CN113894460B - Self-propagating brazing film and preparation method thereof - Google Patents
Self-propagating brazing film and preparation method thereof Download PDFInfo
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- CN113894460B CN113894460B CN202111163160.4A CN202111163160A CN113894460B CN 113894460 B CN113894460 B CN 113894460B CN 202111163160 A CN202111163160 A CN 202111163160A CN 113894460 B CN113894460 B CN 113894460B
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- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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- H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/29138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/29155—Nickel [Ni] as principal constituent
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- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/29163—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
- H01L2224/29166—Titanium [Ti] as principal constituent
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- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/838—Bonding techniques
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Abstract
The invention provides a self-propagating brazing film and a preparation method thereof, wherein a solder layer comprises a first solder layer, a self-propagating multilayer film and a second solder layer which are sequentially stacked, a chip and a substrate are welded together through the reaction of the self-propagating multilayer film, and the melting point of the first solder layer and/or the second solder layer is lower than the highest instantaneous reaction temperature of the self-propagating multilayer film. Therefore, device damage caused by process temperature and process time in the welding process is effectively avoided, a low-cost and high-melting-point lead-free solder is provided for the application field of third-generation semiconductor devices, and the lead-free solder is a competitive solution for high-temperature, power and large-area electronic interconnection.
Description
Technical Field
The invention relates to the technical field of semiconductor packaging, in particular to a self-propagating brazing film used as packaging connection and a preparation method thereof.
Background
Since power electronics plays a key role in many low-carbon technical fields, such as electric vehicles, power generation distribution of renewable energy sources, smart grid and the like, power electronics technology is determined as a development field with strategic priority by all countries in the world. The use of third generation Wide Band Gap (WBG) semiconductor silicon carbide and gallium nitride, etc. lays the foundation for developing new generation power electronic devices with higher efficiency, higher use temperature, higher power density and lower cost. However, the service temperature of the conventional tin-based solder cannot exceed 200 ℃, and the high working temperature of the WBG device caused by high voltage and high current conversion rate cannot be met. Therefore, new high temperature resistant interconnect materials have been the focus of research, and typical applications represent that high lead solders (e.g., 95Pb-5Sn with a melting point of 305 ℃) are widely studied and are currently the preferred method. However, the high toxicity of lead is a great hidden danger to human body and environment, and the establishment of economic and efficient lead-free substitute products is urgent. The existing lead-free material solution has certain technical pain points and sticking points in different application technical layers, such as:
(1) The gold-based solder (such as Au-20Sn, au-12Ge and Au-3 Si) has excellent thermal conductivity and electrical conductivity and good creep resistance, and can complete welding without soldering flux. However, gold is expensive as a noble metal, and the brittle Intermetallics (IMCs) of gold-based solders at the interconnect interface are prone to reliability problems.
(2) The nano silver paste can be sintered at a low temperature of 250 ℃, shows good electrical conductivity, thermal conductivity and high tensile strength, but is easy to migrate under the action of an electric field, so that the problem of low service reliability exists, and meanwhile, due to incomplete sintering caused by the large specific surface area of the material, high porosity and low air tightness are easy to cause, so that the application of the nano silver paste in device packaging is limited.
(3) Transient liquid phase diffusion bonding (TLP) induces interdiffusion of solid and liquid phases by melting of a low melting point metal layer (e.g., sn) and a high melting point metal layer (e.g., cu) by means of an alternating stack of the low melting point metal layer at 250 ℃, thereby allowing the entire pad to form intermetallic compounds (IMCs) having high melting point shear strength. However, this technique is highly dependent on wet plating processes and is prone to non-uniform interfaces with the risk of poor interconnect reliability.
In summary, the third generation semiconductor device application field needs low-cost, high-melting point lead-free solder as a competitive solution for high-temperature and power electronic interconnection, and reduces device damage caused by process time and temperature in the soldering process.
Disclosure of Invention
In order to solve the problems, the invention provides a self-propagating brazing technology and a product with high melting point, high reliability and low cost.
Specifically, the technical scheme provided by the invention is as follows:
the self-propagating brazing film comprises a first brazing filler metal layer, a self-propagating multilayer film and a second brazing filler metal layer which are sequentially arranged, wherein the self-propagating multilayer film comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si and Al-CuO x And the Al-Pt thin film, wherein the melting point of the first brazing filler metal layer and the melting point of the second brazing filler metal layer are lower than the instantaneous reaction highest temperature of the self-propagating multilayer film. The self-propagating brazing film structure provided by the invention can be designed to reduce the melting point of the contact part of the self-propagating brazing film structure and the substrate or the chip, thereby avoiding the damage to the device or the chip and ensuring the safety of the device or the chip in a brazing process window.
