WO2017043541A1 - 接合用銅ペースト、接合体の製造方法及び半導体装置の製造方法 - Google Patents
接合用銅ペースト、接合体の製造方法及び半導体装置の製造方法 Download PDFInfo
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- WO2017043541A1 WO2017043541A1 PCT/JP2016/076333 JP2016076333W WO2017043541A1 WO 2017043541 A1 WO2017043541 A1 WO 2017043541A1 JP 2016076333 W JP2016076333 W JP 2016076333W WO 2017043541 A1 WO2017043541 A1 WO 2017043541A1
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- Prior art keywords
- bonding
- copper
- copper paste
- particles
- copper particles
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Classifications
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
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- H01L23/49503—Lead-frames or other flat leads characterised by the die pad
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- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
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- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
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- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73221—Strap and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Definitions
- the present invention relates to a bonding copper paste, a method for manufacturing a bonded body using the same, a method for manufacturing a semiconductor device, and a bonded body and a semiconductor device.
- Patent Document 1 proposes a technique for sintering silver nanoparticles at a low temperature to form a sintered silver layer. It is known that such sintered silver has high connection reliability with respect to the power cycle (Non-Patent Document 1).
- Patent Document 2 discloses a bonding paste containing cupric oxide particles and a reducing agent as a bonding material for bonding a semiconductor element and an electrode.
- Patent Document 3 listed below discloses a bonding material including copper nanoparticles and copper microparticles or copper submicroparticles, or both.
- thermocompression process involving pressurization Since the method described in Patent Document 1 requires densification of the sintered silver layer in order to obtain high connection reliability, a thermocompression process involving pressurization is required. When performing a thermocompression bonding process involving pressurization, there are problems such as a decrease in production efficiency and a decrease in yield. Furthermore, when silver nanoparticles are used, a significant increase in material cost due to silver becomes a problem.
- Patent Document 2 avoids volume shrinkage during the reduction from copper oxide to copper by a thermocompression process.
- the thermocompression process has the problems described above.
- the method described in Patent Document 3 performs sintering without applying pressure, it is still not sufficient for practical use in the following points. That is, the copper nanoparticles need to be modified with a protective agent to suppress oxidation and improve dispersibility.
- the copper nanoparticles have a large specific surface area, in a bonding material mainly composed of copper nanoparticles, The amount of the surface protective agent tends to increase.
- the amount of the dispersion medium tends to increase in order to ensure dispersibility. Therefore, the bonding material described in Patent Document 3 has a large proportion of the surface protective agent or the dispersion medium for storage stability such as storage and coating, and the volumetric shrinkage during sintering tends to increase.
- the density after sintering tends to decrease, and it is difficult to ensure the strength of the sintered body.
- the present invention is a bonding copper paste containing metal particles and a dispersion medium, wherein the metal particles have a volume average particle diameter of 0.12 ⁇ m or more and 0.8 ⁇ m or less, and a maximum diameter is 1 to 20 ⁇ m, flaky micro copper particles having an aspect ratio of 4 or more, and included in the metal particles, the maximum diameter is 1 ⁇ m to 20 ⁇ m and the aspect ratio is less than 2
- a bonding copper paste having a content of 50% by mass or less based on the total amount of flaky micro-copper particles is provided.
- the bonding copper paste of the present invention sufficient bonding strength can be obtained even when bonding without pressure is performed.
- the reason why such an effect is obtained is that the specific sub-micro copper particles and the specific flaky micro-copper particles are contained, and the content of the micro-copper particles having an aspect ratio of 2 or less is limited.
- the flaky micro copper particles in the bonding copper paste are easily oriented substantially parallel to the bonding surface, and sufficient sinterability can be obtained and volume shrinkage during sintering can be sufficiently suppressed. It is conceivable that the strength of the sintered body is ensured and the bonding force with the adherend surface is improved.
- the bonding copper paste of the present invention can obtain the above-described effects by the sub-micro copper particles and the micro-copper particles, it is cheaper than the bonding material mainly composed of expensive copper nanoparticles and It has the advantage that it can be supplied stably. Thereby, for example, when manufacturing a joined body such as a semiconductor device, it is possible to further improve the production stability.
- flakes include flat shapes such as plates and scales.
- aspect ratio means the long side / thickness of a particle.
- the bonding copper paste of the present invention may be used for pressureless bonding.
- “non-pressurized” means a state in which a pressure of 0.01 MPa or less is received in addition to the self-weight of the members to be joined or the self-weight.
- the content of the sub-micro copper particles is 20% by mass or more and 90% by mass or less based on the total of the mass of the sub-micro copper particles and the mass of the flaky micro-copper particles. 1 mass% or more and 90 mass% or less may be sufficient based on the total mass of a metal particle. If the sub-micro copper particles and the flaky micro-copper particles are within the above ranges, it becomes easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste, and the bonding copper paste is used as a semiconductor element. When used for bonding, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the bonding copper paste of the present invention may include at least one metal particle selected from the group consisting of nickel, silver, gold, palladium, and platinum.
- the bonding copper paste further contains the above metal particles, a sintered body in which multiple types of metals are dissolved or dispersed can be obtained, so that the mechanical properties such as yield stress and fatigue strength of the sintered body are improved. Connection reliability is easy to improve.
- the present invention also provides a laminated body in which the first member, the bonding copper paste, and the second member are laminated in this order on the direction in which the weight of the first member acts. Is provided with the process of sintering in the state which received the self weight of the 1st member, or the self weight of the 1st member, and the pressure of 0.01 Mpa or less.
- a bonded body in which members are bonded to each other with a sufficient bonding force by pressureless bonding can be manufactured by using the bonding copper paste.
- the present invention also provides a laminated body in which the first member, the bonding copper paste, and the second member are laminated in this order on the direction in which the weight of the first member acts.
- a method for manufacturing a semiconductor device is provided.
- a semiconductor device having excellent die shear strength can be manufactured by pressureless bonding. Further, the semiconductor device manufactured by the method for manufacturing a semiconductor device of the present invention can be excellent in connection reliability.
- the present invention also provides a joined body comprising a first member, a second member, and a sintered body of the joining copper paste for joining the first member and the second member.
- the first member and the second member are joined via a copper sintered body having a sufficient joining force.
- the joined body of this invention can become the thing excellent in the heat dissipation of a member by providing the sintered compact of copper excellent in thermal conductivity.
- At least one of the first member and the second member includes at least one metal selected from the group consisting of copper, nickel, silver, gold, and palladium on a surface in contact with the sintered body. You may go out. In this case, adhesion between at least one of the first member and the second member and the sintered body can be further improved.
- the present invention also comprises a first member, a second member, and a sintered body of the joining copper paste for joining the first member and the second member, the first member and the first member
- a semiconductor device in which at least one of the two members is a semiconductor element.
- the semiconductor device of the present invention has sufficient die shear strength by providing a copper sintered body having sufficient bonding strength and high thermal conductivity and melting point, excellent connection reliability, and power cycle resistance. Can also be excellent.
- the present invention it is possible to provide a bonding copper paste capable of obtaining sufficient bonding strength even when bonding is performed without applying pressure.
- the present invention can further provide a method for manufacturing a bonded body and a method for manufacturing a semiconductor device using the bonding copper paste, and a bonded body and a semiconductor device.
- 3 is an SEM image showing flaky micro copper particles MA-C025. It is a schematic cross section which shows an example of the joined body manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment. It is a schematic cross section which shows an example of the semiconductor device manufactured using the copper paste for joining of this embodiment.
- FIG. 1 is a SEM image showing a cross-sectional morphology of the bonding copper paste of Example 1.
- FIG. 6 is a SEM image showing a cross-sectional morphology of the bonding copper paste of Example 4.
- FIG. 6 is a SEM image showing a cross-sectional morphology of a bonding copper paste of Example 6.
- FIG. 4 is a SEM image showing a cross section of a sintered body in a joined body using the joining copper paste of Example 2.
- FIG. 4 is a SEM image which shows the cross section of the sintered compact in the joined body using the copper paste for joining of Example 4.
- FIG. 6 It is a SEM image which shows the cross section of the sintered compact in the joined body using the copper paste for joining of Example 6.
- FIG. 1 It is a SEM image which shows the cross section of the sintered compact in the joined body using the copper paste for joining of the comparative example 3.
- FIG. 1 It is a SEM image which shows the cross section of the sintered compact in the joined body using the copper paste for joining of the comparative example 4.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to the following embodiments.
- the copper paste for bonding of this embodiment is a copper paste for bonding containing metal particles and a dispersion medium, and the metal particles include sub-micro copper particles and flaky micro-copper particles.
- Metal particles examples of the metal particles according to this embodiment include sub-micro copper particles, flaky micro-copper particles, copper particles other than these, and other metal particles.
- sub-micro copper particles examples include those containing copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less.
- copper particles having a volume average particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less are used. it can.
- the volume average particle diameter of the sub-micro copper particles is 0.12 ⁇ m or more, effects such as suppression of the synthesis cost of the sub-micro copper particles, good dispersibility, and suppression of the use amount of the surface treatment agent are easily obtained.
- the volume average particle diameter of the sub-micro copper particles is 0.8 ⁇ m or less, an effect that the sinterability of the sub-micro copper particles is excellent is easily obtained.
- the volume average particle diameter of the sub-micro copper particles may be 0.15 ⁇ m or more and 0.8 ⁇ m or less, 0.15 ⁇ m or more and 0.6 ⁇ m or less, and 0 It may be from 2 ⁇ m to 0.5 ⁇ m, and may be from 0.3 ⁇ m to 0.45 ⁇ m.
- the volume average particle diameter means a 50% volume average particle diameter.
- the light scattering particle size It can be determined by a method of measuring with a distribution measuring device (for example, a Shimadzu nanoparticle size distribution measuring device (SALD-7500 nano, manufactured by Shimadzu Corporation)).
- SALD-7500 nano Shimadzu nanoparticle size distribution measuring device
- a light scattering particle size distribution analyzer hexane, toluene, ⁇ -terpineol, or the like can be used as a dispersion medium.
- the sub-micro copper particles can contain 10% by mass or more of copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less. From the viewpoint of the sinterability of the bonding copper paste, the sub-micro copper particles can contain 20% by mass or more and 30% by mass or more of copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less. , 100% by mass.
- the content ratio of the copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less in the sub-micro copper particles is 20% by mass or more, the dispersibility of the copper particles is further improved, the viscosity is increased, and the paste concentration is decreased. It can be suppressed more.
- the particle size of the copper particles can be determined by the following method.
- the particle size of the copper particles can be calculated from an SEM image, for example.
- the copper particle powder is placed on a carbon tape for SEM with a spatula to obtain a sample for SEM.
- the sample for SEM is observed with a SEM apparatus at a magnification of 5000 times.
- a quadrilateral circumscribing the copper particles of this SEM image is drawn by image processing software, and one side thereof is set as the particle size of the particles.
- the content of the sub-micro copper particles may be 20% by mass or more and 90% by mass or less, 30% by mass or more and 85% by mass or less, and 35% by mass or more based on the total mass of the metal particles. 85 mass% or less may be sufficient, and 40 mass% or more and 80 mass% or less may be sufficient. If the content of the sub-micro copper particles is within the above range, it becomes easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste, and the bonding copper paste can be used for bonding semiconductor elements. When used, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the content of the sub-micro copper particles may be 20% by mass or more and 90% by mass or less based on the total mass of the sub-micro copper particles and the mass of the flaky micro-copper particles. If the content of the sub-micro copper particles is 20% by mass or more, the space between the flaky micro-copper particles can be sufficiently filled, and the bonding strength of the bonded body manufactured by sintering the bonding copper paste. When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability. If the content of the sub-micro copper particles is 90% by mass or less, volume shrinkage when the bonding copper paste is sintered can be sufficiently suppressed, so that the bonded body manufactured by sintering the bonding copper paste.
- the semiconductor device When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the content of the sub-micro copper particles is 30% by mass or more and 85% by mass or less based on the total mass of the sub-micro copper particles and the mass of the flaky micro-copper particles. It may be 35 mass% or more and 85 mass% or less, and may be 40 mass% or more and 80 mass% or less.
- the shape of the sub-micro copper particles is not particularly limited.
- Examples of the shape of the sub-micro copper particles include a spherical shape, a lump shape, a needle shape, a flake shape, a substantially spherical shape, and an aggregate thereof.
- the shape of the sub-micro copper particles may be spherical, substantially spherical, or flaky. From the viewpoint of combustibility, dispersibility, miscibility with flaky microparticles, etc., Alternatively, it may be approximately spherical.
- the “flakes” include flat shapes such as plates and scales.
- the sub-micro copper particles may have an aspect ratio of 5 or less or 3 or less from the viewpoints of dispersibility, filling properties, and miscibility with the flaky micro particles.
