WO2014024849A1 - 半導体装置の製造方法及びフリップチップ実装用接着剤 - Google Patents

半導体装置の製造方法及びフリップチップ実装用接着剤 Download PDF

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Publication number
WO2014024849A1
WO2014024849A1 PCT/JP2013/071167 JP2013071167W WO2014024849A1 WO 2014024849 A1 WO2014024849 A1 WO 2014024849A1 JP 2013071167 W JP2013071167 W JP 2013071167W WO 2014024849 A1 WO2014024849 A1 WO 2014024849A1
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Prior art keywords
adhesive
semiconductor device
less
reaction rate
manufacturing
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PCT/JP2013/071167
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English (en)
French (fr)
Inventor
さやか 脇岡
弘章 中川
善雄 西村
周治郎 定永
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to EP13827102.8A priority Critical patent/EP2881979A4/en
Priority to CN201380013477.7A priority patent/CN104170070B/zh
Priority to JP2013539033A priority patent/JP5564151B1/ja
Priority to CA2870001A priority patent/CA2870001A1/en
Priority to US14/391,781 priority patent/US9209155B2/en
Priority to KR1020147024961A priority patent/KR102020084B1/ko
Publication of WO2014024849A1 publication Critical patent/WO2014024849A1/ja
Priority to US14/933,145 priority patent/US9748195B2/en

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    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Definitions

  • the present invention relates to a method for manufacturing a semiconductor device capable of suppressing voids and realizing high reliability.
  • the present invention also relates to an adhesive for flip chip mounting used in the method for manufacturing the semiconductor device.
  • flip chip mounting using a semiconductor chip having a large number of protruding electrodes formed on the surface has attracted attention and is rapidly spreading as a method for mounting a semiconductor chip on a substrate.
  • a liquid sealing adhesive in the gap between the semiconductor chip and the substrate
  • flip chip mounting using underfill has problems such as high manufacturing cost, long time for underfill filling, and limitations in reducing the distance between electrodes and the distance between the semiconductor chip and the substrate. Yes.
  • the adhesive is thermally cured in a pressurized atmosphere, the void is shrunk, the semiconductor chip and the substrate are temporarily bonded, and then the temporary bonded body is heated in a pressurized atmosphere.
  • a method of reducing the void by the above has been proposed (for example, Patent Documents 1 to 3).
  • Patent Documents 1 to 3 A method of reducing the void by the above has been proposed.
  • Patent Documents 1 to 3 A method of reducing the void by the above.
  • air is easily trapped by the unevenness of the substrate, so that the void has not been sufficiently suppressed.
  • An object of this invention is to provide the manufacturing method of the semiconductor device which can implement
  • Another object of the present invention is to provide an adhesive for flip chip mounting used in the method for manufacturing a semiconductor device.
  • the present invention includes a step 1 of aligning a semiconductor chip on which a protruding electrode made of solder having a tip portion is formed on a substrate via an adhesive, and heating the semiconductor chip to a temperature equal to or higher than a solder melting point.
  • the adhesive has an activation energy ⁇ E determined by differential scanning calorimetry and Ozawa method of 100 kJ / mol or less, a reaction rate after 2 seconds at 260 ° C. of 20% or less, and a reaction rate after 4 seconds at 260 ° C. This is a method for manufacturing a semiconductor device having 40% or less. The present invention is described in detail below.
  • the inventor reliably heats the bumps of the semiconductor chip and the electrode portions of the substrate by heating the semiconductor chip to a temperature above the solder melting point. Then, a method of removing the voids by heating the adhesive in a pressurized atmosphere was studied. However, in such a method, even if heating is performed in a pressurized atmosphere, voids cannot be sufficiently removed if the curing of the adhesive has progressed too much when the protruding electrodes are joined.
  • a process 1 is performed in which a semiconductor chip on which a protruding electrode having a tip portion made of solder is formed is aligned on a substrate with an adhesive.
  • the alignment step 1 generally, using a mounting device such as a flip chip bonder, the position of the protruding electrode of the semiconductor chip, the electrode portion of the substrate, and the alignment mark provided on the semiconductor chip and the substrate Is automatically recognized in the X and Y directions and the rotation direction ( ⁇ direction).
  • the semiconductor chip examples include a semiconductor chip made of a semiconductor such as silicon or gallium arsenide and having a protruding electrode having a tip portion made of solder formed on the surface. It should be noted that the protruding electrode having the tip portion made of solder may be formed of a part of the protruding electrode, or the entire protruding electrode may be made of solder, as long as the tip portion is made of solder.
  • the method of supplying the adhesive is not particularly limited. For example, a method of sticking a film-like adhesive on a substrate or a semiconductor chip, filling a syringe with a paste-like adhesive, and attaching a precision nozzle to the syringe tip And a method of discharging onto a substrate using a dispenser device.
  • a film adhesive to the wafer by atmospheric pressure lamination, vacuum lamination, etc., or applying or printing a paste adhesive by spin coating or the like to form a coating film, blade dicing
  • a method of dividing into semiconductor chips by laser dicing or the like can be used.
  • Air may be entrained in normal pressure laminating, but the pressure is applied to the adhesive using a pressure oven similar to step 3 for removing voids (eg, PCO-083TA (manufactured by NTT Atvans Technology)).
  • the voids may be removed by heating under.
  • the adhesive has an activation energy ⁇ E determined by differential scanning calorimetry and the Ozawa method of 100 kJ / mol or less, a reaction rate after 2 seconds of 260 ° C. is 20% or less, and a reaction rate after 4 seconds of 260 ° C. is 40% or less. It is. Adhesives satisfying the activation energy ⁇ E determined by differential scanning calorimetry and the Ozawa method, the reaction rate after 260 ° C. for 2 seconds, and the reaction rate after 260 ° C. for 4 seconds have a relatively high curing rate (reaction rate).
  • the curing can be suppressed as much as possible even after the thermal history at the time of joining the protruding electrodes in the step 2 of temporarily bonding the adhesive, and the adhesive has little variation in curing. I can say that.
  • the protruding electrode is securely bonded in the step 2 of temporarily bonding the adhesive, and then the void 3 is removed, so that the highly accurate bonding of the protruding electrode and the suppression of the void are performed. And both.
  • the differential scanning calorimetry can be performed using a DSC apparatus (for example, DSC 6220 (manufactured by SII Nano Technology)).
  • the Ozawa method can be performed using reaction rate analysis software (for example, manufactured by SII Nanotechnology), and means the analysis method shown below.
  • reaction rate analysis software for example, manufactured by SII Nanotechnology
  • differential scanning calorimetry with different heating rates is performed three or more times for the sample, and the reciprocal of temperature T and the logarithm (log B) of heating rate B are plotted.
  • the activation energy ⁇ E is calculated based on the following formula (1).
  • the reaction rate when held at 260 ° C. for 2 seconds or 260 ° C. for 4 seconds is calculated based on the constant temperature deterioration formula of the following formula (2).
  • ⁇ represents a constant temperature deterioration time.
  • the activation energy ⁇ E is preferably 90 kJ / mol or less, and more preferably 80 kJ / mol or less.
  • the lower limit of the activation energy ⁇ E is not particularly limited, but a preferable lower limit is 50 kJ / mol.
  • the curing of the adhesive proceeds in the step 2 of temporarily bonding the adhesive.
  • the void cannot be sufficiently removed even if the step 3 of removing the void is performed, or the curing of the adhesive proceeds before the protruding electrode is melted and joined in the step 2 of temporarily bonding the adhesive.
  • the adhesive bites between the upper and lower electrodes, resulting in poor bonding.
  • the reaction rate after 2 seconds at 260 ° C. is preferably 15% or less, and more preferably 12% or less.
  • the reaction rate after 4 seconds at 260 ° C. is preferably 30% or less, and more preferably 25% or less.
  • the lower limit of the reaction rate after 2 seconds at 260 ° C. is not particularly limited, but the preferable lower limit is 3%.
  • the lower limit of the reaction rate after 4 seconds at 260 ° C. is not particularly limited, but the preferable lower limit is 10%.
  • the reaction rate after 2 seconds at 260 ° C. is less than 3%, or when the reaction rate after 4 seconds at 260 ° C. is less than 10%, it takes time to cure the adhesive, and the semiconductor device is shortened for a short time. May not be able to be manufactured.
