonitrile, poly-(methyl methacrylate), poly-(vinyl acetate), poly-(2-vinylpyridine), suitable-1, the 4-polyisoprene, 3, the 4-polychlorobutadiene, ethylenic copolymer, poly-(oxirane), poly-(ethylene glycol), polyformaldehyde, metacetaldehyde, poly-(β-Bing Chunsuanneizhi), poly-(10-decylate), poly-(ethylene terephthalate), polycaprolactam, poly-(11-undecanoic amide), poly-(-phenylene-terephthalic acid (TPA) acid amides), poly-(tetramethylene--benzenesulfonamide), polyester gathers arylide, poly-(phenylate), poly-(diphenyl sulfide), polysulfones, polyimides, polyether-ether-ketone, Polyetherimide, the polyimides of fluoridizing, Polyimidesiloxane, poly--iso-indoles also-quinazoline diones, Polythioetherimide gathers-phenyl-quinoxaline, poly-quinoxalone (polyquuinixalone), acid imide-aryl ether phenyl quinoxaline copolymer, polyquinoxaline, polybenzimidazoles, polybenzoxazole, polynorbornene, poly-(arylene ether), polysilane, parylene, benzocyclobutene, hydroxyl (benzoxazole) copolymer, poly-(siliceous arlydene siloxanes) (poly (silarylene siloxanes)) and polybenzimidazoles.
[0076] other materials that are fit to that are included in the coating composition comprise rubber polymer, the for example block copolymer of monovinylarene and conjugated diene, for example styrene-butadiene, s-B-S (SBS), styrene-isoprene-phenylethene (SIS), styrene-ethylene-butylene-styrene (SEBS) and styrene-ethylene-propylene-styrene (SEPS).
[0077] other materials that are fit to that are included in the coating composition comprise ethane-acetic acid ethyenyl ester polymer, other vinyl acetate and copolymer, for example ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic; Polyolefin, for example polyethylene and polypropylene; Polyvinyl acetate and random copolymer thereof; Polyacrylate; Polyamide; Polyester; And polyvinyl alcohol and copolymer thereof.
[0078] thermoplastic elastomer of Shi Heing comprises butadiene-nitrile (CTBN)/epoxy adduct, the acrylate rubber of carboxy blocking, the butadiene rubber and the nitrile butadiene rubber (NBR) of vinyl-end-blocking.In one embodiment, the CTBN epoxy adduct is by the CTBN of about 20-80wt% and the diglycidyl ether bisphenol-A of about 20-80wt%: bisphenol-A epoxy (DGEBA) is formed.Multiple CTBN material can be available from Noveon Inc., and multiple bisphenol-A epoxy material can be available from Dainippon Ink and Chemicals, Inc. and Shell Chemicals.NBR rubber can be available from Zeon Corporation.
[0079] siloxanes of Shi Heing comprises elastomer polymer, and it comprises that at least one of stretching out on main chain and the main chain give the oxyalkylene segment side chain of transmissibility, and at least one can react the reactive part that forms new covalent bond.The example of the siloxanes that is fit to comprises elastomer polymer, and it is by being prepared as follows: 3-(three (trimethyl silyloxy) silicyl)-propyl methyl acid esters, n-butyl acrylate, glycidyl methacrylate, acrylonitrile and acrylic acid cyano group ethyl ester; 3-(three (trimethyl silyloxy) silicyl)-propyl methyl acid esters, n-butyl acrylate, glycidyl methacrylate and acrylonitrile; And 3-(three (trimethyl silyloxy) silicyl)-propyl methyl acid esters, n-butyl acrylate, glycidyl methacrylate and acrylic acid cyano group ethyl ester.
