WO2017115461A1 - Bonded substrate and method for manufacturing bonded substrate - Google Patents

Bonded substrate and method for manufacturing bonded substrate Download PDF

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Publication number
WO2017115461A1
WO2017115461A1 PCT/JP2016/005212 JP2016005212W WO2017115461A1 WO 2017115461 A1 WO2017115461 A1 WO 2017115461A1 JP 2016005212 W JP2016005212 W JP 2016005212W WO 2017115461 A1 WO2017115461 A1 WO 2017115461A1
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Prior art keywords
copper plate
substrate
bonding
bonded
bonded substrate
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PCT/JP2016/005212
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English (en)
French (fr)
Inventor
Makoto Tani
Yasutaka AWAKURA
Takeshi Kaku
Takashi Ebigase
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NGK Insulators Ltd
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NGK Insulators Ltd
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Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to EP16826189.9A priority Critical patent/EP3398205B1/en
Priority to JP2017535855A priority patent/JP6482144B2/ja
Priority to EP19195538.4A priority patent/EP3598485B1/en
Publication of WO2017115461A1 publication Critical patent/WO2017115461A1/en
Priority to US15/657,710 priority patent/US10784182B2/en
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    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic substrates
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates

Definitions

  • the present invention relates to a substrate on which a power semiconductor is mounted, and particularly to a bonded substrate in which a copper plate is bonded to a ceramic substrate by using a brazing material.
  • a power semiconductor module is used for electric power control of an HEV/EV, an electric railcar, or the like.
  • the power semiconductor module is composed of, for example, an electric circuit for mounting a power semiconductor such as a switching element, an IGBT, or a MOSFET, as well as an insulating heat-dissipating substrate, a cooling member, and a case body.
  • the power semiconductor module is highly heat-generative because of performing a large electric power control and also is used under a thermal cycle environment. For this reason, reliability (durability) to the thermal cycle is demanded in addition to electric insulation property and heat-dissipating property in the insulating heat-dissipating substrate on which the power semiconductor is mounted.
  • Non-Patent Literature 1 As an insulating heat-dissipating substrate, there has been widely known a DCB substrate in which a thin copper plate is directly bonded to an alumina substrate, an aluminum nitride substrate, a silicon nitride substrate, or the like. Also, a mode has been already known in which a silicon nitride substrate and a copper plate are bonded by the diffusion bonding method (for example, see Non-Patent Literature 1).
  • an insulating heat-dissipating substrate there has been widely known an AMB substrate in which a thin copper plate and a ceramic substrate such as an alumina substrate, an aluminum nitride substrate, or a silicon nitride substrate are bonded through a bonding layer formed by using a brazing material (bonding material) containing an active metal.
  • a brazing material containing Ag for example, see Patent Literature 1 and Patent Literature 2
  • Patent Literature 3 and Patent Literature 4 are both known.
  • heated and pressurized bonding has been already known as a technique for bonding an insulating substrate and a metal plate (circuit substrate) with a brazing material (for example, see Patent Literature 5 to Patent Literature 9).
  • the inventors of the present invention have found out, as a result of eager studies, that in an AMB substrate whose bonding layer is formed by using a brazing material containing Ag, the mode of presence of Ag in a vicinity of the interface between the copper plate and the bonding layer exerts an influence on the reliability to the thermal cycle.
  • Patent Literature 1 discloses or suggests the relationship between the thermal cycle and the mode of presence of Ag in a vicinity of the interface between the copper plate and the bonding layer in the AMB substrate.
  • Patent Literature 1 discloses merely a technique of attaining improvement in the heat-resistant cycle by disposing a brazing material extrusion part with few defects such as voids.
  • Patent Literature 2 discloses merely a technique of improving the heat-resistant cycle property by adjusting the composition of the silicon nitride substrate itself and the number of grain boundaries.
  • the present invention has been made in view of the aforementioned problems, and an object thereof is to provide a bonded substrate mainly for mounting a power semiconductor in which the reliability to a thermal cycle has been enhanced as compared with a conventional one.
  • a first aspect of the present invention provides a bonded substrate including a copper plate bonded to one or both main surface(s) of a nitride ceramic substrate, wherein a bonding layer consisting of TiN intervenes between the nitride ceramic substrate and the copper plate and is adjacent at least to the copper plate, and an Ag distribution region is present in the copper plate.
