WO2017073630A1 - 半導体用接着剤、半導体装置及びそれを製造する方法 - Google Patents
半導体用接着剤、半導体装置及びそれを製造する方法 Download PDFInfo
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Definitions
- the present invention relates to a semiconductor adhesive, a semiconductor device, and a method for manufacturing the same.
- FC connection method FC connection method in which conductive protrusions called bumps are formed on a semiconductor chip or a substrate to directly connect the semiconductor chip and the substrate is becoming widespread.
- Flip chip connection methods include metal bonding using solder, tin, gold, silver, copper, etc., metal bonding by applying ultrasonic vibration, method of maintaining mechanical contact by the shrinkage force of the resin, etc.
- a method of metal bonding using solder, tin, gold, silver, copper, or the like is common.
- a COB (Chip On Board) type connection method that is widely used in BGA (Ball Grid Array), CSP (Chip Size Package), etc. is also a flip chip connection method.
- the flip chip connection method is also widely used in a COC (Chip On Chip) type connection method in which bumps or wirings are formed on a semiconductor chip and connected between the semiconductor chips (see, for example, Patent Document 1).
- COW Chip On Wafer
- the WOW Wafer On Wafer
- a gang bonding method in which a plurality of chips are aligned on a wafer or a map substrate and temporarily press-bonded, and then the plurality of chips are collectively pressure-bonded to ensure connection is also attracting attention.
- the gang bonding method is also used in the above-described TSV-PKG (TSV package) and the like.
- the following methods can be considered. First, a semiconductor chip to which a semiconductor adhesive is supplied from a diced wafer is picked up by a collet and supplied to a pressing member for pressure bonding. Next, after alignment between the chip and the chip or between the chip and the substrate, they are temporarily bonded to each other. Then, the temperature of the pressure-bonding pressing member is increased so as to reach the melting point of the chip-chip or chip-substrate connection part to form a metal bond between the chip and the chip or the chip and the substrate. Crimp together each other. Thus, one flip chip package can be obtained.
- the semiconductor chip is picked up again by the pressure member for pressure bonding.
- the pressing member for pressure bonding adsorbs the surface of the semiconductor chip opposite to the surface to which the semiconductor adhesive is supplied (the surface to be connected) to adsorb the semiconductor chip. Pick up.
- the temperature of the pressure bonding pressing member is increased to a high temperature at which the metal of the connection portion melts, or a semiconductor chip supplied with a semiconductor adhesive It is necessary to lower the temperature to a low temperature that can be picked up. However, it takes time to change the temperature of the pressing member for pressure bonding, and the manufacturing time of the semiconductor device becomes long, so that the productivity is likely to decrease.
- the pressure member for pressure bonding after the main pressure bonding is at a high temperature (for example, 240 ° C. or more if the metal of the connection part is solder).
- a high temperature for example, 240 ° C. or more if the metal of the connection part is solder.
- An object of the present invention according to one aspect is to enable higher productivity in the manufacture of a semiconductor device including connecting connection portions by metal bonding.
- One aspect of the present invention includes a semiconductor chip, a substrate and / or another semiconductor chip, and an adhesive layer interposed therebetween, and each of the semiconductor chip, the substrate, and the other semiconductor chip is made of a metal material.
- the present invention relates to a method for manufacturing a semiconductor device, which includes a connection portion having a formed surface, and a connection portion of a semiconductor chip and a connection portion of a substrate and / or another semiconductor chip are electrically connected by metal bonding.
- the method includes a semiconductor chip, a semiconductor wafer including a substrate, another semiconductor chip, or a portion corresponding to another semiconductor chip, and an adhesive layer disposed therebetween, and the connection of the semiconductor chips
- the laminate and the substrate or other semiconductor chip connecting portions are opposed to each other, and the laminate is heated and pressed by being sandwiched between a pair of opposing pressing members for temporary pressure bonding.
- a step of temporarily press-bonding a semiconductor chip or a semiconductor wafer and a laminated body are heated and pressed by being sandwiched between a pair of opposing pressure-bonding pressing members prepared separately from the pressure-bonding pressing member, whereby the semiconductor chip And a step of electrically connecting the connection portion of the substrate and the connection portion of the substrate or other semiconductor chip by metal bonding in this order.
- At least one of the pair of provisional pressing members is a melting point of the metal material forming the surface of the connection part of the semiconductor chip and the connection part of the substrate or other semiconductor chip when the laminated body is heated and pressurized. It is heated to a temperature lower than the melting point of the metal material forming the surface.
- At least one of the pair of main pressing members is a melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the connection portion of the substrate or other semiconductor chip when the laminated body is heated and pressed. Heating is performed to a temperature equal to or higher than at least one of the melting points of the metal material forming the surface.
- a plurality of semiconductor devices are manufactured by repeating the temporary pressure bonding and the main pressure bonding while maintaining a state where the pressure bonding member is heated to a temperature equal to or higher than the melting point of the metal material forming the surface of the connection member. It can be manufactured continuously.
- connection part of the semiconductor chip and the connection part of the substrate or another semiconductor chip are brought into contact with each other at the time of temporary pressure bonding, metal flow and scattering at the connection part can be suppressed during the main pressure bonding process.
- the process up to the temporary press-bonding and the main press-bonding process are performed using two press-bonding pressing members prepared separately, and the press-bonding press member for press-bonding is maintained at a high temperature. Heating and cooling time can be shortened, and improvement in productivity can be expected.
- the semiconductor adhesive is rapidly heated to a temperature higher than the melting point of the metal in the connection portion during the main crimping process. Due to the lack of flow, voids entrained during pressure bonding may remain or voids may occur due to resin volatilization. Further, since the melting of the metal at the connecting portion and the resin flow occur at the same time, the metal flowing or scattering at the connecting portion and a connection failure due to the resin trap may occur.
- the melt viscosity of the adhesive layer is 7000 Pa ⁇ s or less at the temperature at which the pressing member for temporary pressure bonding is heated. It may be.
- the melt viscosity of the adhesive layer at the time of the temporary press-bonding step is 7000 Pa ⁇ s or less, it is possible to further effectively suppress the generation of voids and poor connection due to the resin trap.
- the temporary pressure bonding and the main pressure bonding can be performed by separate pressure bonding members.
- the main pressure bonding a larger number of semiconductor chips are pressure-bonded than in the temporary pressure bonding, so that there is a tendency to use a pressure-bonding pressing member having a large-area pressure bonding head.
- a large-area crimping head is required when a plurality of semiconductor chips are finally crimped together.
- a small crimping head for example, tool size of less than about 20 mm
- a large-area crimping head for example, tool size of 20 mm
- the height difference between packages increases as the area increases even with the same parallelism. Therefore, in the batch connection for crimping a plurality of semiconductor chips, since the area of the crimping head becomes large, unevenness (height difference) is likely to occur in the pressing portion, and a portion when a plurality of semiconductor chips are crimped to form a package. Connection failure may occur. In a semiconductor package in which the thickness of the semiconductor chip is reduced, or the package is reduced in size, thickness, etc., higher connection accuracy is required.
- a plurality of laminated bodies may be heated and pressurized in a lump by being sandwiched between opposing crimping heads.
- the sheet for collective connection may have a storage elastic modulus of 10 GPa or less at 250 ° C.
- the amount of displacement here is 250 ° C. in a compression test in which a bar-shaped pressing jig having a circular end surface with a diameter of 8 ⁇ m is pressed against the main surface of the batch connection sheet in a direction in which the main surface and the end surface are parallel. This is the amount of displacement when the compressive load is 100 N under the environment.
- the stacked body in the step of electrically connecting the connection portion of the semiconductor chip and the connection portion of the substrate or another semiconductor chip by metal bonding, the stacked body is in a heating furnace or a hot plate. Above, at least one melting point of the melting point of the metal material forming the surface of the connection part of the semiconductor chip or the melting point of the metal material forming the surface of the connection part of the substrate or another semiconductor chip Heated to a temperature of
- the step of temporarily press-bonding at a temperature lower than the melting point of the metal material forming the surface of the connection portion, and the step of heating at a temperature higher than the melting point of the metal material forming the surface of the connection portion The time required for heating and cooling the temporary pressure bonding pressing member can be shortened. Therefore, a semiconductor device can be manufactured with high productivity in a short time compared with the case where the pressure bonding is performed with one pressure bonding member. As a result, many highly reliable semiconductor devices can be manufactured in a short time.
- a plurality of laminated bodies may be heated at once in a heating furnace or on a hot plate.
- the adhesive layer in the above method may be a layer containing an adhesive for semiconductors described in [1] to [7] below.
- the adhesive layer may be a layer formed of a thermosetting resin having a molecular weight of 10,000 or less and a thermosetting resin composition containing the curing agent. That is, the adhesive layer may be a layer containing this thermosetting resin composition.
- the thermosetting resin composition may further contain a polymer component having a weight average molecular weight of 10,000 or more.
- the weight average molecular weight of the polymer component may be 30000 or more.
- the glass transition temperature of the polymer component may be 100 ° C. or lower.
- the adhesive layer may be a layer formed by an adhesive film prepared in advance.
- the plurality of chips are collectively heat-pressed with a large-area crimping tool to ensure the connection.
- a high temperature such as a reflow furnace or oven
- the method of securing the connection by heat treatment in a treatable tank (second process) is expected to improve productivity because the second process can assemble a plurality of packages at once.
- connection failure or void generation due to insufficient fluidity occurs, it is necessary to cool the crimping tool.
- Tool cooling is omitted by assembling the package into the first process (the process of aligning and pre-bonding) and the second process (the process of securing the connection by heat treatment at a temperature equal to or higher than the melting point of the metal of the connection part). Can improve productivity.
- connection part In the second step, from the viewpoint of suppression of fillet and damage to the connection part, a method of securing the connection by heat treatment in a high temperature processable tank such as a reflow furnace or oven with low load or no load is expected.
- ⁇ Voiding in the first process and securing the connection (contact) can improve the mountability (void suppression, ensuring the connection) after the second process.
- the fluidity of the adhesive for semiconductors is poor and voids are likely to remain, ensuring connection (contact). It was difficult. If void suppression and securing of connection (contact) are not sufficient in the first step, voids may remain after the second step, resulting in poor connection.
- Yet another aspect of the present invention has been made to solve the above-described problems, and even when used in a method of manufacturing a semiconductor device through the first step and the second step, a void is provided. It is possible to provide a semiconductor adhesive capable of ensuring a good connection (contact) while suppressing the above-mentioned and obtaining a good reflow resistance, a method of manufacturing a semiconductor device using the same, and a semiconductor device Objective.
- Another aspect of the present invention is a method of assembling in a lump (reflow furnace) that can ensure high fluidity in the first process and ensure void suppression and connection (contact), so that high productivity can be expected in the second process.
- the following [1] to [7] are provided mainly for the purpose of ensuring high reliability (void suppression, connection securing, reflow resistance) even in heat treatment such as the above.
- An adhesive for semiconductor comprising (a) a resin component having a weight average molecular weight of less than 10,000, (b) a curing agent, and (c) a silanol compound represented by the following general formula (1).
- R 1 represents an alkyl group or a phenyl group
- R 2 represents an alkylene group.
- connection When manufacturing through the first step of crimping at a temperature lower than the melting point of the metal of the part and the second step of forming a metal bond by heat treatment at a temperature higher than the melting point of the metal of the connection part, the connection
- connection portions can be connected to each other by metal bonding.
- 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device. It is a schematic cross section which shows other one Embodiment of a semiconductor device. It is a schematic cross section which shows other one Embodiment of a semiconductor device. It is a schematic cross section which shows other one Embodiment of a semiconductor device.
- FIG. 1 is a process diagram showing an example of a process of temporarily press-bonding a substrate to a semiconductor chip in a method of manufacturing a semiconductor device according to this embodiment.
- the semiconductor chip 1 having the semiconductor chip body 10 and the bumps 30 as connection parts is changed to the substrate 2 having the substrate body 20 and wirings 16 as connection parts.
- the laminated body 3 is formed by superposing the adhesive layer 40 between them while arranging them. After the semiconductor chip 1 is formed by dicing a semiconductor wafer, it is picked up and transported to the substrate 2, and is aligned so that the bumps 30 and the wirings 16 as connection portions are arranged to face each other.
- the laminated body 3 is formed on a stage 42 of a pressing device 43 for temporary pressure bonding having a pressure bonding head 41 and a stage 42 as a pair of pressing members for temporary pressure bonding arranged opposite to each other.
- the bumps 30 are provided on the wiring 15 provided on the semiconductor chip body 10.
- the wiring 16 of the substrate 2 is provided at a predetermined position on the substrate body 20. Each of the bump 30 and the wiring 16 has a surface formed of a metal material.
- the adhesive layer 40 may be a layer formed by sticking an adhesive film prepared in advance to the substrate 2.
- the adhesive film can be attached by heating press, roll lamination, vacuum lamination or the like.
- the supply area and thickness of the adhesive film are appropriately set according to the size of the semiconductor chip 1 or the substrate 2, the height of the connection portion, and the like.
- the adhesive film may be attached to the semiconductor chip 1.
- the semiconductor chip 1 to which the adhesive film is attached may be manufactured by attaching the adhesive film to the semiconductor wafer, and then dicing the semiconductor wafer to separate the semiconductor wafer.
- the laminated body 3 is heated and pressed by being sandwiched between a stage 42 and a pressure-bonding head 41 as a temporary pressure-bonding pressing member, whereby the substrate 2 is applied to the semiconductor chip 1.
- the crimping head 41 is disposed on the semiconductor chip 1 side of the stacked body 3
- the stage 42 is disposed on the substrate 2 side of the stacked body 3.
- the temporary pressure bonding may be performed so that the connection portion of the semiconductor chip 1 and the connection portion of the substrate 2 are in contact with each other. Thereby, it becomes easy to form a metal joint between the connection parts in the subsequent heating process, and the biting of the adhesive layer between the connection parts can be reduced, and the connectivity is further improved.
- the melting point of the metal material forming the surface of the bump 30 as the connection portion of the semiconductor chip 1 When at least one of the stage 42 and the pressure bonding head 41 heats and pressurizes the laminated body 3 for temporary pressure bonding, the melting point of the metal material forming the surface of the bump 30 as the connection portion of the semiconductor chip 1, and The substrate 2 is heated to a temperature lower than the melting point of the metal material forming the surface of the wiring 16 as the connection portion of the substrate 2.
- the pressure member for temporary pressing is low temperature so that heat is not transferred to the semiconductor chip or the like when the semiconductor chip is picked up.
- the pressure member for temporary pressure bonding may be heated to a high temperature to increase the fluidity of the adhesive layer so that voids at the time of entrainment can be eliminated.
- the difference between the temperature of the pressing member when picking up the semiconductor chip and the temperature of the pressing member when temporarily press-bonding may be small. This temperature difference may be 100 ° C. or less, or 60 ° C. or less. This temperature difference may be constant. When the temperature difference is 100 ° C. or less, the cooling time of the temporary pressure bonding pressing member is shortened, and the productivity tends to be further improved.
- the temperature of the temporary pressure bonding pressing member may be lower than the reaction start temperature of the adhesive layer.
- the reaction start temperature is DSC (Perkin Elmer, DSC-Pyrs1)
- the sample amount is 10 mg
- the heating rate is 10 ° C./min
- the measurement atmosphere is air or nitrogen. This is the On-set temperature when measured.
- the temperature of the stage 42 and / or the pressure-bonding head 41 is, for example, 30 ° C. or higher and 130 ° C. or lower during pick-up of the semiconductor chip, and is 50, for example, during heating and pressurization of the laminate 3 for temporary pressure bonding. It may be from 150 ° C to 150 ° C.
- the melt viscosity of the adhesive layer was 7000 Pa ⁇ s or less at the temperature T at which the pressing member for temporary pressing is heated for temporary pressing (temperature of the pressing member for temporary pressing while heating and pressing the laminate). May be.
- the “melt viscosity” is a rheometer (manufactured by Anton Paar Japan Co., Ltd., MCR301) under the conditions of a sample thickness: 400 ⁇ m, a heating rate of 10 ° C./min, and a frequency: 1 Hz.
- the temperature T at which the pressing member for temporary pressure bonding is heated for temporary pressure bonding may be a temperature that is equal to or lower than the reaction start temperature of the adhesive layer, has the lowest viscosity of the adhesive layer, and allows the resin to flow easily. However, if the viscosity is too low, the resin crawls up the chip side surface and adheres to the pressure-bonding pressing member, which may reduce productivity. Therefore, in the step of temporary pressure bonding, the melt viscosity of the adhesive layer may be 1000 Pa ⁇ s or more at the temperature T at which the temporary pressure bonding pressing member is heated for temporary pressure bonding.
- the load for provisional pressure bonding is, for example, 0 per pin (1 bump) of the semiconductor chip from the viewpoint of eliminating the voids between the semiconductor chips or between the semiconductor chip and the substrate and sufficiently bringing the respective connecting portions into contact with each other. 0.009 to 0.2N.
- FIG. 2 is a process diagram showing an example of a main press-bonding process in which the connection part of the semiconductor chip and the connection part of the substrate are electrically connected by metal bonding.
- a pressing device 46 for main press-bonding having a stage 45 and a press-bonding head 44 as a press-bonding press member prepared separately from the pressing device 43 is used.
- the laminate 3 is further heated and pressurized.