  • the adhesive may be a film or a paste, but is particularly preferably a film adhesive.
  • the adhesive When the adhesive is in paste form, it is necessary to supply the adhesive for each semiconductor chip.
  • the adhesive when the adhesive is in the form of a film, the adhesive can be supplied all at once on the substrate or wafer, and a large number of semiconductor chips with adhesive can be produced in large quantities by dicing, greatly reducing the process. There is expected.
  • a film-like adhesive has a high melt viscosity, it is difficult to achieve both highly accurate projection electrode bonding and void suppression using a film-like adhesive.
  • an adhesive satisfying the above ranges of activation energy ⁇ E obtained by differential scanning calorimetry and the Ozawa method, the reaction rate after 2 seconds at 260 ° C., and the reaction rate after 4 seconds at 260 ° C. is used. Even if the adhesive is in the form of a film, it is possible to achieve both highly accurate projection electrode bonding and void suppression.
  • the adhesive preferably contains at least a thermosetting resin and a thermosetting agent, and preferably further contains a curing accelerator. Since the activation energy ⁇ E is unique to the reaction system, for example, by selecting the type of the thermosetting resin, thermosetting agent, curing accelerator, etc. to be combined, the activation energy ⁇ E of the adhesive is within the above range. Can be adjusted. On the other hand, since the reaction rate also depends on the concentration of the reaction system, for example, the reaction rate of the adhesive can be adjusted to the above range by adjusting the content of each component, particularly the addition amount of the curing accelerator. it can. Specifically, the reaction rate tends to increase as the amount of the curing accelerator added increases, and the reaction rate tends to decrease as the amount increases. However, since the appropriate addition amount of the curing accelerator varies depending on each reaction system, it is necessary to appropriately adjust the content of each component in order to adjust the reaction rate of the adhesive to the above range.
  • thermosetting resin is not specifically limited, For example, the compound hardened
  • the thermosetting resin include urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, acrylic resin, polyester resin, polyamide resin, polybenzimidazole resin, diallyl phthalate resin, xylene resin, alkyl -Benzene resin, epoxy acrylate resin, silicon resin, urethane resin and the like.
  • an epoxy resin is preferable from the viewpoint of easily adjusting the activation energy ⁇ E and the reaction rate of the adhesive to the above ranges and the physical properties of the cured product.
  • the epoxy resin preferably has a low functional group concentration, that is, a high epoxy equivalent. Since an epoxy resin having a high epoxy equivalent has a low reaction probability with a thermosetting agent and a low reactivity, it is easy to adjust the reaction rate of the adhesive within the above range by using such an epoxy resin.
  • the epoxy resin preferably has an epoxy equivalent of 200 or more, and more preferably 250 or more.
  • the epoxy resin is not particularly limited.
  • bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type and bisphenol S type
  • novolac type epoxy resins such as phenol novolak type and cresol novolak type
  • resorcinol type epoxy Resin aromatic epoxy resin such as trisphenolmethane triglycidyl ether, naphthalene type epoxy resin, fluorene type epoxy resin, cyclopentadiene type or dicyclopentadiene type epoxy resin
  • polyether modified epoxy resin NBR modified epoxy resin, CTBN modified epoxy
  • examples thereof include resins and hydrogenated products thereof.
  • a cyclopentadiene type or dicyclopentadiene type epoxy resin having a bulky structure is preferable. Since the cyclopentadiene type or dicyclopentadiene type epoxy resin has large steric hindrance and low reactivity, it is easy to adjust the reaction rate of the adhesive within the above range by using such an epoxy resin.
  • These epoxy resins may be used independently and may use 2 or more types together.
  • the epoxy resin may be an epoxy resin that is liquid at room temperature, or may be an epoxy resin that is solid at room temperature, or may be used in appropriate combination.
  • commercially available products include, for example, bisphenol A type epoxy resins such as EPICLON 840, 840-S, 850, 850-S, EXA-850CRP (above, manufactured by DIC), EPICLON 830, Bisphenol F type epoxy resins such as 830-S and EXA-830CRP (made by DIC), naphthalene type epoxy resins such as EPICLON HP-4032 and HP-4032D (made by DIC), EPICLON EXA-7015 (DIC) And hydrogenated bisphenol A type epoxy resin such as EX-252 (manufactured by Nagase ChemteX), and resorcinol type epoxy resin such as EX-201 (manufactured by Nagase ChemteX).
  • epoxy resins that are solid at room temperature
  • commercially available products include, for example, bisphenol A type epoxy resins such as EPICLON 860, 10550, 1055 (manufactured by DIC), and bisphenol S such as EPICLON EXA-1514 (manufactured by DIC).
  • Type epoxy resin naphthalene type epoxy resin such as EPICLON HP-4700, HP-4710, HP-4770 (manufactured by DIC), dicyclopentadiene type epoxy resin such as EPICLON HP-7200 series (made by DIC), EPICLON Examples thereof include cresol novolac type epoxy resins such as HP-5000 and EXA-9900 (manufactured by DIC).
  • thermosetting agent is not specifically limited, A conventionally well-known thermosetting agent can be suitably selected according to the said thermosetting resin.
  • the thermosetting agent may be, for example, an acid anhydride curing agent, a phenol curing agent, an amine curing agent, a latent curing agent such as dicyandiamide, or a cationic catalytic curing. Agents and the like. These thermosetting agents may be used independently and may use 2 or more types together. Among these, an acid anhydride curing agent is preferable because of excellent physical properties of the cured product.
  • acid anhydride curing agents commercially available products include, for example, YH-306, YH-307 (manufactured by Mitsubishi Chemical Corporation, liquid at room temperature (25 ° C.)), YH-309 (manufactured by Mitsubishi Chemical Corporation, acid Anhydride type curing agent, solid at normal temperature (25 ° C.)) and the like.
  • the content of the thermosetting agent is not particularly limited.
  • an epoxy resin is used as the thermosetting resin and a thermosetting agent that reacts with an epoxy group in an equal amount is used, the content of the thermosetting agent is in the adhesive.
  • the preferable lower limit with respect to the total amount of epoxy groups contained in is 60 equivalents, and the preferable upper limit is 110 equivalents. If the content is less than 60 equivalents, the adhesive may not be sufficiently cured. Even if the content exceeds 110 equivalents, it does not particularly contribute to the curability of the adhesive and may cause voids due to volatilization of excess thermosetting agent.
  • the more preferable lower limit of the content is 70 equivalents, and the more preferable upper limit is 100 equivalents.
  • the said hardening accelerator is not specifically limited, For example, an imidazole series hardening accelerator, a tertiary amine type hardening accelerator, etc. are mentioned. Of these, imidazole-based curing accelerators are preferred because the reaction rate of the adhesive is easily adjusted to the above range and the reaction system for adjusting the physical properties of the cured product is easily controlled.
  • the imidazole curing accelerator is not particularly limited, and examples thereof include Fujicure 7000 (manufactured by T & K TOKA, liquid at room temperature (25 ° C.)), 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, Imidazole-based curing accelerator with basicity protected with isocyanuric acid (trade name “2MA-OK”, manufactured by Shikoku Kasei Kogyo Co., Ltd., solid at room temperature (25 ° C.)), 2MZ, 2MZ-P, 2PZ, 2PZ-PW, 2P4MZ , C11Z-CNS, 2PZ-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, C11Z-A, 2E4MZ-A, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ, 2PHZ-PW
  • thermosetting agents content of the said hardening accelerator is not specifically limited
  • the preferable minimum with respect to 100 weight part of thermosetting agents is 0.5 weight part, and a preferable upper limit is 50 weight part.
  • a preferable upper limit is 50 weight part.
  • the content is less than 0.5 parts by weight, heating at a high temperature for a long time may be required for thermosetting the adhesive.
  • the content exceeds 50 parts by weight, the storage stability of the adhesive may be insufficient, or voids may be caused by volatilization of an excessive curing accelerator.
  • a more preferred lower limit of the content is 1 part by weight, and a more preferred upper limit is 30 parts by weight.
  • the adhesive when the adhesive is a film adhesive, it is preferable that the adhesive further contains a high molecular weight compound.
  • the high molecular weight compound is not particularly limited.
  • Known high molecular weight compounds such as benzene resin, epoxy acrylate resin, silicon resin, and urethane resin can be used.
  • a high molecular weight compound having an epoxy group is preferable.