Furthermore, the first brazing filler metal layer and/or the second brazing filler metal layer are/is in gradient distribution corresponding to the melting point, and the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer are in gradient distribution gradually decreasing along the thickness direction away from the self-propagating multilayer film. In the present invention, the melting point is in a decreasing gradient distribution, including a smooth decreasing gradient distribution, such as a linear decreasing or a convex/concave linear decreasing gradient distribution, and also including a step-type decreasing gradient distribution. The first brazing filler metal layer and/or the second brazing filler metal layer are/is distributed in a gradient mode corresponding to the melting point, and the components of the first brazing filler metal layer and/or the second brazing filler metal layer are/is also distributed in a gradient mode along the thickness direction. The materials and thicknesses of the first and second solder layers may be the same or different. In the self-propagating brazing film structure provided by the invention, the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer are designed to be distributed in a gradient manner, so that a central high temperature generated by the self-propagating brazing film and a steep temperature area facing to an adjacent area are reserved, a tiny heat affected area is reserved, the heat adaptation of the brazing filler metal to a self-propagating multilayer film and a chip/device/substrate is greatly improved, and the heat reliability of the whole welding spot is improved.
Further, the material of the first brazing filler metal layer and/or the second brazing filler metal layer comprises tin base, gold base, lead base, silver base, zinc base, bismuth base, indium base, aluminum base or copper base alloy.
Furthermore, the material of the first brazing filler metal layer and/or the second brazing filler metal layer comprises one or two of binary or ternary tin base, binary or ternary zinc base, binary or ternary gold base and binary or ternary bismuth base alloy.
Further, the melting point range of the first brazing filler metal layer and/or the second brazing filler metal layer at the position close to the self-propagating multilayer film is 1100-400 ℃, and the melting point range at the position far away from the self-propagating multilayer film is 100-400 ℃.
As a further preferable scheme, the melting point range of the first solder layer and/or the second solder layer at the position close to the self-propagating multilayer film is 1064-420 ℃, and the melting point range at the position far from the self-propagating multilayer film is 196-381 ℃.
In particular, for temperature sensitive devices, the melting point of the first solder layer and/or the second solder layer at a location far from the self-propagating multilayer film, such as the contact area with the chip or substrate, i.e. the interface area of the solder, ranges from 100 ℃ to 250 ℃, preferably from 196 ℃ to 232 ℃. For high temperature or high power devices, the first solder layer and/or the second solder layer have a melting point in the range of 250-385, preferably 271-381, at a location far from the self-propagating multilayer film, such as a contact area with the chip or substrate, i.e. a soldered interface area.
Further, for temperature sensitive devices, the material of the first solder layer and/or the second solder layer is preferably a tin-copper alloy system, a tin-nickel alloy system or a zinc-tin alloy system, and the melting point of the material at the position of the far self-spreading multilayer film, such as a contact area with a chip or a substrate, namely a welding interface area, ranges from 196 ℃ to 232 ℃.
Further, for high temperature devices, the material of the first solder layer and/or the second solder layer is preferably a bismuth-based alloy system or a zinc-aluminum-based alloy system, and the melting point of the first solder layer and/or the second solder layer is in a range of 271 ℃ to 381 ℃ at a position far away from the self-propagating multilayer film, such as a contact area with a chip or a substrate, namely a welding interface area.
The thickness of the first brazing filler metal layer and/or the second brazing filler metal layer is generally 5 to 150um, and more preferably 10 to 50um.
The self-propagating multilayer film is of a general periodic structure, and the thickness of the self-propagating multilayer film is 0.01mm-0.5mm.
The invention also provides a preparation method of the self-propagating brazing film, which comprises the following steps:
selecting a substrate;
preparing a self-propagating multilayer film on the substrate, wherein the self-propagating multilayer film comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si, al-CuO x One or more of Al-Pt thin films;
peeling the substrate;
and respectively preparing a first brazing filler metal layer and a second brazing filler metal layer on opposite surfaces of the self-propagating multilayer film, wherein the melting point of the first brazing filler metal layer and/or the second brazing filler metal layer far away from the self-propagating multilayer film is lower than the highest instantaneous reaction temperature of the self-propagating multilayer film.
Further, dry deposition or wet deposition is adopted to control the components of the first brazing filler metal layer and/or the second brazing filler metal layer in the thickness direction far away from the self-propagating multilayer film to be in gradient distribution, so that the gradient distribution of the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer in the thickness direction far away from the self-propagating multilayer film is obtained.