- the laminated body 3 is heated and pressed by being sandwiched between the stage 45 and the pressure bonding head 44, whereby the bumps 30 and the wiring 16 are electrically connected by metal bonding.
- the semiconductor chip 1 and the substrate 2 are finally bonded.
- the crimping head 44 is disposed on the semiconductor chip 1 side of the multilayer body 3
- the stage 45 is disposed on the substrate 2 side of the multilayer body 3.
- the melting point of the metal material forming the surface of the bump 30 as the connection portion of the semiconductor chip 1, or the connection portion of the substrate 2 Are heated to a temperature equal to or higher than at least one of the melting points of the metal material forming the surface of the wiring 16.
- This heating temperature (the temperature of the stage 45 and / or the pressure bonding head 44 in the main pressure bonding) may be 230 ° C. or higher or 250 ° C. or higher when the metal material of the connection portion includes solder, or 330 ° C. or lower or 300 ° C. It may be the following. When the heating temperature is 230 ° C. or higher or 250 ° C.
- the solder in the connecting portion is melted and a sufficient metal bond is easily formed.
- the heating temperature is 330 ° C. or lower or 300 ° C. or lower, voids are less likely to be generated, and solder scattering can be further suppressed.
- the temperature in the main pressure bonding may be constant during the main pressure bonding process from the viewpoint of eliminating the cooling time and improving the productivity.
- the temperature of the stage 45 and / or the pressure-bonding head 44 may be maintained at a certain level or higher while the plurality of semiconductor devices are continuously manufactured by sequentially heating and pressing the plurality of stacked bodies 3. In other words, while the stage 45 and / or the pressure-bonding head 44 is maintained at a certain level or more, the laminated bodies 3 may be sequentially replaced and the main pressure-bonding may be continuously performed a plurality of times. By maintaining the apparatus at a certain range of temperatures, the cooling time is not required and productivity is further improved.
- the temperature of the stage 45 and / or the pressure bonding head 44 may fluctuate slightly due to heat escape when contacting the outside air and the semiconductor chip, but may vary if the fluctuation range is ⁇ 10 ° C. or less. There is no.
- the temperature of the stage 45 and / or the pressure bonding head 44 may be higher than the reaction start temperature of the adhesive layer when the laminate is heated and pressed. Void suppression and connectivity tend to be further improved by promoting the curing of the adhesive layer during the main press bonding.
- the temporary pressure bonding pressing member and the main pressure bonding pressing member may be installed in two or more separate devices, respectively, or may be installed together in one device. You may use the 2 head type apparatus provided with the pressing member for temporary crimping
- the method of manufacturing the semiconductor device may include the step of crimping the semiconductor chips to each other.
- a semiconductor wafer before dicing including a plurality of portions corresponding to the semiconductor chip 1 may be used.
- the semiconductor chips are pressed while being heated at a temperature equal to or higher than the melting point of the bumps to connect the semiconductor chips, and the gap between the semiconductor chips is filled with an adhesive film so that the connection portion is sealed.
- the metal material of the connection portion includes solder
- the semiconductor chip may be heated so that the temperature of the connection portion (solder portion) is 230 ° C. or higher or 250 ° C. or higher.
- connection load depends on the number of bumps, but is set in consideration of absorption of bump height variation and control of the amount of bump deformation.
- connection time may be set to a short time from the viewpoint of improving productivity.
- the metal joint may be formed at the connection portion while melting the solder and removing the oxide film and surface impurities.
- the crimping time for temporary crimping and the connection time for crimping may be set in a short time from the viewpoint of improving productivity.
- the short connection time means that the time during which the connecting portion is heated to 230 ° C. or more during the connection formation (final pressing) (for example, the time for using the solder) is 5 seconds or less.
- the connection time may be 4 seconds or less or 3 seconds or less.
- a pressing device for temporary pressure bonding or main pressure bonding a flip chip bonder, a pressure oven, or the like can be used.
- a plurality of chips may be crimped.
- a plurality of semiconductor chips may be temporarily bonded to a wafer or a map substrate one by one, and then a plurality of chips may be bonded together in a batch.
- a plurality of chips are crimped in three dimensions.
- a plurality of semiconductor chips may be stacked one by one and temporarily bonded, and then the plurality of chips may be collectively bonded together.
- a method for manufacturing a semiconductor device is also for main pressure bonding including a stage and a pressure bonding head after a semiconductor chip and a substrate or another semiconductor chip are temporarily fixed to obtain a laminated body.
- a step of performing a final pressure bonding with the pressing member; The step of temporarily fixing the semiconductor chip and the substrate or another semiconductor chip to obtain a laminated body may be the same mode as the temporary pressure bonding of the first embodiment.
- a plurality of laminated bodies arranged on the stage and a batch connection sheet arranged so as to cover them are sandwiched between the stage and a pressure-bonding head facing the stage, thereby collectively.
- FIG. 3 is a process diagram showing an example of a main press-bonding process in which the connection part of the semiconductor chip and the connection part of the substrate are electrically connected by metal bonding using the collective connection sheet.
- a laminated body having a semiconductor wafer and a plurality of semiconductor chips may be arranged on a stage and covered with a batch connection sheet.
- a press for main pressure bonding having a stage 45 and a pressure bonding head 44 as a pressure bonding member 44 prepared separately from the pressing device 43 for temporary pressure bonding.
- the laminated body 3 is further heated and pressurized.
- a plurality of laminated bodies 3 are arranged on the stage 45, and a collective connection sheet 47 is arranged so as to cover the laminated bodies 3.
- the batch connection sheet 47 and the plurality of laminates 3 are both sandwiched between the stage 45 and the pressure bonding head 44, whereby the plurality of laminates are heated and pressed together, whereby the bumps 30 and the wirings 16 are connected. Electrical connection is made by metal bonding.
- the crimping head 44 is disposed on the semiconductor chip 1 side of the multilayer body 3
- the stage 45 is disposed on the substrate 2 side of the multilayer body 3.
- the area of the surface of the crimping head 44 that contacts the semiconductor chip may be 50 mm ⁇ 50 mm or more from the viewpoint of improving the productivity of the semiconductor device by crimping more semiconductor chips at once.
- the area of the surface of the pressure-bonding head 44 that comes into contact with the semiconductor chip may be about 330 mm ⁇ 330 mm from the viewpoint that it can accommodate a 12-inch wafer.
- the raw material for the collective connection sheet is not particularly limited as long as it is a resin exhibiting a specific storage elastic modulus and displacement at 250 ° C.
- the resin include polytetrafluoroethylene resin, polyimide resin, phenoxy resin, epoxy resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin. , Polyvinyl acetal resin, urethane resin, and acrylic rubber.
- the sheet for batch connection is selected from polytetrafluoroethylene resin, polyimide resin, epoxy resin, phenoxy resin, acrylic resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin from the viewpoint of excellent heat resistance and film formability. It may be a sheet containing at least one resin.
- the resin for the collective connection sheet is a sheet containing at least one resin selected from polytetrafluoroethylene resin, polyimide resin, phenoxy resin, acrylic resin, and acrylic rubber from the viewpoint of particularly excellent heat resistance and film formability. There may be. These resins can be used singly or in combination of two or more.
- the storage elastic modulus of the collective connection sheet at 250 ° C. may be, for example, a storage elastic modulus of 10 GPa or less, or 8 GPa or less.
- the collective connection sheet at 250 ° C. has an appropriate softness, and thus absorbs the height difference between a plurality of laminated bodies to express good parallelism. There exists a tendency which can pressurize a laminated body more uniformly. Therefore, the storage elastic modulus of the collective connection sheet at 250 ° C.
- the storage elastic modulus at 250 ° C. can be measured using a general elastic modulus measuring apparatus. For example, using a modulus measuring device RSA2 (Rheometric Scientific), etc., the viscoelasticity of the sample is measured while raising the temperature from ⁇ 30 ° C. to 300 ° C. at a frequency of 10 Hz and a heating rate of 5 ° C./min.
- the storage elastic modulus at 250 ° C. can be obtained from the result.
- the sheet for batch connection may have a storage elastic modulus at 250 ° C. satisfying the above range, and further exhibit a sufficient displacement at 250 ° C., for example, 40 ⁇ m or more. If this displacement amount is 40 ⁇ m or more, particularly good connection can be ensured when a plurality of semiconductor chips are finally bonded together.
- the displacement at 250 ° C. may be 200 ⁇ m or less.
- the amount of displacement is a compression test in which a bar-shaped pressing jig having a circular end surface with a diameter of 8 ⁇ m is pressed against the main surface of the batch connection sheet in a direction in which the main surface and the end surface are parallel. This means the amount of displacement when the compressive load is 100 N under an environment of 250 ° C.
- the amount of displacement can be measured using, for example, an electromechanical universal testing machine (manufactured by INSTRON).
- the batch connection sheet may have high heat resistance. From the viewpoint of increasing the productivity of the semiconductor device, the collective connection sheet may not be melted and adhered to the semiconductor chip when pressed at a temperature of 250 ° C. or higher.
- the collective connection sheet is highly transparent from the viewpoint of enabling the press bonding member to recognize the alignment mark (recognition mark for alignment) on the semiconductor chip or substrate covered by the collective connection sheet. You may have.
- the transmittance at the wavelength of 550 nm of the collective connection sheet may be, for example, 10% or more.
- the thickness of the collective connection sheet can be appropriately designed to satisfy the above properties.
- the thickness may be, for example, 50 ⁇ m or more, 80 ⁇ m or more, or 100 ⁇ m or more.
- the thickness of the collective connection sheet may be 300 ⁇ m or less.
- the batch connection sheet may be a commercially available elastic sheet.
- the commercially available elastic body sheet include NITOFLON 900UL (manufactured by Nitto Denko Corporation), Upilex SGA (manufactured by Ube Industries), and the like.
- the sheet for batch connection having the above specific storage elastic modulus and displacement amount, it is possible to sufficiently absorb the height difference between the plurality of laminated bodies to express good parallelism and pressurize them uniformly. Therefore, a better connection can be ensured for any semiconductor device. In addition, even if the adhesive that protrudes from the semiconductor chip at the time of pressure bonding adheres to the batch connection sheet, it can be easily replaced, so that the productivity is hardly lowered.
- Third Embodiment In the method of manufacturing a semiconductor device according to the third embodiment, following the temporary pressure bonding similar to that of the first embodiment, as shown in FIG. By heating in 60, the bump 30 of the semiconductor chip 1 and the wiring 16 of the substrate 2 are electrically connected by metal bonding.
- the method according to the third embodiment is the same as that of the first embodiment except for this point.
- a plurality of laminated bodies may be heated in one heating furnace 60 to collectively connect the plurality of laminated bodies.
- the gas in the heating furnace 60 is the melting point of the metal material forming the surface of the connection part of the semiconductor chip 1 or the melting point of the metal material forming the surface of the connection part of the substrate 2 when the stacked body is heated. Are heated to a temperature equal to or higher than the melting point of at least one of them.
- the temperature of the gas in the heating furnace 60 may be 230 ° C. or higher and 330 ° C. or lower when the metal material of the connection portion includes solder while the laminate is heated.
- the temperature of the gas in the heating furnace 60 is 230 ° C. or higher, the solder at the connection portion melts and a sufficient metal bond is easily formed.
- the temperature of the gas in the heating furnace 60 is 330 ° C. or less, voids are unlikely to occur, and solder scattering can be further suppressed.
- the pressure in the heating furnace 60 is not particularly limited, but may be atmospheric pressure.
- the temperature of the gas in the heating furnace 60 may be higher than the reaction start temperature of the adhesive layer while heating the laminate. Void suppression and connectivity can be further improved by promoting the curing of the adhesive layer during the heating step.
- the laminated body may be heated in a state where a weight is placed on the laminated body or the laminated body is fastened with clips. Thereby, the curvature and the connection failure which arise by the thermal expansion difference between a semiconductor chip and a board
- the heating furnace a reflow furnace, an oven, or the like can be used.
- the laminate may be heated on a hot plate.
- the temperature of the hot plate can be set to the same temperature as the air in the heating furnace.
- the step of connecting the connecting portion may not only form the metal bond but also promote the curing of the adhesive layer.
- the heat of the pressure member for pressure bonding is hardly transmitted to the fillet that is an adhesive that protrudes from the side surface of the chip during pressure bonding. For this reason, a further heat treatment step is required to further cure the fillet portion and the like after the connection.
- a reflow furnace, an oven, a hot plate, or the like that applies heat to the entire laminated body is used without using a pressing member for crimping, the heat treatment after connection can be shortened or eliminated.
- connection part in the semiconductor device according to the present embodiment may be any of metal bonding between the bump and the wiring and metal bonding between the bump and the bump.
- flip chip connection for obtaining electrical connection through an adhesive layer can be used.
- FIG. 5 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB type connection mode of a semiconductor chip and a substrate).
- a semiconductor device 100 shown in FIG. 5A includes a semiconductor chip 1, a substrate (wiring circuit substrate) 2, and an adhesive layer 40 interposed therebetween.
- the semiconductor chip 1 includes a semiconductor chip body 10, wiring 15 disposed on the surface of the semiconductor chip body 10 on the substrate 2 side, and bumps 30 as connection portions disposed on the wiring 15.
- the substrate 2 includes a substrate body 20 and wirings 16 as connection portions disposed on the surface of the substrate body 20 on the semiconductor chip 1 side.
- the bump 30 of the semiconductor chip 1 and the wiring 16 of the substrate 2 are electrically connected by metal bonding.
- the semiconductor chip 1 and the substrate 2 are flip-chip connected by wirings 16 and bumps 30.
- the wirings 15 and 16 and the bumps 30 are sealed from the external environment by being sealed with the adhesive layer 40.
- the 5B includes a semiconductor chip 1, a substrate 2, and an adhesive layer 40 interposed therebetween.
- the semiconductor chip 1 has bumps 32 arranged on the surface of the semiconductor chip 1 on the substrate 2 side as a connection portion.
- the substrate 2 has bumps 33 arranged on the surface of the substrate 2 on the semiconductor chip 1 side as a connection portion.
- the bumps 32 of the semiconductor chip 1 and the bumps 33 of the substrate 2 are electrically connected by metal bonding.
- the semiconductor chip 1 and the substrate 2 are flip-chip connected by bumps 32 and 33.
- the bumps 32 and 33 are sealed from the external environment by being sealed with the adhesive layer 40.
- FIG. 6 is a schematic cross-sectional view showing another embodiment of a semiconductor device (COC type connection mode between semiconductor chips).
- the configuration of the semiconductor device 300 shown in FIG. 6A is the same as that of the semiconductor device 100 except that the two semiconductor chips 1 are flip-chip connected via the wiring 15 and the bump 30.
- the configuration of the semiconductor device 400 shown in FIG. 6B is the same as that of the semiconductor device 200 except that the two semiconductor chips 1 are flip-chip connected via the bumps 32.
- connection portions such as the wiring 15 and the bumps 32 may be metal films called pads (for example, gold plating) or post electrodes (for example, copper pillars).
- pads for example, gold plating
- post electrodes for example, copper pillars
- one semiconductor chip has copper pillars and connection bumps (solder: tin-silver) as connection portions, and the other semiconductor chip has gold plating as connection portions. If the part reaches a temperature equal to or higher than the melting point of the solder with the lowest melting point among the metal materials of the connection part, the solder melts and a metal bond is formed between the connection parts, and electrical connection between the connection parts is possible Become.
- the semiconductor chip body 10 is not particularly limited, and various semiconductors such as elemental semiconductors composed of the same kind of elements such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphide can be used.
- the substrate 2 is not particularly limited as long as it is a printed circuit board, and does not require a metal layer formed on the surface of an insulating substrate mainly composed of glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, or the like.
- a circuit board on which wiring (wiring pattern) is formed by printing can be used.
- connection portions such as the wirings 15 and 16, the bumps 30, and the bumps 32 and 33 (conductive protrusions)
- gold, silver, copper, and solder as main components
- the main components are, for example, tin-silver, tin- Lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel, or the like
- the connecting portion may have a structure in which these metals are laminated.
- metal materials copper and solder are relatively inexpensive. From the viewpoint of improving connection reliability and suppressing warpage, the connecting portion may contain solder.
- the main components are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel Etc.
- main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, nickel Etc.
- the pad may have a structure in which these metals are laminated. From the viewpoint of connection reliability, the pad may contain gold and / or solder.
- a metal layer as a component may be formed. This metal layer may be composed of only a single component or may be composed of a plurality of components.
- the metal layer may have a structure in which a plurality of metal layers are stacked.
- the metal layer may include relatively inexpensive copper and / or solder. From the viewpoint of improving connection reliability and suppressing warpage, the metal layer may contain solder.
- a semiconductor device (package) as shown in FIG. 5 or FIG. 6 is laminated, gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin) -Silver-copper), tin, nickel, etc. may be used for electrical connection.
- the metal for connection may be relatively inexpensive copper and / or solder.
- an adhesive layer may be flip-chip connected or stacked between semiconductor chips to form a hole penetrating the semiconductor chip and connected to the electrode on the pattern surface.
- FIG. 7 is a schematic cross-sectional view showing another embodiment (semiconductor chip stacked type (TSV)) of a semiconductor device.
- TSV semiconductor chip stacked type
- the wiring 15 formed on the interposer body 50 as a substrate is connected to the bumps 30 of the semiconductor chip 1, so that the semiconductor chip 1 and the interposer 5 are flip-chip connected. ing.