  • the cured product of the adhesive By adding the high molecular weight compound having the epoxy group, the cured product of the adhesive exhibits excellent flexibility. That is, the cured product of the adhesive has excellent mechanical strength, heat resistance and moisture resistance derived from the epoxy resin as the thermosetting resin, and excellent flexibility derived from the high molecular weight compound having the epoxy group. Therefore, it has excellent thermal cycle resistance, solder reflow resistance, dimensional stability, etc., and exhibits high joint reliability and high conduction reliability.
  • the high molecular weight compound having an epoxy group is not particularly limited as long as it is a high molecular weight compound having an epoxy group at the terminal and / or side chain (pendant position).
  • an epoxy group-containing acrylic rubber, an epoxy group-containing butadiene rubber examples thereof include bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing urethane resin, and epoxy group-containing polyester resin.
  • an epoxy group-containing acrylic resin is preferable because a polymer compound containing a large amount of epoxy groups can be obtained and the cured product has better mechanical strength and heat resistance.
  • These high molecular weight compounds having an epoxy group may be used alone or in combination of two or more.
  • the preferred lower limit of the weight average molecular weight of the high molecular weight compound having the epoxy group is 10,000, and the preferred upper limit is 1,000,000. It is. If the weight average molecular weight is less than 10,000, the film forming property of the adhesive may be insufficient, or the flexibility of the cured product of the adhesive may not be sufficiently improved. When the weight average molecular weight exceeds 1,000,000, it becomes difficult to supply the adhesive to a certain thickness in the alignment step 1 or the melt viscosity of the adhesive becomes too high in the void removal step 3 to flow. In some cases, the voids may be lowered and the voids may not be removed sufficiently.
  • the high molecular weight compound having the epoxy group When the high molecular weight compound having the epoxy group is used as the high molecular weight compound, particularly when the epoxy group-containing acrylic resin is used, the high molecular weight compound having the epoxy group has a low functional group concentration, that is, a high epoxy equivalent. preferable. Since a high molecular weight compound having a high epoxy equivalent has low reactivity, it is easy to adjust the reaction rate of the adhesive within the above range by using such a high molecular weight compound.
  • the high molecular weight compound having an epoxy group preferably has an epoxy equivalent of 200 or more, and more preferably 250 or more.
  • content of the said high molecular weight compound in the said adhesive agent is not specifically limited, A preferable minimum is 3 weight% and a preferable upper limit is 30 weight%. If the content is less than 3% by weight, sufficient reliability against thermal strain may not be obtained. When content exceeds 30 weight%, the heat resistance of an adhesive agent may fall.
  • the adhesive preferably further contains an inorganic filler.
  • the content of the inorganic filler is preferably 60% by weight or less. When the content exceeds 60% by weight, the fluidity of the adhesive is lowered in the step 3 of removing the void, and the void may not be sufficiently removed.
  • the minimum of content of the said inorganic filler in the said adhesive agent is not specifically limited, From a viewpoint of ensuring the intensity
  • the inorganic filler is not particularly limited, and examples thereof include silica, alumina, aluminum nitride, boron nitride, silicon nitride, silicon carbide, magnesium oxide, and zinc oxide.
  • spherical silica is preferable because of excellent fluidity, and spherical silica surface-treated with a methylsilane coupling agent, a phenylsilane coupling agent, or the like is more preferable.
  • the average particle size of the inorganic filler is not particularly limited, but is preferably about 0.01 to 1 ⁇ m from the viewpoint of the transparency, fluidity, bonding reliability, and the like of the adhesive.
  • the above-mentioned adhesive is further provided with a diluent, a thixotropy-imparting agent, a solvent, an inorganic ion exchanger, an anti-bleeding agent, an imidazole silane coupling agent or other adhesiveness-imparting agent, an adhesion-imparting agent, rubber particles, etc.
  • You may contain other additives, such as a stress relaxation agent.
  • the method for producing the adhesive is not particularly limited.
  • a predetermined amount of a curing accelerator, a high molecular weight compound, an inorganic filler, and other additives may be blended in the thermosetting resin and the thermosetting agent as necessary.
  • the method of mixing is mentioned.
  • the mixing method is not particularly limited, and examples thereof include a method using a homodisper, a universal mixer, a Banbury mixer, a kneader, a bead mill, a homogenizer, and the like.
  • the adhesive has a preferable lower limit of 10 Pa ⁇ s and a preferable upper limit of 10 4 Pa ⁇ s in the minimum melt viscosity in the temperature range from room temperature to the solder melting point. If the minimum melt viscosity is less than 10 Pa ⁇ s, the fillet protrudes too much and may contaminate other devices. If the minimum melt viscosity exceeds 10 4 Pa ⁇ s, the void may not be sufficiently removed.
  • the minimum melt viscosity in the temperature range from room temperature to the solder melting point can be measured using a rheometer.
  • the semiconductor chip is then heated to a temperature equal to or higher than the solder melting point to melt-bond the protruding electrode of the semiconductor chip and the electrode portion of the substrate, and the adhesive Step 2 for temporary bonding is performed.
  • the step 2 of temporarily bonding the adhesive is also generally performed using a mounting apparatus such as a flip chip bonder.
  • the solder melting point is usually about 215 to 235 ° C.
  • the preferable lower limit of the temperature above the solder melting point is 240 ° C., and the preferable upper limit is 300 ° C. If the temperature is lower than 240 ° C., the protruding electrode may not be sufficiently melted and electrode bonding may not be formed. When temperature exceeds 300 degreeC, a volatile component may generate
  • a preferable lower limit is 0.1 seconds, and a preferable upper limit is 5 seconds. If the holding time is less than 0.1 seconds, the protruding electrode may not be sufficiently melted and electrode bonding may not be formed. When the holding time exceeds 5 seconds, a volatile component may be generated from the adhesive and the void may be increased. Further, the curing of the adhesive progresses, and the fluidity of the adhesive is lowered in the step 3 of removing the void, and the void may not be sufficiently removed.
  • step 2 of temporarily bonding the adhesive it is preferable to apply pressure to the semiconductor chip.
  • the pressure is not particularly limited as long as the electrode bond is formed, but is preferably 0.3 to 3 MPa.
  • step 3 is then performed in which the adhesive is heated in a pressurized atmosphere to remove voids.
  • a pressurized atmosphere means a pressure atmosphere higher than normal pressure (atmospheric pressure).
  • Examples of a method for heating the adhesive in a pressurized atmosphere include a method using a pressure oven (for example, PCO-083TA (manufactured by NTT Atvans Technology)).
  • the preferable lower limit of the pressure of the pressure oven is 0.2 MPa, and the preferable upper limit is 10 MPa. If the pressure is less than 0.2 MPa, the void may not be sufficiently removed. When the pressure exceeds 10 MPa, the adhesive itself is deformed, which may adversely affect the reliability of the semiconductor device.
  • the more preferable lower limit of the pressure is 0.3 MPa, and the more preferable upper limit is 1 MPa.
  • the preferable lower limit of the heating temperature when the adhesive is heated in a pressurized atmosphere is 60 ° C.
  • the preferable upper limit is 150 ° C.
  • the heating time at the time of heating the said adhesive agent in a pressurized atmosphere is 10 minutes or more.
  • step 4 for completely curing the adhesive may be performed.
  • a method for completely curing the adhesive for example, after performing step 3 for removing voids, a method for completely curing the adhesive by raising the temperature in a pressurized atmosphere as it is, heating the adhesive under normal pressure And a method of complete curing.
  • the heating temperature for completely curing the adhesive is not particularly limited, but is preferably about 150 to 200 ° C.
  • a chip mounting adhesive is also one aspect of the present invention.
  • the manufacturing method of the semiconductor device which can suppress a void and can implement
  • Examples 1 to 5 and Comparative Examples 1 to 5 (1) Manufacture of adhesives Each material described in Table 1 was added to MEK as a solvent according to the formulation composition described in Table 2, and an adhesive solution was manufactured by stirring and mixing using a homodisper. The obtained adhesive solution was applied on a release PET film using an applicator so that the thickness after drying was 30 ⁇ m, and dried to produce a film-like adhesive. Until use, the surface of the obtained adhesive layer was protected with a release PET film (protective film).