Further, the material of the first brazing filler metal layer and/or the second brazing filler metal layer comprises tin base, gold base, lead base, silver base, zinc base, bismuth base, indium base, aluminum base or copper base alloy. Furthermore, the material of the first brazing filler metal layer and/or the second brazing filler metal layer comprises one or two of binary or ternary tin base, binary or ternary zinc base, binary or ternary gold base and binary or ternary bismuth base alloy.
Further, the dry deposition comprises setting deposition rates of different targets; or, during the wet deposition, the concentration of the metal ion source in the electroplating liquid medicine component or the electroplating process parameter is set.
Further, the preparing the self-propagating multilayer thin film includes alternately depositing cathode targets of at least two materials on the substrate.
Further, when the dry deposition is adopted, the deposition rate of different target materials is set to be 0.1n for examplem/s-20nm/s; when the wet deposition is adopted, the method comprises the steps of setting the components of electroplating liquid or setting the parameters of the electroplating process, such as the current density of 1mA/cm 2 -100mA/cm 2 。
The self-propagating brazing film and the preparation method thereof provided by the invention provide a high-melting-point, high-reliability and low-cost solder for the application field of third-generation semiconductor devices, are a competitive solution for high-temperature and power electronic interconnection, and have the following remarkable excellent effects compared with the prior art:
(1) The area of the self-propagating brazing film close to the substrate and the device is designed to have a lower melting point, and particularly the first brazing filler metal layer and/or the second brazing filler metal layer are arranged in a gradient distribution with the melting point gradually decreasing along the thickness direction, so that the whole welding point can be melted in the brazing process, the possibility of heat damage to a device chip is reduced, the heat adaptation of the brazing filler metal layer to the self-propagating film and the chip/device/substrate is increased, and the reliability of the whole welding point is improved.
(2) The type of a usable solder system is greatly expanded, a part of melting points are higher than the tolerance temperature of the device and are also included in the possibility of welding materials, the dependence of a high-temperature/high-power device on a lead type, gold type or silver type solder system is reduced, the reliability of a welding point and the cost performance of a material selection process are obviously improved, and the use of soldering flux is avoided.
(3) As a super high speed welding process, the productivity is considerable.
(4) The welding wire is flat, the gap height of the device is uniform, and the device is suitable for large-area large-size welding.
Drawings
FIG. 1 is a schematic structural diagram of a self-propagating solder film according to an embodiment of the present invention;
FIG. 2 is a schematic view of a welding temperature distribution corresponding to a self-propagating brazing film according to an embodiment of the present invention;
FIG. 3 is a schematic view of a method for preparing a self-propagating solder film according to an embodiment of the present invention;
FIG. 4 is an ultrasonic scanning microscope image of a solder joint in a self-propagating solder film application according to an embodiment of the present invention;
FIG. 5 is a graph showing the shear strength of the die pad of the self-propagating solder film as a function of aging time according to one embodiment of the present invention.
Detailed Description
The invention and the manner of attaining it may be better understood by reference to the following detailed description of exemplary embodiments and the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Like reference numerals may refer to like elements throughout. In the drawings, the thickness of layers and regions may be exaggerated for clarity.
The present invention proposes a self-propagating solder film, as shown in fig. 1, which is applied to connect a chip 4 with a substrate 5. In the present invention, the chip includes an integrated circuit chip, a MEMS chip, an LED chip, etc., and the substrate is a package substrate or a supporting substrate, such as a ceramic or glass, metal substrate. The self-propagating brazing film comprises a first brazing filler metal layer 3, a self-propagating multilayer film 1 and a second brazing filler metal layer 2 which are sequentially stacked, wherein the first brazing filler metal layer 3 is used for connecting a substrate 5, namely the first brazing filler metal layer 3 is arranged between the substrate 5 and the self-propagating multilayer film 1; the second solder layer 2 is used for connecting the chip 4, i.e. the second solder layer 2 is interposed between the chip 4 and the self-propagating multilayer film 1.
The self-propagating multilayer film provided by the invention comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si and Al-CuO x And one or more of Al-Pt thin films.
The self-propagating multilayer film is an ABAB periodic structure, the thickness of a single layer is 10-100nm, the total thickness is 10-2000 mu m, the reaction speed of the self-propagating multilayer film is in inverse proportion to the diffusion distance, namely the smaller the thickness of the single layer film is, the faster the combustion speed is, for example, an Al-Ni system, the reaction speed is 2-10m/s, and the highest reaction temperature is more than 1700 ℃.