- An adhesive layer 40 is interposed between the semiconductor chip 1 and the interposer 5.
- the semiconductor chip 1 is repeatedly laminated via the wiring 15, the bumps 30 and the adhesive layer 40.
- the wirings 15 on the pattern surface on the front and back sides of the semiconductor chip 1 are connected to each other by through electrodes 34 filled in holes that penetrate the inside of the semiconductor chip body 10.
- the through electrode 34 copper, aluminum, or the like can be used.
- the through electrode 34 passes vertically through the semiconductor chip 1, the distance between the semiconductor chips 1 facing each other and between the semiconductor chip 1 and the interposer 5 can be shortened, and flexible connection is possible.
- the adhesive layer according to the present embodiment can be applied as a sealing material between the semiconductor chips 1 facing each other and between the semiconductor chip 1 and the interposer 5 in such a TSV technology.
- a semiconductor chip can be directly mounted on a motherboard without using an interposer.
- the adhesive layer according to this embodiment can also be applied when such a semiconductor chip is directly mounted on a mother board.
- the adhesive layer according to the present embodiment can also be applied when sealing or filling a gap between substrates when two printed circuit boards are stacked.
- the adhesive layer can be, for example, a layer formed of a thermosetting resin having a molecular weight of 10,000 or less and a thermosetting resin composition containing the curing agent.
- the adhesive layer may be a layer including a thermosetting resin having a molecular weight of 10,000 or less and a thermosetting resin composition containing the curing agent.
- thermosetting resin is a compound which can form a crosslinked structure by heating.
- the thermosetting resin may have a molecular weight of 10,000 or less. Since the thermosetting resin composition contains a compound that reacts with the curing agent to form a crosslinked structure (thermosetting resin), voids generated by decomposition or the like of components having a low molecular weight upon heating are suppressed. This is advantageous in terms of heat resistance.
- thermosetting resin include an epoxy resin and an acrylic resin.
- the weight average molecular weight of the thermosetting resin may be 100 to 9000 or 300 to 7000 from the viewpoint of heat resistance and fluidity.
- the method for measuring the weight average molecular weight of the thermosetting resin is the same as the method for measuring the weight average molecular weight of the polymer component (d) described later.
- Acrylic resin is a compound having one or more (meth) acryloyl groups in the molecule.
- the acrylic resin include a skeleton derived from a compound selected from bisphenol A, bisphenol F, naphthalene, phenol novolak, cresol novolak, phenol aralkyl, biphenyl, triphenylmethane, dicyclopentadiene, fluorene, adamantane and isocyanuric acid and
- Examples include (meth) acrylate having a (meth) acryloyloxy group, and various polyfunctional (meth) acrylic compounds.
- the acrylic resin may be selected from (meth) acrylates having a skeleton derived from a compound selected from bisphenol A, bisphenol F, naphthalene, fluorene, adamantane and isocyanuric acid.
- An acrylic resin can be used individually by 1 type or in combination of 2 or more types.
- the content of the acrylic resin may be 10 to 50 parts by mass or 15 to 40 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin composition. If content of an acrylic resin is 10 mass% or more, since a hardening component exists enough, it will become easy to control the flow after hardening of a thermosetting resin composition. If content of an acrylic resin is 50 mass% or less, the curvature of the package by hardened
- the acrylic resin may be solid at room temperature (25 ° C.). Solid acrylic resins are more advantageous than liquid ones in that voids are less likely to occur and that the thermosetting resin composition before curing (B stage) has a low viscosity (tack) and is excellent in handleability. It is.
- the acrylic resin that is solid at room temperature (25 ° C.) include (meth) acrylates having a skeleton derived from a compound selected from bisphenol A, fluorene, adamantane, and isocyanuric acid.
- the number of (meth) acryloyl groups (the number of functional groups) in the acrylic resin may be 3 or less.
- the number of functional groups is 3 or less, the thermosetting resin composition can be sufficiently cured in a short time, so that a decrease in the curing reaction rate can be further suppressed.
- the curing reaction rate is low, unreacted groups may remain.
- Epoxy resin is a compound having two or more epoxy groups in the molecule.
- the epoxy resin include bisphenol A type, bisphenol F type, naphthalene type, phenol novolac type, cresol novolac type, phenol aralkyl type, biphenyl type, triphenylmethane type and dicyclopentadiene type epoxy resin, and various polyfunctional epoxies.
- Resin From the viewpoint of heat resistance and handleability, the epoxy resin may be selected from bisphenol F type, phenol novolac type, cresol novolac type, biphenyl type, and triphenylmethane type epoxy resin. From the viewpoint of fast curing and heat resistance, the epoxy resin may be selected from bisphenol F type and triphenylmethane type epoxy resins.
- An epoxy resin can be used individually by 1 type or in combination of 2 or more types.
- the content of the epoxy resin may be 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin composition. If content of an epoxy resin is 10 mass parts or more, since a hardening component exists enough, it will become easy to control the flow after hardening of a thermosetting resin composition. If content of an epoxy resin is 50 mass parts or less, the curvature of the package by hardened
- the curing agent is a compound that reacts with the thermosetting resin to form a crosslinked structure with the thermosetting resin.
- the curing agent include phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, phosphine curing agents, azo compounds, and organic peroxides.
- the curing reaction (curing system) may be a radical polymerization (radical polymerization system).
- curing agent can be used individually by 1 type or in combination of 2 or more types.
- the phenol resin curing agent, the acid anhydride curing agent and the amine curing agent can be used singly or as a mixture of two or more.
- the imidazole-based curing agent and the phosphine-based curing agent may each be used alone, but may be used together with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.
- the combination of the thermosetting resin and the curing agent is not particularly limited as long as curing proceeds.
- the curing agent combined with the acrylic resin may be an organic peroxide from the viewpoints of handleability and storage stability.
- the curing agent combined with the epoxy resin is a phenol resin curing agent and an imidazole curing agent, an acid anhydride curing agent and an imidazole curing agent, and an amine curing agent from the viewpoint of excellent handleability, storage stability and curability. You may select from an imidazole type hardening
- thermosetting resin composition When the thermosetting resin composition is cured in a short time, the amount of volatile components such as low molecular components can be reduced, so that generation of voids can be further suppressed.
- the curing agent combined with the acrylic resin may be an organic peroxide or an azo compound from the viewpoints of handleability and storage stability.
- the phenolic resin-based curing agent has two or more phenolic hydroxyl groups in the molecule.
- the phenol resin-based curing agent include phenol novolak, cresol novolak, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol and various polyfunctional phenol resins. These can be used individually by 1 type or in combination of 2 or more types.
- the equivalent ratio of phenol resin curing agent to epoxy resin is 0.3 to 1.5, 0.4 to 0.4 from the viewpoint of excellent curability, adhesion and storage stability. It may be 1.0, or 0.5 to 1.0. When this equivalent ratio is 0.3 or more, the curability is improved and the adhesive force tends to be further improved. When the equivalent ratio is 1.5 or less, excessive unreacted phenolic hydroxyl groups do not remain, water absorption is suppressed to a low level, and insulation reliability tends to be further improved.
- Acid anhydride curing agent examples include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bis. Anhydro trimellitate is mentioned. These can be used individually by 1 type or in combination of 2 or more types.
- the equivalent ratio of the acid anhydride curing agent to the epoxy resin is 0.3 to 1.5, 0.00 from the viewpoint of excellent curability, adhesiveness, and storage stability. It may be 4 to 1.0, or 0.5 to 1.0. When this equivalent ratio is 0.3 or more, the curability is improved and the adhesive force tends to be further improved. When the equivalent ratio is 1.5 or less, the unreacted acid anhydride hardly remains excessively, the water absorption rate is suppressed low, and the insulation reliability tends to be further improved.
- (B3) Amine-based curing agent
- examples of the amine-based curing agent include dicyandiamide and dodecanediamine. These can be used individually by 1 type or in combination of 2 or more types.
- the equivalent ratio of the amine curing agent to the epoxy resin is 0.3 to 1.5, 0.00 from the viewpoint of excellent curability, adhesion and storage stability. It may be 4 to 1.0, or 0.5 to 1.0. When this equivalent ratio is 0.3 or more, the curability is improved and the adhesive force tends to be further improved. When this equivalent ratio is 1.5 or less, unreacted amine hardly remains excessively, and thus insulation reliability tends to be improved.
- imidazole-based curing agent examples include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2′-ethyl-4′-methylimidazolyl-
- imidazole-based curing agents are 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trioxide.
- the content of the imidazole curing agent may be 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the content is 20 parts by mass or less, the thermosetting resin composition is hard to be cured before the metal bond is formed, and therefore, connection failure tends to hardly occur.
- Phosphine curing agent examples include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
- the content of the phosphine curing agent may be 0.1 to 10 parts by mass, or 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
- sclerosis hardenability to improve that this content is 0.1 mass part or more.
- the content is 10 parts by mass or less, since the thermosetting resin composition is hard to be cured before the metal bond is formed, connection failure tends to hardly occur.
- (B6) Azo compound examples include dimethylaminoazobenzene, dimethylaminoazobenzene-carboxylic acid, diethylaminoazobenzene, and diethylaminoazobenzene-carboxylic acid.
- An azo compound can be used individually by 1 type or in combination of 2 or more types.
- the content of the azo compound may be 0.5 to 10 parts by mass, or 1 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin. When this content is 0.5% by mass or more, curability tends to be improved. When the content is 10 parts by mass or less, the thermosetting resin composition is hard to be cured before the metal bond is formed, and thus poor connection tends not to occur.
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester.
- the organic peroxide may be one or more selected from hydroperoxide, dialkyl peroxide and peroxyester from the viewpoint of storage stability.
- the organic peroxide may be one or more selected from hydroperoxide and dialkyl peroxide from the viewpoint of heat resistance. These can be used individually by 1 type or in combination of 2 or more types.
- the content of the organic peroxide is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin.
- this content is 0.5% by mass or more, curability tends to be improved.
- the content is 10 parts by mass or less, the thermosetting resin composition is hard to be cured before the metal bond is formed, and thus poor connection tends not to occur.
- this content is moderately low, curing proceeds rapidly and the number of reactive sites increases, resulting in shortening of the molecular chain or unreacted groups remaining, resulting in a decrease in reliability. It tends not to occur.
- thermosetting resin composition may further contain a polymer component having a weight average molecular weight of 10,000 or more.
- the weight average molecular weight or molecular weight of components other than the polymer component, such as a thermosetting resin and a curing agent, is usually less than 10,000.
- the polymer component include epoxy resin, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, and polyvinyl acetal resin. , Urethane resin and acrylic rubber.
- the high molecular weight component may be selected from an epoxy resin, a phenoxy resin, a polyimide resin, an acrylic resin, an acrylic rubber, a cyanate ester resin, and a polycarbodiimide resin. From the viewpoint of further improving heat resistance and film formability, the high molecular weight component may be selected from an epoxy resin, a phenoxy resin, a polyimide resin, an acrylic resin, and an acrylic rubber. These polymer components can be used alone or in combination of two or more.
- the mass ratio between the polymer component and the acrylic resin is not particularly limited.
- the content of the acrylic resin may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 5 parts by mass with respect to 1 part by mass of the polymer component.
- this mass ratio is 0.01 parts by mass or more, the curability tends to be improved and the adhesive force tends to be further improved.
- the mass ratio between the polymer component and the epoxy resin is not particularly limited.
- the content of the epoxy resin may be 0.01 to 5 parts by mass, 0.05 to 4 parts by mass, or 0.1 to 3 parts by mass with respect to 1 part by mass of the polymer component.
- this mass ratio is 0.01 parts by mass or more, the curability tends to be improved and the adhesive force tends to be further improved.
- the film formation property and film formation property of a thermosetting resin composition to be especially excellent in this mass ratio being 5 mass parts or less.
- the glass transition temperature (Tg) of the polymer component may be 120 ° C. or lower, 100 ° C. or lower, or 85 ° C. or lower from the viewpoint of excellent stickability of the thermosetting resin composition to the substrate and chip.
- the Tg of the high molecular weight component may be 0 ° C. or higher. If the Tg of the polymer component is 120 ° C. or lower, it becomes easy to embed height differences of bumps formed on the semiconductor chip, electrodes formed on the substrate, wiring patterns, etc. in the thermosetting resin composition. Tends to be suppressed and voids are less likely to occur.
- Tg is determined by differential scanning calorimetry using DSC (DSC-7, manufactured by Perkin Elmer Co., Ltd.) with a sample amount of 10 mg, a heating rate of 10 ° C./min, and a measurement atmosphere: air. Mean value.
- the weight average molecular weight of the polymer component may be 10,000 or more in terms of polystyrene, but may be 30000 or more, 40000 or more, or 50000 or more in order to show better film-formability alone.
- the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).
- thermosetting resin composition controls the viscosity and physical properties of the cured product, and generates voids and absorbs moisture when the semiconductor chips are connected to each other or between the semiconductor chip and the substrate.
- a filler may be further contained.
- the filler include an inorganic filler and a resin filler.
- the inorganic filler include insulating inorganic fillers such as glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride.
- the solid filler may be selected from silica, alumina, titanium oxide and boron nitride, and from the viewpoint of shape uniformity (handleability), the solid filler is selected from silica, alumina and boron nitride. Also good.
- the insulating inorganic filler may be a whisker. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.
- the resin filler include polyurethane, polyimide, methyl methacrylate resin, and methyl methacrylate-butadiene-styrene copolymer resin (MBS).
- a filler can be used individually by 1 type or in combination of 2 or more types. The shape, particle size, and content of the filler are not particularly limited.
- the filler may be insulative.
- the thermosetting resin composition according to the present embodiment may not substantially contain a conductive metal filler such as a silver filler or a solder filler.
- the content of the conductive metal filler may be less than 1% by mass based on the entire solid content (components other than the solvent) of the thermosetting resin composition.
- the filler may be appropriately adjusted in physical properties by surface treatment.
- the filler may be a surface-treated filler from the viewpoint of improving dispersibility and adhesive strength.
- the surface treatment agent include glycidyl (epoxy), amine, phenyl, phenylamino, (meth) acrylic, and vinyl compounds.
- silane treatment with a silane compound such as epoxy silane, amino silane, or acrylic silane is preferable because of easy surface treatment.
- the surface treatment agent may be a compound selected from glycidyl, phenylamino, acrylic and methacrylic compounds from the viewpoint of excellent dispersibility, fluidity and adhesive strength. From the viewpoint of storage stability, the surface treatment agent may be a compound selected from phenyl, acrylic and methacrylic compounds.
- the average particle diameter of the filler may be 1.5 ⁇ m or less from the viewpoint of preventing biting during flip chip connection.
- the average particle diameter of the filler may be 1.0 ⁇ m or less from the viewpoint of excellent visibility (transparency).
- the particle diameter of the filler means the major axis diameter of the particles.
- Resin fillers are suitable for improving reflow resistance because they can impart flexibility at a high temperature such as 260 ° C. compared to inorganic fillers. Moreover, since a resin filler can give a softness
- the content of the filler may be 30 to 90% by mass or 40 to 80% by mass based on the total solid content (components other than the solvent) of the thermosetting resin composition.
- the content is 30% by mass or more, the heat radiating property of the thermosetting resin composition is increased, and void generation and moisture absorption can be further suppressed.
- this content is 90% by mass or less, the fluidity of the thermosetting resin composition due to the increase in viscosity can be suppressed, and the filler can be prevented from being trapped (trapping). There is a tendency to further improve.
- thermosetting resin composition according to the present embodiment may further contain a flux agent (that is, a flux activator exhibiting flux activity (activity for removing oxides and impurities)).
- a flux agent that is, a flux activator exhibiting flux activity (activity for removing oxides and impurities)
- the fluxing agent include nitrogen-containing compounds having a lone pair such as imidazoles and amines, carboxylic acids, phenols, and alcohols.
- an organic acid such as carboxylic acid such as 2-methylglutaric acid strongly expresses flux activity and can further improve connectivity and stability.
- the content of the fluxing agent may be 0.005 to 10.0% by mass or 0.005 to 0.05% by mass based on the entire solid content (components other than the solvent) of the thermosetting resin composition. Good.
- thermosetting resin composition according to this embodiment may further contain additives such as an ion trapper, an antioxidant, a silane coupling agent, a titanium coupling agent, and a leveling agent.
- additives such as an ion trapper, an antioxidant, a silane coupling agent, a titanium coupling agent, and a leveling agent.
- An additive can be used individually by 1 type or in combination of 2 or more types. What is necessary is just to adjust suitably content of an additive so that the effect of each additive may express.
- the curing reaction rate when the thermosetting resin composition according to the present embodiment is held at 200 ° C. for 5 seconds may be 80% or more, or 90% or more.
- the curing reaction rate of the thermosetting resin composition when held at 200 ° C. for 5 seconds, which is not higher than the solder melting temperature is 80% or higher, the solder is less likely to scatter and flow at the connection temperature higher than the solder melting temperature.
- the connection reliability and the insulation reliability tend to be further improved.
- the curing reaction rate was 20 ° C. using DSC (DSC-7 model manufactured by Perkin Elmer) for 10 mg of uncured and heat-treated thermosetting resin composition (film adhesive) in an aluminum pan. / Min, by performing differential scanning calorimetry in the temperature range of 30 to 300 ° C.