[0080] curing agent if desired, the polymer chemistry character and the applied treatment conditions of use are depended in the selection of curing agent.As curing agent, described composition can use aromatic amine, no cyclammonium, aliphatic amine, tertiary phosphine, triazine, slaine, aromatic hydroxy compound or these combination.The example of these catalyst comprises imidazoles, glyoxal ethyline for example, the addition compound product of 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanamines ethyl-glyoxal ethyline and imidazoles and trimellitic acid; Tertiary amine, N for example, N-dimethyl benzyl amine, N, accelerine, N, N-dimethyl methyl aniline, N, N-dimethyl-P-anisidine, right-halo-N, accelerine, 2-N-MEA ethanol, three-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N, N, N ', N '-tetramethyl butane diamine, N-methyl piperidine; Phenol, for example phenol, cresols, xylenols, resorcinol and phloroglucin; Organic metal salt, for example lead naphthenate, lead stearate, zinc naphthenate, zinc octoate (zinc octolate), oleic acid tin, dibutyl maleic acid tin, manganese naphthenate, cobalt naphthenate and ferric acetyl acetonade; And inorganic metal salt, for example stannic chloride, zinc chloride and aluminium chloride; Peroxide, for example benzoyl peroxide, lauroyl peroxide, peroxidating decoyl, acetyl peroxide, peroxidating right-chlorobenzoyl and two-tert-butyl group two cross phthalates; Acid anhydrides, for example carboxylic acid anhydrides, maleic anhydride, phthalic anhydride, lauric anhydride, PMA acid anhydride, trimellitic anhydride, hexahydrophthalic anhydride; Six hydrogen PMA acid anhydrides and six hydrogen trimellitic anhydrides, azo-compound, for example azo isobutyronitrile, 2,2 '-azo two propane, m, m '-azoxy styrene, hydrazone (hydrozone) and composition thereof.
[0081] in another embodiment, curing accelerator can be selected from imidazoles, imidazole salts, salt, quaternary phosphonium compound, boric acid (onium borate), the metallo-chelate, 1 of triphenyl phasphine, alkyl-replacement, 8-diazacyclo [5.4.0] 11-7-alkene or its mixture.
[0082] in another embodiment, curing agent can be radical initiator or cationic initiator, and this depends on selects radically curing resin or ion cured resin.If the use radical initiator, it exists with effective dose.Effective dose is normally by weight percent 0.1 of organic compound (not comprising any filler) to 10.Suitable radical initiator comprises peroxide, for example crosses butyl caprylate and dicumyl peroxide and azo-compound, for example 2, and 2 '-azo two (2-methyl-propionitrile) and 2,2 '-azo pair (2-methyl-butyronitrile).
[0083] if make cationic initiator, it exists with effective dose.Effective dose is normally by weight percent 0.1 of organic compound (not comprising any filler) to 10.The preferred cation curing agent comprises the imidazolium compounds of dicyandiamide, the linear novolaks (phenol novolak) of phenol, adipic dihydrazide, diallyl melamine, diaminomaleonitrile (diamino malconitrile), BF3-amine complex, amine salt and modification.
[0084] metallic compound also can be used as the curing accelerator of cyanate system, and includes but not limited to becket alkyl salt, cetylacetone metallic (chelate), metal octoates, metal acetate, metal halide, metal imidazol complex and metal amine complex compound.
[0085] other curing accelerators that can be included in the coating formulation comprise triphenylphosphine, the imidazoles of alkyl-replacement, imidazole salts and boric acid.
[0086] under some situation, the curing more than one type is used in expectation.For example, cation and free radical cause can be expectation, and in this case, radically curing and ion cured resin all can be used for composition.These compositions can contain effective amount of initiator for every type of resin.This composition for example can allow to be caused by the cation that uses the UV irradiation and start solidification process, and at subsequently treatment step, carries out free radical and causes and finish by applying heat.
[0087] if coating contains solvent, it needs drying and/or B-rank treatment step usually.Realize that time and temperature that these are required will change according to used solvent and coating composition, and can need not too much experiment by the technical staff and determine.Drying and/or B-rank are handled and be can be used as the step that the curing with coating separates and carry out (if coating will be cured), and perhaps it can be used as independent treatment step and carries out.
[0088], can still expect the processing of B-rank, or part is handled coating ahead of time if coating does not contain solvent.This can carry out before curing to realize that coating is hardened to the non-sticky state, so that additional processing can be carried out before coating is by full solidification.
[0089] coating can need or not need to solidify, and it depends on the purpose of coating and the composition of coating.If coating needs to solidify really, this curing can be used as independent treatment step and finishes, or combines and finish with another processing operational example such as Reflow Soldering (solder reflow).Curing can be carried out at wafer scale or die-level, and it depends on coating purpose, the composition of coating and the manufacture method of application.