As one embodiment of the invention, the self-propagating multilayer film is alternately deposited with two nanometer-scale thicknesses by high-flux pollution-free vapor depositionWith negative enthalpy of mixing (e.g. Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si, al-CuO) x One or more of Al — Pt thin films). The composite multilayer film material releases negative enthalpy heat (1381J/g for Ni-Al) after being ignited, and can instantaneously (within dozens of milliseconds) reach extremely high heating and quenching speed (about 100K/s) to form local temperature of about 1500 ℃. The temperature in the chip region or the substrate can finally be less than 100 ℃, as shown in fig. 2, by the transfer of the first solder layer, the second solder layer with a gradient distribution of melting points.
The first brazing filler metal layer and the second brazing filler metal layer are weldable metals with melting points lower than the instantaneous local highest temperature of the combustion reaction of the self-propagating multilayer film at the position far away from the self-propagating multilayer film (namely, at the side close to the device/substrate), such as tin-based, gold-based, lead-based, silver-based, zinc-based, bismuth-based, indium-based, aluminum-based and copper-based alloys, and further preferably tin-based, gold-based, silver-based, zinc-based, bismuth-based or copper-based alloys; thereby effectively avoiding the adverse effect of the reaction temperature of the self-propagating multilayer film on the chip.
As a further preferred embodiment of the present invention, in order to further improve the welding performance, the first solder layer and the second solder layer proposed by the present invention are formed in a thickness direction away from the self-propagating multilayer film, that is: the melting point of the compound is gradually decreased in a gradient distribution from the position close to the self-propagating multilayer film (the side of the self-propagating multilayer film) to the position far away from the self-propagating multilayer film (the side of the device/the substrate). In the present invention, the melting point is in a gradient distribution with gradually decreasing, including a gradient distribution with smooth type decreasing, such as linear decreasing or convex/concave decreasing, and also including a gradient distribution with step type decreasing.
The first and second solder layers proposed according to the invention are, for example, distributed in a gradient composition in the thickness direction, so that their melting points are also distributed in a gradient manner. Specifically, a gradient with a gradually decreased melting point is formed from one side of the self-propagating multilayer film to one side of the device/substrate, the lowest point of the melting point gradient is lower than the highest point capable of being borne by a temperature sensitive device (chip), and the highest point is lower than the highest instantaneous temperature of self-propagating brazing so as to ensure that a welding spot is fully melted and the device is safe in a brazing process window.
The transient reaction temperature profile of the self-propagating brazing film is shown in fig. 2. It can be seen from the temperature profile that the entire self-propagating braze film produces a central high temperature and a steep temperature zone facing the adjacent zones, leaving a very small heat affected zone (depth 20-100 microns). The thermal adaptation of the solder to self-propagating multilayer films and chips/devices/substrates can be greatly improved, and the thermal reliability of the whole solder joint can be improved.
The thickness of the first brazing filler metal layer and the second brazing filler metal layer provided by the invention is generally 5-150um, and more preferably 10-50um.
As an embodiment of the invention, the first solder layer and/or the second solder layer, at the far self-propagating multilayer film, has a melting point in the range of 100 ℃ to 250 ℃. As a further preferred embodiment of the present invention, the material of the first solder layer and/or the second solder layer is preferably a tin-copper alloy system, a tin-nickel alloy system or a zinc-tin alloy system, and the melting point range thereof is set to be 196 ℃ to 232 ℃ far from the self-propagating multilayer film. The self-propagating brazing film designed in this way is very suitable for being used in temperature sensitive devices.
As an embodiment of the invention, the first solder layer and/or the second solder layer has a melting point in the range of 250-385 at the far self-propagating multilayer film. As a further preferred embodiment of the present invention, the material of the first solder layer and/or the second solder layer is preferably a bismuth-based alloy system or a zinc-aluminum-based alloy system, and the melting point thereof is set to 271 ℃ to 381 ℃ at a position far from the self-propagating multilayer film. The self-propagating brazing film designed in the way is very suitable for devices in high-temperature service.
In the invention, dry deposition or wet deposition can be adopted to prepare the gradually decreasing gradient distribution; when the dry deposition is adopted, the different gradient distributions are realized by uniformly changing, changing the speed or changing the deposition rate of different targets in a stepped manner; when wet deposition is adopted, electroplating process parameters are changed through uniform speed or variable speed to realize smooth degressive gradient distribution, and the step-type degressive gradient distribution is realized by arranging electroplating solution components of different electroplating baths in a gantry line.