  • Step 1 for aligning and Step 2 for temporarily bonding an adhesive A semiconductor chip (WALTS MB50-0101JY, solder melting point 235 ° C., thickness 100 ⁇ m, manufactured by Waltz) on which a protruding electrode having a tip made of solder is formed, and a substrate (WALTS-KIT MB50-) having a Ni / Au electrode 0101JY, manufactured by Waltz).
  • the protective film on one side of the adhesive was peeled off, and pasted on the semiconductor chip using a vacuum laminator (ATM-812M, manufactured by Takatori) at a stage temperature of 80 ° C. and a vacuum of 80 Pa.
  • the semiconductor chip is aligned on the substrate via an adhesive (step 1) and contacted at 160 ° C. under a bonding stage temperature of 120 ° C.
  • the temperature was raised to 260 ° C. and a load was applied at 0.8 MPa for 2 seconds to melt-bond the protruding electrode of the semiconductor chip and the electrode portion of the substrate, and to temporarily bond the adhesive (step 2).
  • Step 3 for removing voids
  • the obtained temporary bonded body is put into a pressure oven (PCO-083TA, manufactured by NTT Advanced Technology), and the adhesive is heated under a pressure atmosphere under the following pressure and heating conditions to remove voids.
  • Step 3 The adhesive was completely cured to obtain a semiconductor device.
  • Electrode bonding state The semiconductor device was cross-section polished using a polishing machine, and the electrode bonding state of the electrode bonding portion was observed using a microscope. There is no biting of the adhesive between the upper and lower electrodes and the electrode bonding state is good, and there is a slight biting of the adhesive between the upper and lower electrodes, but the case where the upper and lower electrodes are bonded is ⁇ The case where there was an adhesive bite between the upper and lower electrodes and the upper and lower electrodes were not joined at all was marked as x.
  • the manufacturing method of the semiconductor device which can suppress a void and can implement

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Abstract

本発明は、ボイドを抑制して高い信頼性を実現することのできる半導体装置の製造方法を提供することを目的とする。また、本発明は、該半導体装置の製造方法に用いられるフリップチップ実装用接着剤を提供することを目的とする。本発明は、半田からなる先端部を有する突起電極が形成された半導体チップを、接着剤を介して基板上に位置合わせする工程１と、前記半導体チップを半田溶融点以上の温度に加熱して、前記半導体チップの突起電極と前記基板の電極部とを溶融接合させるとともに、前記接着剤を仮接着させる工程２と、前記接着剤を加圧雰囲気下で加熱してボイドを除去する工程３とを有し、前記接着剤は、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥが１００ｋＪ／ｍｏｌ以下、２６０℃２秒後における反応率が２０％以下、２６０℃４秒後における反応率が４０％以下である半導体装置の製造方法である。

Description

半導体装置の製造方法及びフリップチップ実装用接着剤
本発明は、ボイドを抑制して高い信頼性を実現することのできる半導体装置の製造方法に関する。また、本発明は、該半導体装置の製造方法に用いられるフリップチップ実装用接着剤に関する。
半導体装置の小型化及び高密度化に伴い、半導体チップを基板に実装する方法として、表面に多数の突起電極が形成された半導体チップを用いたフリップチップ実装が注目され、急速に広まってきている。
フリップチップ実装においては、接合部分の接続信頼性を確保するための方法として、半導体チップの突起電極と基板の電極部とを接合した後に、半導体チップと基板との隙間に液状封止接着剤（アンダーフィル）を注入し、硬化させることが一般的な方法として採られている。しかしながら、アンダーフィルを用いたフリップチップ実装は、製造コストが高い、アンダーフィル充填に時間がかかる、電極間の距離及び半導体チップと基板との距離を狭めるのに限界がある等の問題を抱えている。
そこで、近年、基板上にペースト状接着剤を塗布した後、半導体チップを搭載する方法、半導体ウエハ又は半導体チップ上にフィルム状又はペースト状接着剤を供給した後、接着剤付き半導体チップを基板上に搭載する方法等のいわゆる先塗布型のフリップチップ実装が提案されている。特に接着剤付き半導体チップを基板上に搭載する場合には、半導体ウエハ上に接着剤を一括供給し、ダイシングによって接着剤付き半導体チップを一括で多量に生産できることから、大幅なプロセス短縮が期待される。
しかしながら、先塗布型のフリップチップ実装では、半導体チップの突起電極と基板の電極部とを接触させる際に、半導体チップ又は基板と接着剤との間に空気を巻き込んでボイドを生じたり、半導体チップを基板上に搭載する際の熱圧着工程において、接着剤からの揮発成分によってボイドが生じたりすることがある。このようなボイドは、電極間の短絡を招いたり、接着剤中にクラックを発生させる要因となったりする。また、先塗布型のフリップチップ実装では、熱圧着工程において突起電極の接合と接着剤の熱硬化とを同時に行うことから、精度の高い突起電極の接合とボイドの抑制とを同時に行うことは困難である。
ボイドを抑制するために、接着剤の熱硬化を加圧雰囲気下で行うことによりボイドを収縮させる方法、半導体チップと基板とを仮接合した後、仮接合体を加圧雰囲気下で加熱することによりボイドを小さくする方法等が提案されている（例えば、特許文献１～３）。しかしながら、これらの方法であっても、特に接着剤付き半導体チップを基板上に搭載する場合には基板の凹凸により空気を巻き込みやすいことから、ボイドを充分に抑制するには至っていない。
特開２００４－３１１７０９号公報 特開２００９－００４４６２号公報 特許第４６４０３８０号公報