  • a second aspect of the present invention provides the bonded substrate according to the first aspect, wherein an Ag-rich phase is present discretely at an interface between the bonding layer and the copper plate.
  • a third aspect of the present invention provides the bonded substrate according to the first or second aspect, wherein the Ag distribution region is present in the copper plate to be in contact with an interface between the copper plate and the bonding layer.
  • a fourth aspect of the present invention provides a method for manufacturing a bonded substrate including a copper plate bonded to one or both main surface(s) of a nitride ceramic substrate, the method comprising an application step of spreading a brazing material paste containing at least Ag and Ti to one or both main surface(s) of the nitride ceramic substrate and a bonding step of heating and pressurizing the copper plate and the nitride ceramic substrate in vacuum or in an Ar atmosphere in a state in which the copper plate is superposed onto the surface(s) of the nitride ceramic substrate where the brazing material paste has been applied, wherein, by performing the application step and the bonding step, in the bonded substrate, a bonding layer consisting of TiN is generated between the nitride ceramic substrate and the copper plate so as to be adjacent at least to the copper plate, and Ag contained in the brazing material paste is diffused in the copper plate to form an Ag distribution region in the copper plate.
  • a fifth aspect of the present invention provides the method for manufacturing a bonded substrate according to the fourth aspect, wherein, by performing the application step and the bonding step, further in the bonded substrate, an Ag-rich phase is made to be present discretely at an interface between the bonding layer and the copper plate.
  • a bonded substrate having a high reliability to a thermal cycle and being excellent in the heat-dissipation property.
  • Fig. 1 shows a view schematically illustrating a cross-sectional configuration of a bonded substrate 10 (10A, 10B) according to an embodiment of the present invention.
  • Fig. 2 shows a cross-sectional view schematically illustrating a fine structure in an interface region between a bonding layer 2 and a copper plate 3 of the bonded substrate 10A.
  • Fig. 3 shows a cross-sectional view schematically illustrating a fine structure in an interface region between a bonding layer 2 and a copper plate 3 of the bonded substrate 10B.
  • Fig. 4 shows a view schematically illustrating a cross-sectional configuration of a bonded substrate 20.
  • FIG. 5 shows a cross-sectional view schematically illustrating a fine structure in an interface region from a bonding layer 2 to a copper plate 3 of the bonded substrate 20.
  • Fig. 6 shows a cross-sectional view schematically illustrating a fine structure in an interface region between a bonding layer 7 and a copper plate 3 of a bonded substrate 30.
  • Fig. 7 shows a view showing together an SEM image with respect to an interface vicinity of Example 9 and an EPMA element mapping image with respect to Ti, Ag, and Cu.
  • Fig. 1 shows a view schematically illustrating a cross-sectional configuration of a bonded substrate 10 (10A, 10B) according to an embodiment of the present invention.
  • the bonded substrate 10 is a substrate on which a power semiconductor not illustrated in the drawings, such as a switching element, an IGBT, or a MOSFET, for example, is mounted in a power semiconductor module including the power semiconductor.
  • the bonded substrate 10 generally has a configuration in which a copper plate 3 is bonded to one main surface of a ceramic substrate 1 through a bonding layer 2.
  • a bonded substrate 10 is obtained by spreading a brazing material in a paste form containing at least Ag and Ti onto one main surface of the ceramic substrate 1, thereafter superposing the copper plate 3 onto the surface on which the brazing material has been applied, and heating and pressurizing in vacuum or in an Ar atmosphere (by heated and pressurized bonding in vacuum or in an Ar atmosphere).
  • the bonded substrate 10 has a configuration in which the bonding layer 2 is adjacent to both the ceramic substrate 1 and the copper plate 3 at different interfaces.
  • Fig. 1 it is assumed that the ceramic substrate 1 and the bonding layer 2 form an interface I1, and the bonding layer 2 and the copper plate 3 form an interface I2.
  • a nitride ceramic substrate such as a silicon nitride (Si 3 N 4 ) substrate or an aluminum nitride (AlN) substrate is exemplified.
  • the planar shape and size of the ceramic substrate 1 are not particularly limited; however, from the viewpoint of achieving scale reduction of the power semiconductor module, a ceramic substrate 1 having a rectangular shape in a plan view with one side being about 20 mm to 70 mm long and with a thickness of 0.1 mm to 1.0 mm is exemplified.