[0090] if use curing schedule, curing temperature is usually 80 ℃ to 250 ℃ scope, and the time period that is solidificated in minute scope in several seconds to 120 realizes that this depends on selected concrete resin chemical property and curing agent.The time of every kind of coating composition and temperature-curable curve can be different, and different components can be designed to provide the cure profile that is suitable for concrete industrially preparing process.
[0091] depend on final application, one or more fillers can be included in the coating composition, and interpolation is used to improve rheological property and reduces stress usually.In order to be coated with the active face of wafer, filler is an electric insulation.The example of the insulating packing that is fit to comprises the ethene polymers of aluminium oxide, aluminium hydroxide, silica, vermiculite, mica, wollastonite, calcium carbonate, titanium dioxide, sand, glass, barium sulfate, zirconium, carbon black, organic filler and halogenation, as tetrafluoroethene, trifluoro-ethylene, 1,1-difluoroethylene, PVF, vinylidene chloride and vinyl chloride.Filler particles can have any suitable size from the nanometer size to several millimeters scopes.To any concrete final use, in the technological know-how that is chosen in those of ordinary skills of this size.Filler can with by weight all 0 to 95% of compositions amount exist.
[0092] in one embodiment, fusion agent is added into coating composition.Fusion agent is mainly removed metal oxide and is prevented reoxidizing of solder bump.The selection of fusion agent should be depended on the metallurgical property of applied resin chemical property and salient point.But some major requirement of fusion agent is the curing that it should not influence coating resin, should not have very much corrosivity, should be in reflux course degasification too much, should with resin compatible and/or merge residue should with resin compatible.
[0093] example of the fusion agent of Shi Heing comprises and contains one or more hydroxyls (OH), or carboxyl (COOH) or the two compound that has concurrently, organic carboxyl acid for example, acid anhydrides and alcohol, gum rosin for example, dodecanedioic acid (can be used as Corfree M2 buys from Aldrich), decanedioic acid, poly sebacic polyanhydride, maleic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene glycol, glycerine, tartaric acid, adipic acid, citric acid, malic acid, glutaric acid, glycerine, 3-[two (glycidol oxygen methyl) methoxyl group]-1, the 2-propylene glycol, D-ribose, the D cellobiose, cellulose, 3-cyclic ethylene-I, the I-dimethanol; The amine fusion agent, the fatty amine that for example has 1-10 carbon atom, for example trimethylamine, triethylamine, n-propylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, secondary amylamine, 2-ethyl butyl amine, positive heptyl amice, 2 ethyl hexylamine, n-octyl amine and t-octanylamine; Use has the epoxy resin of the crosslinking agent of Fusogenic properties.Other fusion agent comprises organic alcohol.Fusion agent also can be a compound, and it has (i) aromatic ring, (ii) at least one-OH ,-NHR (wherein R is hydrogen or low alkyl) or-SH base, the (iii) electrophilic on the aromatic ring or give electron substituent group and (iv) do not have imido grpup.Fusion agent exists with effective dose; Normally, the scope of effective dose is 1% to 30% by weight.
[0094] in another embodiment, coupling agent can be added into coating composition.Normally, coupling agent is a silane, for example epoxy type silane coupler, amine type silane coupler or sulfydryl type silane coupler.If use, coupling agent uses with effective dose.Typical effective dose is the amount that goes up by weight to 5%.
[0095] in further execution mode, surfactant can be added into coating composition.The surfactant that is fit to comprises organic crylic acid polymer, siloxanes, polyethylene glycol, polyoxyethylene/polyoxypropylene block copolymers, based on the polyoxyethylene/polyoxypropylene block copolymers of ethylenediamine, based on the polyoxyalkylene of polyalcohol, based on polyoxyalkylene and the fatty alcohol polyoxyalkylene alkyl ethers and their mixture of fatty alcohol.If use, surfactant uses with effective dose: common effective dose is for going up the amount to 5% by weight.