本発明は、ボイドを抑制して高い信頼性を実現することのできる半導体装置の製造方法を提供することを目的とする。また、本発明は、該半導体装置の製造方法に用いられるフリップチップ実装用接着剤を提供することを目的とする。
本発明は、半田からなる先端部を有する突起電極が形成された半導体チップを、接着剤を介して基板上に位置合わせする工程１と、前記半導体チップを半田溶融点以上の温度に加熱して、前記半導体チップの突起電極と前記基板の電極部とを溶融接合させるとともに、前記接着剤を仮接着させる工程２と、前記接着剤を加圧雰囲気下で加熱してボイドを除去する工程３とを有し、前記接着剤は、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥが１００ｋＪ／ｍｏｌ以下、２６０℃２秒後における反応率が２０％以下、２６０℃４秒後における反応率が４０％以下である半導体装置の製造方法である。
以下、本発明を詳述する。
本発明者は、精度の高い突起電極の接合とボイドの抑制とを両立するために、半導体チップを半田溶融点以上の温度に加熱して、半導体チップの突起電極と基板の電極部とを確実に接合させ、その後、接着剤を加圧雰囲気下で加熱してボイドを除去する方法を検討した。ただし、このような方法では、加圧雰囲気下で加熱したとしても、突起電極を接合する際に接着剤の硬化が進行しすぎている場合には、ボイドを充分に除去することはできない。
突起電極を接合する際の条件を調整することで接着剤の硬化を抑えることも考えられるが、突起電極を接合するためには半田溶融点以上の温度（２４０～２８０℃程度）で保持する必要があるため、条件の調整のみで接着剤の硬化を抑えるのには限界がある。
従って、接着剤として、突起電極を接合させる際の熱履歴を経ても硬化が極力抑えられる接着剤、即ち、硬化速度（反応速度）の比較的遅い接着剤を用いる必要がある。しかしながら、従来、接着剤の反応速度の評価方法は、客観性又は定量性に欠けるものであった。
一方、熱分析、反応速度解析等の分野では、試料の示差走査熱量測定（ＤＳＣ測定、Ｄｉｆｆｅｒｅｎｔｉａｌ　ｓｃａｎｎｉｎｇ　ｃａｌｏｒｉｍｅｔｒｙ）により得られたデータから活性化エネルギーΔＥ、及び、一定温度における所定の反応率に到達する時間を求める「小澤（沢）法」とよばれる解析方法が知られている。
本発明者は、半導体装置の製造方法に用いられる接着剤に対して、小澤法を適用することを検討した。その結果、本発明者は、示差走査熱量測定及び小澤法により、接着剤を一定温度で一定時間保持した場合の反応率をより客観的かつ定量的に評価できること、このような方法よって求めた活性化エネルギーΔＥ、２６０℃２秒後における反応率及び２６０℃４秒後における反応率が所定範囲を満たす接着剤を用いることで、精度の高い突起電極の接合とボイドの抑制とを両立できることを見出し、本発明を完成させるに至った。
本発明の半導体装置の製造方法では、まず、半田からなる先端部を有する突起電極が形成された半導体チップを、接着剤を介して基板上に位置合わせする工程１を行う。
上記位置合わせする工程１では、一般的に、フリップチップボンダ等の実装用装置を用いて、半導体チップの突起電極、基板の電極部、並びに、半導体チップ及び基板上に設けられたアライメントマークの位置をカメラに認識させることで、Ｘ、Ｙ方向及び回転方向（θ方向）に自動的に位置あわせを行う。
上記半導体チップとして、例えば、シリコン、ガリウム砒素等の半導体からなり、半田からなる先端部を有する突起電極が表面に形成された半導体チップが挙げられる。なお、半田からなる先端部を有する突起電極は、先端部が半田からなっていれば、突起電極の一部が半田からなっていても、突起電極全体が半田からなってもよい。
上記接着剤を供給する方法は特に限定されず、例えば、フィルム状の接着剤を基板上又は半導体チップ上に貼付する方法、ペースト状の接着剤をシリンジに充填し、シリンジ先端に精密ノズルを取り付けて、ディスペンサ装置を用いて基板上に吐出する方法等が挙げられる。
また、予めウエハにフィルム状の接着剤を常圧ラミネート、真空ラミネート等により貼付したり、ペースト状の接着剤をスピンコート法等により塗布又は印刷して塗膜を形成したりした後、ブレードダイシング、レーザーダイシング等により半導体チップに個片化する方法を用いることもできる。常圧ラミネートでは空気が巻き込まれる場合があるが、ボイドを除去する工程３と同様の加圧オーブン（例えば、ＰＣＯ－０８３ＴＡ（ＮＴＴアトバンステクノロジ社製））等を用いて接着剤を加圧雰囲気下で加熱して、ボイドを除去してもよい。
上記接着剤は、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥが１００ｋＪ／ｍｏｌ以下、２６０℃２秒後における反応率が２０％以下、２６０℃４秒後における反応率が４０％以下である。
示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥ、２６０℃２秒後における反応率及び２６０℃４秒後における反応率が上記範囲を満たす接着剤は、硬化速度（反応速度）が比較的遅く反応速度の温度依存性が小さいため、接着剤を仮接着させる工程２において突起電極を接合させる際の熱履歴を経ても硬化が極力抑えられ、かつ、硬化のバラつきが少ない接着剤であるといえる。このような接着剤を用いて、接着剤を仮接着させる工程２において突起電極を確実に接合させ、その後、ボイドを除去する工程３を行うことで、精度の高い突起電極の接合とボイドの抑制とを両立することができる。
なお、示差走査熱量測定は、ＤＳＣ装置（例えば、ＤＳＣ６２２０（エスアイアイ・ナノテクノロジー社製））を用いて行うことができる。また、小澤法は、反応速度解析ソフト（例えば、エスアイアイ・ナノテクノロジー社製）を用いて行うことができ、下記に示す解析方法を意味する。
まず、試料について昇温速度の異なる示差走査熱量測定を３回以上行い、温度Ｔの逆数と、昇温速度Ｂの対数（ｌｏｇＢ）とをプロットする。得られた直線の傾きから、下記式（１）にもとづいて、活性化エネルギーΔＥを算出する。次いで、活性化エネルギーΔＥから、下記式（２）の定温劣化式にもとづいて、２６０℃２秒又は２６０℃４秒保持した場合の反応率を算出する。（小澤丈夫，熱測定１，２（１９７４）、及び、Ｔ．Ｏｚａｗａ，Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ　３８，１８８１（１９６５）参照。）
Figure JPOXMLDOC01-appb-M000001
式（２）中、τは定温劣化時間を表す。
上記活性化エネルギーΔＥが１００ｋＪ／ｍｏｌを超えると、接着剤の反応速度の温度依存性が大きくなり、接着剤を仮接着させる工程２における温度のバラつき、面内の温度分布等の影響を受けやすくなる。その結果、ボイドの制御又は上下電極間への接着剤の噛み込みの制御が困難となる。上記活性化エネルギーΔＥは、９０ｋＪ／ｍｏｌ以下が好ましく、８０ｋＪ／ｍｏｌ以下がより好ましい。
上記活性化エネルギーΔＥの下限は特に限定されないが、好ましい下限は５０ｋＪ／ｍｏｌである。上記活性化エネルギーΔＥが５０ｋＪ／ｍｏｌ未満であると、比較的低温でも接着剤の硬化が進行しやすくなり、接着剤の貯蔵安定性が低下することがある。
上記２６０℃２秒後における反応率が２０％を超えるか、又は、上記２６０℃４秒後における反応率が４０％を超えると、接着剤を仮接着させる工程２で接着剤の硬化が進行してしまい、ボイドを除去する工程３を行ってもボイドを充分に除去できなかったり、接着剤を仮接着させる工程２において突起電極が溶融して接合する前に接着剤の硬化が進行してしまい、上下電極間に接着剤の噛み込みが生じて接合不良となったりする。上記２６０℃２秒後における反応率は１５％以下が好ましく、１２％以下がより好ましい。上記２６０℃４秒後における反応率は３０％以下が好ましく、２５％以下がより好ましい。
上記２６０℃２秒後における反応率の下限は特に限定されないが、好ましい下限は３％である。上記２６０℃４秒後における反応率の下限は特に限定されないが、好ましい下限は１０％である。上記２６０℃２秒後における反応率が３％未満であるか、又は、上記２６０℃４秒後における反応率が１０％未満であると、接着剤の硬化に時間がかかり、半導体装置を短時間で製造できないことがある。
上記接着剤は、フィルム状であってもペースト状であってもよいが、フィルム状接着剤であることが特に好ましい。
上記接着剤がペースト状である場合には、半導体チップ１個ごとに上記接着剤を供給する必要がある。これに対して、上記接着剤がフィルム状である場合には、基板又はウエハ上に上記接着剤を一括供給し、ダイシングによって接着剤付き半導体チップを一括で多量に生産できることから、大幅なプロセス短縮が期待される。