- aspect ratio indicates the long side / thickness of a particle. The measurement of the long side and thickness of the particle can be obtained, for example, from the SEM image of the particle.
- the sub-micro copper particles may be treated with a specific surface treatment agent.
- the specific surface treatment agent include organic acids having 8 to 16 carbon atoms.
- the organic acid having 8 to 16 carbon atoms include caprylic acid, methylheptanoic acid, ethylhexanoic acid, propylpentanoic acid, pelargonic acid, methyloctanoic acid, ethylheptanoic acid, propylhexanoic acid, capric acid, methylnonanoic acid, and ethyl.
- An organic acid may be used individually by 1 type, and may be used in combination of 2 or more type. By combining such an organic acid and the sub-micro copper particles, the dispersibility of the sub-micro copper particles and the detachability of the organic acid during sintering tend to be compatible.
- the treatment amount of the surface treatment agent may be an amount that adheres to a monolayer to a trilayer on the surface of the sub-micro copper particles. This amount includes the number of molecular layers (n) attached to the surface of the sub-micro copper particles, the specific surface area (A p ) (unit m 2 / g) of the sub-micro copper particles, and the molecular weight (M s ) of the surface treatment agent (M s ) It can be calculated from the unit g / mol), the minimum covering area (S S ) (unit m 2 / piece) of the surface treatment agent, and the Avogadro number (N A ) (6.02 ⁇ 10 23 pieces).
- the specific surface area of the sub-micro copper particles can be calculated by measuring the dried sub-micro copper particles by the BET specific surface area measurement method.
- Minimum coverage of the surface treatment agent if the surface treatment agent is a straight-chain saturated fatty acids, is 2.05 ⁇ 10 -19 m 2/1 molecule.
- calculation from a molecular model, or “Chemistry and Education” Takehiro Ueda, Juno Inafuku, Mori Kaoru, 40 (2), 1992, p114-117) It can be measured by the method described. An example of the method for quantifying the surface treatment agent is shown.
- the surface treatment agent can be identified by a thermal desorption gas / gas chromatograph mass spectrometer of a dry powder obtained by removing the dispersion medium from the bonding copper paste, whereby the carbon number and molecular weight of the surface treatment agent can be determined.
- the carbon content of the surface treatment agent can be analyzed by carbon content analysis. Examples of the carbon analysis method include a high frequency induction furnace combustion / infrared absorption method.
- the amount of the surface treatment agent can be calculated by the above formula from the carbon number, molecular weight, and carbon content ratio of the identified surface treatment agent.
- the treatment amount of the surface treatment agent may be 0.07% by mass or more and 2.1% by mass or less, may be 0.10% by mass or more and 1.6% by mass or less, and may be 0.2% by mass. It may be 1.1% by mass or less.
- sub-micro copper particles As the sub-micro copper particles according to the present embodiment, commercially available ones can be used. Examples of commercially available sub-micro copper particles include CH-0200 (manufactured by Mitsui Mining & Smelting Co., Ltd., volume average particle size 0.36 ⁇ m), HT-14 (manufactured by Mitsui Mining & Smelting Co., Ltd., volume average particle size 0. 41 ⁇ m), CT-500 (manufactured by Mitsui Mining & Smelting Co., Ltd., volume average particle size 0.72 ⁇ m), and Tn—Cu100 (manufactured by Taiyo Nippon Sanso Corporation, volume average particle size 0.12 ⁇ m).
- CH-0200 manufactured by Mitsui Mining & Smelting Co., Ltd., volume average particle size 0.36 ⁇ m
- HT-14 manufactured by Mitsui Mining & Smelting Co., Ltd., volume average particle size 0. 41 ⁇ m
- CT-500 manufactured by Mits
- the flaky micro copper particles include those containing copper particles having a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less and an aspect ratio of 4 or more.
- the average maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the aspect ratio is 4
- the above copper particles can be used. If the average maximum diameter and aspect ratio of the flaky micro-copper particles are within the above ranges, volume shrinkage when the bonding copper paste is sintered can be sufficiently reduced, and the bonding copper paste is sintered. It becomes easy to ensure the joining strength of the joined body. When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the average maximum diameter of the flaky micro copper particles may be 1 ⁇ m or more and 10 ⁇ m or less, or 3 ⁇ m or more and 10 ⁇ m or less.
- the measurement of the maximum diameter and the average maximum diameter of the flaky micro copper particles can be obtained from, for example, an SEM image of the particles, and is obtained as a major axis X and an average value Xav of the major axis of the flaky micro copper particles described later.
- the flaky micro copper particles can contain 50% by mass or more of copper particles having a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less. From the viewpoint of orientation in the bonded body, reinforcing effect, and filling property of the bonding paste, the flaky micro copper particles can contain 70% by mass or more, and 80% by mass or more of copper particles having a maximum diameter of 1 ⁇ m to 20 ⁇ m. And may be included in an amount of 100% by mass. From the viewpoint of suppressing poor bonding, the flaky micro-copper particles preferably do not contain particles having a size exceeding the bonding thickness, such as particles having a maximum diameter exceeding 20 ⁇ m.
- the flaky micro copper particles may have an aspect ratio of 4 or more, or 6 or more. If the aspect ratio is within the above range, the flaky micro-copper particles in the bonding copper paste are oriented substantially parallel to the bonding surface, thereby reducing the volume shrinkage when the bonding copper paste is sintered. It can be suppressed, and it becomes easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste. When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the content of the flaky micro copper particles may be 1% by mass or more and 90% by mass or less, 10% by mass or more and 70% by mass or less, and 20% by mass based on the total mass of the metal particles. It may be 50% by mass or more.
- the content of the flaky micro copper particles is within the above range, it becomes easy to ensure the bonding strength of the bonded body manufactured by sintering the bonding copper paste.
- the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability.
- the total content of the sub-micro copper particles and the content of the flaky micro-copper particles may be 80% by mass or more based on the total mass of the metal particles. If the total of the content of the sub-micro copper particles and the content of the micro-copper particles is within the above range, the volume shrinkage when the bonding copper paste is sintered can be sufficiently reduced, and the bonding copper paste is sintered. It is easy to ensure the bonding strength of the bonded body manufactured in this manner. When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device tends to exhibit good die shear strength and connection reliability. From the viewpoint of further exerting the above effects, the total content of the sub-micro copper particles and the content of the flaky micro-copper particles may be 90% by mass or more based on the total mass of the metal particles. The mass may be 100% by mass or more.
- the shape of the flaky micro copper particles according to the present embodiment can also be defined by parameters of a long diameter (maximum diameter) X, a medium diameter Y (width), and a short diameter (thickness) T.
- the major axis X is the distance between two parallel planes selected so that the distance between the two parallel planes is the maximum among the two parallel planes circumscribing the flaky micro copper particles in the three-dimensional shape of the flaky micro copper particles. is there.
- the medium diameter Y is perpendicular to the parallel two planes giving the major axis X, and is selected so that the distance between the parallel two planes is the maximum among the two parallel planes circumscribing the flaky micro copper particles. Is the distance.
- the short diameter T is perpendicular to the parallel two planes giving the major axis X and the parallel two planes giving the medium diameter Y, and the distance between the two parallel planes is the largest of the two parallel planes circumscribing the flaky micro copper particles.
- the distance between two parallel planes selected to be
- the average value Xav of the major axis may be 1 ⁇ m or more and 20.0 ⁇ m or less, 1 ⁇ m or more and 10 ⁇ m or less, or 3 ⁇ m or more and 10 ⁇ m or less. If Xav is within the above range, in the joined body manufactured by sintering the joining copper paste, the joining copper paste sintered body is easily formed with an appropriate thickness.
- Xav / Tav which is the ratio (aspect ratio) of the average value Xav of the major axis to the average value Tav of the minor axis, may be 4.0 or more, may be 6.0 or more, and may be 10.0 or more. There may be. If Xav / Tav is within the above range, the flaky micro copper particles in the bonding copper paste are likely to be oriented substantially parallel to the bonding surface, and the volume shrinkage when the bonding copper paste is sintered. Therefore, it is easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste. When the bonding copper paste is used for bonding semiconductor elements, it is easy to improve the die shear strength and connection reliability of the semiconductor device.
- Xav / Yav which is the ratio of the average value Xav of the major axis to the average value Yav of the medium diameter, may be 2.0 or less, 1.7 or less, or 1.5 or less. . If Xav / Yav is within the above range, the shape of the flaky micro copper particles becomes flaky particles having a certain area, and the flaky micro copper particles in the bonding copper paste are substantially parallel to the bonding surface. Orientation is facilitated, volume shrinkage when the bonding copper paste is sintered can be suppressed, and it is easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste.
- the bonding copper paste When the bonding copper paste is used for bonding semiconductor elements, it is easy to improve the die shear strength and connection reliability of the semiconductor device.
- Xav / Yav exceeds 2.0, it means that the shape of the flaky micro-copper particles approaches an elongated linear shape.
- Yav / Tav which is the ratio of the average value Yav of the medium diameter to the average value Tav of the short diameter, may be 2.5 or more, 4.0 or more, or 8.0 or more Good. If Yav / Tav is within the above range, the flaky micro copper particles in the bonding copper paste are likely to be oriented substantially parallel to the bonding surface, and the volume shrinkage when the bonding copper paste is sintered. Therefore, it is easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste. When the bonding copper paste is used for bonding semiconductor elements, it is easy to improve the die shear strength and connection reliability of the semiconductor device.
- FIG. 1 is an SEM image showing MA-C025 (manufactured by Mitsui Metal Mining Co., Ltd.) which is an example of flaky micro copper particles.
- a rectangle circumscribing the flaky micro copper particles 9 of this SEM image is drawn by image processing software, and the long side of the rectangle is the major axis X of the particle and the short side of the rectangle is the medium diameter Y of the particle.
- This measurement is performed on 50 or more flaky micro copper particles using a plurality of SEM images, and the average value Xav of the long diameter and the average value Yav of the medium diameter are calculated.
- a method for calculating the short axis T of the flaky micro copper particles from the SEM image is illustrated.
- a copper paste containing flaky micro copper particles is printed on a copper substrate, and a silicon chip is mounted. This is dried with a hot plate or the like in air at 100 ° C. for 30 minutes to prepare a bonded product in which the copper plate and the silicon chip are weakly bonded with the dried bonding copper paste.
- the bonded product is cured with an epoxy casting resin, and the cured sample is shaved with abrasive paper to obtain a cross section near the center of the bonded product. This section is subjected to cross section polisher (CP) processing with argon ions to obtain a sample for SEM.
- CP cross section polisher
- FIG. 6 is an SEM image of the dried film of the bonding copper paste when the bonding copper paste of Example 6 described later is sandwiched between the chip and the substrate and dried at 100 ° C. for 30 minutes.
- a circumscribed rectangle is drawn by image processing software, and the short side of the rectangle is defined as the minor axis T of the particle.
- this measurement is performed on 50 or more flaky micro copper particles, and the average value Tav of the short diameter is calculated.
- the image processing software is not particularly limited, and for example, Microsoft PowerPoint (manufactured by Microsoft) and ImageJ (manufactured by National Institutes of Health) can be used.
- the presence or absence of the treatment with the surface treatment agent is not particularly limited.
- the flaky micro copper particles may be treated with a surface treatment agent.
- the surface treatment agent may be removed at the time of joining.
- Examples of such surface treatment agents include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, and oleic acid; aromatic carboxylic acids such as terephthalic acid, pyromellitic acid, and o-phenoxybenzoic acid; cetyl alcohol Aliphatic alcohols such as stearyl alcohol, isobornylcyclohexanol and tetraethylene glycol; aromatic alcohols such as p-phenylphenol; alkylamines such as octylamine, dodecylamine and stearylamine; fats such as stearonitrile and deconitrile Group nitriles; Silane coupling agents such as alkylalkoxysilanes; Polymer processing agents such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and silicone oligomers.
- a surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the treatment amount of the surface treatment agent may be an amount of a monomolecular layer or more on the particle surface.
- the treatment amount of such a surface treatment agent varies depending on the specific surface area of the flaky micro copper particles, the molecular weight of the surface treatment agent, and the minimum coating area of the surface treatment agent.
- the treatment amount of the surface treatment agent is usually 0.001% by mass or more.
- the specific surface area of the flaky micro copper particles, the molecular weight of the surface treatment agent, and the minimum coating area of the surface treatment agent can be calculated by the method described above.
- the bonding copper paste is prepared only from the above-mentioned sub-micro copper particles, the volume shrinkage and the sintering shrinkage accompanying the drying of the dispersion medium are large. In joining elements and the like, it is difficult to obtain sufficient die shear strength and connection reliability.
- the sub-micro copper particles and the flaky micro-copper particles in combination, volume shrinkage when the bonding copper paste is sintered is suppressed, and the bonded body can have sufficient bonding strength.