[0096] in another embodiment, wetting agent can be included in the coating composition.The chemical property of application need and used resin is depended in the selection of wetting agent.If use, wetting agent uses with effective dose: common effective dose is for going up the amount to 5% by weight.The example of the wetting agent that is fit to comprises Fluorad FC-4430 fluorine-containing surfactant, can be available from 3M; ClariantFluowet OTN, BYK W-990, Surfynol 104 surfactants, Crompton SilwetL-7280, Triton X100 can be available from Rhom and Haas; Has preferably propylene glycol, gamma-butyrolacton, castor oil, glycerine or other aliphatic acid, and silane greater than 240 Mw.
[0097] in further execution mode, flow control agent can be included in the coating composition.The chemical property of application need and used resin is depended in the selection of flow control agent.If use, flow control agent uses with effective dose: effective dose is for going up the amount to 5% by weight.The example of the flow control agent that is fit to comprises Cab-O-Sil TS720, can be available from Cabot; AerosilR202 or R972 can be available from Degussa; Pyrogenic silica; Pyrolysismethod aluminium oxide or pyrogenic metal oxide.
[0098] in another embodiment, adhesion promoter can be included in the coating composition.The chemical property of application need and used resin is depended in the selection of adhesion promoter.If use, adhesion promoter uses with effective dose: effective dose is for going up the amount to 5% by weight.The example of the adhesion promoter that is fit to comprises: silane coupler, and for example Z6040 epoxy silane or Z6020 amine silane can be available from Dow Corning; A186 silane, A187 silane, A174 silane or A1289 can be available from OSI Silquest; Organosilan SI264 can be available from Degussa; Johoku ChemicalCBT-1 carboxyl benzotriazole (Carbobenzotriazole) can be available from Johoku Chemical; The sense BTA; Thiazole; Titanate; And zirconates.
[0099] in further execution mode, degasser (defoamer) can be added into coating composition.The chemical property of application need and used resin is depended in the selection of degasser.If use, degasser uses with effective dose: effective dose is for going up the amount to 5% by weight.The example of the degasser that is fit to comprises Antifoam 1400, can be available from Dow Corning; DuPontModoflow and BYK A-510.
[0100] in some embodiments, these compositions can be prepared with tackifying resin, to improve bonding and to introduce adhesion; The example of tackifying resin comprises the natural resin that exists of naturally occurring resin and modification; Polyterpene resin; Phenol-modified terpene resin; Coumarone-indene resin; Aliphat and aromatic base crude oil hydrocarbon resin; Phthalic acid ester; Hydrogenate hydrocarbon, Foral and hydrogenated wood rosin glycerol ester.
[0101] in some embodiments, can comprise other compositions, for example diluent, for example liquid polybutene or polypropylene; Pertroleum wax, for example paraffin and microwax, polyethylene grease, the animal of hydrogenation, fish and vegetable oil, mineral oil and synthetic wax, cycloalkanes or paraffinic mineral oil.
[0102] in some embodiments, can comprise the monofunctional reactant diluent incrementally postponing the increase of viscosity, and can influence coating material solidified physical property sharply.The diluent that is fit to comprises that the glycidol ether of right-tert-butyl-phenyl glycidyl ether, allyl glycidyl ether, glycerin diglycidyl ether (glycerol diblycidyl ether), alkyl phenol is (as CardoliteNC513, buy from Cardolite Corporation) and butanediol diglycidyl ether (Butanediodiglycidylether) (buying from Aldrich as BDGE), although other diluents can utilize.
[0103] other additives, for example stabilizer, antioxidant, impact modifier and colouring agent, its type and amount are known in the art, also can be added in the coating formulation.
[0104] has 25 ℃ and can be used for this application to the suitable boiling point of 200 ℃ of scopes and the common solvent that is easy to dissolving resin.The example of available solvent comprises ketone, ester, alcohol, ether and other stable common solvent.The solvent that is fit to comprises gamma-butyrolacton, propylene glycol ethyl methyl acetic acid ester (PGMEA) and 4-methyl-2 pentanone.
[0105] if coating is curable, it can expose by heat, ultraviolet (UV) is shone or these combination is solidified.Condition of cure is regulated according to the coating formulation, and is that the professional determines easily.And, coating can be can the B-rank handle or can not handle on the B-rank, this depends on application need.