また、一般的にフィルム状の接着剤は溶融粘度が高いため、フィルム状の接着剤を用いて精度の高い突起電極の接合とボイドの抑制とを両立することは困難であるが、本発明の半導体装置の製造方法では、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥ、２６０℃２秒後における反応率及び２６０℃４秒後における反応率が上記範囲を満たす接着剤を用いることで、上記接着剤がフィルム状であっても精度の高い突起電極の接合とボイドの抑制とを両立することができる。
上記接着剤は、少なくとも熱硬化性樹脂と熱硬化剤とを含有することが好ましく、更に、硬化促進剤を含有することが好ましい。
活性化エネルギーΔＥは反応系に固有のものであることから、例えば、組み合わせる熱硬化性樹脂、熱硬化剤、硬化促進剤等の種類を選択することによって、接着剤の活性化エネルギーΔＥを上記範囲に調整することができる。
一方、反応速度は反応系の濃度にも依存することから、例えば、各成分の含有量、特に硬化促進剤の添加量を調整することによって、接着剤の反応率を上記範囲に調整することができる。具体的には、硬化促進剤の添加量が多いほど反応速度が上がり、少ないほど反応速度が落ちる傾向がある。ただし、適切な硬化促進剤の添加量は個々の反応系によって異なることから、接着剤の反応率を上記範囲に調整するために、各成分の含有量を適宜調整する必要がある。
上記熱硬化性樹脂は特に限定されず、例えば、付加重合、重縮合、重付加、付加縮合、開環重合等の反応により硬化する化合物が挙げられる。上記熱硬化性樹脂として、具体的には例えば、ユリア樹脂、メラミン樹脂、フェノール樹脂、レゾルシノール樹脂、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリベンズイミダゾール樹脂、ジアリルフタレート樹脂、キシレン樹脂、アルキル－ベンゼン樹脂、エポキシアクリレート樹脂、珪素樹脂、ウレタン樹脂等が挙げられる。なかでも、接着剤の活性化エネルギーΔＥ及び反応率を上記範囲に調整しやすい点、また、硬化物の物性等の点から、エポキシ樹脂が好ましい。
上記エポキシ樹脂は、官能基濃度が低い、即ち、エポキシ当量が高いことが好ましい。エポキシ当量が高いエポキシ樹脂は、熱硬化剤との反応確率が低く反応性が低いため、このようなエポキシ樹脂を用いることで、接着剤の反応率を上記範囲に調整しやすくなる。上記エポキシ樹脂は、エポキシ当量が２００以上であることがより好ましく、２５０以上であることが更に好ましい。
上記エポキシ樹脂は特に限定されず、例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型、ビスフェノールＳ型等のビスフェノール型エポキシ樹脂、フェノールノボラック型、クレゾールノボラック型等のノボラック型エポキシ樹脂、レゾルシノール型エポキシ樹脂、トリスフェノールメタントリグリシジルエーテル等の芳香族エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、シクロペンタジエン型又はジシクロペンタジエン型エポキシ樹脂、ポリエーテル変性エポキシ樹脂、ＮＢＲ変性エポキシ樹脂、ＣＴＢＮ変性エポキシ樹脂、及び、これらの水添化物等が挙げられる。なかでも、嵩高い構造を有するシクロペンタジエン型又はジシクロペンタジエン型エポキシ樹脂が好ましい。シクロペンタジエン型又はジシクロペンタジエン型エポキシ樹脂は、立体障害が大きく反応性が低いため、このようなエポキシ樹脂を用いることで、接着剤の反応率を上記範囲に調整しやすくなる。これらのエポキシ樹脂は、単独で用いてもよく、２種以上を併用してもよい。
上記エポキシ樹脂は、常温で液状のエポキシ樹脂であっても、常温で固体のエポキシ樹脂であってもよく、これらを適宜組み合わせて用いてもよい。
上記常温で液状のエポキシ樹脂のうち、市販品として、例えば、ＥＰＩＣＬＯＮ　８４０、８４０－Ｓ、８５０、８５０－Ｓ、ＥＸＡ－８５０ＣＲＰ（以上、ＤＩＣ社製）等のビスフェノールＡ型エポキシ樹脂、ＥＰＩＣＬＯＮ　８３０、８３０－Ｓ、ＥＸＡ－８３０ＣＲＰ（以上、ＤＩＣ社製）等のビスフェノールＦ型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＨＰ－４０３２、ＨＰ－４０３２Ｄ（以上、ＤＩＣ社製）等のナフタレン型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＥＸＡ－７０１５（ＤＩＣ社製）、ＥＸ－２５２（ナガセケムテックス社製）等の水添ビスフェノールＡ型エポキシ樹脂、ＥＸ－２０１（ナガセケムテックス社製）等のレゾルシノール型エポキシ樹脂等が挙げられる。
上記常温で固体のエポキシ樹脂のうち、市販品として、例えば、ＥＰＩＣＬＯＮ　８６０、１０５５０、１０５５（以上、ＤＩＣ社製）等のビスフェノールＡ型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＥＸＡ－１５１４（ＤＩＣ社製）等のビスフェノールＳ型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＨＰ－４７００、ＨＰ－４７１０、ＨＰ－４７７０（以上、ＤＩＣ社製）等のナフタレン型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＨＰ－７２００シリーズ（ＤＩＣ社製）等のジシクロペンタジエン型エポキシ樹脂、ＥＰＩＣＬＯＮ　ＨＰ－５０００、ＥＸＡ－９９００（以上、ＤＩＣ社製）等のクレゾールノボラック型エポキシ樹脂等が挙げられる。
上記熱硬化剤は特に限定されず、従来公知の熱硬化剤を上記熱硬化性樹脂に合わせて適宜選択することができる。上記熱硬化性樹脂としてエポキシ樹脂を用いる場合、上記熱硬化剤として、例えば、酸無水物系硬化剤、フェノール系硬化剤、アミン系硬化剤、ジシアンジアミド等の潜在性硬化剤、カチオン系触媒型硬化剤等が挙げられる。これらの熱硬化剤は、単独で用いてもよく、２種以上を併用してもよい。なかでも、硬化物の物性等に優れることから、酸無水物系硬化剤が好ましい。
上記酸無水物系硬化剤のうち、市販品として、例えば、ＹＨ－３０６、ＹＨ－３０７（以上、三菱化学社製、常温（２５℃）で液状）、ＹＨ－３０９（三菱化学社製、酸無水物系硬化剤、常温（２５℃）で固体）等が挙げられる。
上記熱硬化剤の含有量は特に限定されず、上記熱硬化性樹脂としてエポキシ樹脂を用い、エポキシ基と等量反応する熱硬化剤を用いる場合、上記熱硬化剤の含有量は、接着剤中に含まれるエポキシ基の総量に対する好ましい下限が６０当量、好ましい上限が１１０当量である。含有量が６０当量未満であると、接着剤を充分に硬化させることができないことがある。含有量が１１０当量を超えても、特に接着剤の硬化性には寄与せず、過剰な熱硬化剤が揮発することによってボイドの原因となることがある。含有量のより好ましい下限は７０当量、より好ましい上限は１００当量である。
上記硬化促進剤は特に限定されず、例えば、イミダゾール系硬化促進剤、３級アミン系硬化促進剤等が挙げられる。なかでも、接着剤の反応率を上記範囲に調整しやすい点、また、硬化物の物性等の調整をするための反応系の制御をしやすい点から、イミダゾール系硬化促進剤が好ましい。
上記イミダゾール系硬化促進剤は特に限定されず、例えば、フジキュアー７０００（Ｔ＆Ｋ　ＴＯＫＡ社製、常温（２５℃）で液状）、イミダゾールの１位をシアノエチル基で保護した１－シアノエチル－２－フェニルイミダゾール、イソシアヌル酸で塩基性を保護したイミダゾール系硬化促進剤（商品名「２ＭＡ－ＯＫ」、四国化成工業社製、常温（２５℃）で固体）、２ＭＺ、２ＭＺ－Ｐ、２ＰＺ、２ＰＺ－ＰＷ、２Ｐ４ＭＺ、Ｃ１１Ｚ－ＣＮＳ、２ＰＺ－ＣＮＳ、２ＰＺＣＮＳ－ＰＷ、２ＭＺ－Ａ、２ＭＺＡ－ＰＷ、Ｃ１１Ｚ－Ａ、２Ｅ４ＭＺ－Ａ、２ＭＡＯＫ－ＰＷ、２ＰＺ－ＯＫ、２ＭＺ－ＯＫ、２ＰＨＺ、２ＰＨＺ－ＰＷ、２Ｐ４ＭＨＺ、２Ｐ４ＭＨＺ－ＰＷ、２Ｅ４ＭＺ・ＢＩＳ、ＶＴ、ＶＴ－ＯＫ、ＭＡＶＴ、ＭＡＶＴ－ＯＫ（以上、四国化成工業社製）等が挙げられる。これらのイミダゾール系硬化促進剤は、単独で用いてもよく、２種以上を併用してもよい。
上記硬化促進剤の含有量は特に限定されないが、熱硬化剤１００重量部に対する好ましい下限が０．５重量部、好ましい上限が５０重量部である。含有量が０．５重量部未満であると、接着剤の熱硬化のために高温で長時間の加熱を必要とすることがある。含有量が５０重量部を超えると、接着剤の貯蔵安定性が不充分となったり、過剰な硬化促進剤が揮発することによってボイドの原因となったりすることがある。含有量のより好ましい下限は１重量部、より好ましい上限は３０重量部である。