- the bonding copper paste is used for bonding semiconductor elements, an effect that the semiconductor device exhibits good die shear strength and connection reliability can be obtained.
- the maximum diameter contained in the metal particles is 1 ⁇ m or more and 20 ⁇ m or less, and the content of the micro copper particles having an aspect ratio of less than 2 is 1 ⁇ m or more and 20 ⁇ m or less. Based on the total amount of flaky micro copper particles having an aspect ratio of 4 or more, it is preferably 50% by mass or less, and more preferably 30% by mass or less.
- the flaky micro copper particles in the bonding copper paste are oriented substantially parallel to the bonding surface. Therefore, volume shrinkage when the bonding copper paste is sintered can be more effectively suppressed.
- the content of the micro copper particles having a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less and an aspect ratio of less than 2 has a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less, and the aspect ratio is Based on the total amount of four or more flaky micro copper particles, it may be 20% by mass or less, or 10% by mass or less.
- flaky micro copper particles As the flaky micro copper particles according to this embodiment, commercially available ones can be used. Examples of commercially available flaky micro copper particles include MA-C025 (Mitsui Metal Mining Co., Ltd., average maximum diameter 4.1 ⁇ m), 3L3 (Fukuda Metal Foil Powder Co., Ltd., volume maximum diameter 7.3 ⁇ m). ) 1110F (Mitsui Metal Mining Co., Ltd., average maximum diameter 5.8 ⁇ m), 2L3 (Fukuda Metal Foil Powder Co., Ltd., average maximum diameter 9 ⁇ m).
- the micro copper particles to be blended include flaky micro copper particles having a maximum diameter of 1 ⁇ m to 20 ⁇ m, an aspect ratio of 4 or more, and a maximum diameter of 1 ⁇ m to 20 ⁇ m.
- the content of the micro copper particles having an aspect ratio of less than 2 is 50% by mass or less, preferably 30% by mass or less based on the total amount of the flaky micro copper particles. .
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the flaky micro copper particles have an aspect ratio of 4 or more
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less.
- the content of the micro copper particles having a ratio of less than 2 may be 50% by mass or less, preferably 30% by mass or less, based on the total amount of the flaky micro copper particles.
- metal particles other than copper particles As a metal particle, other metal particles other than submicro copper particle and micro copper particle may be included, for example, particles, such as nickel, silver, gold
- the other metal particles may have a volume average particle size of 0.01 ⁇ m or more and 10 ⁇ m or less, 0.01 ⁇ m or more and 5 ⁇ m or less, or 0.05 ⁇ m or more and 3 ⁇ m or less. When other metal particles are contained, the content thereof may be less than 20% by mass or less than 10% by mass based on the total mass of the metal particles from the viewpoint of obtaining sufficient bondability. May be. Other metal particles may not be included.
- the shape of other metal particles is not particularly limited.
- the sintered body of the copper paste for joining can have sufficient joining strength with respect to a specific adherend by adding multiple types of metal particles.
- the bonding copper paste is used for bonding semiconductor elements, the die shear strength and connection reliability of the semiconductor device are likely to be improved.
- the dispersion medium is not particularly limited, and may be volatile.
- volatile dispersion media include monovalent and polyvalent pentanol, hexanol, heptanol, octanol, decanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, ⁇ -terpineol, isobornylcyclohexanol (MTPH), and the like.
- Dihydric alcohols ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol isobutyl ether, diethylene glycol hexyl ether, triethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Butyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol Ethers such as butyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether,
- Examples of mercaptans having an alkyl group having 1 to 18 carbon atoms include ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, i-butyl mercaptan, t-butyl mercaptan, pentyl mercaptan, and hexyl mercaptan. And dodecyl mercaptan.
- Examples of mercaptans having a cycloalkyl group having 5 to 7 carbon atoms include cyclopentyl mercaptan, cyclohexyl mercaptan, and cycloheptyl mercaptan.
- the content of the dispersion medium may be 5 to 50 parts by mass, where the total mass of the metal particles is 100 parts by mass.
- the bonding copper paste can be adjusted to a more appropriate viscosity, and it is difficult to inhibit the sintering of the copper particles.
- wetting additives such as nonionic surfactants and fluorosurfactants; antifoaming agents such as silicone oil; ion trapping agents such as inorganic ion exchangers, etc., are added as appropriate to the copper paste for bonding. May be.
- the metal particles are sub-micro copper particles having a volume average particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less, preferably 0.15 ⁇ m or more and 0.8 ⁇ m or less.
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the flaky micro copper particles have an aspect ratio of 4 or more, and the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less, and the aspect ratio is less than 2
- the copper paste for joining whose content of micro copper particles is 50 mass% or less, Preferably it is 30 mass% or less on the basis of the said flaky micro copper particle whole quantity is mentioned.
- blends is mentioned.
- another aspect of the bonding copper paste of the present embodiment includes metal particles and a dispersion medium, and the metal particles have a maximum diameter of 0.12 ⁇ m or more and 0.8 ⁇ m or less, preferably 0.15 ⁇ m or more.
- Examples include a copper paste for bonding in which the content of micro copper particles having an aspect ratio of less than 2 of 20 ⁇ m or less is 50% by mass or less, preferably 30% by mass or less, based on the total amount of flaky micro copper particles.
- the maximum diameter of the particles is determined by a method of observing, with a scanning electron microscope (SEM), copper particles as raw materials or dry copper particles obtained by removing volatile components from the bonding copper paste.
- SEM scanning electron microscope
- the contents of the sub-micro copper particles and the flaky micro-copper particles in the present embodiment can be the same as the ranges described above.
- the bonding copper paste can be prepared by mixing the above-mentioned sub-micro copper particles, flaky micro-copper particles, other metal particles, and optional additives in a dispersion medium. You may perform a stirring process after mixing of each component.
- the bonding copper paste may adjust the maximum particle size of the dispersion by classification operation. At this time, the maximum particle size of the dispersion liquid can be 20 ⁇ m or less, and can also be 10 ⁇ m or less.
- the bonding copper paste is prepared by mixing sub-micro copper particles, a surface treatment agent and a dispersion medium in advance and performing a dispersion treatment to prepare a dispersion of sub-micro copper particles, and further flaky micro-copper particles and other metal particles. And optional additives may be mixed.
- a dispersion treatment to prepare a dispersion of sub-micro copper particles, and further flaky micro-copper particles and other metal particles.
- optional additives may be mixed.
- the stirring treatment can be performed using a stirrer.
- the stirrer include a rotation / revolution stirrer, a reiki machine, a twin-screw kneader, a three-roll mill, a planetary mixer, and a thin-layer shear disperser.
- Classification operation can be performed using, for example, filtration, natural sedimentation, and centrifugation.
- the filter for filtration include a metal mesh, a metal filter, and a nylon mesh.
- Examples of the dispersion treatment include a thin layer shear disperser, a bead mill, an ultrasonic homogenizer, a high shear mixer, a narrow gap three-roll mill, a wet super atomizer, a supersonic jet mill, and an ultra high pressure homogenizer.
- the bonding copper paste may be adjusted to a viscosity suitable for each printing / coating method when molding.
- the viscosity of the bonding copper paste may be, for example, a Casson viscosity at 25 ° C. of 0.05 Pa ⁇ s to 2.0 Pa ⁇ s, and 0.06 Pa ⁇ s to 1.0 Pa ⁇ s. Also good.
- the flaky micro copper particles are in contact with the member (interface between the paste layer and the member), It tends to be oriented almost in parallel.
- the degree of orientation order S can be calculated by equation (1).
- S 1/2 ⁇ (3 ⁇ cos 2 ⁇ > ⁇ 1) (1)
- ⁇ represents an angle formed by the interface and the flaky micro copper particles
- ⁇ cos 2 ⁇ > represents an average value of a plurality of cos 2 ⁇ values.
- the degree of orientation order S can be 0.88 or more and 1.00 or less.
- the degree of orientation order S is within such a range, the flaky micro copper particles in the bonding copper paste are aligned substantially parallel to the bonding surface. Therefore, volume shrinkage when the bonding copper paste is sintered can be suppressed, and it becomes easy to secure the bonding strength of the bonded body manufactured by sintering the bonding copper paste. When used for element bonding, it is easy to improve the die shear strength and connection reliability of the semiconductor device.
- the orientation order S can be determined from, for example, an SEM image of a dried copper paste for bonding.
- the bonding copper paste is printed on the copper substrate, and the silicon chip is mounted. This is sintered with a hot plate or the like in air at 100 ° C. for 30 minutes, thereby preparing an adhesive that is weakly bonded to the copper paste for bonding the copper plate and silicon chip by drying.
- This adhesive is poured with epoxy casting resin so that the entire adhesive is filled and cured. Cut the cast adhesive near the cross section to be observed, grind the cross section by polishing, and perform CP processing to make a sample.
- the cross section of the sample is observed with a SEM apparatus at a magnification of 5000 times.
- the angle formed by the major axis of the shape derived from the flaky micro copper particles with the interface is measured using image processing software having an angle measurement function.
- the orientation order S can be calculated by measuring ⁇ in a shape derived from 50 or more randomly selected flaky micro-copper particles and substituting it into equation (1).
- the image processing software is not particularly limited, and for example, ImageJ (manufactured by National Institutes of Health) can be used.
- the degree of orientation order S takes a value from 0 to 1, and is 1 in a completely oriented state and 0 in a completely random state.
- the bonding copper paste of the present embodiment the above-mentioned sub-micro copper particles and the above-mentioned flaky micro-copper particles are used in combination, and by limiting the content of specific micro-copper particles, good sintering Properties can be obtained, and volume shrinkage during sintering can be suppressed. Therefore, the bonding copper paste of the present embodiment can ensure the bonding force with the member without excessive pressurization, and the bonded body manufactured by sintering the bonding copper paste is sufficient. It can have bonding strength. When the bonding copper paste is used for bonding semiconductor elements, the semiconductor device exhibits good die shear strength and connection reliability. That is, the bonding copper paste of this embodiment may be used as a bonding material for pressureless bonding.
- the bonding copper paste of this embodiment can obtain the above-described effects by the sub-micro copper particles and the micro-copper particles, it is cheaper than a bonding material mainly composed of expensive copper nanoparticles. And it has the advantage that it can supply stably. Thereby, for example, when manufacturing a joined body such as a semiconductor device, it is possible to further improve the production stability.
- FIG. 2 is a schematic cross-sectional view showing an example of a joined body manufactured using the joining copper paste of the present embodiment.
- the joined body 100 of the present embodiment includes the first member 2, the second member 3, and the sintered body 1 of the joining copper paste for joining the first member and the second member. .
- Examples of the first member 2 and the second member 3 include semiconductor elements such as IGBT, diode, Schottky barrier diode, MOS-FET, thyristor, logic, sensor, analog integrated circuit, LED, semiconductor laser, and transmitter. , Lead frame, ceramic substrate with metal plate (for example, DBC), base material for mounting semiconductor elements such as LED package, metal wiring such as copper ribbon and metal frame, block body such as metal block, power supply member such as terminal, heat dissipation A board, a water cooling board, etc. are mentioned.
- semiconductor elements such as IGBT, diode, Schottky barrier diode, MOS-FET, thyristor, logic, sensor, analog integrated circuit, LED, semiconductor laser, and transmitter.
- DBC ceramic substrate with metal plate
- base material for mounting semiconductor elements such as LED package
- metal wiring such as copper ribbon and metal frame
- block body such as metal block
- power supply member such as terminal, heat dissipation A board, a water cooling board, etc.
- the first member 2 and the second member 3 may contain metal on the surfaces 4a and 4b that are in contact with the sintered body of the bonding copper paste.
- the metal include copper, nickel, silver, gold, palladium, platinum, lead, tin, and cobalt.
- a metal may be used individually by 1 type and may be used in combination of 2 or more type.
- the surface in contact with the sintered body may be an alloy containing the above metal. Examples of the metal used for the alloy include zinc, manganese, aluminum, beryllium, titanium, chromium, iron, and molybdenum in addition to the above metals.
- the member containing metal on the surface in contact with the sintered body examples include, for example, a member having various metal plating, a wire, a chip having metal plating, a heat spreader, a ceramic substrate to which a metal plate is attached, and a lead frame having various metal plating. Or the lead frame which consists of various metals, a copper plate, and copper foil are mentioned.
- the first member 2 may be a metal wiring such as a metal frame, a block body having thermal conductivity and conductivity such as a metal block, or the like.
- the die shear strength of the joined body may be 10 MPa or more, 15 MPa or more, 20 MPa or more, or 30 MPa from the viewpoint of sufficiently joining the first member and the second member. It may be the above.
- the die shear strength can be measured using a universal bond tester (4000 series, manufactured by DAGE) or the like.