[0106] front of wafer or active face are by any method coating that is suitable for equably material being applied to the salient point wafer, and it includes but not limited to stencilization, spin coating, the coating of curtain formula, meniscus coating (meniscus coating) or spray distribution (jet dispensing).Coating temperature, pressure, speed and other coating condition are determined by the coating of the methods and applications that use, and can not needed too much experiment to determine by the professional and technical personnel.The thickness that coating is applied to wafer can be the height that is lower than, is equal to or higher than solder bump, and this depends on the coating of employed coating process, use and the needs of concrete semiconductor packages.Do not contain at coating under the situation of solvent, paint thickness is generally equal to the height of salient point expose portion.Contain at coating under the situation of solvent, wetting paint thickness is usually above the expose portion of solder bump, i.e. its covered protection material partially or completely.After solvent was removed, final coating thickness was generally equal to the expose portion of solder bump.
[0107] coating is hardened can carry out treatment step subsequently, comprises the applying of grinding back surface, back-protective material, cutting, simple grainization and die attachment.The method for curing of using depends on the coating of selection and the manufacture method of application.Under the situation of thermoplastic coating, applied wafer is cooled to the temperature that is lower than the thermoplastic resin fusing point.But under the situation of the coating of handling on the B-rank, sclerosis is by finishing with heat or UV irradiation B-rank processing coating.By being exposed to heat and/or UV irradiation, thermohardening lacquer is hardened to realize the curing of coating.The cured coating conditions needed can not needed too much experiment and is easy to determine by the professional and technical personnel.
[0108] randomly, in case coating is hardened, protective materials can be removed from the upper surface of salient point.Normally, by melting with heat and/or the protective materials that volatilizees is finished this removal.Can hot B-rank handle and/or during heat-setting coating, the removal of protective materials can perhaps be carried out with the heating steps that separates carrying out with the identical heating process that is used for cured coating when using.Depend on salient point metallurgical property, packaging structure, protective materials character and applied adhesion equipment, may there is no need before die attachment and solder bump backflow, to remove protective materials.In some cases, for example for thermocompression bonding, when die attachment when substrate and welding form, protective materials is physically shifted by heat, pressure or the combination of the two.Also can clean (carrying out etching) by plasma or in ultrasonic bath, clean and remove protective materials with surfactant or soap with Ionized gas.
[0109] after coating is hardened, wafer cutting and simple grain are turned to singulated dies with conventional method.Applied tube core can adhere to any conventional method, and it comprises that ten put method and thermocompression bonding.Picking up under the situation of the method for putting, can carry out on scolder on the pad (solder-on-pad) or the pad flux (flux-on-pad) welding and aim at and flux in reflux course, helping.
[0110] embodiment
[0111] embodiment 1-5 uses the coating formulation preparation that contains 13wt% (percentage by weight) bisphenol-A epoxy, 22wt% gamma-butyrolacton and 51wt% silica filler.The remaining 14wt% of coating formulation is the combination of common curing agent, adhesion promoter and other additives that use in adhesive formulation.The viscosity that this coating has is that 5100cP and thixotropic index are 1.5.Use spin coating and do not use the inventive method (promptly protective materials not being applied to the salient point top) to be coated with wafer, and embodiment 1 presents as a comparison.The inventive method is used for embodiment 2 to 4.In embodiment 2, use wafer, and all surfaces of salient point covers with protective materials with 240 microns salient points.In embodiment 3, salient point be 130 microns and with protective materials only be applied to the projection the top.In embodiment 4, salient point is 450 microns high and protective materials is applied to 200 microns at the top of height of projection.In embodiment 5, test the surface energy feature of three kinds of waxes, and compare the performance of drying relatively of their use the inventive method.
[0112] comparative example 1---unshielded material
[0113] 6 " silicon wafer is 450 micron thickness and is raised with 300 micron pitch and arranges and highly be 240 microns Sn/Ag/Cu salient point, is 200 microns with this wafer of solvent-borne type epoxy material spin coating to the degree of depth.Be spin-coated on N 2Carry out in room temperature under the atmosphere, the coating cycle regimen is with 350rpm spin coating 15 seconds, then with 800rpm spin coating 5 seconds.Handle at 135 ℃ with B-rank treatment step and to remove solvent in 20 minutes, cause forming sclerosis, non-stick coating.Then, check wafer and salient point with the SEM that has back scattered electron detector.Salient point is almost completely covered by coating, and it is shown as black in the SEM image, only has a spot of solder bump to present white on color.