- the calorific value ⁇ H (J / g) of an untreated sample is “ ⁇ H1”
- the calorific value ⁇ H (J / g) of the sample after heat treatment at 200 ° C. for 5 seconds on a hot plate was “ ⁇ H2”
- thermosetting resin composition contains an anionically polymerizable epoxy resin (particularly, an epoxy resin having a weight average molecular weight of less than 10,000). It may be difficult to adjust the reaction rate to 80% or more.
- the thermosetting resin composition contains an acrylic resin and an epoxy resin, the content of the epoxy resin may be 20 parts by mass or less with respect to 80 parts by mass of the acrylic resin.
- thermosetting resin composition according to this embodiment can be used for pressure bonding at a high temperature of 200 ° C. or higher. Further, in a flip chip package in which a metal such as solder is melted to form a connection, further excellent curability is exhibited.
- the adhesive layer according to the present embodiment may be a layer formed of an adhesive film prepared in advance from the viewpoint of improving productivity.
- the example of the production method of an adhesive film is shown below.
- a resin varnish is prepared by adding a thermosetting resin, a curing agent, a polymer component, a filler, other additives, etc. in an organic solvent and then dissolving or dispersing by stirring, mixing, kneading, etc. To do.
- the organic solvent is reduced by heating, and the base film An adhesive film is formed thereon.
- a film may be formed by spin-coating a resin varnish on a wafer or the like, and then an adhesive film may be formed on the wafer by a solvent drying method.
- the base film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions when the organic solvent is volatilized.
- the polyester film, the polypropylene film, the polyethylene terephthalate film, the polyimide film, the polyetherimide film, the poly Examples include ether naphthalate film and methylpentene film.
- the base film is not limited to a single layer composed of one of these films, and may be a multilayer film composed of two or more films.
- the heating conditions for volatilizing the organic solvent from the resin varnish after application may be, for example, in the range of 50 to 200 ° C. and 0.1 to 90 minutes. If there is no influence on the void and viscosity adjustment after mounting, the heating condition may be set so that the organic solvent volatilizes to 1.5% or less.
- An adhesive for a semiconductor includes (a ′) a resin component having a weight average molecular weight of less than 10,000, (b) a curing agent, and (f) the following general formula (1): The silanol compound represented by these is contained.
- R 1 represents an alkyl group, a phenyl group or a group comprising a combination thereof, and R 2 represents an alkylene group. You may use this adhesive agent for semiconductors as a thermosetting resin composition in order to form an adhesive bond layer in the manufacturing method of the above-mentioned semiconductor device.
- the semiconductor adhesive according to this embodiment may further contain (c) a polymer component having a weight average molecular weight of 10,000 or more, a flux agent, a filler, and the like.
- a polymer component having a weight average molecular weight of 10,000 or more a polymer component having a weight average molecular weight of 10,000 or more, a flux agent, a filler, and the like.
- (a ′) The resin component having a weight average molecular weight of less than 10,000 is not particularly limited, but (b) is a compound (thermosetting resin) that reacts with a curing agent. May be. A component having a small weight average molecular weight can be decomposed during heating and cause voids, but high heat resistance is easily secured by reacting the component with a curing agent.
- Examples of the resin component having a weight average molecular weight of less than 10,000 include epoxy resins and acrylic resins.
- the (d) curing agent and other aspects relating to the semiconductor adhesive can be the same as the “(d) curing agent” and other aspects relating to the thermosetting resin composition described above.
- the silanol compound represented by the general formula (1) may be solid at 25 ° C from the viewpoint of heat resistance.
- R 1 in formula (1) may be an alkyl group or a phenyl group from the viewpoints of heat resistance and fluidity.
- R 1 may be a group composed of a combination of an alkyl group and a phenyl group (an alkyl-substituted phenyl group or a phenylalkyl group).
- Examples of the group represented by R 1 include a phenyl group, a propyl group, a phenylpropyl group, and a phenylmethyl group.
- R 2 in the formula (1) is not particularly limited, but may be an alkylene group having a weight average molecular weight of 100 to 5000 from the viewpoint of heat resistance.
- a silanol compound in which R 2 is an alkylene group having a weight average molecular weight of 100 to 5,000 usually has a weight average molecular weight in the range of about 100 to 5,000. From the viewpoint of high reactivity (cured product strength), the silanol compound may be a trifunctional silanol.
- (f) silanol compound additive to the adhesive for semiconductor improves the fluidity and further improves the void suppression and high connectivity.
- fluidity improves (viscosity decreases), it becomes easy to eliminate voids entrained during chip contact.
- the silanol compound has high heat resistance and its thermal weight loss is small. Generation of voids can be further suppressed by using a silanol compound having high heat resistance. If the thermal weight loss is small, the volatile content is small and voids are reduced, and the reliability (reflow resistance) is further improved.
- the content of the silanol compound may be 2 to 20% by mass based on the total amount of the adhesive for semiconductors (components other than the solvent). From the viewpoint of high fluidity and cured product strength (adhesive strength, etc.) 2 to 10% by mass, or 2 to 9% by mass. When the content is 2% by mass or more, a more remarkable effect is easily exhibited in terms of high fluidization. When the content is 20% by mass or less, the strength after curing tends to increase and a particularly high adhesive force tends to be exhibited. (F) When the content of the silanol compound is small to some extent, the ratio of the cured product of the epoxy resin or the acrylic resin is increased, so that it is presumed that higher adhesive force is expressed.
- the semiconductor adhesive may be a film, that is, an adhesive film.
- the film-like semiconductor adhesive can be produced by the same method as the above-described method for producing an adhesive film except that the resin varnish contains (f) a silanol compound.
- the adhesive for a semiconductor according to the present embodiment includes, for example, a semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or each connection portion of a plurality of semiconductor chips is electrically connected to each other. In a connected semiconductor device, it is particularly preferably used for sealing a connection portion.
- connection portion in the semiconductor device may be either metal bonding between the bump and the wiring or metal bonding between the bump and the bump.
- flip-chip connection that obtains electrical connection via a semiconductor adhesive may be used. Examples of the semiconductor device are as shown in FIGS. The connection is made between the bump-bump, the bump-pad, and the bump-wiring described above.
- the method for manufacturing a semiconductor device may include connecting a semiconductor chip and a printed circuit board, or a plurality of semiconductor chips using the semiconductor adhesive according to the present embodiment.
- the semiconductor chip and the wiring circuit board are connected to each other via a semiconductor adhesive, and the connection portions of the semiconductor chip and the wiring circuit board are electrically connected to each other.
- connection portions can be connected to each other by metal bonding. That is, the connection portions of the semiconductor chip and the printed circuit board are connected to each other by metal bonding, or the connection portions of the plurality of semiconductor chips are connected to each other by metal bonding.
- the semiconductor adhesive according to the present embodiment can also be used as a thermosetting resin composition in the semiconductor device according to the first, second, or third embodiment described above. Since the adhesive for semiconductors according to this embodiment has high fluidity at high temperatures, it is particularly useful in the third embodiment in which a heating furnace or a hot plate is used as a heating device for main pressure bonding.
- the semiconductor device 600 includes a substrate (for example, a glass epoxy substrate) 2 having a substrate body 20 and wiring (copper wiring) 15 as a connection portion, and a wiring (for example, copper pillar, copper post) 15 as a semiconductor chip body 10 and a connection portion.
- the semiconductor chip 1 having the bumps 30 (connection bumps, solder bumps) is connected to each other through an adhesive layer 40 formed of a semiconductor adhesive.
- the wiring 15 of the semiconductor chip 1 and the wiring 15 of the substrate 2 are electrically connected by bumps 30 (connection bumps, solder bumps).
- a solder resist 70 is disposed on the surface of the substrate body 20 where the wirings 15 are formed, except for the positions where the bumps 30 are formed.
- the wiring 15 on the substrate 2 is plated with gold.
- the metal of the connection part is solder (tin-silver) -gold, and connection is possible if the solder having a low melting point reaches the melting point or higher.
- the semiconductor device 600 may be one in which semiconductor chips are connected to each other. That is, instead of the substrate 2, another semiconductor chip may be connected to the semiconductor chip 1.
- a semiconductor adhesive film adhesive or the like as the adhesive layer 40 is pasted on the substrate 2 on which the solder resist 70 is formed. Affixing can be performed by a hot press, roll lamination, vacuum lamination, or the like. The supply area and thickness of the adhesive layer 40 are appropriately set according to the size of the semiconductor chip 1 or the substrate 2, the bump height, and the like.
- the adhesive layer 40 may be affixed to the semiconductor chip 1, and after adhering the semiconductor adhesive of the present embodiment to a semiconductor wafer, the semiconductor wafer is separated into semiconductor chips 1 by dicing, whereby the adhesive layer 40 You may produce the semiconductor chip 1 which stuck.
- the bumps 30 on the wiring 15 of the semiconductor chip 1 and the wiring 15 of the substrate 2 are connected using a connecting device (crimping device) such as a flip chip bonder.
- a connecting device such as a flip chip bonder.
- pressure bonding first process, provisional pressure bonding
- first process, provisional pressure bonding is performed, and the semiconductor chip 1 and the substrate 2 are heated to a temperature equal to or higher than the melting point of the bump 30
- second process, main pressure bonding While connecting, the space
- the main press bonding (the main connection step, the second step) may be performed so that the metal of either one of the connection portions has a melting point or higher.
- the semiconductor chip 1 and the substrate 2 may be heated so that the temperature of the bump 30 is 250 ° C. or higher.
- connection load of the temporary crimping depends on the number of bumps, but is set in consideration of absorbing bump height variations and controlling the amount of bump deformation.
- the connection portion metal between the semiconductor chip 1 and the substrate 2 may be in contact.
- a good bondability is particularly obtained because the metal bond is easily formed after the second step and the biting of the adhesive for the semiconductor is reduced. easy.
- the connection metal between the semiconductor chip 1 and the substrate 2 forms a contact or metal bond, so that the load can be increased.
- the load may be, for example, 0.009 N to 0.3 N per pin (one bump) of the semiconductor chip.
- Temporary pressure bonding (first step) may be performed in a short time from the viewpoint of improving productivity.
- the temporary press bonding time may be 5 seconds or less, or 3 seconds or less, or 2 seconds or less from the viewpoint of improving productivity.
- Temporary pressure bonding (first step) temperature (temperature of the pressure bonding apparatus) may be so low that heat is not transferred when the pressure bonding tool picks up a semiconductor chip (with a semiconductor adhesive).
- first step temperature temperature of the pressure bonding apparatus
- Temporary pressure bonding (first step) temperature temperature of the pressure bonding apparatus
- the difference between the temperature at which the crimping tool picks up the semiconductor chip and the temperature at the time of contact between the semiconductor chips or between the semiconductor chip and the substrate may be reduced.
- This temperature difference may be 100 ° C. or less or 60 ° C. or less, or may be constant (same set temperature).
- the reaction start temperature is DSC (Perkin Elmer, DSC-Pyrs1), sample amount 10 mg, heating rate 10 ° C./min, measurement atmosphere: On-set in differential scanning calorimetry under the conditions of air or nitrogen atmosphere Refers to temperature.
- the heating temperature in the main bonding (second process) needs to be higher than the melting point of the solder on the package.
- the metal of the connection portion is solder, 230 ° C. or higher and 330 ° C. or lower is preferable.
- the temperature is low, the metal at the connection portion does not melt and a sufficient metal bond is not formed.
- the temperature is high, voids are likely to be generated, and solder is likely to be scattered.
- the heating temperature in the main pressure bonding (main connection step, second step) is higher than the reaction start temperature of the semiconductor adhesive so that not only the metal bond formation but also the curing of the semiconductor adhesive is promoted. Also good. By promoting the curing of the adhesive for the semiconductor during this connection process, it is possible to particularly effectively suppress further void generation and connection failure.
- the heating (second step) of the main pressure bonding is not particularly limited, but can be performed using a heating device such as a reflow furnace, an oven, or a hot plate.
- a heating device such as a reflow furnace, an oven, or a hot plate.
- the heating device include a reflow furnace (manufactured by Tamura Corporation) and a clean oven (manufactured by ESPEC).
- a weight may be placed on them, or they may be sandwiched between clips. Good. Thereby, it is possible to more effectively suppress warpage and connection failure caused by a difference in thermal expansion between semiconductor chips or between a semiconductor chip and a semiconductor adhesive.
- a plurality of chips may be crimped together.
- stack pressure bonding which is often seen in a TSV structure package, a plurality of chips are three-dimensionally pressure bonded.
- the plurality of chips may be finally press-bonded together in a second step.
- Example of examination mainly related to first embodiment 1-1. Production of Adhesive Film The compounds used for production of the adhesive film are shown below.
- Thermosetting resin acrylic resin / ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300)
- An acrylate compound having a fluorene skeleton (Osaka Gas Chemical Co., Ltd., EA0200, number of functional groups of acryloyl group: 2)
- Polyfunctional solid epoxy resin having epoxy resin and triphenolmethane skeleton Japan Epoxy Resin Co., Ltd., EP1032H60
- Bisphenol F type liquid epoxy resin (Japan Epoxy Resin Co., Ltd., YL983U)
- phenoxy resin (ZX1356) as a polymer component was added, and the mixture was again stirred with a bead mill for 30 minutes.
- a curing agent Park Mill D
- the beads were removed by filtration to obtain a varnish.
- the obtained varnish was coated with a small precision coating apparatus (manufactured by Yasui Seiki Co., Ltd.), and the coating film was dried (70 ° C./10 min) with a clean oven (manufactured by ESPEC) to obtain an adhesive film.
- Example 1-1 Two pressing members I and II (FCB3, manufactured by Panasonic) having an opposing stage and a pressing head are prepared, the pressing member I is used as a temporary pressing member, and the pressing member II is used as a main pressing member.
- a semiconductor device was manufactured according to the following procedure.
- the produced adhesive film of Production Example 1-1 was cut out (8 mm ⁇ 8 mm ⁇ 0.045 mmt), a semiconductor chip (chip size: 10 mm ⁇ 10 mm ⁇ 0.4 mmt, metal of connection part: Au, product name: WALTS-TEG (IP80, manufactured by WALTS).
- the semiconductor chip to which the adhesive film was attached was supplied onto the stage of the pressing member I as a temporary pressing member.
- a semiconductor chip on this stage and a semiconductor chip with solder bumps (chip size: 7.3 mm ⁇ 7.3 mm ⁇ 0.15 mmt, metal at connection part: copper pillar + solder, bump height: copper pillar + solder meter about 45 ⁇ m , Bump number 1048 pins, pitch 80 ⁇ m, product name: WALTS-TEG CC80, manufactured by WALTS) were aligned so that the respective connection portions face each other. Thereafter, a laminated body composed of the semiconductor chip, the adhesive film, and the semiconductor chip was sandwiched between the pressure-bonding head and the stage and pressurized and heated to temporarily press-bond the semiconductor chips.
- the temporary pressure bonding conditions and the main pressure bonding conditions are as follows. These conditions were set so that void evaluation and connection evaluation related to the obtained semiconductor device were “A”. -Temporary pressure bonding conditions Temperature of pressure bonding head: 80 ° C, load: 75N, stage temperature: 80 ° C -Main crimping conditions Crimping head temperature: 280 ° C, load: 75N, stage temperature: 80 ° C A plurality of semiconductor devices were continuously manufactured while simultaneously operating the two pressing members I and II in parallel. Table 2 shows the results of manufacturing time required for provisional pressure bonding and main pressure bonding, manufacturing time per semiconductor device package (PKG), and the number of semiconductor devices produced per hour (UPH).
- Table 2 shows the manufacturing time required for each stage, the manufacturing time per semiconductor device package (PKG), and the number of packages produced per hour (UPH).
- Example 1-2 A semiconductor device was produced in the same manner as in Example 1 except that the adhesive film of Production Example 1-2 was used. The results are shown in Table 3.
- Comparative Example 1-2 A semiconductor device was manufactured in the same manner as Comparative Example 1 except that the adhesive film of Production Example 1-2 was used. The results are shown in Table 3.
- Example 1-3 A semiconductor device was manufactured in the same manner as in Example 1 except that the adhesive film of Production Example 1-3 was used. The results are shown in Table 4.
- the manufacturing time of the semiconductor device can be shortened, and the number of semiconductor devices produced per hour (UPH) can be increased. Can do.
- phenoxy resin (ZX1356) as a polymer component was added, and the mixture was again stirred with a bead mill for 30 minutes.
- a curing agent Park Mill D
- the beads were removed by filtration to obtain a varnish.
- the obtained varnish was coated with a small precision coating apparatus (manufactured by Yasui Seiki Co., Ltd.), and the coating film was dried (70 ° C./10 min) with a clean oven (manufactured by ESPEC) to obtain an adhesive film.
- compression-bonding process was measured with the following method.
- Example 2 Manufacturing of a semiconductor device (Example 1) Two pressing members I and II (FCB3, manufactured by Panasonic) having an opposing stage and a pressing head are prepared, the pressing member I is used as a temporary pressing member, and the pressing member II is used as a main pressing member.
- a semiconductor device was manufactured according to the following procedure.
- the produced adhesive film of Production Example 2-1 was cut out (8 mm ⁇ 8 mm ⁇ 0.045 mmt), a semiconductor chip (chip size: 10 mm ⁇ 10 mm ⁇ 0.4 mmt, metal of connection part: Au, product name: WALTS-TEG (IP80, manufactured by WALTS).