- the thermal conductivity of the sintered copper paste for bonding may be 100 W / (m ⁇ K) or more, or 120 W / (m ⁇ K) or more, from the viewpoint of heat dissipation and connection reliability at high temperatures. It may be 150 W / (m ⁇ K) or more.
- the thermal conductivity can be calculated from the thermal diffusivity, specific heat capacity, and density of the sintered body of the bonding copper paste.
- the orientation order S of the flaky micro-copper particles in the joined body can be 0.88 or more and 1.00 or less.
- the degree of orientation order S in the joined body can be calculated by the above-described method using the joined body as an object of analysis instead of an adhesive that is weakly bonded with the dried joining copper paste.
- the joining copper paste and the second member are arranged in this order on the first member, the direction in which the weight of the first member works.
- a laminated body is prepared, and the bonding copper paste is sintered in a state where it receives the weight of the first member or the weight of the first member and a pressure of 0.01 MPa or less.
- the laminate can be prepared, for example, by providing the bonding copper paste of the present embodiment on a necessary portion of the second member and then placing the first member on the bonding copper paste.
- any method can be used as long as the bonding copper paste can be deposited.
- Examples of such methods include screen printing, transfer printing, offset printing, jet printing, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, slit coat, letterpress printing, intaglio printing, gravure printing.
- Printing, stencil printing, soft lithography, bar coating, applicator, particle deposition method, spray coater, spin coater, dip coater, electrodeposition coating, and the like can be used.
- the thickness of the bonding copper paste may be 1 ⁇ m or more and 1000 ⁇ m or less, 10 ⁇ m or more and 500 ⁇ m or less, 50 ⁇ m or more and 200 ⁇ m or less, 10 ⁇ m or more and 3000 ⁇ m or less, or 15 ⁇ m or more. It may be 500 ⁇ m or less, 20 ⁇ m or more and 300 ⁇ m or less, 5 ⁇ m or more and 500 ⁇ m or less, 10 ⁇ m or more and 250 ⁇ m or less, or 15 ⁇ m or more and 150 ⁇ m or less.
- the bonding copper paste provided on the second member may be appropriately dried from the viewpoint of suppressing flow during sintering and generation of voids.
- the gas atmosphere at the time of drying may be air, an oxygen-free atmosphere such as nitrogen or a rare gas, or a reducing atmosphere such as hydrogen or formic acid.
- the drying method may be drying at room temperature, drying by heating, or drying under reduced pressure.
- heat drying or reduced pressure drying for example, hot plate, hot air dryer, hot air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic A heating device, a heater heating device, a steam heating furnace, a hot plate press device, or the like can be used.
- the drying temperature and time may be appropriately adjusted according to the type and amount of the dispersion medium used.
- the drying temperature and time for example, the drying may be performed at 50 ° C. or higher and 180 ° C. or lower for 1 minute or longer and 120 minutes or shorter.
- Examples of the method of arranging the first member on the bonding copper paste include a chip mounter, a flip chip bonder, a carbon or ceramic positioning jig.
- the copper paste for bonding can be sintered by heat-treating the laminate.
- heat-treating the laminate for example, hot plate, hot air dryer, hot air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device, A heater heating device, a steam heating furnace, or the like can be used.
- the gas atmosphere during sintering may be an oxygen-free atmosphere from the viewpoint of suppressing oxidation of the sintered body, the first member, and the second member.
- the gas atmosphere at the time of sintering may be a reducing atmosphere from the viewpoint of removing the surface oxides of the copper particles of the bonding copper paste.
- the oxygen-free atmosphere include introduction of oxygen-free gas such as nitrogen and rare gas, or under vacuum.
- the reducing atmosphere include pure hydrogen gas, hydrogen and nitrogen mixed gas typified by forming gas, nitrogen containing formic acid gas, hydrogen and rare gas mixed gas, and rare gas containing formic acid gas. Can be mentioned.
- the maximum temperature reached during the heat treatment may be 250 ° C. or higher and 450 ° C. or lower, from the viewpoint of reducing thermal damage to the first member and the second member and improving the yield, and may be 250 ° C. or higher and 400 ° C. or lower. Or 250 ° C. or more and 350 ° C. or less. If the ultimate temperature is 200 ° C. or higher, the sintering tends to proceed sufficiently when the ultimate temperature holding time is 60 minutes or less.
- the ultimate temperature holding time may be from 1 minute to 60 minutes, from 1 minute to less than 40 minutes, or from 1 minute to 1 minute from the viewpoint of volatilizing all the dispersion medium and improving the yield. It may be less than 30 minutes.
- the bonded body can have sufficient bonding strength even when bonding without pressure is performed when the laminate is sintered. That is, sufficient bonding strength in a state in which only the own weight of the first member laminated on the bonding copper paste or the pressure of 0.01 MPa or less, preferably 0.005 MPa or less, in addition to the own weight of the first member. Can be obtained. If the pressure applied during the sintering is within the above range, a special pressurizing device is not required, and the void reduction, die shear strength and connection reliability can be further improved without impairing the yield. Examples of the method for receiving the pressure of the bonding copper paste of 0.01 MPa or less include a method of placing a weight on the first member.
- the first member and the second member may be a semiconductor element.
- the semiconductor element include a power module including a diode, a rectifier, a thyristor, a MOS gate driver, a power switch, a power MOSFET, an IGBT, a Schottky diode, and a fast recovery diode, a transmitter, an amplifier, and an LED module.
- the joined body is a semiconductor device.
- the obtained semiconductor device can have sufficient die shear strength and connection reliability.
- FIG. 3 is a schematic cross-sectional view showing an example of a semiconductor device manufactured using the bonding copper paste of this embodiment.
- a semiconductor device 110 shown in FIG. 3 includes a semiconductor element 8 connected to a lead frame 5a via a sintered body 1 of a bonding copper paste according to this embodiment, and a mold resin 7 for molding them. .
- the semiconductor element 8 is connected to the lead frame 5 b through the wire 6.
- a power composed of a diode, a rectifier, a thyristor, a MOS gate driver, a power switch, a power MOSFET, an IGBT, a Schottky diode, a fast recovery diode, and the like.
- Examples include modules, transmitters, amplifiers, high-brightness LED modules, sensors, and the like.
- the semiconductor device can be manufactured in the same manner as the manufacturing method of the joined body described above. That is, the method for manufacturing a semiconductor device uses a semiconductor element as at least one of the first member and the second member, and the first member and the copper paste for bonding on the side in which the weight of the first member acts. And a laminated body in which the second member is laminated in this order, and the bonding copper paste is subjected to the weight of the first member or the weight of the first member and the pressure of 0.01 MPa or less.
- a step of sintering For example, a step of providing a bonding copper paste on the lead frame 5a and arranging and heating the semiconductor element 8 can be mentioned.
- the obtained semiconductor device can have sufficient die shear strength and connection reliability even when bonding is performed without applying pressure.
- the semiconductor device of the present embodiment has a sufficient bonding strength, and has a copper sintered body having a high thermal conductivity and a high melting point, thereby having a sufficient die shear strength, excellent connection reliability, and a power cycle. It can be excellent in tolerance.
- the above method can reduce damage to the semiconductor element when a metal wiring or a block body is bonded to the semiconductor element as the first member.
- a semiconductor device in which a member such as a metal wiring or a block body is bonded on a semiconductor element will be described below.
- a first electrode As one embodiment of such a semiconductor device, a first electrode, a semiconductor element electrically connected to the first electrode, and a second electrode electrically connected to the semiconductor element via a metal wiring And an electrode having a sintered body of the bonding copper paste between the semiconductor element and the metal wiring and between the metal wiring and the second electrode.
- FIG. 4 is a schematic cross-sectional view showing an example of the semiconductor device.
- a semiconductor device 200 shown in FIG. 4 includes an insulating substrate 21 having a first electrode 22 and a second electrode 24, and a semiconductor bonded on the first electrode 22 by the sintered copper paste 1 for bonding.
- An element 23 and a metal wiring 25 that electrically connects the semiconductor element 23 and the second electrode 24 are provided.
- the metal wiring 25 and the semiconductor element 23, and the metal wiring 25 and the second electrode 24 are joined by the sintered body 1 of the joining copper paste.
- the semiconductor element 23 is connected to the third electrode 26 through a wire 27.
- the semiconductor device 200 includes a copper plate 28 on the side opposite to the surface on which the electrodes and the like of the insulating substrate 21 are mounted.
- the structure is sealed with an insulator 29.
- the semiconductor device 200 has one semiconductor element 23 on the first electrode 22, but may have two or more. In this case, the plurality of semiconductor elements 23 can be joined to the metal wiring 25 by the sintered body 1 of the joining copper paste.
- FIG. 5 is a schematic cross-sectional view showing another example of a semiconductor device.
- the block body 30 is provided between the semiconductor element 23 and the metal wiring 25, and the semiconductor element 23 and the block body 30, and the block body 30 and the metal wiring 25 are used for bonding.
- the semiconductor device 200 has the same configuration as that of the semiconductor device 200 shown in FIG. 4 except that it is joined by the sintered body 1 of copper paste.
- the position of the block body 30 can be changed as appropriate, and may be provided between the first electrode 22 and the semiconductor element 23, for example.
- FIG. 6 is a schematic cross-sectional view showing another example of a semiconductor device.
- the semiconductor device 220 shown in FIG. 6 is the same as the semiconductor device 220 except that the semiconductor element 23, the block body 30, and the sintered body 1 of the joining copper paste for joining them are further provided on the first electrode 22.
- 5 has the same configuration as that of the semiconductor device 210 shown in FIG.
- the semiconductor device 220 has two semiconductor elements on the first electrode 22, but may have three or more. Also in this case, the three or more semiconductor elements 23 can be joined to the metal wiring 25 by the sintered body 1 of the joining copper paste via the block bodies 30 respectively.
- the position of the block body 30 can be changed as appropriate, and may be provided between the first electrode 22 and the semiconductor element 23, for example.
- the insulating substrate 21 examples include ceramics such as alumina, aluminum nitride, and silicon nitride, high thermal conductive particle / resin composite, polyimide resin, polymaleimide resin, and the like.
- Examples of the metal constituting the first electrode 22, the second electrode 24, and the third electrode 26 include copper, nickel, silver, gold, palladium, platinum, lead, tin, and cobalt. These metals may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the electrode may have the alloy containing the said metal in the surface which contact
- Examples of the metal wiring include a metal frame having a strip shape, a plate shape, a cube shape, a cylindrical shape, an L shape, a U shape, a hemiform shape, and the like.
- Examples of the material for the metal wiring include silver, copper, iron, aluminum, molybdenum, tungsten, tantalum, niobium, and alloys thereof. These metal wiring surfaces may be coated with nickel, copper, gold, silver or the like by plating, sputtering or the like for oxidation resistance and adhesion.
- the metal wiring may have a width of 1 ⁇ m to 30 ⁇ m and a thickness of 20 ⁇ m to 5 mm.
- the block body those excellent in thermal conductivity and conductivity are preferable, and for example, silver, copper, iron, aluminum, molybdenum, tungsten, tantalum, niobium, or an alloy thereof can be used.
- the surface of the block body may be coated with nickel, copper, gold, silver or the like by plating, sputtering, or the like for oxidation resistance and adhesion. By providing the block body on the semiconductor element, the heat dissipation is further improved.
- the number of block bodies can be changed as appropriate.
- Examples of the insulator 29 include silicone gel, polymaleimide resin, polyimide resin, and polyamideimide resin.
- the semiconductor devices shown in FIGS. 4 to 6 can be used for power modules that require large capacity and high reliability.
- an insulating substrate including a first electrode and a second electrode is prepared, and a copper paste for bonding, a semiconductor element, and further bonding if necessary are provided on the first electrode.
- Copper paste, block body, bonding copper paste are provided in this order from the first electrode side, bonding copper paste is provided on the second electrode, bonding copper paste on the semiconductor element or block body, and second The step of arranging metal wiring on the bonding copper paste on the electrode to cross-link these bonding copper pastes, the bonding copper paste, the weight of each member or the weight of each member and 0.01 MPa or less And a step of sintering in a state where the pressure is received.
- the metal wiring having the bridge portion can be joined without being deformed, and the area on the semiconductor element is smaller than that of the semiconductor element. Even when the members are joined, damage to the semiconductor element can be further reduced.
- FIG. 7 is a schematic cross-sectional view showing still another example of the semiconductor device.
- a semiconductor device 300 shown in FIG. 7 includes a first electrode 22, a semiconductor element 23 bonded to the first electrode 22 by the sintered body 1 of the bonding copper paste, the semiconductor element 23, and the second electrode. 24, and a metal wiring 25 that electrically connects to the wiring 24.
- the metal wiring 25 and the semiconductor element 23, and the metal wiring 25 and the second electrode 24 are joined by the sintered body 1 of the joining copper paste.