  • the copper plate 3 may have a planar size equal to the planar size of the ceramic substrate 1 or may have a planar size slightly smaller than the planar size of the ceramic substrate 1.
  • the configuration illustrated in Fig. 1 corresponds to the former case. In the latter case, an outer peripheral part of the ceramic substrate 1 is exposed without being bonded to the copper plate 3. Meanwhile, the thickness is preferably about 0.5 mm to 2.0 mm from the viewpoint of achieving scale reduction of the power semiconductor module.
  • the power semiconductor is mounted on a non-bonded surface (a main surface opposite to the side where the bonding layer 2 is present) of the copper plate 3 constituting the bonded substrate 10.
  • the copper plate 3 may be prepared as a circuit substrate having an electric circuit pattern formed on itself, and the power semiconductor may be mounted on the electric circuit pattern.
  • the copper plate is generally referred to simply as a copper plate 3, including a circuit substrate on which such an electric circuit pattern is formed.
  • the bonding layer 2 is a layer containing TiN as a major component. Such a bonding layer 2 is made of by Ti contained as an active metal in the brazing material and N constituting the ceramic substrate 1, in the process of the above-described heated and pressurized bonding.
  • the bonding layer 2 is generally formed to have a thickness of submicron order to about several ⁇ m. However, the bonding layer 2 is not necessarily formed to have a uniform thickness due to having a smaller thickness as compared with the surface undulation of the ceramic substrate 1 and the copper plate 3, and there may be variation (in-layer variation) depending on the places.
  • FIG. 2 and Fig. 3 show a cross-sectional view schematically illustrating a fine structure in an interface region between the bonding layer 2 and the copper plate 3 of the bonded substrate 10 (10A, 10B) according to the present embodiment.
  • Fig. 4 shows a view schematically illustrating a cross-sectional configuration of a bonded substrate 20 having a configuration different from that of the bonded substrate 10 according to the present embodiment, which is shown for comparison.
  • Fig. 5 shows a cross-sectional view schematically illustrating a fine structure in an interface region from the bonding layer 2 to the copper plate 3 of the bonded substrate 20.
  • the bonded substrate 10 and the bonded substrate 20 are both obtained by subjecting the ceramic substrate 1 and the copper plate 3 to heated and pressurized bonding using a brazing material containing Ag in addition to Ti; however, the bonded substrate 10 and the bonded substrate 20 are fabricated to be different from each other by making the bonding conditions different during the bonding.
  • the brazing material it is possible to use one in which Cu, Sn, In, or the like has been added for lowering the melting point, or one in which Ti has been added to an alloy powder of these.
  • an Ag-Cu-Ti-based brazing material one that contains Ag, Cu, and Ti in a composition weight ratio of 30 to 70%, 0 to 40%, and 0.1 to 20%, respectively, can be exemplified, and it is also possible to use a commercially available one that satisfies these composition ranges.
  • the bonding layer 2 is in direct contact with the copper plate 3.
  • Ag atoms are distributed in the copper plate 3, at least in a vicinity of an interface I2 to the bonding layer 2, as schematically illustrated by dots in Fig. 2 and Fig. 3.
  • the Ag atoms are distributed in a mode in which the concentration becomes smaller according as the distance from the interface I2 becomes larger (according as the distance to the non-bonded surface of the copper plate 3 becomes smaller).
  • Fig. 2 and Fig. 3 are illustrated such that the dots are more densely distributed in a region having a larger abundance ratio of the Ag atoms.
  • the Ag atoms existing in the copper plate 3 are none other than those that have been originally contained in the brazing material but have been diffused (solid-dissolved) into the copper plate 3 that is in a solid state, in the process of heated and pressurized bonding.
  • the abundance ratio (solid dissolution ratio) of the Ag atoms in the Ag distribution region 3d is at most 15 at% at the maximum.
  • the bonded substrate 20 is common to the bonded substrate 10 in that the Ag distribution region 3d is formed in the copper plate 3; however, the bonded substrate 20 is different from the bonded substrate 10 in that the bonding layer 2 and the copper plate 3 do not directly constitute an interface and that an Ag-Cu layer (layer made of an Ag-Cu alloy) 6, which should be referred to as a subbonding layer, intervenes therebetween.
  • the Ag-Cu layer 6 is formed approximately over the entire surface of the bonding layer 2.