[0114] embodiment 2---the inventive method (having protective materials)
[0115] 6 " silicon wafer is 450 micron thickness and is raised with 300 micron pitch and arranges and highly be 240 microns Sn/Ag/Cu salient point that this wafer is prepared according to the methods of the invention.Applied protective materials is a paraffin, sells with trade (brand) name Parowax, and it has 53 ℃ of fusing points.Protective materials is used with such method, and is long-pending by all surfaces that covers salient point on 135 ℃ of paper washers (paper pad) that have salient point surface to be pressed in to soak into paraffin with wafer.The degree of depth of pressing is controlled by pad (shims).Wax hardens lubricious to form on salient point by being cooled to room temperature.Then, with the SEM that has back scattered electron detector with 45 * to 150 * multiplication factor check wafer and salient point.Wax has covered solder bump and presented black in image.The face that just (salient point arranged) with solvent-borne type epoxy material spin coating wafer.This is spin-coated on N 2Carry out in room temperature under the atmosphere, the scheme in coating cycle is with 350rpm spin coating 150 seconds, then with 800rpm spin coating 5 seconds.Handle at 135 ℃ with B-rank treatment step and to remove solvent in 20 minutes, cause forming sclerosis, inviscid 190 micron thickness coatings (upwards measuring) from wafer surface.The B-rank are handled and are also melted wax and expose salient point, and minimum wax residue is arranged on the top of solder bump.Then, with the SEM that has back scattered electron detector with 45 * to 150 * multiplication factor check wafer and salient point.Salient point almost completely exposes (presenting white in the SEM image), has minimum wax or coating visible residue (it presents black in the SEM image).
[0116] embodiment 3---the inventive method (having protective materials)
[0117] 6 " silicon wafer is 450 micron thickness and is raised with 190 micron pitch and arranges and highly be 130 microns Sn63/37Pb salient point that this wafer is prepared according to the methods of the invention.Applied protective materials is a paraffin, sells with trade (brand) name Parowax, and it has 53 ℃ of fusing points.By being pressed on the paper washer that soaks into paraffin at 135 ℃ of salient point surfaces that have with wafer, top to the degree of depth that protective materials is applied to solder ball is 50 microns (measuring towards wafer downwards from the salient point top).The degree of depth of pressing is controlled by pad.Wax hardens lubricious to form on salient point by being cooled to room temperature.Then, with the SEM that has back scattered electron detector with 150 * multiplication factor check wafer and salient point.Wax has covered the top of solder bump and presented black in image, and solder bump presents white.Then, with the face that just (salient point arranged) of solvent-borne type epoxy material spin coating wafer.This is spin-coated on N 2Carry out in room temperature under the atmosphere, the scheme in coating cycle is with 800rpm spin coating 60 seconds, then with 1200rpm spin coating 30 seconds.Handle at 135 ℃ with B-rank treatment step and to remove solvent in 20 minutes, cause forming sclerosis, inviscid 90 micron thickness coatings (upwards measuring) from wafer surface.The B-rank are handled and are also melted wax and expose salient point, have minimum remaining wax on the top of soldered ball.Then, with the SEM that has back scattered electron detector with 150 * multiplication factor check wafer and salient point.Salient point almost completely exposes (presenting white in the SEM image), has minimum wax or coating visible residue (it presents black in the SEM image).