- the semiconductor element 23 is connected to the third electrode 26 through a wire 27.
- the structure is sealed with a sealing material 31.
- the semiconductor device 300 has one semiconductor element 23 on the first electrode 22, but may have two or more. In this case, the plurality of semiconductor elements 23 can be joined to the metal wiring 25 by the sintered body 1 of the joining copper paste.
- FIG. 8 is a schematic cross-sectional view showing another example of a semiconductor device.
- a block body 30 is provided between the semiconductor element 23 and the metal wiring 25, and the semiconductor element 23 and the block body 30, and the block body 30 and the metal wiring 25 are respectively bonded copper.
- the semiconductor device 300 has the same configuration as that of the semiconductor device 300 shown in FIG.
- the position of the block body 30 can be changed as appropriate, and may be provided between the first electrode 22 and the semiconductor element 23, for example.
- FIG. 9 is a schematic cross-sectional view showing another example of a semiconductor device.
- the semiconductor device 320 shown in FIG. 9 is the same as the semiconductor device 320 except that the semiconductor element 23, the block body 30, and the sintered body 1 of the joining copper paste for joining them are further provided on the first electrode 22. 8 has the same configuration as the semiconductor device 310 shown in FIG.
- the semiconductor device 320 has two semiconductor elements on the first electrode 22, but may have three or more. Also in this case, the three or more semiconductor elements 23 can be joined to the metal wiring 25 by the sintered body 1 of the joining copper paste via the block bodies 30 respectively.
- the position of the block body 30 can be changed as appropriate, and may be provided between the first electrode 22 and the semiconductor element 23, for example.
- the first electrode 22 and the second electrode 24 shown in FIGS. 7 to 9 may be a lead frame, a copper plate, a copper / molybdenum sintered body, or the like.
- sealing material 31 examples include a heat-resistant solid sealing material and a high thermal conductive composite.
- the sintered copper paste 1 for bonding can be the same as that described in the semiconductor devices 200 to 220.
- the semiconductor device of the embodiment shown in FIGS. 7 to 9 can be used for a miniaturized power module by adopting a lead frame or the like as the first electrode and the second electrode.
- Such a semiconductor device can be manufactured in the same manner as the semiconductor device manufacturing method described above.
- the semiconductor device includes a first heat conductive member, a second heat conductive member, and a semiconductor element disposed between the first heat conductive member and the second heat conductive member.
- FIG. 10 is a schematic cross-sectional view showing an example of this embodiment.
- a semiconductor device 400 shown in FIG. 10 includes a first heat conductive member 32, a semiconductor element 23 bonded on the first heat conductive member 32 via a sintered body 1 of bonding copper paste, and a semiconductor element 23.
- a block body 30 joined on the block body 30 via the bonding copper paste sintered body 1, and a second heat conductive member 33 joined on the block body 30 via the bonding copper paste sintered body 1; .
- the semiconductor element 23 is connected to the electrode 34 via the wire 35.
- the space between the first heat conductive member 32 and the second heat conductive member is sealed with a sealing material 31.
- the semiconductor device 400 includes two semiconductor elements, but may include one or three or more, and the number of block bodies can be changed as appropriate.
- the position of the block body 30 can be changed as appropriate, and may be provided between the first electrode 22 and the semiconductor element 23, for example.
- the heat conducting member has both a function of releasing heat generated from the semiconductor element 23 to the outside and a function as an electrode for electrically connecting the semiconductor element to the outside.
- a heat conducting member for example, copper, aluminum, or an alloy thereof is used.
- the semiconductor device shown in FIG. 10 can have a double-sided cooling structure with excellent heat dissipation by providing heat conducting members on both sides of the semiconductor element.
- a bonding copper paste, a semiconductor element, a bonding copper paste, a block body, a bonding copper paste, a second heat conductive member, and a first heat conductive member are formed on the first heat conductive member.
- a laminated body laminated in this order from the side is prepared, and the copper paste for bonding is manufactured by a method including a step of sintering under the weight of each member or the weight of each member and a pressure of 0.01 MPa or less. be able to.
- the said laminated body may be laminated
- a straight line was drawn from end to end of the scale bar at the bottom of the image (scale showing 10 ⁇ m in this example), and the length of the straight line was recorded (3.7 cm in this example). Subsequently, a rectangle was drawn so as to circumscribe the shape derived from the flaky micro copper particles.
- a 1.81 cm ⁇ 1.37 cm rectangle was drawn on a shape derived from a certain flaky micro copper particle.
- the long side of the rectangle (1.81 cm in this example) was the long diameter X of the flaky micro copper particles
- the short side of the rectangle (1.37 cm in this example) was the medium diameter Y of the flaky micro copper particles.
- the long diameter X and the medium diameter Y were calculated as follows.
- This operation was repeated without duplication on the shape derived from the flaky micro copper particles on the screen.
- the shape derived from the flaky micro copper particles protruding from the edge of the screen and having an image cut off was not selected.
- the shape derived from 50 or more flaky micro copper particles was measured, and the average length measurement result was calculated.
- the average value Xav of the long diameter and the average value Yav of the medium diameter of the flaky micro copper particles were obtained.
- an adhesive material was obtained in which the copper plate and the silicon chip were weakly bonded with the dried bonding copper paste.
- This adhesive is fixed in a cup with a sample clip (Sampklip I, manufactured by Buehler), and an epoxy casting resin (Epomount, manufactured by Refinetech Co., Ltd.) is poured into the cup until the entire adhesive is filled, and is placed in a vacuum desiccator. The mixture was allowed to stand and decompressed for 1 minute to degas. Thereafter, the defoamed adhesive was allowed to stand at room temperature for 10 hours, the epoxy casting resin was cured, and a sample was prepared. The sample was cut in the vicinity of the silicon chip using Refine So Excel (Refine Tech Co., Ltd.).
- the sample was cut to the vicinity of the center of the adhesive with a polishing apparatus (Refine Polisher HV, manufactured by Refinetech Co., Ltd.) equipped with water-resistant abrasive paper (Carbo Mac paper, manufactured by Refinetech Co., Ltd.).
- the polished sample was made into a size that could be processed with an ion milling device by scraping off excess epoxy casting resin.
- an ion milling device IM4000, manufactured by Hitachi High-Technologies Corporation
- cross-section processing was performed on the sized sample under the conditions of an argon gas flow rate of 0.07 to 0.1 cm 3 / min and a processing time of 120 minutes. This was used as a sample for SEM.
- This SEM sample was observed with an SEM apparatus (NeoScope JCM-5000, manufactured by JEOL Ltd.) at an applied voltage of 10 kV.
- the long side of the rectangle (1.79 cm in this example) corresponds to the long diameter X or medium diameter Y of the flaky micro copper particles.
- the short side (0.36 cm in this example) of the rectangle was defined as the short diameter T of the flaky micro copper particles.
- the shape derived from 50 or more flaky micro copper particles was measured, and the average length measurement result was calculated. As a result, an average value Tav of the minor axis of the flaky micro copper particles was obtained.
- the average value Tav of the short diameter the average value Xav of the long diameter obtained from “(1) Calculation of the long diameter and the medium diameter of the flaky micro copper particles”, and the average value Yav of the medium diameter, the flake shape
- the ratios of long diameter / medium diameter (Xav / Yav), long diameter / short diameter (Xav / Tav) and medium diameter / short diameter (Yav / Tav) in the micro copper particles were calculated.
- the Measure button in the ROI Manager window was pressed. Since the measured angle is displayed in the Results window, it is saved in a file by [File] ⁇ [Save As].
- the angle was measured in the same manner.
- the saved result file was read with Microsoft Excel.
- the silicon chip was pushed in the horizontal direction at a measurement speed of 500 ⁇ m / s and a measurement height of 100 ⁇ m, and the die shear strength of the joined body was measured.
- the average value of the measured values of the eight bonded bodies was defined as the die shear strength.
- the gas was changed to 300 mL / min of hydrogen gas, the temperature was raised to 350 ° C., and sintering treatment was performed for 60 minutes to obtain a sintered body. Thereafter, the argon gas was changed to 0.3 L / min and cooled, and the sintered body was taken out into the air at 50 ° C. or lower.
- the plate-like sintered body was peeled from the glass plate and polished with a sandpaper (# 800) to obtain a plate-like sample having a size of 10 ⁇ 10 mm 2 and a flat surface. The length, width, and thickness of the plate sample were measured, and the weight of the plate sample was measured. The density of the plate sample was calculated from these values.
- a joined body was manufactured by the method described in “(5) Measurement of die shear strength”.
- the manufactured joined body is fixed in a cup with a sample clip (Sampklip I, manufactured by Bühler), and an epoxy casting resin (Epomount, manufactured by Refinetech Co., Ltd.) is poured into the cup until the entire joined body is filled, and inside the vacuum desiccator And deaerated under reduced pressure for 1 minute. Then, it left still at room temperature for 10 hours, the epoxy casting resin was hardened, and the sample was prepared.
- the sample was cut in the vicinity of the silicon chip using Refine So Excel (Refine Tech Co., Ltd.).
- test piece for temperature cycling is set in a temperature cycle tester (TSA-72SE-W, manufactured by Espec Corp.), low temperature side: ⁇ 40 ° C., high temperature side: 200 ° C., each step: 15 minutes, defrost cycle:
- TSA-72SE-W temperature cycle tester
- low temperature side ⁇ 40 ° C.
- high temperature side 200 ° C.
- defrost cycle A temperature cycle connection reliability test was conducted under the conditions of automatic, number of cycles: 300 cycles.
- an ultrasonic flaw detector Insight Insight-300
- SAT images of the bonded state of the copper sintered body and the adherend interface before and after the temperature cycle connection reliability test were obtained, and the presence or absence of peeling was examined. A case where 20% by area or more of the joint part was peeled was defined as defective (x).
- Example 1 As dispersion medium, 0.5 g of ⁇ -terpineol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 g of isobornylcyclohexanol (MTPH, manufactured by Nippon Terpene Chemical Co., Ltd.) and HT-14 (Mitsui Metals) as sub-micro copper particles 7 g (manufactured by Mining Co., Ltd.) was mixed in a plastic bottle and treated with an ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Co., Ltd.) for 1 minute at 19.6 kHz, 600 W to obtain a dispersion.
- MTPH isobornylcyclohexanol
- HT-14 Mitsubishi Metals
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less, the content of the flaky micro copper particles having an aspect ratio of 4 or more, and the maximum diameter is 1 ⁇ m or more and 20 ⁇ m.
- the content of the micro copper particles having an aspect ratio of less than 2 was converted from the particle size distribution obtained by measurement for 50 or more particles. Based on this converted value, the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less, and the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less based on the total amount of flaky micro copper particles having an aspect ratio of 4 or more.
- the content ratio of the copper particles was calculated.
- Example 2 A joining copper paste 2 was obtained in the same manner as in Example 1 except that 3L3 (Fukuda Metal Foil Powder Co., Ltd.) was used as the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 2.
- Example 3 A joining copper paste 3 was obtained in the same manner as in Example 1 except that 1110F (manufactured by Mitsui Mining & Smelting Co., Ltd.) was used as the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 3.
- Example 4 A joining copper paste 4 was obtained in the same manner as in Example 1 except that TN-Cu100 (manufactured by Taiyo Nippon Sanso Corporation) was used as the sub-micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 4.
- Example 5 A joining copper paste 5 was obtained in the same manner as in Example 1 except that CH-0200 (Mitsui Metals Mining Co., Ltd.) was used as the sub-micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 5.
- Example 6 A bonding copper paste 6 was obtained in the same manner as in Example 1 except that CT-500 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was used as the copper particles. Various measurements and analyzes were performed using the bonding copper paste 6.
- Example 7 A joining copper paste 7 was obtained in the same manner as in Example 1 except that silver particles LM1 (manufactured by Toxen Industries Co., Ltd.) was used as an additive. Various measurements and analyzes were performed using the bonding copper paste 7.
- Example 8 A joining copper paste 8 was obtained in the same manner as in Example 1 except that nickel particles Ni-HWQ (Fukuda Metal Foil Powder Co., Ltd.) was used as an additive. Various measurements and analyzes were performed using the bonding copper paste 8.
- Example 9 In the same manner as in Example 1 except that spherical copper particles 1300Y (manufactured by Mitsui Metal Mining Co., Ltd.) were used as micro copper particles having a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less and an aspect ratio of less than 2. Copper paste 9 was obtained. Various measurements and analyzes were performed using the bonding copper paste 9.
- spherical copper particles 1300Y manufactured by Mitsui Metal Mining Co., Ltd.
- Example 1 A bonding copper paste 10 was obtained in the same manner as in Example 1 except that the flaky micro copper particles were not added. Various measurements and analyzes were performed using the bonding copper paste 10.