  • the Ag-Cu layer 6 is made of both of or either one of an Ag-rich phase and a Cu-rich phase.
  • the Ag-rich phase is an Ag-Cu alloy in which Ag is contained at 80% or more, the rest being Cu.
  • the Cu-rich phase is an Ag-Cu alloy in which Cu is contained at 80 to 96%, the rest being Ag.
  • the compositions of both the Ag-rich phase and the Cu-rich phase may vary from the above-described composition ratio when a brazing material additive (Sn, In, or the like) is contained.
  • the distribution state of the Ag atoms that is, the diffusion of Ag, the presence or absence of the Ag-Cu layer 6, and the like in the copper plate 3 can be confirmed, for example, by analyzing the composition distribution using the cross-section of the bonded substrates 10 and 20 as a target by EPMA.
  • the Ag distribution region 3d in the copper plate 3 is a region formed in such a manner that Ag in the brazing material is diffused into the copper plate 3 that maintains a solid state even during the process of heated and pressurized bonding, so that the matrix of crystal lattice in the region is basically constituted of Cu atoms, and the content of Ag is slight.
  • the Ag-Cu layer 6 is formed in such a manner that the Ag atoms and the Cu atoms are alloyed during the process of heated and pressurized bonding, so that the Ag-Cu layer 6 is constituted of both of or either one of the Ag-rich phase and the Cu-rich phase, as described above.
  • the crystal lattice of the Ag-Cu layer 6 (arrangement of the Ag atoms and the Cu atoms) depends on the alloy composition.
  • the Ag-Cu layer 6 and the Ag distribution region 3d in the copper plate 3 are different from each other with respect to the forming process and the composition ratio thereof.
  • the difference in configuration between the bonded substrate 10 and the bonded substrate 20 as described above means that the bonding conditions under which the bonded substrate 20 is formed is different from the bonding conditions under which the bonded substrate 10 is formed.
  • a bonded substrate formed by bonding a ceramic substrate and another member in the case where there is a difference in thermal expansion coefficient between a ceramic plate and another member existing along the ceramic plate, when a temperature change is given to the bonded substrate, a difference is generated in thermal expansion of the ceramic plate and the other member to generate a thermal stress. If a thermal cycle is continuously applied to such a bonded substrate, this thermal stress is repeatedly generated, and material destruction occurs in the ceramic substrate at some time point to generate cracks.
  • the two are common to have a configuration in which the bonding layer 2 and the ceramic substrate 1 are adjacent to each other; however, because the bonding layer 2 has a thermal expansion coefficient of approximately the same degree as that of the ceramic substrate 1, almost no thermal stress is generated between the bonding layer 2 and the ceramic substrate 1 both in the bonded substrate 10 and in the bonded substrate 20.
  • the bonding layer 2 can be equated with the ceramic substrate 1 both in the bonded substrate 10 and in the bonded substrate 20 in considering the thermal stress.
  • the Ag-Cu layer 6 is adjacent to the bonding layer 2 in the bonded substrate 20. Further, the copper plate 3 and the Ag-Cu layer 6 each have a thermal expansion coefficient different from that of the ceramic substrate 1. For this reason, it can be grasped that a thermal stress is generated between the copper plate 3 and the ceramic substrate 1 in the bonded substrate 10, and a thermal stress is generated between the Ag-Cu layer 6 and the ceramic substrate 1 in the bonded substrate 20.
  • the copper plate 3 has a smaller proof strength (a smaller yield stress) than the Ag-Cu layer 6 against mechanical deformation, so that the thermal stress generated due to the difference in thermal expansion coefficient between the ceramic substrate 1 and the copper plate 3 in the bonded substrate 10 is smaller than the thermal stress generated due to the difference in thermal expansion coefficient between the ceramic substrate 1 and the Ag-Cu layer 6 in the bonded substrate 20.
  • the bonded substrate 10 according to the present embodiment in which the ceramic substrate 1 and the copper plate 3 are bonded in a mode where the Ag-Cu layer does not intervene while using a brazing material containing Ag and Ti, has a higher reliability to the thermal cycle than the bonded substrate 20 constituted such that the Ag-Cu layer 6 intervenes.
  • a fine undulation is randomly present generally on the surface of the ceramic substrate 1 and the copper plate 3 constituting the bonded substrate 10, so that the interfaces I1 and I2 formed between the two and the bonding layer 2 as a result of bonding by the brazing material also have a random undulation as viewed in a microscopic view.