- the semiconductor chip to which the adhesive film was attached was supplied onto the stage of the pressing member I as a temporary pressing member.
- a semiconductor chip on this stage and a semiconductor chip with solder bumps (chip size: 7.3 mm ⁇ 7.3 mm ⁇ 0.15 mmt, metal at connection part: copper pillar + solder, bump height: copper pillar + solder meter about 45 ⁇ m , Bump number 1048 pins, pitch 80 ⁇ m, product name: WALTS-TEG CC80, manufactured by WALTS) were aligned so that the respective connection portions face each other. Thereafter, the laminated body composed of the semiconductor chip, the adhesive film, and the semiconductor chip was sandwiched between the pressure bonding head and the stage, and was pressed and heated, so that the semiconductor chips were temporarily pressure bonded so that the connection portions were in contact with each other.
- the laminated body after the temporary pressure bonding was heated and pressed by being sandwiched between pressing members II as pressing members for main pressure bonding, and the semiconductor chips were electrically connected.
- the temporary pressure bonding conditions and the main pressure bonding conditions are as shown in Table 6.
- the stage temperature was 80 ° C. and the pressure bonding time was 2 seconds.
- Examples 2-2 to 2-8 Semiconductor devices of Examples 2-2 to 2-8 were manufactured in the same manner as in Example 1 except that the temperature and load of the pressure-bonding head in the temporary pressure-bonding process and the main pressure-bonding process were changed as shown in Table 2.
- connection resistance value of the manufactured semiconductor device was measured using a multimeter (trade name “R6871E” manufactured by ADVANTEST), thereby evaluating continuity after the provisional pressure bonding step and the main pressure bonding step.
- the case where the peripheral portion is conductive (the resistance value is displayed) is “A”
- the case where the conductive portion is not conductive (the resistance value is not displayed) is “B”.
- the case where the initial connection resistance value on the inner periphery of the peripheral portion is 45 ⁇ or less and the initial connection resistance value on the outer periphery is 85 ⁇ or less is “A”
- the initial connection resistance value on the inner periphery is 45 ⁇ .
- the case where the initial connection resistance value of the outer periphery exceeds 85 ⁇ and the case of no conduction (resistance value is not displayed) are all set to “B”.
- the results are shown in Table 6.
- melt viscosity of the adhesive layer is 7000 Pa at the pressure-bonding head temperature in the temporary pressure-bonding step. -It was confirmed that being less than s contributes to the suppression of the generation of voids and the improvement of the reliability of the semiconductor device.
- Thermosetting resin epoxy resin / Triphenolmethane skeleton-containing polyfunctional solid epoxy resin (EP 1032H60, Japan Epoxy Resin Co., Ltd., weight average molecular weight: 800 to 2000) ⁇ Bisphenol F type liquid epoxy resin (YL983U, Japan Epoxy Resin Co., Ltd., molecular weight: about 336) Flexible semi-solid epoxy resin (YL7175-1000, Japan Epoxy Resin Co., Ltd., weight average molecular weight: 1000 to 5000)
- Acrylic resin / fluorene skeleton acrylate resin (EA0200, Osaka Gas Chemical Co., Ltd., bifunctional group, molecular weight: about 546)
- thermosetting resin compositions A and B were prepared using thermosetting resin compositions A and B.
- a specific manufacturing method is described below.
- a thermosetting resin, a filler, and, if necessary, a flux agent were added to methyl ethyl ketone so that the concentration of the nonvolatile content (solid content) was 60% by mass.
- beads of ⁇ 1.0 mm and ⁇ 2.0 mm were added to the mixed solution in the same mass as the solid content, and the mixture was stirred for 30 minutes with a bead mill (Fritch Japan Co., Ltd., planetary pulverizer P-7).
- the polymer component was added to the mixture and stirred for 30 minutes with a bead mill.
- the curing agent and, if necessary, an additive were added and stirred, the beads were removed by filtering the mixed solution, and the filtrate was obtained as the thermosetting resin composition A or B.
- thermosetting resin composition A or B is applied with a small precision coating device (Yurui Seiki), dried (70 ° C / 10 minutes) in a clean oven (manufactured by ESPEC), and bonded. An agent film was obtained.
- This semiconductor chip with an adhesive film is connected to a semiconductor chip with solder bumps through the adhesive film (chip size: 7.3 mm ⁇ 7.3 mm ⁇ 0.15 mmt, bump height: copper pillar + solder height meter about 45 ⁇ m, number of bumps 1048 pins, pitch 80 ⁇ m, product name: WALTS-TEG CC80, manufactured by WALTS) and temporarily bonded with FCB3 (manufactured by Panasonic, pressure bonding head area: 7.3 mm ⁇ 7.3 mm) to prepare a laminate. .
- the laminated body using the thermosetting resin composition A was temporarily pressure-bonded by setting the temperature of the pressure-bonding head of FCB3 to 130 ° C. and heating and pressing at a pressure of 50 N for 3 seconds.
- the laminate using the thermosetting resin composition B was temporarily pressure-bonded by setting the temperature of the pressure-bonding head of FCB3 to 130 ° C. and heating and pressurizing at a pressure of 100 N for 3 seconds.
- Nine laminated bodies after provisional pressure bonding were prepared, and nine laminated bodies were installed on the stage of a batch connection apparatus (Alpha Design, HTB-MM) having a pressure bonding head area of 100 mm ⁇ 100 mm. After the installation, a 100 mm ⁇ 100 mm batch connection sheet was placed on the laminated body, and finally subjected to final pressure bonding to obtain a semiconductor device.
- the main pressure bonding was performed by setting the stage temperature to 80 ° C., setting the temperature of the pressure bonding head to 250 ° C., and heating and pressing at a pressure of 900 N (100 N per laminated body) for 5 seconds.
- the displacement amount of the batch connection sheet at 250 ° C. was measured using an electromechanical universal testing machine (manufactured by INSTRON, 5900 series) and Bluehill 3 software.
- the batch connection sheet is placed in a 250 ° C. tank, and the main surface of the batch connection sheet and the end surface of the pressing jig are parallel using a bar-shaped pressing jig having a circular end surface with a diameter of 8 ⁇ m.
- a compression test was carried out by pressing in the direction. With a pressing jig, a load of 100 N (about 2 MPa) was applied to the batch connection sheet at a speed of 0.001 mm / sec. The displacement at the time when the compressive load became 0N to 100N and 5 seconds passed and the load was stabilized at 100N was recorded as the displacement amount of the film thickness of the batch connection sheet.
- Table 8 shows the results of manufacturing the semiconductor device in a lump using the thermosetting resin composition A and various lump connecting sheets.
- Table 9 shows the results of manufacturing semiconductor devices in a batch using the thermosetting resin composition B and various batch connection sheets.
- phenoxy resin (ZX1356) as a polymer component was added, and the mixture was again stirred with a bead mill for 30 minutes.
- a curing agent Park Mill D
- the obtained varnish was coated with a small precision coating apparatus (manufactured by Yasui Seiki Co., Ltd.) and dried (70 ° C./10 min) in a clean oven (manufactured by ESPEC) to obtain an adhesive film.
- Example 4-1 Manufacturing of semiconductor device (Example 4-1) The produced adhesive film of Production Example 4-1 was cut out (8 mm ⁇ 8 mm ⁇ 0.045 mmt), a semiconductor chip (chip size: 10 mm ⁇ 10 mm ⁇ 0.4 mmt, metal of connection part: Au, product name: WALTS-TEG (IP80, manufactured by WALTS). Next, the semiconductor chip to which the adhesive film was attached was supplied onto a stage of a pressing member prepared as a temporary pressing member.
- a semiconductor chip on this stage and a semiconductor chip with solder bumps (chip size: 7.3 mm ⁇ 7.3 mm ⁇ 0.15 mmt, metal at connection part: copper pillar + solder, bump height: copper pillar + solder meter about 45 ⁇ m , Bump number 1048 pins, pitch 80 ⁇ m, product name: WALTS-TEG CC80, manufactured by WALTS) were aligned so that the respective connection portions face each other. Thereafter, a laminated body composed of the semiconductor chip, the adhesive film, and the semiconductor chip was sandwiched between the pressure-bonding head and the stage and pressurized and heated to temporarily press-bond the semiconductor chips.
- the obtained laminate was transported to a reflow furnace and heated at a maximum temperature of 260 ° C. for 600 seconds to electrically connect the chips.
- a plurality of laminated bodies were formed in the temporary press bonding process, and a plurality of semiconductor devices were manufactured at a time by conveying them all at once to a reflow furnace.
- Table 11 shows the manufacturing time required for each of the provisional pressure bonding process and the heating process per semiconductor device package (PKG) and the manufacturing time per semiconductor device 100 package (PKG).
- -Temporary pressure bonding conditions Temperature of pressure bonding head: 80 ° C, load: 75N, stage temperature: 80 ° C
- connection evaluation By measuring the connection resistance value of the manufactured semiconductor device using a multimeter (trade name “R6871E” manufactured by ADVANTEST), initial conduction after mounting was evaluated. When the initial connection resistance value on the inner periphery of the peripheral part is 45 ⁇ or less and the initial connection resistance value on the outer periphery is 85 ⁇ or less, “A” is given. When the initial connection resistance value on the inner periphery exceeds 45 ⁇ , The case where the connection resistance value exceeded 85 ⁇ and the case where the connection resistance value was not conducted (the resistance value was not displayed) were all set to “B”.
- Example 4-1 A semiconductor device was manufactured in the same manner as in Example 4-1, except that the conditions were changed in the following points.
- the semiconductor chip and the bumped semiconductor chip were aligned on the stage of the pressing member.
- the pressure of the pressure-bonding head was raised to 280 ° C. in 1 second while being pressed by the pressure-bonding head and the stage of the pressing member, and then held in that state for 2 seconds.
- the semiconductor chip and the semiconductor chip with bumps were pressure-bonded to each other and electrically connected.
- the total time taken for crimping was 3 seconds.
- the temperature of the pressure bonding head was cooled from 280 ° C. to the semiconductor chip supply temperature of 80 ° C.
- a plurality of semiconductor devices were manufactured using the pressing member. In manufacturing the semiconductor device, conditions are set so that the connection evaluation is “A”. Table 11 shows the results of manufacturing time required for each stage of the crimping process and manufacturing time per semiconductor device 100 package (PKG).
- Example 4-2 A semiconductor device was manufactured in the same manner as in Example 4-1, except that an oven was used instead of the reflow furnace as the heating device, and the laminate was heated in an oven at 260 ° C. for 600 seconds. The results are shown in Table 12.
- Example 4-3 A semiconductor device was manufactured in the same manner as in Example 4-1, except that the adhesive film of Production Example 4-2 was used. The results are shown in Table 13.
- Comparative Example 4-2 A semiconductor device was manufactured in the same manner as Comparative Example 4-1, except that the adhesive film of Manufacturing Example 4-2 was used. The results are shown in Table 13.
- Example 4-4 A semiconductor device was manufactured in the same manner as in Example 4-3 except that an oven was used instead of the reflow furnace as the heating device, and the laminate was heated in an oven at 260 ° C. for 600 seconds. The results are shown in Table 14.
- the manufacturing time of the semiconductor device can be shortened.
- Example 5-1 An organic solvent (methyl ethyl ketone) was added to the epoxy resin, 2MAOK, 2-methylglutaric acid, inorganic filler, resin filler, and silanol so that NV (nonvolatile content) was 60% by mass. Then, ⁇ 1.0 mm and ⁇ 2.0 mm beads were added in the same mass as the solid content, and the mixture was stirred for 30 minutes with a bead mill (Fritsch Japan KK, planetary pulverizer P-7). Thereafter, ZX1356 was added, and the mixture was again stirred with a bead mill for 30 minutes. The beads used for stirring were removed by filtration. The produced varnish (adhesive for semiconductor) is applied with a small precision coating device (Yurui Seiki), and the coating film is dried (70 ° C / 10 min) in a clean oven (ESPEC) to obtain a film adhesive It was.
- NV nonvolatile content
- Examples 5-2 to 5-4, Reference Examples 5-1 to 5-3 A film adhesive was produced in the same manner as the film adhesive production method of Example 5-1, except that the materials used were changed as shown in Table 15.
- the compounding amount of each material is the compounding amount of non-volatile content, and the unit is parts by mass.
- Positioning was performed at 130 ° C./100 N / 3 s and provisional pressure bonding was performed (first step).
- the laminated body after the temporary pressure bonding was subjected to main pressure bonding by passing it through a reflow furnace (manufactured by Tamura Corporation) reaching a maximum temperature of 260 ° C. for about 600 s (10 min) to obtain a sample of a semiconductor device package.
- a reflow furnace manufactured by Tamura Corporation
- a maximum temperature of 260 ° C. for about 600 s (10 min) to obtain a sample of a semiconductor device package.
- whether or not initial conduction was possible was measured using a multimeter (manufactured by ADVANTEST, R6871E). Samples having a connection resistance value of 32.0 to 38.0 ⁇ at the peripheral part (inner peripheral part) were evaluated as A (good connection), and other resistance values or Open were evaluated as B (bad connection).
- the semiconductor adhesives of Examples 5-1 to 5-4 to which the solid silanol represented by the general formula (1) is added can be connected with a boyless after both the first step and the second step, and the connection can be secured. It was confirmed that the reflow resistance was also satisfied.