- Example 2 A joining copper paste 11 was obtained in the same manner as in Example 1 except that spherical copper particles 1300Y (manufactured by Mitsui Metal Mining Co., Ltd.) were used instead of the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 11.
- Example 3 A joining copper paste 12 was obtained in the same manner as in Example 1 except that spherical copper particles 1100Y (Mitsui Metal Mining Co., Ltd.) were used instead of the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 12.
- Example 4 A joining copper paste 13 was obtained in the same manner as in Example 1 except that spherical copper particles 1050Y (Mitsui Metal Mining Co., Ltd.) were used instead of the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 13.
- Example 5 A joining copper paste 14 was obtained in the same manner as in Example 1 except that spherical copper particles 1020Y (Mitsui Metal Mining Co., Ltd.) were used instead of the flaky micro copper particles. Various measurements and analyzes were performed using the bonding copper paste 14.
- Tables 1 to 3 show the compositions and test results of Examples and Comparative Examples.
- the shape of the copper particles used in the examples and comparative examples is as follows.
- TN-Cu100 50% volume average particle size 0.12 ⁇ m, content of copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less 90 mass% CH-0200: 50% volume average particle size 0.36 ⁇ m, content of copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less 100% by mass CT-500: 50% volume average particle size 0.72 ⁇ m, content of copper particles having a particle size of 0.12 ⁇ m or more and 0.8 ⁇ m or less 80% by mass
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the maximum diameter is 1 ⁇ m or more
- (Flake micro copper particles) MA-C025 content of copper particles having an average maximum diameter of 4.1 ⁇ m, an aspect ratio of 7.9, and a maximum diameter of 1 ⁇ m or more and 20 ⁇ m or less of 100% by mass
- 3L3 content of copper particles having an average maximum diameter of 7.3 ⁇ m, an aspect ratio of 26, and a maximum diameter of 1 ⁇ m to 20 ⁇ m, 100% by mass
- 1110F content of copper particles having an average maximum diameter of 5.8 ⁇ m, an aspect ratio of 20, and a maximum diameter of 1 ⁇ m to 20 ⁇ m, 100% by mass
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the content of the flaky micro copper particles having an aspect ratio of 4 or more is 100% by mass
- the maximum diameter is 1 ⁇ m or more and 20 ⁇ m or less
- the aspect The content of micro copper particles having a ratio of less than 2 was 0% by mass.
- said volume average particle diameter was calculated
- SALD-7500 nano manufactured by Shimadzu Corporation
- (1) to (5) To measure the 50% volume average particle size.
- WingSALDII-7500-for Japan V3.1 was started up on the personal computer attached to the measuring device, and the manual was initialized by pressing the manual. After the initialization was completed, the save file name was specified, “Next” was clicked, measurement conditions and particle size distribution calculation conditions were set as follows, and “Next” was clicked.
- Measurement condition The average number of detection times of diffraction / scattered light (measurement number: 1): 128, measurement number: 1, measurement interval (seconds): 2 ⁇ Measured light absorption range maximum value: 0.2, minimum value: 0 Blank area / measurement area Blank measurement allowable variation maximum value: 150, measurement optimum range (MAX): 45000, measurement optimum range (MIN): 15000 (Particle size distribution calculation conditions) Refractive index selection: reference sample / forward metal / semiconductor, etc.
- Measurement was performed by selecting “Measurement” from the above screen. The operations (1) to (4) were repeated 4 times and the measurement was performed 4 times. (5) Statistics WingSALDII-7500- for Japan V3. , Click “Open”, select the measured file, WingSALDII-7500-for Japan V3. Measurement data was displayed on the screen. Click “Overlay”, the 50.000% diameter was displayed at the bottom of the screen, and the average value of 4 times was defined as the 50% volume average particle diameter.
- FIGS. 15 to 18 are SEM images of bonded bodies prepared by sandwiching the bonding copper pastes of Examples 1, 2, 4, and 6 between the chip 12 and the substrate 15 and performing a sintering process at 350 ° C. for 25 minutes. is there. From these figures, it can be seen that the state of the bonding copper paste before sintering is reflected even after sintering. That is, it has a structure in which the shape 14 derived from the non-flaked copper particles fills the gap of the shape 13 derived from the flaky micro copper particles, and the shape 13 derived from the flaky micro copper particles is the chip 12 or the substrate 15. It is oriented substantially parallel to the bonding surface.
- the bonded body prepared using the bonding copper paste of the present invention is a bonded copper containing only non-flaked copper particles (for example, spherical copper particles) due to the reinforcing effect in which the orientation structure is closely packed as described above. It can have a copper sintered body with higher connection reliability than a sintered body formed from a paste.
- FIG. 14 is an SEM image of a dried film of the bonding copper paste prepared by sandwiching the bonding copper paste of Comparative Example 4 between the chip and the substrate and performing a heat treatment at 100 ° C. for 30 minutes.
- the bonding copper paste of Comparative Example 4 is a bonding copper paste containing only non-flaked copper particles 11.
- 19 and 20 are SEM images of bonded bodies prepared by sandwiching the bonding copper paste of Comparative Examples 3 and 4 between the chip 12 and the substrate 15 and performing a sintering process at 350 ° C. for 25 minutes.
- the copper paste for bonding prepared using only non-flaky copper particles is sintered in a form close to point contact between non-flaky copper particles, and the adhesion area cannot be secured sufficiently to the adherend surface, etc. Therefore, sufficient joining cannot be secured, and the result of the connection reliability test after joining is not excellent.
- the thermal stress generated by the difference in thermal expansion coefficient between the bonded members was applied to the bonding layer. Even in this case, it is considered that high connection reliability can be maintained. This is considered that the connection reliability was improved because the orientation structure derived from the flaky micro copper particles hindered the propagation of cracks generated in the sintered body of the copper paste for bonding due to thermal stress.
- this sintered body is composed of metallic copper connected by metal bonds, it exhibits a high thermal conductivity of 100 W / (m ⁇ K) or more, and promptly dissipates heat when mounting electronic devices that generate large amounts of heat. Is possible.
- the bonding copper paste according to the present invention even if there is no pressure, it is firmly bonded by metal bonding, so that the material of the adherend surface has bonding strength against copper, nickel, silver and gold.
- the represented die shear strength can be 20 MPa or more.
- the bonding copper paste according to the present invention has a very effective property for bonding electronic devices that generate large amounts of heat such as power devices, logic, and amplifiers. For this reason, when the bonding copper paste according to the present invention is applied, higher input power can be allowed and the operation can be performed at a high operating temperature.