  • a bonded substrate 10A in which the voids 4 are present in such a mode is particularly referred to as a bonded substrate 10A.
  • the bonded substrate 10 in which the Ag-rich phase 5 is present in such a mode is particularly referred to as a bonded substrate 10B.
  • the Ag-rich phase 5 is an uneven distributing region of an Ag-rich Ag-Cu alloy in which the abundance ratio of Ag exceeds 60 at% and is 100 at% or less.
  • the Ag-rich phase 5 is basically discretely present at the interface I2 between the bonding layer 2 and the copper plate 3
  • the Ag-rich phase 5 is structurally differentiated from the Ag-Cu layer 6 that is provided in a mode of being adjacent to the entire surface of the bonding layer 2 in the bonded substrate 20.
  • the bonding layer 2 and the copper plate 3 never directly constitute an interface.
  • the difference in configuration between the bonded substrate 10A and the bonded substrate 10B means that the bonding conditions for obtaining the two are different, under the premise that the Ag-Cu layer 6 is not formed.
  • formation of the Ag-rich phase 5 in the bonded substrate 10B can be also grasped as a situation in which the sites that may possibly become voids 4 under different bonding conditions are filled with the Ag-rich phase 5.
  • the bonded substrate 10B formed to have a voidless structure by presence of the Ag-rich phase 5 at the positions that may become voids 4 tends to have a larger insulation breakdown voltage (insulation breakage voltage) than the bonded substrate 10A in which the voids 4 are incorporated.
  • insulation breakage voltage insulation breakdown voltage
  • the size (maximum size) of the Ag-rich phase 5 is, for example, about 0.1 ⁇ m to 3 ⁇ m in the thickness direction of the bonded substrate 10 and is, for example, about 0.1 ⁇ m to 5 ⁇ m in a plane that is perpendicular to the thickness direction.
  • the area ratio of the Ag-rich phase 5 in the plane that is perpendicular to the thickness direction should be about 1% to 20%, and the interval between the Ag-rich phases 5 should be about 1 ⁇ m to 100 ⁇ m.
  • the bonded substrate 10 (10A, 10B) according to the present embodiment is obtained by subjecting the ceramic substrate 1 and the copper plate 3 to heated and pressurized bonding using a brazing material containing Ag and Ti.
  • a known technique can be applied; however, it is necessary to carry out the bonding at least under bonding conditions (bonding atmosphere, bonding temperature, bonding pressure, amount of spreading the brazing material) in which the Ag-Cu layer 6 is not formed.
  • the bonding atmosphere it is necessary to set the bonding atmosphere to be vacuum or an Ar atmosphere because, if Ti as an active metal is oxidized or nitrided, it is inherently impossible to carry out the bonding.
  • the bonding pressure is preferably 5 MPa or more. This is because, the lower the bonding pressure is, the more the Ag-Cu layer 6 and the voids 4 tend to be formed. Also, the bonding pressure is preferably 25 MPa or less. This is because, the higher the bonding pressure is, the less likely the Ag-Cu layer 6 and the voids 4 tend to be formed; however, when the bonding pressure is too high, the ceramic substrate 1 may be destroyed at the time of bonding.
  • the bonding temperature it is preferable to set the bonding temperature to be about 800°C to 1000°C in view of using a brazing material containing Ag and Ti.
  • a temperature range from 800°C to 1000°C the higher the bonding temperature is, the less likely the Ag-Cu layer 6 tends to be formed, and the lower the bonding temperature is, the more likely the Ag-Cu layer 6 tends to be formed.
  • the application amount (application thickness) of the brazing material it is preferable to define the application amount (application thickness) of the brazing material so that the thickness of the bonding layer obtained after bonding becomes 0.1 ⁇ m to 5 ⁇ m.
  • the bonding pressure is set to be 5 MPa to 25 MPa; the bonding temperature is set to be 850°C; and the application amount (application thickness) of the brazing material is defined so that the thickness of the bonding layer obtained after bonding becomes 0.1 ⁇ m to 5 ⁇ m, a voidless bonded substrate 10B is obtained in which the Ag-rich phase 5 is discretely present while the Ag-Cu layer 6 is not formed.