- SYMBOLS 1 ... Semiconductor chip, 2 ... Board
Abstract
Description
[2]上記R1がフェニル基である、[1]記載の半導体用接着剤。
[3]上記(c)シラノール化合物が25℃で固形である、[1]又は[2]記載の半導体用接着剤。
[4](d)10000以上の重量平均分子量を有する高分子成分を更に含有する、[1]~[3]のいずれかに記載の半導体用接着剤。
[5]上記(d)10000以上の重量平均分子量を有する高分子成分が、重量平均分子量30000以上であり、且つ、ガラス転移温度が100℃以下である、[4]記載の半導体用接着剤。
[6]フィルム状である、[1]~[5]のいずれかに記載の半導体用接着剤。
[7]半導体チップ及び配線回路基板のそれぞれの接続部が互いに電気的に接続された半導体装置、又は、複数の半導体チップのそれぞれの接続部が互いに電気的に接続された半導体装置を、上記接続部の金属の融点より低温で圧着する第一工程と、上記接続部の金属の融点以上の高温で加熱処理することで金属結合を形成する第二工程と、を経て製造する際に、上記接続部の封止に用いられる、[1]~[6]のいずれかに記載の半導体用接着剤。
第一の実施形態
図1は、本実施形態に係る半導体装置の製造方法において、半導体チップに基板を仮圧着する工程の一例を示す工程図である。
第二の実施形態に係る半導体装置の製造方法も、半導体チップと基板又は他の半導体チップとを仮固定して積層体を得た後、ステージと圧着ヘッドを備える本圧着用押圧部材により本圧着する工程を備える。半導体チップと基板又は他の半導体チップとを仮固定して積層体を得る工程は、第一の実施形態の仮圧着と同様の態様であり得る。第二の実施形態は、ステージ上に配置された複数の積層体とそれらを覆うように配置された一括接続用シートとを、ステージとステージに対向する圧着ヘッドとで挟むことによって、一括して複数の積層体が加熱及び加圧されて本圧着される点で第一の実施形態と異なり、その他は第一の実施形態と同様である。図3は、一括接続用シートを用いて、半導体チップの接続部と基板の接続部とを金属接合によって電気的に接続する本圧着の工程の一例を示す工程図である。半導体ウエハと複数の半導体チップとを有する積層体をステージ上に配置し、それを一括接続用シートで覆ってもよい。
一括接続用シートの原料は、250℃において特定の貯蔵弾性率と変位量を示す樹脂であれば特に限定されない。樹脂としては、例えば、ポリテトラフルオロエチレン樹脂、ポリイミド樹脂、フェノキシ樹脂、エポキシ樹脂、ポリアミド樹脂、ポリカルボジイミド樹脂、シアネートエステル樹脂、アクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂、及びアクリルゴムが挙げられる。一括接続用シートは、耐熱性及びフィルム形成性に優れるという観点から、ポリテトラフルオロエチレン樹脂、ポリイミド樹脂、エポキシ樹脂、フェノキシ樹脂、アクリル樹脂、アクリルゴム、シアネートエステル樹脂、及びポリカルボジイミド樹脂から選ばれる少なくとも1種の樹脂を含むシートであってもよい。一括接続用シートの樹脂は、耐熱性及びフィルム形成性に特に優れるという観点から、ポリテトラフルオロエチレン樹脂、ポリイミド樹脂、フェノキシ樹脂、アクリル樹脂及びアクリルゴムから選ばれる少なくとも1種の樹脂を含むシートであってもよい。これらの樹脂は、1種を単独で又は2種以上を組み合わせて用いることができる。
第三の実施形態に係る半導体装置の製造方法では、第一の実施形態と同様の仮圧着に続いて、図4に示すように、仮圧着された積層体3を加熱炉60内で加熱することによって、半導体チップ1のバンプ30と、基板2の配線16とを金属接合によって電気的に接続する。第三の実施形態に係る方法は、これ以外の点では第一の実施形態と同様である。1つの加熱炉60内で複数の積層体を加熱して、複数の積層体における接続を一括して行ってもよい。
本実施形態に係る半導体装置の製造方法によって得られる半導体装置について説明する。本実施形態に係る半導体装置における接続部は、バンプと配線との金属接合、及び、バンプとバンプとの金属接合のいずれでもよい。本実施形態に係る半導体装置では、例えば、接着剤層を介して電気的な接続を得るフリップチップ接続を用いることができる。
接着剤層は、例えば、10000以下の分子量を有する熱硬化性樹脂、及びその硬化剤を含有する熱硬化性樹脂組成物によって形成された層であることができる。言い換えると、接着剤層は、10000以下の分子量を有する熱硬化性樹脂、及びその硬化剤を含有する熱硬化性樹脂組成物を含む層であってもよい。
熱硬化性樹脂は、加熱により架橋構造を形成し得る化合物である。熱硬化性樹脂は10000以下の分子量を有していてもよい。熱硬化性樹脂組成物が硬化剤と反応して架橋構造を形成する化合物(熱硬化性樹脂)を含むことで、分子量が小さい成分が加熱時に分解等して発生させるボイドが抑制されるため、耐熱性の点で有利である。熱硬化性樹脂としては、エポキシ樹脂、アクリル樹脂等が挙げられる。
アクリル樹脂は、分子内に1個以上の(メタ)アクリロイル基を有する化合物である。アクリル樹脂としては、例えば、ビスフェノールA、ビスフェノールF、ナフタレン、フェノールノボラック、クレゾールノボラック、フェノールアラルキル、ビフェニル、トリフェニルメタン、ジシクロペンタジエン、フルオレン、アダマンタン及びイソシアヌル酸から選ばれる化合物に由来する骨格及び(メタ)アクリロイルオキシ基を有する(メタ)アクリレート、並びに各種多官能(メタ)アクリル化合物が挙げられる。耐熱性の観点から、アクリル樹脂を、ビスフェノールA、ビスフェノールF、ナフタレン、フルオレン、アダマンタン及びイソシアヌル酸から選ばれる化合物に由来する骨格を有する(メタ)アクリレートから選択してもよい。アクリル樹脂は、1種を単独で又は2種以上を組み合わせて用いることができる。
エポキシ樹脂は、分子内に2個以上のエポキシ基を有する化合物である。エポキシ樹脂としては、例えば、ビスフェノールA型、ビスフェノールF型、ナフタレン型、フェノールノボラック型、クレゾールノボラック型、フェノールアラルキル型、ビフェニル型、トリフェニルメタン型及びジシクロペンタジエン型エポキシ樹脂、並びに各種多官能エポキシ樹脂が挙げられる。耐熱性、取り扱い性の観点から、エポキシ樹脂を、ビスフェノールF型、フェノールノボラック型、クレゾールノボラック型、ビフェニル型、及びトリフェニルメタン型エポキシ樹脂から選択してもよい。速硬化性及び耐熱性の観点から、エポキシ樹脂を、ビスフェノールF型及びトリフェニルメタン型エポキシ樹脂から選択してもよい。エポキシ樹脂は、1種を単独で又は2種以上を組み合わせて用いることができる。
硬化剤は、熱硬化性樹脂と反応して、熱硬化性樹脂とともに架橋構造を形成する化合物である。硬化剤としては、例えば、フェノール樹脂系硬化剤、酸無水物系硬化剤、アミン系硬化剤、イミダゾール系硬化剤、ホスフィン系硬化剤、アゾ化合物及び有機過酸化物が挙げられる。硬化反応(硬化系)はラジカル重合ラジカル重合系)であってもよい。硬化剤は、1種を単独で又は2種以上を組み合わせて用いることができる。フェノール樹脂系硬化剤、酸無水物系硬化剤及びアミン系硬化剤は、それぞれ1種を単独で又は2種以上の混合物として使用することができる。イミダゾール系硬化剤及びホスフィン系硬化剤はそれぞれ単独で用いてもよいが、フェノール樹脂系硬化剤、酸無水物系硬化剤又はアミン系硬化剤と共に用いてもよい。
フェノール樹脂系硬化剤は、分子内に2個以上のフェノール性水酸基を有する。フェノール樹脂系硬化剤としては、例えば、フェノールノボラック、クレゾールノボラック、フェノールアラルキル樹脂、クレゾールナフトールホルムアルデヒド重縮合物、トリフェニルメタン型多官能フェノール及び各種多官能フェノール樹脂が挙げられる。これらは1種を単独で又は2種以上を組み合わせて用いることができる。
酸無水物系硬化剤としては、例えば、メチルシクロヘキサンテトラカルボン酸二無水物、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物及びエチレングリコールビスアンヒドロトリメリテートが挙げられる。これらは1種を単独で又は2種以上を組み合わせて用いることができる。
アミン系硬化剤としては、例えば、ジシアンジアミド、ドデカンジアミン等が挙げられる。これらは1種を単独で又は2種以上を組み合わせて用いることができる。
イミダゾール系硬化剤としては、例えば、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノ-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾールトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-ウンデシルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-エチル-4’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体、2-フェニルイミダゾールイソシアヌル酸付加体、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、及び、エポキシ樹脂とイミダゾール類の付加体が挙げられる。硬化性、保存安定性及び接続信頼性に優れる観点から、イミダゾール系硬化剤を、1-シアノエチル-2-ウンデシルイミダゾール、1-シアノ-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾールトリメリテイト、1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-エチル-4’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体、2-フェニルイミダゾールイソシアヌル酸付加体、2-フェニル-4,5-ジヒドロキシメチルイミダゾール及び2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールから選択してもよい。これらは1種を単独で又は2種以上を組み合わせて用いることができる。また、これらをマイクロカプセル化した潜在性硬化剤として用いてもよい。
ホスフィン系硬化剤としては、例えば、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラ(4-メチルフェニル)ボレート及びテトラフェニルホスホニウム(4-フルオロフェニル)ボレートが挙げられる。これらは1種を単独で又は2種以上を組み合わせて用いることができる。
アゾ化合物としては、例えば、ジメチルアミノアゾベンゼン、ジメチルアミノアゾベンゼン-カルボン酸、ジエチルアミノアゾベンゼン、及びジエチルアミノアゾベンゼン-カルボン酸が挙げられる。アゾ化合物は、1種を単独で又は2種以上を組み合わせて用いることができる。
有機過酸化物としては、例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネイト、パーオキシエステル等が挙げられる。有機過酸化物は、保存安定性の観点から、ハイドロパーオキサイド、ジアルキルパーオキサイド及びパーオキシエステルから選択される1種以上であってもよい。有機過酸化物は、耐熱性の観点から、ハイドロパーオキサイド及びジアルキルパーオキサイドから選択される1種以上であってもよい。これらは1種を単独で又は2種以上を組み合わせて用いることができる。
本実施形態に係る熱硬化性樹脂組成物は、10000以上の重量平均分子量を有する高分子成分を更に含有していてもよい。熱硬化性樹脂、硬化剤等の、高分子成分以外の成分の重量平均分子量又は分子量は、通常、10000未満である。高分子成分としては、例えば、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリカルボジイミド樹脂、シアネートエステル樹脂、アクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂及びアクリルゴムが挙げられる。耐熱性及びフィルム形成性に優れるという観点から、高分子量成分を、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、アクリル樹脂、アクリルゴム、シアネートエステル樹脂及びポリカルボジイミド樹脂から選択してもよい。耐熱性及びフィルム形成性に更に優れるという観点から、高分子量成分を、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、アクリル樹脂及びアクリルゴムから選択してもよい。これらの高分子成分は、1種を単独で又は2種以上を組み合わせて用いることができる。
本実施形態に係る熱硬化性樹脂組成物は、粘度及び硬化物の物性を制御するため、及び、半導体チップ同士、又は半導体チップと基板とを接続した際のボイドの発生及び吸湿率の更なる抑制のために、フィラーを更に含有していてもよい。フィラーとしては、例えば、無機フィラー及び樹脂フィラーが挙げられる。無機フィラーとしては、例えば、ガラス、シリカ、アルミナ、酸化チタン、カーボンブラック、マイカ及び窒化ホウ素等の絶縁性無機フィラーが挙げられる。取り扱い性の観点から、無垢フィラーをシリカ、アルミナ、酸化チタン及び窒化ホウ素から選択してもよいし、形状統一性(取り扱い性)の観点から、無垢フィラーをシリカ、アルミナ及び窒化ホウ素から選択してもよい。絶縁性無機フィラーはウィスカーであってもよい。ウィスカーとしては、例えば、ホウ酸アルミニウム、チタン酸アルミニウム、酸化亜鉛、珪酸カルシウム、硫酸マグネシウム及び窒化ホウ素が挙げられる。樹脂フィラーとしては、例えば、ポリウレタン、ポリイミド、メタクリル酸メチル樹脂及びメタクリル酸メチル-ブタジエン-スチレン共重合樹脂(MBS)が挙げられる。フィラーは、1種を単独で又は2種以上を組み合わせて用いることができる。フィラーの形状、粒径、及び含有量は特に制限されない。
本実施形態に係る熱硬化性樹脂組成物は、フラックス剤(すなわち、フラックス活性(酸化物及び不純物を除去する活性)を示すフラックス活性剤)を更に含有していてもよい。フラックス剤としては、例えば、イミダゾール類及びアミン類等の非共有電子対を有する含窒素化合物、カルボン酸類、フェノール類及びアルコール類が挙げられる。アルコール等に比べて有機酸(2-メチルグルタル酸等のカルボン酸など)がフラックス活性を強く発現し、接続性及び安定性をより向上させることができる。
硬化反応率(%)=(ΔH1-ΔH2)/ΔH1×100
一実施形態に係る半導体用接着剤は、(a’)重量平均分子量10000未満の樹脂成分、(b)硬化剤、及び、(f)下記一般式(1):
(a’)重量平均分子量10000未満の樹脂成分としては、特に制限はないが、(b)硬化剤と反応する化合物(熱硬化性樹脂)であってもよい。重量平均分子量が小さい成分は加熱時に分解等してボイドの原因となり得るが、当該成分が硬化剤と反応することで高い耐熱性が確保され易い。(a)重量平均分子量10000未満の樹脂成分としては、例えば、エポキシ樹脂、アクリル樹脂等が挙げられる。(a’)重量平均分子量10000未満の樹脂成分は、熱硬化性樹脂である場合、上述の「(a)熱硬化性樹脂」と同様の態様であることができる。
上記一般式(1)で表されるシラノール化合物は、耐熱性の観点から、25℃で固形であってもよい。式(1)中のR1は耐熱性、流動性の観点からアルキル基又はフェニル基であってもよい。R1はアルキル基とフェニル基との組み合わせからなる基(アルキル置換フェニル基又はフェニルアルキル基)であってもよい。R1で示される基としては、例えば、フェニル基、プロピル基、フェニルプロピル基、及びフェニルメチル基が挙げられる。式(1)中のR2は特に制限はないが、耐熱性の観点から重量平均分子量100~5000のアルキレン基であってもよい。R2が重量平均分子量100~5000のアルキレン基であるシラノール化合物は、通常、約100~5000の範囲の重量平均分子量を有する。高反応性(硬化物強度)の観点から、シラノール化合物は3官能シラノールであってもよい。
1-1.接着剤フィルムの作製
接着剤フィルムの作製に使用した化合物を以下に示す。
アクリル樹脂
・エトキシ化イソシアヌル酸トリアクリレート(新中村化学工業株式会社製、A-9300)
・フルオレン骨格を有するアクリレート化合物(大阪ガスケミカル株式会社製、EA0200、アクリロイル基の官能基数:2)
エポキシ樹脂
・トリフェノールメタン骨格を有する多官能固形エポキシ樹脂(ジャパンエポキシレジン株式会社製、EP1032H60)
・ビスフェノールF型液状エポキシ樹脂(ジャパンエポキシレジン株式会社製、YL983U)
・ジクミル過酸化物(日油株式会社製、パークミルD)
・2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体(四国化成株式会社製、2MAOK-PW)
・フェノキシ樹脂(東都化成株式会社製、ZX1356、Tg:約71℃、重量平均分子量:約63000)
・アクリルゴム(日立化成株式会社製、KH-C865、Tg:0~12℃、重量平均分子量:450000~650000)
無機フィラー
・シリカフィラー(株式会社アドマテックス製、SE2050、平均粒径:0.5μm)・エポキシシランで表面処理されたシリカフィラー(株式会社アドマテックス製、SE2050SEJ、平均粒径:0.5μm)
・メタクリル表面処理ナノシリカフィラー(株式会社アドマテックス製、YA050CSM
、以下「SMナノシリカ」と表記する、平均粒径:約50nm)
樹脂フィラー
・有機フィラー(ロームアンドハースジャパン(株)製、EXL-2655:コアシェルタイプ有機微粒子)
・2-メチルグルタル酸(アルドリッチ製、融点:約77℃、以下「グルタル酸」と表記する)
表1に示す配合量(単位:質量部)のアクリル樹脂(A9300)、無機フィラー(SE2050、SE2050SEJ及びSMナノシリカ)及び樹脂フィラー(EXL2655)を、不揮発分(固形分、溶媒以外の成分)の濃度が60質量%になるように、溶媒としてのメチルエチルケトンに加えた。次いで、Φ1.0mm、Φ2.0mmのビーズを、メチルエチルケトンに加えたアクリル樹脂及び無機フィラーの合計量と同じ量加え、ビーズミル(フリッチュ・ジャパン株式会社製、遊星型微粉砕機P-7)で30分撹拌した。その後、高分子成分としてのフェノキシ樹脂(ZX1356)を加え、再度、ビーズミルで30分撹拌した。撹拌後、硬化剤(パークミルD)を添加して攪拌し、ビーズをろ過によって除去してワニスを得た。得られたワニスを小型精密塗工装置(株式会社廉井精機製)で塗工し、塗膜をクリーンオーブン(ESPEC製)で乾燥(70℃/10min)して、接着剤フィルムを得た。
使用した材料を表1に示すように変更したこと以外は製造例1-1と同様にして、接着剤フィルムを得た。フラックス剤は、熱硬化性樹脂と同時に添加した。
(実施例1-1)