[0118] embodiment 4---the inventive method (having protective materials)
[0119] the single silicon die that salient point arranged is measured as 450 micron thickness and is raised with 800 micron pitch and arranges and highly be measured as 475 microns Sn/Ag/Cu salient point, and this tube core is prepared according to the methods of the invention.Applied protective materials is a paraffin, sells with trade (brand) name Parowax, and it has 53 ℃ of fusing points.By 100 ℃ with wafer the salient point surface hand is arranged on the paper washer that soaks into paraffin, protective materials is applied to the degree of depth is approximately 200 microns (from salient point tops downwards towards tube core measure).Wax hardens lubricious to form on salient point by being cooled to room temperature.Then, with the SEM that has back scattered electron detector with 35 * multiplication factor check tube core and salient point.Wax has covered the top of solder bump and presented black in image, and solder bump presents white.The face that just (salient point arranged) with solvent-borne type epoxy material spin coating tube core.This is spin-coated under the ambiance and carries out in room temperature, and the scheme in coating cycle is with 350rpm spin coating 150 seconds, then with 800rpm spin coating 5 seconds.Handle 30 minutes removal solvents with B-rank treatment step at 135 ℃, cause forming the non-adhesive layer of sclerosis.The B-rank are handled and are also melted wax and expose salient point, have minimum remaining wax on the top of solder bump.Then, with the SEM that has back scattered electron detector with 35 * multiplication factor check wafer and salient point.Salient point almost completely exposes (presenting white in the SEM image), has minimum wax or coating visible residue (it presents black in the SEM image).
[0120] embodiment 5---and surface energy characterizes
[0121] protective materials causes that validity that coating dries from salient point is subjected to the influence of dispersed (or nonpolar) and polar interaction between coating and the protective materials.These interactional effects can characterize to determine and quantize by all surfaces that carries out material.
[0122] the Kruss tensometer is used to measure contact angle, calculates so that carry out surface energy.Use the liquid of known surface energy that three kinds of protective materialss (paraffin Parowax, Clarus CSXMicroblend 35 and Accublend M300) are carried out the contact angle measurement.The liquid that uses is deionized water, hexane, glycerine, hexyl ester bismaleimides and methyl-ethyl ketone.Protective materials is poured in the thick flat-disk of 2cm.Set drop (Sessile drops) (＜2mm diameter) is placed on the surface of dish, and it is on the sample stage of Kruss tensometer.At room temperature carry out all measurements.CCD video camera module video camera (video camera module camera) is used for the image of drop on the indicator surface.Kruss ' droplet profile analysis software is used to detect baseline and uses the Tangent-1 method to measure contact angle.The contact angle of measuring is shown in table 1.
[0123] table 1---various liquid are measured at the lip-deep contact angle of different preventing protective material
Water Glycerine Hexane MEK SRM-1
Parowax 108.6 109.2 0 28.4 64.5
AccuBlend M-300 91.2 100.2 0 3.3 55.2
Microblend 101.6 94.2 0 3.12 54.9
[0124] similarly, test is used for the contact angle of solvent-borne type epoxy coating (materials A) on the following substrate of known surface character of embodiment 1-3: glass, silicon, bismaleimides-triazine (BT), nylon 66 and polyethylene.The set of materials A is dripped (uncured) and is placed on these substrates of Kruss tensometer sample stage in room temperature, and measures contact angle.Contact angle is shown in table 2.
[0125] table 2---the contact angle of materials A is measured on the substrate with known surface character
Glass Polished silicon BT Nylon Polyethylene
Materials A 43.9 35.7 50.9 42 71.2
[0126] the contact angle measurement is used for gauging surface character.Total surface can be broken down into nonpolar dispersion component and (use γ LWRepresent) and polar component (γ +Expression acidity and γ -Expression alkalescence).Use the liquid (L) of measurement and the contact angle θ between the solid (S), use related contact angle of following equation and solid/liquid surface nature:
1 2 γ L ( 1 + cos θ ) = ( γ L LW γ S LW ) 1 / 2 + ( γ L + γ S - ) 1 / 2 + ( γ S - γ L + ) 1 / 2
[0127] in this embodiment, the surface nature (γ of solid or liquid LW, γ +And γ -) be known, and the liquid/solid of known properties is measured contact angle θ with at least three kinds of mensurations.These feasible three kinds of surface nature (γ that can calculate unknown solid/liquid LW, γ +And γ -).These result of calculations are shown in table 3.