  • the bonding pressure is set to be 1 MPa to 1.5 MPa; the bonding temperature is set to be 800°C; and the application amount (application thickness) of the brazing material is defined so that the thickness of the bonding layer obtained after bonding becomes 10 ⁇ m to 20 ⁇ m, the Ag-Cu layer 6 is eventually formed (the bonded substrate 20 is obtained).
  • the bonding pressure is set to be 5 MPa to 25 MPa; the bonding temperature is set to be 950°C; and the application amount (application thickness) of the brazing material is defined so that the thickness of the bonding layer obtained after bonding becomes 0.1 ⁇ m to 5 ⁇ m, a bonded substrate 10A is obtained in which voids 4 are present though both the Ag-Cu layer 6 and the Ag-rich phase 5 are not formed. This seems to be because, in the case of such bonding conditions, the Ag atoms do not remain between the bonding layer 2 and the copper plate 3 but are diffused into the copper plate 3.
  • a bonded substrate having a high reliability to a thermal cycle and having an excellent heat-dissipating property can be obtained by allowing the bonded substrate obtained by subjecting a ceramic substrate and a copper plate to heated and pressurized bonding using an Ag-Cu-Ti-based brazing material to have a configuration in which Ag is diffused into the copper plate while an Ag-Cu layer does not intervene between the bonded layer made of TiN and the copper plate.
  • a bonded substrate having a high reliability not only to a thermal cycle but also to electric insulation breakage can be obtained by allowing the interface between the bonding layer and the copper plate in the bonded substrate in which such an Ag-Cu layer does not intervene, to have a configuration in which the Ag-rich phase is discretely present while voids are absent.
  • the bonded substrate is configured by bonding the copper plate 3 onto one main surface side of the ceramic substrate 1.
  • the bonded substrate may be configured by bonding the copper plate 3 also onto the other main surface side in a mode similar to that of the above-described embodiment.
  • the bonded substrate may be configured by bonding the copper plate 3 to both the two main surfaces of the ceramic substrate 1.
  • bonded substrates 10A at six levels in which the combination of the material and thickness of the ceramic substrate 1 and the thickness of the copper plate (Cu plate) 3 was varied in various ways were fabricated by heated and pressurized bonding.
  • the material of the ceramic substrate 1 was set to be silicon nitride (Si 3 N 4 ) or aluminum nitride (AlN).
  • silicon nitride (Si 3 N 4 ) substrate the thickness was set to be 0.32 mm.
  • the thickness was set to be 0.63 mm.
  • the thickness of the copper plate 3 was varied to five levels of 0.3 mm, 0.6 mm, 1 mm, 1.5 mm, and 2.0 mm for the case where the ceramic substrate 1 was the silicon nitride (Si 3 N 4 ) substrate.
  • the thickness of the copper plate 3 was set be 0.3 mm for the case where the ceramic substrate 1 was the aluminum nitride (AlN) substrate.
  • Example 7 to Example 12 bonded substrates 10B at six levels in which the combination of the material and thickness of the ceramic substrate 1 and the thickness of the copper plate 3 was set to be the same as in Example 1 to Example 6 were fabricated by heated and pressurized bonding.
  • bonded substrates 20 at six levels in which the combination of the material and thickness of the ceramic substrate 1 and the thickness of the copper plate 3 was set to be the same as in Example 1 to Example 6 were fabricated by heated and pressurized bonding.
  • Example 1 to Example 12 and Comparative Example 1 to Comparative Example 6 as the brazing material to be used in heated and pressurized bonding, one having a composition weight ratio of Ag: 51%, Cu: 24%, In: 11%, and Ti: 14% was used, and the bonding atmosphere was set to be vacuum.
  • Example 1 to Example 6 the amount of spreading the brazing material was defined so that the thickness of the bonding layer obtained after bonding would be within a range of 0.1 ⁇ m to 3 ⁇ m in terms of in-layer variation.
  • Example 7 to Example 12 the amount of spreading the brazing material was defined so that the thickness of the bonding layer obtained after bonding would be within a range of 0.1 ⁇ m to 3 ⁇ m in terms of in-layer variation.
  • the amount of spreading the brazing material was defined so that the thickness of the bonding layer obtained after bonding would be within a range of 13 ⁇ m to 20 ⁇ m in terms of such in-layer variation.
  • the bonding pressure for Example 1 to Example 12 was set to be 20 MPa
  • the bonding pressure for Comparative Example 1 to Comparative Example 6 was set to be 1 MPa which was a less heavy load than that for Example 1 to Example 12.