- SYMBOLS 1 Sintered body of copper paste for joining, 2 ... First member, 3 ... Second member, 5a, 5b ... Lead frame, 6 ... Wire, 7 ... Mold resin, 8 ... Semiconductor element, 9 ... Flakes Micro copper particles, 10 ... flaky micro copper particles (unsintered), 11 ... non-flaked micro copper particles (unsintered), 12 ... chip (material: Si, copper), 13 ... flaky micro copper particles Shape derived from (after sintering), 14 ... Shape derived from non-flaked micro copper particles (after sintering), 15 ... Substrate (copper), 100 ... Bonded body, 110 ... Semiconductor device, 21 ...
- Insulating substrate 22 ... 1st electrode, 23 ... Semiconductor element, 24 ... 2nd electrode, 25 ... Metal wiring, 26 ... 3rd electrode, 27 ... Wire, 28 ... Copper plate, 29 ... Insulator, 30 ... Block body, 31 ... Sealing material 32 ... first heat conducting member 33 ... second Conducting member, 34 ... electrode, 35 ... wire, 200 ... semiconductor device, 210 ... semiconductor device, 220 ... semiconductor device, 300 ... semiconductor device, 310 ... semiconductor device, 320 ... semiconductor device, 400 ... semiconductor device.
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Abstract
Description
本実施形態の接合用銅ペーストは、金属粒子と、分散媒と、を含む接合用銅ペーストであって、金属粒子がサブマイクロ銅粒子及びフレーク状マイクロ銅粒子を含む。
本実施形態に係る金属粒子としては、サブマイクロ銅粒子、フレーク状マイクロ銅粒子、これら以外の銅粒子、その他の金属粒子等が挙げられる。
サブマイクロ銅粒子としては、粒径が0.12μm以上0.8μm以下の銅粒子を含むものが挙げられ、例えば、体積平均粒径が0.12μm以上0.8μm以下の銅粒子を用いることができる。サブマイクロ銅粒子の体積平均粒径が0.12μm以上であれば、サブマイクロ銅粒子の合成コストの抑制、良好な分散性、表面処理剤の使用量の抑制といった効果が得られやすくなる。サブマイクロ銅粒子の体積平均粒径が0.8μm以下であれば、サブマイクロ銅粒子の焼結性が優れるという効果が得られやすくなる。より一層上記効果を奏するという観点から、サブマイクロ銅粒子の体積平均粒径は、0.15μm以上0.8μm以下であってもよく、0.15μm以上0.6μm以下であってもよく、0.2μm以上0.5μm以下であってもよく、0.3μm以上0.45μm以下であってもよい。
フレーク状マイクロ銅粒子としては、最大径が1μm以上20μm以下であり、アスペクト比が4以上の銅粒子を含むものが挙げられ、例えば、平均最大径が1μ以上20μm以下であり、アスペクト比が4以上の銅粒子を用いることができる。フレーク状マイクロ銅粒子の平均最大径及びアスペクト比が上記範囲内であれば、接合用銅ペーストを焼結した際の体積収縮を充分に低減でき、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となる。接合用銅ペーストを半導体素子の接合に用いる場合は半導体装置が良好なダイシェア強度及び接続信頼性を示す傾向にある。より一層上記効果を奏するという観点から、フレーク状マイクロ銅粒子の平均最大径は、1μm以上10μm以下であってもよく、3μm以上10μm以下であってもよい。フレーク状マイクロ銅粒子の最大径及び平均最大径の測定は、例えば、粒子のSEM像から求めることができ、後述するフレーク状マイクロ銅粒子の長径X及び長径の平均値Xavとして求められる。
金属粒子としては、サブマイクロ銅粒子及びマイクロ銅粒子以外のその他の金属粒子を含んでいてもよく、例えば、ニッケル、銀、金、パラジウム、白金等の粒子を含んでいてもよい。その他の金属粒子は、体積平均粒径が0.01μm以上10μm以下であってもよく、0.01μm以上5μm以下であってもよく、0.05μm以上3μm以下であってもよい。その他の金属粒子を含んでいる場合、その含有量は、充分な接合性を得るという観点から、金属粒子の全質量を基準として、20質量%未満であってもよく、10質量%以下であってもよい。その他の金属粒子は、含まれなくてもよい。その他の金属粒子の形状は、特に限定されるものではない。
分散媒は特に限定されるものではなく、揮発性のものであってもよい。揮発性の分散媒としては、例えば、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、デカノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、α-テルピネオール、イソボルニルシクロヘキサノール(MTPH)等の一価及び多価アルコール類;エチレングリコールブチルエーテル、エチレングリコールフェニルエーテル、ジエチレングリコールメチルエーテル、ジエチレングリコールエチルエーテル、ジエチレングリコールブチルエーテル、ジエチレングリコールイソブチルエーテル、ジエチレングリコールヘキシルエーテル、トリエチレングリコールメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル、プロピレングリコールプロピルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールエチルエーテル、ジプロピレングリコールプロピルエーテル、ジプロピレングリコールブチルエーテル、ジプロピレングリコールジメチルエーテル、トリプロピレングリコールメチルエーテル、トリプロピレングリコールジメチルエーテル等のエーテル類;エチレングリコールエチルエーテルアセテート、エチレングリコールブチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、ジエチレングリコールブチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート(DPMA)、乳酸エチル、乳酸ブチル、γ-ブチロラクトン、炭酸プロピレン等のエステル類;N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド等の酸アミド;シクロヘキサノン、オクタン、ノナン、デカン、ウンデカン等の脂肪族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;炭素数1~18のアルキル基を有するメルカプタン類;炭素数5~7のシクロアルキル基を有するメルカプタン類が挙げられる。炭素数1~18のアルキル基を有するメルカプタン類としては、例えば、エチルメルカプタン、n-プロピルメルカプタン、i-プロピルメルカプタン、n-ブチルメルカプタン、i-ブチルメルカプタン、t-ブチルメルカプタン、ペンチルメルカプタン、ヘキシルメルカプタン及びドデシルメルカプタンが挙げられる。炭素数5~7のシクロアルキル基を有するメルカプタン類としては、例えば、シクロペンチルメルカプタン、シクロヘキシルメルカプタン及びシクロヘプチルメルカプタンが挙げられる。
接合用銅ペーストには、必要に応じて、ノニオン系界面活性剤、フッ素系界面活性剤等の濡れ向上剤;シリコーン油等の消泡剤;無機イオン交換体等のイオントラップ剤などを適宜添加してもよい。
(1)体積平均粒径が0.12μm以上0.8μm以下、好ましくは0.15μm以上0.8μm以下であるサブマイクロ銅粒子と、
(2)平均最大径が1μm以上20μm以下であり、アスペクト比が4以上のフレーク状マイクロ銅粒子を含み、且つ、平均最大径が1μm以上20μm以下であり、アスペクト比が2未満のマイクロ銅粒子の含有量が、フレーク状マイクロ銅粒子全量を基準として、50質量%以下、好ましくは30質量%以下であるマイクロ銅粒子と、
を配合してなるものが挙げられる。
接合用銅ペーストは、上述のサブマイクロ銅粒子、フレーク状マイクロ銅粒子、その他の金属粒子及び任意の添加剤を分散媒に混合して調製することができる。各成分の混合後に、撹拌処理を行ってもよい。接合用銅ペーストは、分級操作により分散液の最大粒径を調整してもよい。このとき、分散液の最大粒径は20μm以下とすることができ、10μm以下とすることもできる。
S=1/2×(3<cos2θ>-1)・・・(1)
式中、θは界面とフレーク状マイクロ銅粒子との成す角度を示し、<cos2θ>は複数のcos2θの値の平均値を示す。
配向秩序度Sは、0.88以上1.00以下であることができる。配向秩序度Sがこのような範囲内であれば、接合用銅ペースト内のフレーク状マイクロ銅粒子が、接合面に対して略平行に配向する。そのため、接合用銅ペーストを焼結させたときの体積収縮を抑制でき、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となり、接合用銅ペーストを半導体素子の接合に用いる場合は半導体装置のダイシェア強度及び接続信頼性を向上させやすくなる。
以下、図面を参照しながら好適な実施形態について詳細に説明する。なお、図面中、同一又は相当部分には同一符号を付し、重複する説明は省略する。また、図面の寸法比率は、図示の比率に限られるものではない。
各実施例及び比較例における各特性の測定は、以下の方法により行った。
(1)フレーク状マイクロ銅粒子の長径(最大径)及び中径の算出、並びに長径の平均値及び中径の平均値の算出
フレーク状マイクロ銅粒子を、SEM用のカーボンテープ上にスパチュラで載せ、SEM用サンプルとした。このSEM用サンプルをSEM装置(Philips社製 ESEM XL30、又は、日本電子株式会社製 NeoScope JCM-5000)により、印加電圧10kVで観察した。得られた2000倍のSEM像をMicrosoft PowerPoint(Microsoft社製)で読み込んだ(読み込み時、画像サイズは高さ17.07cm×幅22.75cmであった)。画像下部のスケールバー(本例では10μmを示すスケール)の端から端に対し、直線を引き、その直線の長さを記録した(本例では3.7cm)。続いて、フレーク状マイクロ銅粒子に由来する形状に外接するように長方形を描画した。あるフレーク状マイクロ銅粒子に由来する形状に対して、1.81cm×1.37cmの長方形を描画した。ここで、長方形の長辺(この例では1.81cm)をフレーク状マイクロ銅粒子の長径X、長方形の短辺(この例では1.37cm)をフレーク状マイクロ銅粒子の中径Yとした。10μmのスケールバーが3.7cmの直線という比率から、次のように長径Xと中径Yを算出した。
長径X=1.81cm×10μm/3.7cm=4.89μm
中径Y=1.37cm×10μm/3.7cm=3.70μm
この操作を画面上のフレーク状マイクロ銅粒子に由来する形状に対し、重複無く繰り返した。ただし、画面端からはみ出て像が切断されているフレーク状マイクロ銅粒子に由来する形状は選択しなかった。50個以上のフレーク状マイクロ銅粒子に由来する形状を測定し、測長結果の平均を計算した。この結果、フレーク状マイクロ銅粒子の長径の平均値Xav及び中径の平均値Yavを得た。
銅板(19×25×3mm3)上に厚さ70μmのステンレス板に3×3mm正方形の開口を3行3列有するメタルマスクを載せ、メタルスキージを用いてステンシル印刷により接合用銅ペーストを塗布した。塗布した接合用銅ペースト上に、チタン、ニッケルがこの順で形成され、3×3mm2の被着面がニッケルであるシリコンチップ(チップ厚:600μm)を載せ、ピンセットで軽く押さえた。これをホットプレート(アズワン株式会社製、EC HOTPLATE EC-1200N)にセットし、空気中、100℃、30分の条件で乾燥処理した。これにより、銅板及びシリコンチップが乾燥した接合用銅ペーストによって弱く接着した接着物を得た。この接着物をカップ内にサンプルクリップ(Samplklip I、Buehler社製)で固定し、周囲にエポキシ注形樹脂(エポマウント、リファインテック株式会社製)を接着物全体が埋まるまで流し込み、真空デシケータ内に静置して1分間減圧して脱泡した。その後、脱泡した接着物を室温で10時間静置し、エポキシ注形樹脂を硬化し、サンプルを調製した。リファインソーエクセル(リファインテック株式会社製)を用いて、サンプルをシリコンチップ近傍で切断した。耐水研磨紙(カーボマックペーパー、リファインテック株式会社製)をつけた研磨装置(Refine Polisher HV、リファインテック株式会社製)で、サンプルを接着物の中央付近まで削り断面を出した。研磨したサンプルは、余分なエポキシ注形樹脂を削り落とし、イオンミリング装置で加工できるサイズにした。イオンミリング装置(IM4000、株式会社日立ハイテクノロジーズ製)をCP加工モードで用い、アルゴンガス流量0.07~0.1cm3/min、処理時間120分の条件で、サイズ加工したサンプルを断面加工してSEM用サンプルとした。このSEM用サンプルをSEM装置(日本電子株式会社製、NeoScope JCM-5000)により、印加電圧10kVで観察した。
「(2)接合用銅ペーストの断面モルフォロジー観察」で得られた5000倍のSEM像をMicrosoft PowerPoint(Microsoft社製)で読み込んだ(読み込み時、画像サイズは高さ9.9cm×幅11.74cmであった)。画像下部のスケールバー(本例では5μmを示すスケール)の端から端に対し、直線を引き、その直線の長さを記録した(本例では2.5cm)。続いて、フレーク状マイクロ銅粒子に由来する形状に外接するように長方形を描画した。あるフレーク状マイクロ銅粒子に由来する形状に対して、1.79cm×0.36cmの長方形を描画した。ここで、長方形の長辺(この例では1.79cm)はフレーク状マイクロ銅粒子の長径X又は中径Yに相当する。長方形の短辺(この例では0.36cm)をフレーク状マイクロ銅粒子の短径Tとした。5μmのスケールバーが2.5cmの直線という比率から、次のように短径Tを算出した。
短径T=0.36cm×5μm/2.5cm=0.72μm
この操作を画面上のフレーク状マイクロ銅粒子に由来する形状に対し、重複無く繰り返した。ただし、画面端からはみ出て像が切断されているフレーク状マイクロ銅粒子は選択しなかった。50個以上のフレーク状マイクロ銅粒子に由来する形状を測定し、測長結果の平均を計算した。この結果、フレーク状マイクロ銅粒子の短径の平均値Tavを得た。この短径の平均値Tavと、「(1)フレーク状マイクロ銅粒子の長径及び中径の算出」より得られた長径の平均値Xavと、中径の平均値Yavとを用いて、フレーク状マイクロ銅粒子における長径/中径(Xav/Yav)、長径/短径(Xav/Tav)、中径/短径(Yav/Tav)の比をそれぞれ算出した。
「(2)接合用銅ペーストの断面モルフォロジー観察」で得られた5000倍のSEM像をImageJ(アメリカ国立衛生研究所製)で読み込んだ。SEM像としては、基板又はシリコンチップと接合用銅ペーストとの界面が写っているものを用いた。[T]キーを押してROI Managerウインドウを表示し、Show Allのチェックボックスにチェックを入れた。メインウインドウからStraight Lineを選択した。画像上のフレーク状マイクロ銅粒子の断面の端から端までをクリック→ドラッグでラインを引き、[T]キーを押してROI Managerウインドウに登録した。この操作を画面上のフレーク状マイクロ銅粒に由来する形状に対し、重複無く繰り返した。ただし、画面端からはみ出て像が切断されているフレーク状マイクロ銅粒に由来する形状は選択しなかった。次に、ROI Managerウインドウ内のMeasureボタンを押した。計測された角度がResultsウインドウに表示されるので、[File]→[Save As]でファイルにセーブした。基板又はシリコンチップと接合用銅ペーストとの界面が画像に対し水平からずれている場合には、同様にしてその角度を計測した。セーブされた結果のファイルをMicrosoft Excelで読み込んだ。基板又はシリコンチップと接合用銅ペーストとの界面が画像に対し水平からずれている場合には、測定された各角度データから接合界面の角度を減算した。各角度データθに対しcos2θを求め、その平均値<cos2θ>を算出し、S=1/2×(3<cos2θ>-1)に代入して配向秩序度Sを算出した。
銅板(19×25×3mm3)上に厚さ70μmのステンレス板に3×3mm正方形の開口を3行3列有するメタルマスクを載せ、メタルスキージを用いてステンシル印刷により接合用銅ペーストを塗布した。塗布した接合用銅ペースト上に、チタン、ニッケルがこの順で形成され、3×3mm2の被着面がニッケルであるシリコンチップ(チップ厚:600μm)を載せ、ピンセットで軽く押さえた。これをチューブ炉(株式会社エイブイシー製)にセットし、アルゴンガスを1L/minで流して空気をアルゴンガスに置換した。その後、水素ガスを300mL/minで流しながら昇温10分、350℃、10分の条件で焼結処理して銅板とシリコンチップを銅焼結体で接合した接合体を得た。その後、アルゴンガスを0.3L/minに換えて冷却し、50℃以下で接合体を空気中に取り出した。