対向するステージ及び圧着ヘッドを有する2台の押圧部材I,II(FCB3、パナソニック製)を準備し、押圧部材Iを仮圧着用部材として用い、押圧部材IIを本圧着用押圧部材として用いて、以下の手順で半導体装置を製造した。
作製した製造例1-1の接着剤フィルムを切り抜き(8mm×8mm×0.045mmt)、半導体チップ(チップサイズ:10mm×10mm×0.4mmt、接続部の金属:Au、製品名:WALTS-TEG IP80、WALTS製)上に貼付した。次いで、接着剤フィルムを貼付した半導体チップを、仮圧着用押圧部材としての押圧部材Iのステージ上に供給した。このステージ上の半導体チップと、はんだバンプ付き半導体チップ(チップサイズ:7.3mm×7.3mm×0.15mmt、接続部の金属:銅ピラー+はんだ、バンプ高さ:銅ピラー+はんだ計約45μm、バンプ数1048ピン、ピッチ80μm、製品名:WALTS-TEG CC80、WALTS製)とをそれぞれの接続部が互いに対向するように位置合わせした。その後、半導体チップ、接着剤フィルム及び半導体チップからなる積層体を、圧着ヘッドとステージの間に挟んで加圧及び加熱して、半導体チップ同士を仮圧着した。次いで、仮圧着後の積層体を、本圧着用押圧部材としての押圧部材IIで挟むことで加熱及び加圧して、半導体チップ同士を電気的に接続した。
仮圧着条件及び本圧着条件は下記のとおりである。これら条件は、得られる半導体装置に関するボイド評価及び接続評価が「A」となるように設定された。
・仮圧着条件
圧着ヘッドの温度:80℃、荷重:75N、ステージ温度:80℃
・本圧着条件
圧着ヘッドの温度:280℃、荷重:75N、ステージ温度:80℃
2台の押圧部材I,IIを同時に並行して稼働させながら、半導体装置を複数連続して製造した。仮圧着及び本圧着に要した製造時間、半導体装置1パッケージ(PKG)あたりの製造時間、及び、1時間あたりの半導体装置の生産数(UPH)の結果を表2に示す。
(1)ボイド評価
超音波映像診断装置(Insight-300、インサイト製)により、得られた半導体装置の外観画像を撮り、スキャナGT-9300UF(EPSON社製)で半導体チップ上の接着剤層の画像を取り込んだ。画像処理ソフトAdobe Photoshop(登録商標)を用いて、色調補正、二階調化によりボイド部分を識別し、ヒストグラムにより接着剤層におけるボイド部分の占める割合を算出した。半導体チップ上の接着剤層の面積を100%とした。ボイドの専有面積が10%以下の場合を「A」と、10%を超える場合を「B」と判定した。
作製した半導体装置の接続抵抗値を、マルチメータ(ADVANTEST製、商品名「R6871E」)を用いて測定することにより、実装後の初期導通を評価した。ペリフェラル部分の内周の初期接続抵抗値が45Ω以下で、かつ、外周の初期接続抵抗値が85Ω以下の場合を「A」とし、内周の初期接続抵抗値が45Ωを超える場合、外周の初期接続抵抗値が85Ωを超える場合、及び、導通していない(抵抗値が表示されない)場合を全て「B」とした。
2台の押圧部材I,IIを同じ圧着条件で同時に平行して稼働させながら、製造例1の接着剤フィルムを用いて以下の手順で複数の半導体装置を製造した。
押圧部材I,IIのそれぞれのステージ上で半導体チップとバンプ付半導体チップとを位置合わせした。その後、押圧部材の圧着ヘッドとステージとで加圧しながら、圧着ヘッドの温度を1秒間で280℃まで昇温させた後、その状態で2秒間保持した。これにより、半導体チップとバンプ付半導体チップとを互いに圧着するとともに、電気的に接続した。圧着にかかった時間の合計は3秒であった。その後、圧着ヘッドの温度を280℃から半導体チップ供給温度の80℃まで冷却した。上記の圧着の条件は、半導体装置のボイド評価及び接続評価が「A」となるように設定された。
各段階に要した製造時間、半導体装置1パッケージ(PKG)あたりの製造時間、及び、1時間あたりのパッケージの生産数(UPH)の結果を表2に示す。
製造例1-2の接着剤フィルムを用いたこと以外は実施例1と同様にして半導体装置を製造した。結果を表3に示す。
製造例1-2の接着剤フィルムを用いたこと以外は比較例1と同様にして半導体装置を製造した。結果を表3に示す。
製造例1-3の接着剤フィルムを用いたこと以外は実施例1と同様にして半導体装置を製造した。結果を表4に示す。
製造例1-3の接着剤フィルムを用い、圧着ヘッドの温度を1秒間で280℃まで昇温させた後、4秒間保持して、圧着にかかった時間の合計が5秒であったこと以外は比較例1と同様にして半導体装置を製造した。結果を表4に示す。
2-1.接着剤フィルムの作製
接着剤フィルムの作製に使用した化合物を以下に示す。
アクリル樹脂
・フルオレンに由来する骨格を有するアクリレート(大阪ガスケミカル株式会社製、EA0200、アクリロイル基の数:2)
・ジクミル過酸化物(日油株式会社製、パークミルD)
・アクリルゴム(日立化成株式会社製、KH-C865、Tg:0~12℃、重量平均分子量:450000~650000)
無機フィラー
・シリカフィラー(株式会社アドマテックス製、SE2050、平均粒径:0.5μm)
・エポキシシランで表面処理したシリカフィラー(株式会社アドマテックス製、SE2050SEJ、平均粒径:0.5μm)
・メタクリル表面処理ナノシリカフィラー(株式会社アドマテックス製、YA050CSM
、以下「SMナノシリカ」と表記する、平均粒径:約50nm)
樹脂フィラー
・有機フィラー(ロームアンドハースジャパン(株)製、EXL-2655:コアシェルタイプ有機微粒子)
表5に示す配合量(単位:質量部)のアクリル樹脂(A9300)、無機フィラー(SE2050、SE2050SEJ及びSMナノシリカ)及び樹脂フィラー(EXL2655)を、不揮発分(固形分、溶媒以外の成分)の濃度が60質量%になるように、溶媒としてのメチルエチルケトンに加えた。次いで、Φ1.0mm、Φ2.0mmのビーズを、固形分と同じ量加え、ビーズミル(フリッチュ・ジャパン株式会社製、遊星型微粉砕機P-7)で30分撹拌した。その後、高分子成分としてのフェノキシ樹脂(ZX1356)を加え、再度、ビーズミルで30分撹拌した。撹拌後、硬化剤(パークミルD)を添加して攪拌し、ビーズをろ過によって除去してワニスを得た。得られたワニスを小型精密塗工装置(株式会社廉井精機製)で塗工し、塗膜をクリーンオーブン(ESPEC製)で乾燥(70℃/10min)して、接着剤フィルムを得た。
レオメーター(株式会社アントンパール・ジャパン製、MCR301)にて、サンプル厚み:400μm、昇温速度10℃/分、周波数:1Hzの条件で、測定治具(ディスポーザブルプレート(直径8mm)及びディスポーザブルサンプルディッシュ)を用いて、表6に示される仮圧着工程時の圧着ヘッド温度(℃)における溶融粘度を測定した。結果を表6に示す。
(実施例1)
対向するステージ及び圧着ヘッドを有する2台の押圧部材I,II(FCB3、パナソニック製)を準備し、押圧部材Iを仮圧着用部材として用い、押圧部材IIを本圧着用押圧部材として用いて、以下の手順で半導体装置を製造した。
作製した製造例2-1の接着剤フィルムを切り抜き(8mm×8mm×0.045mmt)、半導体チップ(チップサイズ:10mm×10mm×0.4mmt、接続部の金属:Au、製品名:WALTS-TEG IP80、WALTS製)上に貼付した。次いで、接着剤フィルムを貼付した半導体チップを、仮圧着用押圧部材としての押圧部材Iのステージ上に供給した。このステージ上の半導体チップと、はんだバンプ付き半導体チップ(チップサイズ:7.3mm×7.3mm×0.15mmt、接続部の金属:銅ピラー+はんだ、バンプ高さ:銅ピラー+はんだ計約45μm、バンプ数1048ピン、ピッチ80μm、製品名:WALTS-TEG CC80、WALTS製)とをそれぞれの接続部が互いに対向するように位置合わせした。その後、半導体チップ、接着剤フィルム及び半導体チップからなる積層体を、圧着ヘッドとステージの間に挟んで加圧及び加熱して、接続部同士が接触するように半導体チップ同士を仮圧着した。次いで、仮圧着後の積層体を、本圧着用押圧部材としての押圧部材IIで挟むことで加熱及び加圧して、半導体チップ同士を電気的に接続した。仮圧着条件及び本圧着条件は表6に示したとおりである。仮圧着及び本圧着のいずれにおいても、ステージ温度は80℃であり、圧着時間は2秒であった。
仮圧着工程及び本圧着工程における圧着ヘッドの温度、及び荷重を表2に示すように変更した以外は実施例1と同様にして、実施例2-2~2-8の半導体装置を製造した。
得られた半導体装置について、ボイド評価及び接続評価を行った。
超音波映像診断装置(Insight-300、インサイト製)により、得られた半導体装置の外観画像を撮り、スキャナGT-9300UF(EPSON社製)で半導体チップ上の接着剤層の画像を取り込み、画像処理ソフトAdobe Photoshop(登録商標)を用いて、色調補正、二階調化によりボイド部分を識別し、ヒストグラムによりボイド部分の占める割合を算出した。半導体チップ上の接着剤層の面積を100%とした。ボイドの専有面積が5%以下の場合を「A」と評価し、5%を超える場合を「B」とした。結果を表6に示す。
作製した半導体装置の接続抵抗値を、マルチメータ(ADVANTEST製、商品名「R6871E」)を用いて測定することにより、仮圧着工程後及び本圧着工程後の導通を評価した。仮圧着工程後は、ペリフェラル部分において導通している(抵抗値が表示される)場合を「A」とし、導通していない(抵抗値が表示されない)場合を「B」とした。本圧着工程後は、ペリフェラル部分の内周の初期接続抵抗値が45Ω以下で、かつ、外周の初期接続抵抗値が85Ω以下の場合を「A」とし、内周の初期接続抵抗値が45Ωを超える場合、外周の初期接続抵抗値が85Ωを超える場合、及び、導通していない(抵抗値が表示されない)場合を全て「B」とした。結果を表6に示す。
3-1.原材料
実施例で使用した一括接続用シートを以下に示す。
・ニトフロン900UL(日東電工株式会社、厚み50μm、100μm)
・ユーピレックスSGA(宇部興産株式会社、50μm、100μm(50μm×2))
・アルミニウム箔(住軽アルミ箔株式会社、100μm(20μm×5))
(a)熱硬化性樹脂
エポキシ樹脂
・トリフェノールメタン骨格含有多官能固形エポキシ樹脂(EP1032H60、ジャパンエポキシレジン株式会社、重量平均分子量:800~2000)
・ビスフェノールF型液状エポキシ樹脂(YL983U、ジャパンエポキシレジン株式会社、分子量:約336)
・可撓性半固形状エポキシ樹脂(YL7175-1000、ジャパンエポキシレジン株式会社、重量平均分子量:1000~5000)
アクリル樹脂
・フルオレン骨格アクリレート樹脂(EA0200、大阪ガスケミカル株式会社、2官能基、分子量:約546)
・2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体(2MAOK-PW、四国化成株式会社製)
・ジクミル過酸化物(パークミルD、日油株式会社)
・フェノキシ樹脂(ZX1356-2、東都化成株式会社、Tg:約71℃、重量平均分子量:約63000)
・アクリルゴム(KH-C865、日立化成製、Tg:0~12℃、重量平均分子量:450000~650000)
樹脂フィラー
・有機フィラー(EXL-2655、ロームアンドハースジャパン株式会社、コアシェルタイプ有機微粒子)
無機フィラー
・シリカフィラー(SE2050、株式会社アドマテックス、平均粒径0.5μm)
・メタクリル表面処理ナノシリカフィラー(YA050C-SM、株式会社アドマテックス、平均粒径約50nm)
・2-メチルグルタル酸(アルドリッチ、融点約77℃)
・3-メタクリロキシプロピルトリメトキシシラン(OFS6030、東レダウコーニング株式会社)
各種原材料を表7に示す配合割合で混合し、熱硬化性樹脂組成物A及びBを調製した。具体的な作製方法を以下に示す。熱硬化性樹脂、フィラー、及び必要に応じてフラックス剤を、不揮発分(固形分)の濃度が60質量%になるようにメチルエチルケトンに添加した。その後、この混合液にΦ1.0mm、Φ2.0mmのビーズを固形分と同質量加え、ビーズミル(フリッチュ・ジャパン株式会社、遊星型微粉砕機P-7)で30分間撹拌した。混合液に高分子成分を加え、ビーズミルで30分間攪拌した。攪拌後、硬化剤及び必要に応じて添加剤を加えて攪拌し、混合液をろ過することでビーズを取り除き、ろ液を熱硬化性樹脂組成物A又はBとして得た。
作製した熱硬化性樹脂組成物A又はBを小型精密塗工装置(廉井精機)で塗工し、クリーンオーブン(ESPEC製)で乾燥(70℃/10分)し、接着剤フィルムを得た。
8mm×8mm×0.045mmtのサイズを有する接着剤フィルムを、半導体チップ(10mm、0.4mm厚、接続部金属:Au、製品名:WALTS-TEG IP80、WALTS製)に貼付した。この接着フィルム付き半導体チップを、接着フィルムを介してはんだバンプ付き半導体チップ(チップサイズ:7.3mm×7.3mm×0.15mmt、バンプ高さ:銅ピラー+はんだ高さ計約45μm、バンプ数1048ピン、ピッチ80μm、製品名:WALTS-TEG CC80、WALTS製)に接触させ、これをFCB3(パナソニック製、圧着ヘッド面積:7.3mm×7.3mm)で仮圧着し、積層体を作製した。熱硬化性樹脂組成物Aを用いた積層体は、FCB3の圧着ヘッドの温度を130℃に設定し、50Nの圧力で3秒間加熱加圧することで、仮圧着した。熱硬化性樹脂組成物Bを用いた積層体は、FCB3の圧着ヘッドの温度を130℃に設定し、100Nの圧力で3秒間加熱及び加圧することで、仮圧着した。仮圧着後の積層体を9個準備し、圧着ヘッドの面積が100mm×100mmである一括接続用装置(アルファデザイン製、HTB-MM)のステージ上に積層体を9個設置した。設置後、100mm×100mmの一括接続用シートを積層体の上に被せ、一括で本圧着し、半導体装置を得た。本圧着は、ステージ温度を80℃に設定し、圧着ヘッドの温度を250℃に設定し、900N(積層体1個あたり100N)の圧力で5秒間加熱及び加圧することで行った。
[250℃における一括接続用シートの貯蔵弾性率]
一括接続用シートから切り出した幅4mm、長さ40mmの試験片の粘弾性を、弾性率測定装置RSA2(Rheometric Scientific, Inc.)を用いて、周波数10Hz、昇温速度5℃/分の条件で-30℃から300℃まで昇温しながら測定した。測定結果から250℃における貯蔵弾性率を求めた。
250℃における一括接続用シートの変位量は、電気機械式万能試験機(INSTRON製、5900シリーズ)、Bluehill3ソフトウエアを用いて測定した。250℃の槽内に一括接続用シートを設置し、直径8μmの円形の端面を有する棒状の押圧用冶具を用いて、一括接続用シートの主面と押圧用治具の端面とが平行になる向きで押し当てる圧縮試験を行った。押圧用治具によって、0.001mm/秒のスピードで100N(約2MPa)の荷重を一括接続用シートに加えた。圧縮荷重が0Nから100Nになってから5秒経過し、荷重が100Nで安定した時点の変位量を、一括接続用シートの膜厚の変位量として記録した。
本圧着後にマルチメータ(ADVANTEST製、R6871E)を用いて、半導体装置の初期導通の可否を測定した。ペリフェラル部分の内周の初期接続抵抗値が40Ω以下、外周の初期接続抵抗値が85Ω以下である半導体装置をOK、それよりも高い抵抗値又は未接続の半導体装置をNGとして評価した。9個の半導体装置の中でOK評価となる数が、9個全ての場合に総合評価をA、それ以外をBとして判定した。
4-1.接着剤フィルムの作製
接着剤フィルムの作製に使用した化合物を以下に示す。
アクリル樹脂
・エトキシ化イソシアヌル酸トリアクリレート(新中村化学工業株式会社製、A-9300、アクリロイル基の官能基数:3)
・フルオレンに由来する骨格を有するアクリレート化合物(大阪ガスケミカル株式会社製、EA0200、アクリロイル基の官能基数:2)
・ジクミル過酸化物(日油株式会社製、パークミルD)
・フェノキシ樹脂(東都化成株式会社製、ZX1356、Tg:約71℃、重量平均分子量:約63000)
・アクリルゴム(日立化成株式会社製、KH-C865、Tg:0~12℃、重量平均分子量:450000~650000)
無機フィラー
・シリカフィラー(株式会社アドマテックス製、SE2050、平均粒径:0.5μm)・エポキシシランで表面処理されたシリカフィラー(株式会社アドマテックス製、SE2050SEJ、平均粒径:0.5μm)
・メタクリル表面処理ナノシリカフィラー(株式会社アドマテックス製、YA050CSM
、以下「SMナノシリカ」と表記する、平均粒径:約50nm)
樹脂フィラー
・有機フィラー(ロームアンドハースジャパン(株)製、EXL-2655:コアシェルタイプ有機微粒子)
表1に示す配合量(単位:質量部)のアクリル樹脂(A9300)、無機フィラー(SE2050、SE2050SEJ及びSMナノシリカ)及び樹脂フィラー(EXL2655)を、不揮発分(固形分、溶媒以外の成分)の濃度が60質量%になるように、溶媒としてのメチルエチルケトンに加えた。次いで、Φ1.0mm、Φ2.0mmのビーズを、メチルエチルケトンに加えたアクリル樹脂及び無機フィラーの合計量と同じ量加え、ビーズミル(フリッチュ・ジャパン株式会社製、遊星型微粉砕機P-7)で30分撹拌した。その後、高分子成分としてのフェノキシ樹脂(ZX1356)を加え、再度、ビーズミルで30分撹拌した。撹拌後、硬化剤(パークミルD)を添加して攪拌し、ビーズをろ過によって除去してワニスを得た。得られたワニスを小型精密塗工装置(株式会社廉井精機製)で塗工し、クリーンオーブン(ESPEC製)で乾燥(70℃/10min)して、接着剤フィルムを得た。
使用した材料を表10に示すように変更したこと以外は製造例4-1と同様にして、接着剤フィルムを得た。
(実施例4-1)
作製した製造例4-1の接着剤フィルムを切り抜き(8mm×8mm×0.045mmt)、半導体チップ(チップサイズ:10mm×10mm×0.4mmt、接続部の金属:Au、製品名:WALTS-TEG IP80、WALTS製)上に貼付した。次いで、接着剤フィルムを貼付した半導体チップを、仮圧着用押圧部材として準備した押圧部材のステージ上に供給した。このステージ上の半導体チップと、はんだバンプ付き半導体チップ(チップサイズ:7.3mm×7.3mm×0.15mmt、接続部の金属:銅ピラー+はんだ、バンプ高さ:銅ピラー+はんだ計約45μm、バンプ数1048ピン、ピッチ80μm、製品名:WALTS-TEG CC80、WALTS製)とをそれぞれの接続部が互いに対向するように位置合わせした。その後、半導体チップ、接着剤フィルム及び半導体チップからなる積層体を、圧着ヘッドとステージの間に挟んで加圧及び加熱して、半導体チップ同士を仮圧着した。
・仮圧着条件
圧着ヘッドの温度:80℃、荷重:75N、ステージ温度:80℃
[接続評価]
作製した半導体装置の接続抵抗値を、マルチメータ(ADVANTEST製、商品名「R6871E」)を用いて測定することにより、実装後の初期導通を評価した。ペリフェラル部分の内周の初期接続抵抗値が45Ω以下で、かつ、外周の初期接続抵抗値が85Ω以下の場合を「A」とし、内周の初期接続抵抗値が45Ωを超える場合、外周の初期接続抵抗値が85Ωを超える場合、及び、導通していない(抵抗値が表示されない)場合を全て「B」とした。