  • bonded substrates 30 at six levels were obtained by forming a Ti film having a value of thickness within a range of 10 nm to 100 nm on the ceramic substrate 1 instead of using a brazing material while setting the combination of the material and thickness of the ceramic substrate 1 and the thickness of the copper plate 3 to be the same as in Example 1 to Example 6, superposing the copper plate 3 on the Ti film, and performing heated and pressurized bonding.
  • the bonding atmosphere was set to be vacuum.
  • the bonding temperature was set to be 1000°C, and the bonding pressure was set to be 20 MPa.
  • Fig. 6 shows a cross-sectional view schematically illustrating a fine structure in an interface region between a bonding layer 7 and a copper plate 3 of such a bonded substrate 30.
  • the ceramic substrate 1 and the copper plate 3 are bonded by the bonding layer 7.
  • voids 4 are present at an interface part between the copper plate 3 and the bonding layer 7.
  • a cut surface obtained by cutting perpendicularly to the bonding surface was observed with an electron microscope, so as to confirm the presence or absence of an Ag-Cu layer that was continuous to the bonding layer between the bonding layer and the copper plate, and to confirm the presence or absence of an Ag-rich phase.
  • the observation was carried out at three sites as a target including the right and left ends and the central part in the substrate in-plane direction of the cut surface.
  • the observation magnification ratio was set to be 1000 times, and the observation width at each site in the substrate in-plane direction was set to be 0.1 mm. In such a case, a region in which Ag was unevenly present with a thickness of 0.5 ⁇ m to 3 ⁇ m and a width of 0.5 ⁇ m to 5 ⁇ m was determined as an Ag-rich phase.
  • composition mapping was carried out with an EDS at each observation site of the cut surface with respect to an area of 10 ⁇ m of the copper plate 3 in the thickness direction from the bonding interface between the bonding layer 2 and the copper plate 3.
  • Table 1 shows a list of the conditions of the ceramic substrate and the copper plate (Cu plate), presence or absence of the Ag-Cu layer that is continuous to the bonding layer, presence or absence of Ag diffusion into the copper plate (Cu plate), and the Ag-rich phase in the bonded substrates according to Example 1 to Example 12 and Comparative Example 1 to Comparative Example 12.
  • Example 1 to Example 12 were common to each other in that the Ag-Cu layer that was continuous to the bonding layer was absent and that Ag was diffused into the copper plate 3. However, in Example 1 to Example 6, the Ag-rich phase was absent, whereas in Example 7 to Example 12, the Ag-rich phase was present.
  • Example 1 to Example 6 voids were present at the interface between the bonding layer and the copper plate. Also, the mode of distribution of the Ag-rich phase in Example 7 to Example 12 was similar to the mode of distribution of the voids in Example 1 to Example 6.
  • Fig. 7 shows a view showing together an SEM image (upper stage) with respect to an interface vicinity of Example 9 and an EPMA element mapping image (lower stage) with respect to Ti, Ag, and Cu. From Fig.
  • Comparative Example 7 to Comparative Example 12 the Ag-Cu layer that was continuous to the bonding layer was absent likewise in Example 1 to Example 12; however, Comparative Example 7 to Comparative Example 12 were different from Example 1 to Example 12 in that the diffusion of Ag into the copper plate was not confirmed.
  • thermo cycle test With respect to each of the bonded substrates according to Example 1 to Example 12 and Comparative Example 1 to Comparative Example 12, a thermal cycle test was carried out. In each of the Examples and Comparative Examples, the number of test samples was set to be five. The test was carried out by giving to each sample a thermal cycle of -55°C (15 minutes) / 150°C (15 minutes) for 3000 cyc (cycles), during which, for every 100 cycles (that is, for a total of 30 times), confirmation was made on peeling-off of the bonding part and presence or absence of cracks in the ceramic substrate (hereafter, these are generally referred to as “destruction” together) by an outer appearance confirmation with a stereoscopic microscope and ultrasonic flaw detection.
  • Table 2 shows a list of the evaluation timing at which the destruction was confirmed (how many times of evaluation at which the destruction was confirmed) in the thermal cycle test with respect to all the samples of the bonded substrates according to Example 1 to Example 12 and Comparative Example 1 to Comparative Example 12, and an average value for the respective five samples. For example, if the destruction was confirmed at the 29th evaluation timing, it means that the destruction occurred between the 2800th cycle and the 2900th cycle. A sample in which no destruction was confirmed at the 30th evaluation after giving 3000 cycles of the thermal cycle is denoted as “not confirmed”.