接合体の接着強度は、ダイシェア強度により評価した。1kNのロードセルを装着した万能型ボンドテスタ(4000シリーズ、DAGE社製)を用い、測定スピード500μm/s、測定高さ100μmでシリコンチップを水平方向に押し、接合体のダイシェア強度を測定した。8個の接合体の測定した値の平均値をダイシェア強度とした。
厚さ1mmのテフロン(登録商標)板に15×15mm2の開口を設けた。ガラス板上にこのテフロン(登録商標)板を置き、開口部に接合用銅ペーストを充填し、メタルスキージで開口から溢れた銅ペーストを除去した。テフロン(登録商標)板をはずし、チューブ炉にセットし、アルゴンガスを0.3L/minで流しながら、150℃に加熱して1時間保持して分散媒を除去した。そのまま、ガスを水素ガス300mL/minに換え、350℃に昇温して60分焼結処理して、焼結体を得た。その後、アルゴンガスを0.3L/minに換えて冷却し、50℃以下で焼結体を空気中に取り出した。板状の焼結体をガラス板から剥離し、紙やすり(800番)で研磨して10×10mm2のサイズで表面が平坦な板状サンプルを得た。板状サンプルの縦、横、厚みの寸法を測定し、板状サンプルの重量を測定した。これらの値から板状サンプルの密度を算出した。
「(5)ダイシェア強度の測定」に記載の方法で接合体を製造した。製造した接合体をカップ内にサンプルクリップ(Samplklip I、Buehler社製)で固定し、周囲にエポキシ注形樹脂(エポマウント、リファインテック株式会社製)を接合体全体が埋まるまで流し込み、真空デシケータ内に静置して1分間減圧して脱泡した。その後、室温で10時間静置し、エポキシ注形樹脂を硬化し、サンプルを調製した。リファインソーエクセル(リファインテック株式会社製)を用いて、サンプルをシリコンチップ近傍で切断した。耐水研磨紙(カーボマックペーパー、リファインテック株式会社製)をつけた研磨装置(Refine Polisher HV、リファインテック株式会社製)で接合体の中央付近まで削り断面を出した。研磨したサンプルは、余分なエポキシ注形樹脂を削り落とし、イオンミリング装置で加工できるサイズにした。イオンミリング装置(IM4000、株式会社日立ハイテクノロジーズ製)をCP加工モードで用い、アルゴンガス流量0.07~0.1cm3/min、処理時間120分の条件で、サイズ加工したサンプルを断面加工してSEM用サンプルとした。このSEM用サンプルをSEM装置(日本電子株式会社製、NeoScope JCM-5000)により、銅焼結体断面を印加電圧10kVで観察した。
「(7)接合体の断面モルフォロジー観察」で得られた5000倍のSEM像をImageJ(アメリカ国立衛生研究所製)で読み込んだ。SEM像としては、基板又はシリコンチップと接合用銅ペーストの界面が写っているものを用いた。「(4)接合用銅ペーストの配向秩序度の算出」と同様の手順で、接合体の配向秩序度Sを算出した。
「(6)焼結体の密度」で作製した板状サンプルを用い、熱拡散率をレーザーフラッシュ法(LFA467、ネッチ社製)で測定した。この熱拡散率と、示差走査熱量測定装置(DSC8500、パーキンエルマー社製)で得られた比熱容量と、「(6)焼結体の密度」で求めた密度との積により、25℃における焼結体の熱伝導率[W/(m・K)]を算出した。
「(5)ダイシェア強度の測定」と同様にして、銅板(19×25×3mm3)と3×3mm2の被着面がニッケルであるシリコンチップ(チップ厚:600μm)とを銅焼結体で接合した接合体を得た。接合体上にシリコーン樹脂(SE1880、東レ・ダウコーニング株式会社製)をシリコンチップが覆われるようにスポイトでコートし、減圧デシケータ内で3分脱泡した。脱泡後、70℃にした温風循環オーブン内に30分、150℃にした温風循環オーブン内に60分保持することで硬化し、温度サイクル用試験片を得た。この温度サイクル用試験片を温度サイクル試験機(TSA-72SE-W、エスペック株式会社製)にセットし、低温側:-40℃、高温側:200℃、各ステップ:15分、除霜サイクル:自動、サイクル数:300サイクルの条件で温度サイクル接続信頼性試験を実施した。超音波探傷装置(インサイト Insight-300)を用い、温度サイクル接続信頼性試験前後の銅焼結体及び被着体界面の接合状態のSAT像を得て、剥離の有無を調べた。接合部の20面積%以上が剥離した場合を不良(×)とした。
分散媒としてα-テルピネオール(和光純薬工業株式会社製)0.5g及びイソボルニルシクロヘキサノール(MTPH、日本テルペン化学株式会社製)0.5gと、サブマイクロ銅粒子としてHT-14(三井金属鉱業株式会社製)7gとをポリ瓶に混合し、超音波ホモジナイザー(US-600、日本精機株式会社製)により19.6kHz、600W、1分処理し分散液を得た。この分散液に、フレーク状マイクロ銅粒子としてMA-C025(三井金属鉱業株式会社製)3gを添加し、スパチュラで乾燥粉がなくなるまでかき混ぜた。ポリ瓶を密栓し、自転公転型攪拌装置(Planetry Vacuum Mixer ARV-310、株式会社シンキー製)を用いて、2000rpmで2分間撹拌し、減圧下、2000rpmで2分間撹拌して接合用銅ペースト1を得た。この接合用銅ペースト1を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子として3L3(福田金属箔粉工業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト2を得た。接合用銅ペースト2を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子として1110F(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト3を得た。接合用銅ペースト3を用いて、各種の測定及び分析を行った。
サブマイクロ銅粒子としてTN-Cu100(太陽日酸株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト4を得た。接合用銅ペースト4を用いて、各種の測定及び分析を行った。
サブマイクロ銅粒子としてCH-0200(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト5を得た。接合用銅ペースト5を用いて、各種の測定及び分析を行った。
銅粒子としてCT-500(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト6を得た。接合用銅ペースト6を用いて、各種の測定及び分析を行った。
添加剤として銀粒子LM1(トクセン工業株式会製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト7を得た。接合用銅ペースト7を用いて、各種の測定及び分析を行った。
添加剤としてニッケル粒子Ni-HWQ(福田金属箔粉工業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト8を得た。接合用銅ペースト8を用いて、各種の測定及び分析を行った。
最大径が1μm以上20μm以下であり、アスペクト比が2未満のマイクロ銅粒子として、球状銅粒子1300Y(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト9を得た。接合用銅ペースト9を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子を添加しなかったこと以外は、実施例1と同様の方法により、接合用銅ペースト10を得た。接合用銅ペースト10を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子の代わりに球状銅粒子1300Y(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト11を得た。接合用銅ペースト11を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子の代わりに球状銅粒子1100Y(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト12を得た。接合用銅ペースト12を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子の代わりに球状銅粒子1050Y(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト13を得た。接合用銅ペースト13を用いて、各種の測定及び分析を行った。
フレーク状マイクロ銅粒子の代わりに球状銅粒子1020Y(三井金属鉱業株式会社製)を用いたこと以外は、実施例1と同様の方法により、接合用銅ペースト14を得た。接合用銅ペースト14を用いて、各種の測定及び分析を行った。
(サブマイクロ銅粒子)
HT-14:50%体積平均粒径0.36μm、粒径が0.12μm以上0.8μm以下の銅粒子の含有量100質量%
TN-Cu100:50%体積平均粒径0.12μm、粒径が0.12μm以上0.8μm以下の銅粒子の含有量90質量%
CH-0200:50%体積平均粒径0.36μm、粒径が0.12μm以上0.8μm以下の銅粒子の含有量100質量%
CT-500:50%体積平均粒径0.72μm、粒径が0.12μm以上0.8μm以下の銅粒子の含有量80質量%
上記サブマイクロ銅粒子において、最大径が1μm以上20μm以下であり、アスペクト比が4以上のフレーク状マイクロ銅粒子の含有量、及び最大径が1μm以上20μm以下であり、アスペクト比が2未満のマイクロ銅粒子の含有量は、いずれも0質量%であった。
(フレーク状マイクロ銅粒子)
MA-C025:平均最大径4.1μm、アスペクト比7.9、最大径が1μm以上20μm以下の銅粒子の含有量100質量%
3L3:平均最大径7.3μm、アスペクト比26、最大径が1μm以上20μm以下の銅粒子の含有量100質量%
1110F:平均最大径5.8μm、アスペクト比20、最大径が1μm以上20μm以下の銅粒子の含有量100質量%
上記フレーク状マイクロ銅粒子において、最大径が1μm以上20μm以下であり、アスペクト比が4以上のフレーク状マイクロ銅粒子の含有量は100質量%であり、最大径が1μm以上20μm以下であり、アスペクト比が2未満のマイクロ銅粒子の含有量は0質量%であった。
(マイクロ銅粒子)
1300Y:平均最大径3.3μm、アスペクト比1
(50%体積平均粒径)
島津ナノ粒子径分布測定装置(SALD-7500nano、株式会社島津製作所製)と付属のソフトウェア(WingSALDII-7500- for Japanese V3.、株式会社島津製作所製)を用いて、以下の(1)~(5)に従って50%体積平均粒径を測定した。
(1)ソフトウェアの設定
測定装置付属のパソコンでWingSALDII-7500- for Japanese V3.1を起動し,マニュアルを押し装置の初期化を行った。初期化が終わった後に、保存ファイル名を指定し「次へ」をクリックし、測定条件及び粒子径分布計算条件を以下のように設定し、「次へ」をクリックした。
(測定条件)
・回折/散乱光の検出
平均回数(測定回数:1):128、測定回数:1、測定間隔(秒):2
・測定吸光範囲
最大値:0.2、最小値:0
・ブランク領域/測定領域
ブランク測定許容変動最大値:150、測定最適範囲(MAX):45000、測定最適範囲(MIN):15000
(粒子径分布計算条件)
屈折率の選択:参照試料/順金属/半導体等(固体値)
サンプルの物質:4 Copper(銅)
屈折率の選択:1.18-2.21、「側方/後方センサを評価する」にチェックを入れた
(2)ブランク測定
島津ナノ粒子径分布測定装置SALD-7500nano用回分セル(SALD-BC75、株式会社島津製作所製)をSALD-7500nanoに取り付けて測定を行った。SALD-BC75に付属のロート付き回分セル(部品番号S347-61030-41、株式会社島津製作所製、以下「回分セル」という。)内にα-テルピネオール(和光純薬工業株式会社製)を回分セルの2つの標線の間に収まるようにスポイトで滴下した。WingSALDII-7500- for Japanese V3.の画面上から「診断」、「調整」を選択し、位置センサー出力が装置許容範囲内であることを確認した。「キャンセル」をクリックし元の画面に戻り、ブランク測定を選択し測定を行った。
(3)測定溶液の調製
SALD-BC75に付属の回分セルホルダ(部品番号S347-62301、株式会社島津製作所製)のかくはんレバー上に測定したい接合用銅ペーストを2mg載せ、ロート付き回分セルにセットした。次に、WingSALDII-7500- for Japanese V3.の画面上から「スターラ」を選択し、15分間撹拌を行った。
(4)測定
撹拌後、WingSALDII-7500- for Japanese V3.の画面上から「測定」を選択し測定を行った。(1)~(4)の操作を4回繰り返し、4回測定した。
(5)統計
WingSALDII-7500- for Japanese V3.を起動し、「開く」をクリックし、測定したファイルを選択し、WingSALDII-7500- for Japanese V3.の画面上に測定データを表示した。「重ね描き」をクリックし、画面下段に50.000%径を表示し、4回の平均値を50%体積平均粒径とした。
図11~13は、実施例1、4及び6の接合用銅ペーストをチップ12と基板との間に挟み、100℃、30分の熱処理を行い調製した接合用銅ペーストの乾燥膜のSEM像である。接合用銅ペースト中で、フレーク状マイクロ銅粒子10の隙間を非フレーク状銅粒子11(サブマイクロ銅粒子)が埋める構造をとっている。これらの接合用銅ペーストは、特定の平均最大径及びアスペクト比を有することで、基板上に印刷塗布する際のせん断力、又は、チップ12をマウントした際の微小な圧力によって、フレーク状マイクロ銅粒子10がチップ12又は基板との界面に対して略平行となるように配向しやすい。
Claims (9)
- 金属粒子と、分散媒と、を含む接合用銅ペーストであって、
前記金属粒子が、体積平均粒径が0.12μm以上0.8μm以下であるサブマイクロ銅粒子と、最大径が1μm以上20μm以下であり、アスペクト比が4以上のフレーク状マイクロ銅粒子とを含み、且つ、前記金属粒子に含まれる、最大径が1μm以上20μm以下であり、アスペクト比が2未満のマイクロ銅粒子の含有量が、前記フレーク状マイクロ銅粒子全量を基準として、50質量%以下である、接合用銅ペースト。 - 無加圧接合用である、請求項1に記載の接合用銅ペースト。
- 前記サブマイクロ銅粒子の含有量が、前記サブマイクロ銅粒子の質量及び前記フレーク状マイクロ銅粒子の質量の合計を基準として、20質量%以上90質量%以下であり、前記フレーク状マイクロ銅粒子の含有量が、前記金属粒子の全質量を基準として、1質量%以上90質量%以下である、請求項1又は2に記載の接合用銅ペースト。
- 前記金属粒子が、ニッケル、銀、金、パラジウム、白金からなる群から選択される少なくとも1種の金属粒子を含む、請求項1~3のいずれか一項に記載の接合用銅ペースト。
- 第一の部材、該第一の部材の自重が働く方向側に、請求項1~4のいずれか一項に記載の接合用銅ペースト、及び第二の部材がこの順に積層されている積層体を用意し、前記接合用銅ペーストを、前記第一の部材の自重、又は前記第一の部材の自重及び0.01MPa以下の圧力を受けた状態で焼結する工程を備える、接合体の製造方法。
- 第一の部材、該第一の部材の自重が働く方向側に、請求項1~4のいずれか一項に記載の接合用銅ペースト、及び第二の部材がこの順に積層されている積層体を用意し、前記接合用銅ペーストを、前記第一の部材の自重、又は前記第一の部材の自重及び0.01MPa以下の圧力を受けた状態で焼結する工程を備え、
前記第一の部材及び前記第二の部材の少なくとも一方が半導体素子である、半導体装置の製造方法。 - 第一の部材と、第二の部材と、前記第一の部材と前記第二の部材とを接合する請求項1~4のいずれか一項に記載の接合用銅ペーストの焼結体と、を備える、接合体。
- 前記第一の部材及び第二の部材の少なくとも一方が、前記焼結体と接する面に、銅、ニッケル、銀、金及びパラジウムからなる群から選択される少なくとも1種の金属を含む、請求項7に記載の接合体。
- 第一の部材と、第二の部材と、前記第一の部材と前記第二の部材とを接合する請求項1~4のいずれか一項に記載の接合用銅ペーストの焼結体と、を備え、
前記第一の部材及び前記第二の部材の少なくとも一方が半導体素子である、半導体装置。
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US15/757,896 US11040416B2 (en) | 2015-09-07 | 2016-09-07 | Copper paste for joining, method for manufacturing joined body, and method for manufacturing semiconductor device |
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SG11201801844XA SG11201801844XA (en) | 2015-09-07 | 2016-09-07 | Copper paste for joining, method for manufacturing joined body, and method for manufacturing semiconductor device |
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JP2017539199A JP6819598B2 (ja) | 2015-09-07 | 2016-09-07 | 接合用銅ペースト、接合体の製造方法及び半導体装置の製造方法 |
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