上記接着剤は、フィルム状の接着剤である場合には、更に、高分子量化合物を含有することが好ましい。上記高分子量化合物を用いることで、接着剤に製膜性、可撓性等を付与するとともに、接着剤の硬化物に強靭性を持たせ、高い接合信頼性を確保することができる。
上記高分子量化合物は特に限定されず、例えば、ユリア樹脂、メラミン樹脂、フェノール樹脂、レゾルシノール樹脂、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリベンズイミダゾール樹脂、ジアリルフタレート樹脂、キシレン樹脂、アルキル－ベンゼン樹脂、エポキシアクリレート樹脂、珪素樹脂、ウレタン樹脂等の公知の高分子量化合物が挙げられる。なかでも、エポキシ基を有する高分子量化合物が好ましい。
上記エポキシ基を有する高分子量化合物を添加することで、接着剤の硬化物は、優れた可撓性を発現する。即ち、上記接着剤の硬化物は、上記熱硬化性樹脂としてのエポキシ樹脂に由来する優れた機械的強度、耐熱性及び耐湿性と、上記エポキシ基を有する高分子量化合物に由来する優れた可撓性とを兼備することとなるので、耐冷熱サイクル性、耐ハンダリフロー性、寸法安定性等に優れるものとなり、高い接合信頼性及び高い導通信頼性を発現することとなる。
上記エポキシ基を有する高分子量化合物は、末端及び／又は側鎖（ペンダント位）にエポキシ基を有する高分子量化合物であれば特に限定されず、例えば、エポキシ基含有アクリルゴム、エポキシ基含有ブタジエンゴム、ビスフェノール型高分子量エポキシ樹脂、エポキシ基含有フェノキシ樹脂、エポキシ基含有アクリル樹脂、エポキシ基含有ウレタン樹脂、エポキシ基含有ポリエステル樹脂等が挙げられる。なかでも、エポキシ基を多く含む高分子化合物を得ることができ、硬化物の機械的強度及び耐熱性がより優れたものとなることから、エポキシ基含有アクリル樹脂が好ましい。これらのエポキシ基を有する高分子量化合物は、単独で用いてもよく、２種以上を併用してもよい。
上記高分子量化合物として、上記エポキシ基を有する高分子量化合物、特に、エポキシ基含有アクリル樹脂を用いる場合、上記エポキシ基を有する高分子量化合物の重量平均分子量の好ましい下限は１万、好ましい上限は１００万である。重量平均分子量が１万未満であると、接着剤の製膜性が不充分となったり、接着剤の硬化物の可撓性が充分に向上しなかったりすることがある。重量平均分子量が１００万を超えると、位置合わせする工程１において接着剤を一定の厚みに供給することが困難となったり、ボイドを除去する工程３において接着剤の溶融粘度が高くなりすぎて流動性が低下し、ボイドを充分に除去できなかったりすることがある。
上記高分子量化合物として、上記エポキシ基を有する高分子量化合物、特に、エポキシ基含有アクリル樹脂を用いる場合、上記エポキシ基を有する高分子量化合物は、官能基濃度が低い、即ち、エポキシ当量が高いことが好ましい。エポキシ当量が高い高分子量化合物は、反応性が低いため、このような高分子量化合物を用いることで、接着剤の反応率を上記範囲に調整しやすくなる。上記エポキシ基を有する高分子量化合物は、エポキシ当量が２００以上であることがより好ましく、２５０以上であることが更に好ましい。
上記接着剤における上記高分子量化合物の含有量は特に限定されないが、好ましい下限は３重量％、好ましい上限は３０重量％である。含有量が３重量％未満であると、熱ひずみに対する充分な信頼性が得られないことがある。含有量が３０重量％を超えると、接着剤の耐熱性が低下することがある。
上記接着剤は、更に、無機フィラーを含有することが好ましい。上記無機フィラーの含有量は、６０重量％以下であることが好ましい。含有量が６０重量％を超えると、ボイドを除去する工程３において接着剤の流動性が低下し、ボイドを充分に除去できないことがある。
上記接着剤における上記無機フィラーの含有量の下限は特に限定されないが、接着剤の硬化物の強度及び接合信頼性を確保する観点から、好ましい下限は１０重量％である。
上記無機フィラーは特に限定されず、例えば、シリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化珪素、炭化珪素、酸化マグネシウム、酸化亜鉛等が挙げられる。なかでも、流動性に優れることから球状シリカが好ましく、メチルシランカップリング剤、フェニルシランカップリング剤等で表面処理された球状シリカがより好ましい。表面処理された球状シリカを用いることで、接着剤の増粘を抑えることができ、ボイドを除去する工程３において極めて効率的にボイドを除去することができる。
上記無機フィラーの平均粒子径は特に限定されないが、接着剤の透明性、流動性、接合信頼性等の観点から、０．０１～１μｍ程度が好ましい。
上記接着剤は、必要に応じて、更に、希釈剤、チキソトロピー付与剤、溶媒、無機イオン交換体、ブリード防止剤、イミダゾールシランカップリング剤等の接着性付与剤、密着性付与剤、ゴム粒子等の応力緩和剤等のその他の添加剤を含有してもよい。
上記接着剤を製造する方法は特に限定されず、例えば、熱硬化性樹脂及び熱硬化剤に、必要に応じて硬化促進剤、高分子量化合物、無機フィラー及びその他の添加剤を所定量配合して混合する方法が挙げられる。上記混合の方法は特に限定されず、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー、ビーズミル、ホモジナイザー等を使用する方法が挙げられる。
上記接着剤は、常温から半田溶融点までの温度域における最低溶融粘度の好ましい下限が１０Ｐａ・ｓ、好ましい上限が１０４Ｐａ・ｓである。最低溶融粘度が１０Ｐａ・ｓ未満であると、フィレットのはみ出しが多すぎて、他デバイスを汚染してしまうことがある。最低溶融粘度が１０４Ｐａ・ｓを超えると、ボイドを充分に除去できないことがある。
なお、常温から半田溶融点までの温度域における最低溶融粘度は、レオメーターを用いて測定することができる。
本発明の半導体装置の製造方法では、次いで、上記半導体チップを半田溶融点以上の温度に加熱して、上記半導体チップの突起電極と上記基板の電極部とを溶融接合させるとともに、上記接着剤を仮接着させる工程２を行う。
上記接着剤を仮接着させる工程２もまた、一般的に、フリップチップボンダ等の実装用装置を用いて行われる。
半田溶融点は、通常、２１５～２３５℃程度である。上記半田溶融点以上の温度の好ましい下限は２４０℃、好ましい上限は３００℃である。温度が２４０℃未満であると、突起電極が充分に溶融せず、電極接合が形成されないことがある。温度が３００℃を超えると、接着剤から揮発成分が発生してボイドを増加させることがある。また、接着剤の硬化が進行してしまい、ボイドを除去する工程３において接着剤の流動性が低下し、ボイドを充分に除去できないことがある。
上記接着剤付き半導体チップを半田溶融点以上の温度に加熱する時間（保持時間）は、好ましい下限が０．１秒、好ましい上限が５秒である。保持時間が０．１秒未満であると、突起電極が充分に溶融せず、電極接合が形成されないことがある。保持時間が５秒を超えると、接着剤から揮発成分が発生してボイドを増加させることがある。また、接着剤の硬化が進行してしまい、ボイドを除去する工程３において接着剤の流動性が低下し、ボイドを充分に除去できないことがある。
上記接着剤を仮接着させる工程２では、上記半導体チップに対して圧力をかけることが好ましい。圧力は、電極接合が形成される圧力であれば特に限定されないが、０．３～３ＭＰａが好ましい。
本発明の半導体装置の製造方法では、次いで、上記接着剤を加圧雰囲気下で加熱してボイドを除去する工程３を行う。
加圧雰囲気下とは、常圧（大気圧）より高い圧力雰囲気下を意味する。上記ボイドを除去する工程３では、ボイドを単に成長させないだけではなく、積極的に除去できるものと考えられることから、本発明の半導体装置の製造方法では、仮に接着剤に空気が巻き込まれた場合であってもボイドを除去することができる。
上記接着剤を加圧雰囲気下で加熱する方法として、例えば、加圧オーブン（例えば、ＰＣＯ－０８３ＴＡ（ＮＴＴアトバンステクノロジ社製））を用いる方法等が挙げられる。
上記加圧オーブンの圧力の好ましい下限は０．２ＭＰａ、好ましい上限は１０ＭＰａである。圧力が０．２ＭＰａ未満であると、ボイドを充分に除去できないことがある。圧力が１０ＭＰａを超えると、接着剤自体の変形が生じ、半導体装置の信頼性に悪影響を及ぼすことがある。圧力のより好ましい下限は０．３ＭＰａ、より好ましい上限は１ＭＰａである。