  • Example 1 to Example 5 and Example 7 to Example 11 in which silicon nitride (Si 3 N 4 ) was used as the ceramic substrate the destruction was confirmed generally at the 25th evaluation timing and afterwards.
  • the destruction was not confirmed even at the 30th evaluation timing after giving 3000 cycles of the thermal cycle in all the samples.
  • Example 6 and Example 12 in which aluminum nitride (AlN) was used as the ceramic substrate the destruction was confirmed at the 16th to 17th evaluation timing in average.
  • AlN aluminum nitride
  • Example thermal resistance measurement A thermal resistance measurement was carried out on each of the bonded substrates according to Example 1 to Example 12 and Comparative Example 1 to Comparative Example 12 as a target.
  • a bonded substrate was prepared in which a copper plate having a plane size of 20 mm ⁇ 20 mm had been bonded to both surfaces of a ceramic substrate having a plane size of 21 mm ⁇ 21 mm under the conditions according to each Example or Comparative Example.
  • a semiconductor chip having a size of 8 mm ⁇ 8 mm was mounted by soldering at the center on one side of the bonded substrate. Then, the other surface of copper plate that is opposite to the semiconductor chip mounting surface with the ceramic substrate sandwiched therebetween was bonded by soldering onto a copper base plate having a plane size of 50 mm ⁇ 50 mm and a thickness of 4 mm, and the copper base plate was disposed on a cooling plate via a thermal grease to obtain a module for evaluation.
  • the measurement was carried out in accordance with the standard JESD51-14 of JEDEC. In each of the Examples and Comparative Examples, the number of test samples was set to be five.
  • Table 3 shows a list of the result of thermal resistance measurement with respect to all the samples of the bonded substrates according to Example 1 to Example 12 and Comparative Example 1 to Comparative Example 12 and an average value for the respective five samples.
  • Example 1 to Example 5 As shown in Table 3, among the bonded substrates in which silicon nitride (Si 3 N 4 ) was used as the ceramic substrate, in Example 1 to Example 5, Example 7 to Example 11, and Comparative Example 1 to Comparative Example 5 in which diffusion of Ag into the copper plate occurred, the value of thermal resistance is approximately about 0.135 K/W to 0.15 K/W, whereas in Comparative Example 7 to Comparative Example 11 in which diffusion of Ag into the copper plate did not occur, the value of thermal resistance tends to be as high as approximately about 0.25 K/W to 0.28 K/W.
  • Example 6 Example 12, and Comparative Example 6 (the value of thermal resistance is approximately about 0.20 K/W to 0.21 K/W), and Comparative Example 12 (the value of thermal resistance is approximately about 0.334 K/W to 0.341 K/W) all of which aluminum nitride (AlN) was used as the ceramic substrate, though the absolute values are different.
  • AlN aluminum nitride
  • Insulation breakdown voltage measurement An insulation breakdown voltage (insulation breakage voltage) measurement was carried out on each of the bonded substrates according to Example 1 to Example 12 as a target. In each of the Examples, the number of test samples was set to be ten. The measurement was carried out by applying an alternating-current voltage between a non-bonded surface of the copper plate serving as a circuit surface of the bonded substrate and a non-bonded surface of the ceramic substrate serving as a heat-dissipating surface, in an insulating oil.
  • Table 4 shows a list of the result of measurement of insulation breakdown voltage as well as an average value with respect to all the samples of the bonded substrates according to Example 1 to Example 12 and standard deviation ⁇ for the respective ten samples.
  • Example 1 to Example 6 in which the Ag-rich phase was not confirmed while voids were confirmed at the interface between the bonding layer and the copper plate, the average value of the insulation breakdown voltage was 8.3 kV/mm at the maximum, and the value of ⁇ was 1.6 kV/mm at the minimum.
  • Example 7 to Example 12 in which the Ag-rich phase was confirmed while voids were not confirmed at the interface between the bonding layer and the copper plate, the average value of the insulation breakdown voltage was 8.8 kV/mm at the minimum, and the value of ⁇ was 1.3 kV/mm at the maximum.

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