以下の点で条件を変更をしたこと以外は実施例4-1と同様にして、半導体装置を製造した。押圧部材のステージ上で半導体チップとバンプ付半導体チップとを位置合わせした。その後、押圧部材の圧着ヘッドとステージとで加圧しながら、圧着ヘッドの温度を1秒間で280℃まで昇温させた後、その状態で2秒間保持した。これにより、半導体チップとバンプ付半導体チップとを互いに圧着し、電気的に接続した。圧着にかかった時間の合計は3秒であった。その後、圧着ヘッドの温度を280℃から半導体チップ供給温度の80℃まで冷却した。押圧部材を用いて、半導体装置を複数製造した。上記の半導体装置の製造では、上記の接続評価が「A」となるように条件が設定されている。圧着工程の各段階に要した製造時間、半導体装置100パッケージ(PKG)あたりの製造時間の結果を表11に示す。
加熱装置としてリフロ炉の代わりにオーブンを用い、積層体を260℃のオーブン内で600秒加熱したこと以外は実施例4-1と同様にして半導体装置の製造を行った。結果を表12に示す。
製造例4-2の接着剤フィルムを用いたこと以外は実施例4-1と同様にして半導体装置の製造を行った。結果を表13に示す。
製造例4-2の接着剤フィルムを用いこと以外は比較例4-1と同様にして半導体装置の製造を行った。結果を表13に示す。
加熱装置としてリフロ炉の代わりにオーブンを用い、積層体を260℃のオーブン内で600秒加熱したこと以外は実施例4-3と同様にして半導体装置の製造を行った。結果を表14に示す。
5-1.原材料
実施例で使用した化合物を以下に示す。
(i)重量平均分子量10000未満の樹脂成分
(エポキシ樹脂)
・トリフェノールメタン骨格含有多官能固形エポキシ樹脂(ジャパンエポキシレジン株式会社、EP1032H60、以下「EP1032」とする)、重量平均分子量:800~2000
・ビスフェノールF型液状エポキシ樹脂(ジャパンエポキシレジン株式会社、YL983U、以下「YL983」とする)重量平均分子量:約336
・可とう性半固形状エポキシ(ジャパンエポキシレジン株式会社、YL7175-1000、以下「YL7175」とする)、重量平均分子量:1000~5000
(ii)硬化剤
・2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加体(四国化成株式会社製、2MAOK-PW、以下「2MAOK」とする)
(iii)重量平均分子量10000以上の高分子成分
・フェノキシ樹脂(東都化成株式会社、ZX1356-2、Tg:約71℃、Mw:約63000、以下「ZX1356」とする)
(iv)フラックス剤(カルボン酸)
・2-メチルグルタル酸(アルドリッチ、融点約77℃、以下「グルタル酸」とする)
(v)フィラー
(無機フィラー)
・シリカフィラー(株式会社アドマテックス、SE2050、平均粒径0.5μm)
・フェニル表面処理ナノシリカフィラー(株式会社アドマテックス、YA050C-SP、以下SPナノシリカとする、平均粒径約50nm)
(樹脂フィラー)
・有機フィラー(ロームアンドハースジャパン(株)社製、EXL-2655:コアシェルタイプ有機微粒子)
(vi)シリコーンレジン
以下の化学式で表される基本構造を有するシリコーンレジンを準備した。
・固形シラノール、R1:フェニル基又はプロピル基、R2:アルキレン基、X:H(東レダウコーニング(株)社製、RSN-6018、分子量:約2000)
・固形シラノール、R1:フェニル基、R2:アルキレン基、X:H(東レダウコーニング(株)社製、FCA107、分子量:約3000)
(その他のシリコーンレジン)
・液状シリコーンレジン、R1:メチル基、R2:アルキレン基、X:CH3(東レダウコーニング(株)社製、SR2402、分子量:約1500)
(実施例5-1)
エポキシ樹脂、2MAOK、2-メチルグルタル酸、無機フィラー、樹脂フィラー及びシラノールに、NV(不揮発分)が60質量%になるように有機溶媒(メチルエチルケトン)を添加した。その後、φ1.0mm、φ2.0mmのビーズを固形分と同質量加え、ビーズミル(フリッチュ・ジャパン株式会社、遊星型微粉砕機P-7)で30分撹拌した。その後、ZX1356を加え、再度、ビーズミルで30分撹拌した。撹拌に用いたビーズをろ過によって除去した。作製したワニス(半導体用接着剤)を小型精密塗工装置(廉井精機)で塗工し、塗膜をクリーンオーブン(ESPEC製)で乾燥(70℃/10min)し、フィルム状接着剤を得た。
使用した材料を表15に示すように変更したことを除いては、実施例5-1のフィルム状接着剤の作製方法と同様にして、フィルム状接着剤を作製した。表15中、各材料の配合量は不揮発分の配合量であり、単位は質量部である。
(1)熱重量減少量評価
約10mgのシリコーンレジン単体をPtパンに入れ、35℃から400℃までの熱重量減少をTG/DTA測定装置(セイコーインスツルメンツ株式会社製、EXSTAR6000)で測定した。昇温速度は10℃/minとした。260℃の熱重量減少量が20%以下のサンプルをA、260℃の熱重量減少量が20%より多い場合をBと評価した。
レオメーターMCR301(株式会社アントンパール・ジャパン製)を用いた。ステージ上に半導体用接着剤を供給し、ボイドが入らないように測定治具を設置した。測定条件は、ステージと測定治具(φ8mm)の間隔0.3mm、振り角gamma=5%、周波数f=1Hz、ノーマルフォースFN=0μN、昇温速度10℃/min、測定範囲30℃~180℃とした。粘度曲線から130℃(下記(3)の第一工程の温度)の粘度を求めた。
作製したフィルム状接着剤を切り抜き(7.3mm×7.3mm×0.045mmt)、はんだバンプ付き半導体チップ(チップサイズ:7.3mm×7.3mm×0.15mmt、バンプ高さ:銅ピラー+はんだ計約45μm、バンプ数1048、ピッチ80μm、WALTS-TEG CC80ModelI、WALTS製)上に貼付し、受け側の半導体チップ(チップサイズ:10mm×10mm×0.1mmt、WALTS-TEG IP80、WALTS製)にFCB3(パナソニック製)で仮圧着した。ステージ温度は80℃とした。130℃/100N/3sで位置合わせして仮圧着した(第一工程)。仮圧着後の積層体を最高温度260℃に到達するリフロ炉(タムラ製作所製)に約600s(10min)通すことで本圧着させて、半導体装置パッケージのサンプルを得た。第一工程後及び第二工程後のそれぞれで、マルチメータ(ADVANTEST製、R6871E)を用いて初期導通の可否を測定した。ペリフェラル部(内周部)の接続抵抗値が32.0~38.0ΩのサンプルをA(接続良好)、それ以外の抵抗値又はOpenをB(接続不良)と評価した。
上記(3)で作製したサンプルについて、第一工程後及び第二工程後のそれぞれで、超音波映像診断装置(Insight-300、インサイト製)により、外観画像を撮り、スキャナGT-9300UF(EPSON社製)でチップ上の半導体用接着剤からなる層(接着剤層)の画像を取り込んだ。画像処理ソフトAdobe Photoshopを用いて、色調補正、二階調化により画像からボイド部分を識別し、ヒストグラムによりボイド部分の占める割合を算出した。チップ上の半導体用接着剤部分の面積を100%として、ボイド発生率が5%以下をA、ボイド発生率が5%より多い場合をBと評価した。
上記(3)で作製したパッケージを封止材(日立化成製、CEL9750ZHF10)を用いて、モールドした(条件:180℃/6.75MPa/90s)。次に、クリーンオーブン(ESPEC製)中で175℃で5時間アフターキュアを行った。その後、JEDEC level 2条件で高温吸湿後、リフロ評価(リフロ炉:タムラ製作所製)を行った(リフロ炉を3回通した)。リフロ後、剥離なく、接続良好なサンプルをA、剥離又は接続不良が生じたサンプルをBとした。接続評価方法は上記(3)と同様な方法で行った。
Claims (18)
- 半導体チップと、基板及び/又は他の半導体チップと、これらの間に介在する接着剤層とを備え、前記半導体チップ、前記基板、及び前記他の半導体チップのそれぞれが金属材料によって形成された表面を有する接続部を有し、前記半導体チップの接続部と前記基板及び/又は前記他の半導体チップの接続部とが金属接合によって電気的に接続されている、半導体装置を製造する方法であって、
前記半導体チップと、前記基板、前記他の半導体チップ、又は、前記他の半導体チップに相当する部分を含む半導体ウエハと、これらの間に配置された前記接着剤層とを有し、前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とが対向配置されている、積層体を、対向する一対の仮圧着用押圧部材で挟むことによって加熱及び加圧し、それにより前記半導体チップに前記基板、前記他の半導体チップ又は前記半導体ウエハを仮圧着する工程と、
前記積層体を、前記仮圧着用押圧部材とは別に準備された、対向する一対の本圧着用押圧部材で挟むことによって加熱及び加圧し、それにより前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とを金属接合によって電気的に接続する工程と、をこの順に備え、
前記一対の仮圧着用押圧部材のうち少なくとも一方が、前記積層体を加熱及び加圧する時に、前記半導体チップの接続部の表面を形成している金属材料の融点、及び前記基板又は前記他の半導体チップの接続部の表面を形成している金属材料の融点よりも低い温度に加熱され、
前記一対の本圧着用押圧部材のうち少なくとも一方が、前記積層体を加熱及び加圧する時に、前記半導体チップの接続部の表面を形成している金属材料の融点、又は前記基板若しくは前記他の半導体チップの接続部の表面を形成している金属材料の融点のうち少なくともいずれか一方の融点以上の温度に加熱される、
方法。 - 前記一対の本圧着用押圧部材のうち少なくとも一方が、前記半導体チップの接続部の表面を形成している金属材料の融点、又は前記基板若しくは前記他の半導体チップの接続部の表面を形成している金属材料の融点のうち少なくともいずれか一方の融点以上の温度に加熱された状態を維持しながら、複数の半導体装置を連続的に製造する、請求項1に記載の方法。
- 前記接着剤層の溶融粘度が、前記仮圧着用押圧部材が加熱される温度において7000Pa・s以下である、請求項2に記載の方法。
- 半導体チップと、基板及び/又は他の半導体チップと、これらの間に介在する接着剤層とを備え、前記半導体チップ、前記基板、及び前記他の半導体チップのそれぞれが金属材料によって形成された表面を有する接続部を有し、前記半導体チップの接続部と前記基板及び/又は前記他の半導体チップの接続部とが金属接合によって電気的に接続されている、半導体装置を製造する方法であって、
前記半導体チップと、前記基板、前記他の半導体チップ、又は、前記他の半導体チップに相当する部分を含む半導体ウエハと、これらの間に配置された前記接着剤層とを有し、前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とが対向配置されている、積層体を、対向する一対の仮圧着用押圧部材で挟むことによって加熱及び加圧し、それにより前記半導体チップに前記基板又は前記他の半導体チップ又は前記半導体ウエハを仮圧着する工程と、
ステージ上に配置された複数の前記積層体又は複数の前記半導体チップ、前記半導体ウエハ及び前記接着剤を有する前記積層体とそれらを覆うように配置された一括接続用シートとを、前記ステージと該ステージに対向する圧着ヘッドとで挟むことによって一括して複数の前記積層体を加熱及び加圧し、それにより前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とを金属接合によって電気的に接続する工程と、をこの順に備え、
前記一対の仮圧着用押圧部材のうち少なくとも一方が、前記積層体を加熱及び加圧する時に、前記半導体チップの接続部の表面を形成している金属材料の融点、及び前記基板又は前記他の半導体チップの接続部の表面を形成している金属材料の融点よりも低い温度に加熱され、
前記ステージ及び前記圧着ヘッドのうち少なくとも一方が、前記半導体チップの接続部の表面を形成している金属材料の融点、又は前記基板若しくは前記他の半導体チップの接続部の表面を形成している金属材料の融点のうち少なくともいずれか一方の融点以上の温度に加熱され、
前記一括接続用シートが、250℃における10GPa以下の貯蔵弾性率と、250℃における40μm以上の変位量とを有し、
前記変位量が、直径8μmの円形の端面を有する棒状の押圧用治具を、前記一括接続用シートの主面に、前記主面と前記端面とが平行になる向きで押し当てる圧縮試験において、250℃の環境下で圧縮荷重が100Nであるときの変位量である、方法。 - 前記R1がフェニル基である、請求項5に記載の半導体用接着剤。
- 前記(c)シラノール化合物が25℃で固形である、請求項5又は6に記載の半導体用接着剤。
- (d)10000以上の重量平均分子量を有する高分子成分を更に含有する、請求項5~7のいずれか一項に記載の半導体用接着剤。
- 前記(d)10000以上の重量平均分子量を有する高分子成分が、30000以上の重量平均分子量、及び、100℃以下のガラス転移温度を有する、請求項8に記載の半導体用接着剤。
- 半導体チップ及び配線回路基板のそれぞれの接続部が互いに電気的に接続された半導体装置、又は、複数の半導体チップのそれぞれの接続部が互いに電気的に接続された半導体装置を、前記接続部の金属の融点より低温で圧着する第一工程と、前記接続部の金属の融点以上の高温で加熱処理することで金属結合を形成する第二工程と、を経て製造する際に、前記接続部を封止する接着剤層を形成するために用いられる、請求項5~9のいずれか一項に記載の半導体用接着剤。
- 半導体チップと、基板及び/又は他の半導体チップと、これらの間に介在する接着剤層とを備え、前記半導体チップ、前記基板、及び前記他の半導体チップのそれぞれが金属材料によって形成された表面を有する接続部を有し、前記半導体チップの接続部と前記基板及び/又は前記他の半導体チップの接続部とが金属接合によって電気的に接続されている、半導体装置を製造する方法であって、
前記半導体チップと、前記基板、前記他の半導体チップ、又は、前記他の半導体チップに相当する部分を含む半導体ウエハと、これらの間に配置された前記接着剤層とを有し、前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とが対向配置されている、積層体を、対向する一対の仮圧着用押圧部材で挟むことによって加熱及び加圧し、それにより前記半導体チップに前記基板、前記他の半導体チップ又は前記半導体ウエハを仮圧着する工程と、
前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とを金属接合によって電気的に接続する工程と、
をこの順に備え、
前記一対の仮圧着用押圧部材のうち少なくとも一方が、前記積層体を加熱及び加圧する時に、前記半導体チップの接続部の表面を形成している金属材料の融点、及び前記基板又は前記他の半導体チップの接続部の表面を形成している金属材料の融点よりも低い温度に加熱され、
前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とを金属接合によって電気的に接続する工程において、前記積層体が、加熱炉内又はホットプレート上で、前記半導体チップの接続部の表面を形成している金属材料の融点、又は前記基板若しくは前記他の半導体チップの接続部の表面を形成している金属材料の融点のうち少なくともいずれか一方の融点以上の温度に加熱される、方法。 - 複数の前記積層体が前記加熱炉内又は前記ホットプレート上で一括して加熱される、請求項11に記載の方法。
- 前記接着剤層が、請求項5~9のいずれか一項に記載の半導体用接着剤を含む層である、請求項11又は12に記載の方法。
- 前記接着剤層が、10000以下の分子量を有する熱硬化性樹脂、及びその硬化剤を含有する熱硬化性樹脂組成物を含む層である、請求項1~4、11及び12のいずれか一項に記載の方法。
- 前記熱硬化性樹脂組成物が、10000以上の重量平均分子量を有する高分子成分を更に含有する、請求項14に記載の方法。
- 前記高分子成分の重量平均分子量が30000以上であり、前記高分子成分のガラス転移温度が100℃以下である、請求項15に記載の方法。
- 前記接着剤層が、予め準備された接着剤フィルムによって形成された層である、請求項1~4及び11~16のいずれか一項に記載の方法。
- 前記半導体チップの接続部と前記基板又は前記他の半導体チップの接続部とを接触させるとともに前記半導体チップに前記基板又は前記他の半導体チップを仮圧着する、請求項1~4及び11~17のいずれか一項に記載の方法。
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CN111480218B (zh) * | 2017-12-18 | 2023-07-21 | 株式会社力森诺科 | 半导体装置、半导体装置的制造方法和粘接剂 |
CN112041972A (zh) * | 2018-04-27 | 2020-12-04 | 日东电工株式会社 | 半导体装置制造方法 |
EP3787011A4 (en) * | 2018-04-27 | 2022-06-08 | Nitto Denko Corporation | SEMICONDUCTOR DEVICE MANUFACTURING PROCESS |
US11594513B2 (en) | 2018-04-27 | 2023-02-28 | Nitto Denko Corporation | Manufacturing method for semiconductor device |
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JPWO2017073630A1 (ja) | 2018-08-16 |
US20180312731A1 (en) | 2018-11-01 |
CN108352333A (zh) | 2018-07-31 |
KR20180066139A (ko) | 2018-06-18 |
CN108352333B (zh) | 2021-07-20 |
TWI714653B (zh) | 2021-01-01 |
US20200095481A1 (en) | 2020-03-26 |
US10669454B2 (en) | 2020-06-02 |
KR102064584B1 (ko) | 2020-01-10 |
TW201726863A (zh) | 2017-08-01 |
US11608455B2 (en) | 2023-03-21 |
JP6504263B2 (ja) | 2019-04-24 |
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