上記接着剤を加圧雰囲気下で加熱する際の加熱温度の好ましい下限は６０℃、好ましい上限は１５０℃である。ただし、上記接着剤を加圧雰囲気下で加熱する際には、一定温度及び一定圧力で保持してもよいし、昇温及び／又は昇圧しながら段階的に温度及び／又は圧力を変化させてもよい。
また、ボイドをより確実に除去するためには、上記接着剤を加圧雰囲気下で加熱する際の加熱時間は、１０分以上であることが好ましい。
本発明の半導体装置の製造方法では、ボイドを除去する工程３を行った後、接着剤を完全に硬化させる工程４を行ってもよい。
上記接着剤を完全に硬化させる方法として、例えば、ボイドを除去する工程３を行った後、加圧雰囲気下でそのまま温度を上げて接着剤を完全に硬化させる方法、常圧下で接着剤を加熱して完全に硬化させる方法等が挙げられる。上記接着剤を完全に硬化させる際の加熱温度は特に限定されないが、１５０～２００℃程度が好ましい。
本発明の半導体装置の製造方法では、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥ、２６０℃２秒後における反応率及び２６０℃４秒後における反応率が上記範囲を満たす接着剤を用いて、接着剤を仮接着させる工程２において突起電極を確実に接合させ、その後、ボイドを除去する工程３を行うことで、精度の高い突起電極の接合とボイドの抑制とを両立することができる。本発明の半導体装置の製造方法に用いられ、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥ、２６０℃２秒後における反応率及び２６０℃４秒後における反応率が上記範囲を満たすフリップチップ実装用接着剤もまた、本発明の１つである。
本発明によれば、ボイドを抑制して高い信頼性を実現することのできる半導体装置の製造方法を提供することができる。また、本発明によれば、該半導体装置の製造方法に用いられるフリップチップ実装用接着剤を提供することができる。
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
（実施例１～５及び比較例１～５）
（１）接着剤の製造
表１に記載の各材料を、表２記載の配合組成に従って溶媒としてのＭＥＫに添加し、ホモディスパーを用いて攪拌混合することにより接着剤溶液を製造した。得られた接着剤溶液を、アプリケーターを用いて離型ＰＥＴフィルム上に乾燥後の厚みが３０μｍとなるように塗工し、乾燥することにより、フィルム状の接着剤を製造した。使用時まで、得られた接着剤層の表面を離型ＰＥＴフィルム（保護フィルム）で保護した。
（２）示差走査熱量測定及び小澤法
得られた接着剤について、昇温速度１、２、５、１０℃／ｍｉｎの４条件で示差走査熱量測定を行い、温度Ｔの逆数と、昇温速度Ｂの対数（ｌｏｇＢ）とをプロットした。得られた直線の傾きから、上記式（１）にもとづいて、活性化エネルギーΔＥを算出した。次いで、活性化エネルギーΔＥから、上記式（２）の定温劣化式にもとづいて、２６０℃２秒又は２６０℃４秒保持した場合の反応率を算出した。
なお、ＤＳＣ６２２０（エスアイアイ・ナノテクノロジー社製）及び反応速度解析ソフト（エスアイアイ・ナノテクノロジー社製）を使用した。
（３）半導体装置の製造
（３－１）位置合わせする工程１、及び、接着剤を仮接着させる工程２
半田からなる先端部を有する突起電極が形成された半導体チップ（ＷＡＬＴＳ　ＭＢ５０－０１０１ＪＹ、半田溶融点２３５℃、厚さ１００μｍ、ウォルツ社製）と、Ｎｉ／Ａｕ電極を有する基板（ＷＡＬＴＳ－ＫＩＴ　ＭＢ５０－０１０１ＪＹ、ウォルツ社製）とを用意した。接着剤の片面の保護フィルムを剥がし、真空ラミネーター（ＡＴＭ－８１２Ｍ、タカトリ社製）を用いて、ステージ温度８０℃、真空度８０Ｐａで半導体チップ上に貼付した。
フリップチップボンダ（ＦＣ－３０００Ｓ、東レエンジニアリング社製）を用いて、半導体チップを、接着剤を介して基板上に位置合わせし（工程１）、ボンディングステージ温度１２０℃の条件下で、１６０℃接触で２６０℃まで昇温し、０．８ＭＰａで２秒間荷重をかけ、半導体チップの突起電極と基板の電極部とを溶融接合させるとともに、接着剤を仮接着させた（工程２）。
（３－２）ボイドを除去する工程３
得られた仮接着体を、加圧オーブン（ＰＣＯ－０８３ＴＡ、ＮＴＴアドバンステクノロジ社製）に投入し、以下の加圧、加熱条件により接着剤を加圧雰囲気下で加熱してボイドを除去するとともに（工程３）、接着剤を完全に硬化させて、半導体装置を得た。
＜加圧、加熱条件＞
ＳＴＥＰ１：２５℃から８０℃まで１０分で一定昇温、０．５ＭＰａ
ＳＴＥＰ２：８０℃で６０分保持、０．５ＭＰａ
ＳＴＥＰ３：８０℃から１７０℃まで一定昇温、０．５ＭＰａ
ＳＴＥＰ４：１７０℃で１０分保持、０．５ＭＰａ
ＳＴＥＰ５：１７０℃から２５℃まで３０分で降温、０．５ＭＰａ
ＳＴＥＰ６：室温まで６０分で一定降温、０．５ＭＰａ
＜評価＞
実施例及び比較例で得られた半導体装置について、以下の評価を行った。結果を表２に示した。
（１）ボイドの有無
超音波探査映像装置（Ｃ－ＳＡＭ　Ｄ９５００、日本バーンズ社製）を用いて、ボイドを除去する工程３の前後の半導体装置のボイドを観察し、ボイドの有無を評価した。半導体チップ面積に対するボイド発生部分の面積が１％未満であった場合を○、１％以上５％未満であった場合を△、５％以上であった場合を×とした。
（２）電極接合状態
研磨機を用いて半導体装置を断面研磨し、マイクロスコープを用いて電極接合部の電極接合状態を観察した。上下電極間に接着剤の噛み込みが無く、電極接合状態が良好であった場合を○、上下電極間にわずかに接着剤の噛み込みがあるものの、上下電極が接合していた場合を△、上下電極間に接着剤の噛み込みがあり、上下電極が全く接合していなかった場合を×とした。
（３）信頼性評価（ＴＣＴ試験）
半導体装置について－５５℃～１２５℃（３０分／サイクル）の冷熱サイクル試験を行い、１００サイクルごとに導通抵抗値を測定した。導通抵抗値が、冷熱サイクル試験前の初期導通抵抗値に比べ５％以上変化した時点をＮＧ判定とし、５％未満の導通抵抗値が保たれていたサイクル数を評価した。サイクル数が１０００サイクル以上であった場合を○、３００サイクル以上１０００サイクル未満であった場合を△、３００サイクル未満であった場合を×とした。
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
本発明によれば、ボイドを抑制して高い信頼性を実現することのできる半導体装置の製造方法を提供することができる。また、本発明によれば、該半導体装置の製造方法に用いられるフリップチップ実装用接着剤を提供することができる。

Claims (6)

  1. 半田からなる先端部を有する突起電極が形成された半導体チップを、接着剤を介して基板上に位置合わせする工程１と、
    前記半導体チップを半田溶融点以上の温度に加熱して、前記半導体チップの突起電極と前記基板の電極部とを溶融接合させるとともに、前記接着剤を仮接着させる工程２と、
    前記接着剤を加圧雰囲気下で加熱してボイドを除去する工程３とを有し、
    前記接着剤は、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥが１００ｋＪ／ｍｏｌ以下、２６０℃２秒後における反応率が２０％以下、２６０℃４秒後における反応率が４０％以下である
    ことを特徴とする半導体装置の製造方法。
  2. 接着剤は、少なくとも熱硬化性樹脂と熱硬化剤とを含有し、前記熱硬化性樹脂は、エポキシ樹脂であることを特徴とする請求項１記載の半導体装置の製造方法。
  3. 接着剤は、更に、硬化促進剤を含有することを特徴とする請求項１又は２記載の半導体装置の製造方法。
  4. 接着剤は、更に、無機フィラーを含有し、前記無機フィラーの含有量が６０重量％以下であることを特徴とする請求項１、２又は３記載の半導体装置の製造方法。
  5. 接着剤は、フィルム状接着剤であることを特徴とする請求項１、２、３又は４記載の半導体装置の製造方法。
  6. 請求項１、２、３、４又は５記載の半導体装置の製造方法に用いられ、示差走査熱量測定及び小澤法によって求めた活性化エネルギーΔＥが１００ｋＪ／ｍｏｌ以下、２６０℃２秒後における反応率が２０％以下、２６０℃４秒後における反応率が４０％以下であることを特徴とするフリップチップ実装用接着剤。
PCT/JP2013/071167 2012-08-06 2013-08-05 半導体装置の製造方法及びフリップチップ実装用接着剤 WO2014024849A1 (ja)

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