The surface energy feature of [0128] table 3---coating and protective materials
Amount to (mN/m) Polarity (mN/m) Disperse (mN/m) Acid (mN/m) Alkalescence (mN/m)
Materials A 47.5 21.3 26.2 4.7 24.1
Parowax 26.7 5.8 20.9 2.9 2.9
AccuBlend M-300 32 11.9 20.1 5.8 6.1
Microblend 37.2 17 20.2 14.6 4.9
The correlation of (or protection) performance and the surface energy properties of [0129] drying in order to test is used to study the effect of drying having on the simulation tube core of 240 microns salient points with three kinds of protective materialss.Salient point top on the tube core is with the coating of such method, by long-pending at 135 ℃ of all surfaces that have salient point surface to be pressed in to cover salient point on the paper washer that soaks into paraffin with wafer.Each that use three kinds of wax: Parowax, Accu-blend M-300 and Microblend prepares sample.The degree of depth of pressing is controlled by pad.After the room temperature cooling, the wax sclerosis forms lubricious on salient point.Next, materials A is spin-coated on each of these tube cores.The spin coating scheme comprises the coating cycle for rotating 15 seconds with 350rpm, and swing circle is with 800rpm rotation 5 seconds then.Handle 20 minutes removal solvents with B-rank treatment step at 135 ℃, cause forming the non-stick coating of sclerosis.
[0130] measurement of the coating degree of drying from the solder bump top is, based on 240 microns salient point diameter, by digital gray scale analysis (digital gray scale analysis) sample area of 22 salient points is calculated that the salient point area that exposes carries out.The salient point area average percent that exposes is as follows: Parowax 97.4%, Accublend M-30053% and Microblend＜1%.
[0131] trend of Xiang Guan dry performance and surface energy coupling (being low to moderate the highest most) has the maximum effect of drying than the wax of low-surface-energy.Paraffin (Parowax) is compared with materials A has maximum total surface energy difference.The difference of surface energy minimum is found in Microblend between wax and the materials A.
[0132] because the dispersed component of surface energy is all similar for all protective materialss of being tested, the difference of the performance of drying obviously is to cause owing to Microblend has more the relative characteristic interaction that has more alkalescence with materials A of acid feature.Comparatively speaking, Parowax and Accublend lack high acidic components in their surface energy, and therefore more effective to the relatively more alkaline materials A of protection.
[0133] can not depart from the many modifications and variations of spirit and scope of the invention, this is conspicuous to those of ordinary skills.Embodiment described herein only provides in the mode of example, and the present invention is only by claims and be endowed the four corner that right is equal to these claims and limit.

Claims (14)

1. the method for the active face of a coating semiconductor chip, the active face of described semiconductor wafer has deposition solder bump thereon, and described method comprises:
(a) provide semiconductor wafer, its have the front and with described positive opposing backside surface, described front is active and has deposition solder bump thereon,
(b) protective materials is applied to the top of described solder bump,
(c) be coated with the described front of described wafer with coating,
(d) the described coating that hardens, and
(e) randomly, described protective materials is removed from described solder bump.
2. method according to claim 1, wherein said protective materials is a wax.
3. method according to claim 1, wherein said protective materials be applied to whole solder bump height 5% and 100% between.
4. there is the difference of 5mN/m at least in method according to claim 1 between the surface energy of wherein said protective materials and the surface energy of described coating.
5. method according to claim 1, wherein said protective materials are that nonpolar and described coating is polarity.
6. method according to claim 1, wherein said protective materials have the fusing point between-40 ℃ to 300 ℃.
7. method according to claim 1, wherein said protective materials are to apply by the top of the salient point on the described wafer that salient point arranged is immersed in the pad that soaks into described protective materials.
8. method according to claim 1, wherein said protective materials are to apply in the pond by the protective materials that the top of the described solder bump on the described wafer is immersed liquid condition.
9. method according to claim 1, wherein said coating is coated with by spin coating.
10. method according to claim 1, wherein said coating is coated with by stencilization.
11. method according to claim 1, wherein said coating is selected from bismaleimides, epoxy, acrylate and combination thereof.
12. method according to claim 1 is handled but wherein said coating is the B rank.
13. method according to claim 1, wherein said coating is UV-curable.
14. a semiconductor wafer, its have the front and with described back side opposing backside surface, wherein said positive a) be active, b) be raised with solder bump and c) coating with the following method:
I) protective materials is applied to the top of described solder bump,
Ii) be coated with the described front of described wafer with coating,
The described coating that iii) hardens, and
Iv) randomly, melt and/or evaporate described protective materials.
CNA2006800565443A 2006-12-08 2006-12-08 Be coated with the method for the semiconductor wafer of salient point Pending CN101595553A (en)

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