In addition, as another embodiment of the present invention, one of the first solder layer and the second solder layer may be selected as required to have a melting point lower than the maximum temperature of the transient reaction of the self-propagating multilayer film, for example, from the viewpoint of cost saving, if the substrate can withstand high temperature, it is only necessary to ensure the safety of the device between the soldering process windows.
Correspondingly, the invention also provides a preparation method of the self-propagating brazing film sandwich structure, as shown in fig. 3, comprising the following steps:
selecting a substrate; in order to facilitate peeling of the self-propagating multilayer film, in the present embodiment, for example, a plastic film such as PET, or a base material with poor wettability such as silicone oil is selected; wherein when a solid substrate, such as a PET plastic film, is used, a roll-to-roll R2R magnetron sputtering or single-chamber magnetron sputtering apparatus is used;
preparing a self-propagating multilayer film on the substrate, wherein the self-propagating multilayer film comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si, al-CuO x One or more of Al-Pt thin films;
peeling the substrate;
respectively preparing a first brazing filler metal layer and a second brazing filler metal layer on the opposite surfaces of the self-propagating multilayer film; wherein the content of the first and second substances,
the melting point of the first brazing filler metal layer and/or the second brazing filler metal layer is lower than the highest instantaneous reaction temperature of the self-propagating multilayer film. Preferably, the first solder layer and/or the second solder layer may have a gradient melting point distribution in the thickness direction.
The self-propagating multilayer film is realized by means of sputtering deposition and the like, and alternate sputtering of the film is realized by alternately using cathode targets of two or more materials on a substrate.
Specifically, a first brazing filler metal layer and a second brazing filler metal layer are prepared on two sides of a self-propagating multilayer film; and obtaining the brazing filler metal layer by selecting a dry magnetron sputtering or wet electrodeposition method.
In order to reduce the damage to the chip in the welding process, the first brazing filler metal layer and the second brazing filler metal layer are arranged in a gradient distribution from the composition, so that the melting points of the first brazing filler metal layer and the second brazing filler metal layer are also in a gradient distribution, and the two sides of the self-propagating brazing film close to the substrate and the chip have relatively low melting points. The components and the melting point of the brazing filler metal layer are distributed in a gradient manner along the thickness direction of the brazing filler metal layer, and the brazing filler metal layer can be prepared in a dry deposition mode and is realized by using modes such as magnetron sputtering, multi-arc sputtering or chemical vapor deposition; the gradient of the components (melting points) is regulated by gradually regulating the sputtering deposition rate of two or more materials or other process modes.
Further, the brazing filler metal layer can also be prepared by a wet deposition method, such as an electroplating method; when the brazing filler metal layer with the component (melting point) gradient in the thickness direction is prepared in an electroplating mode, the generation of the alloy component gradient is realized by gradually adjusting the components of electroplating liquid medicine (gradually increasing the concentration of one metal source) or adjusting electroplating process parameters such as current density, stirring speed and the like.
Example 1:
the gradient solder layer composition is designed as a binary or ternary tin-based alloy system, such as tin-copper binary alloys and tin-nickel binary alloys. The gradient of the alloy composition in the thickness direction can be achieved by a deposition film method. For example, a tin-copper system, preferably with a copper content of 7.6wt.% or less, the copper content of the solder alloy decreases with increasing distance from the self-propagating multilayer film along the thickness direction of the solder, so that the melting point of the alloy is 415 ℃ near the self-propagating multilayer film (copper content of 7.6 wt.%), and 232 ℃ far from the multilayer film (copper content of 0wt.%, i.e. pure tin), and this gradient is effective to ensure that the entire solder layer is fully melted and wets the interface instantaneously in the self-propagating soldering reaction. For another example, the tin-nickel system, preferably has a nickel content of 10.6wt.% or less, and accordingly, the alloy composition near the self-propagating multilayer film end is, for example, 10.6wt.% nickel, the melting point is 794.5 ℃, the distal component is pure tin, the melting point is 232 ℃, and the nickel content and the melting point decrease from the proximal end to the distal end. The tin-copper system is easy to generate Cu in a liquid phase state 6 Sn 5 And Cu 3 Intermetallic compounds of Sn and the like, cu in the aging or working service process of electronic components 3 Sn phase is easy to generate Kenkard holes so as to influence the reliability of welding spots. Further optimization for adapting to more severe service environmentSolder joint reliability, selection of tin-nickel system, production of Ni during soldering and service 3 Sn 4 And the reaction rate of Ni-Sn is lower than that of Cu-Sn in the intermetallic compounds, so that a more reliable welding spot is easier to form. Further, it is preferable to use tin-copper-nickel ternary alloy in the self-propagating solder sandwich structure, such as adding less than 10at.% of nickel to the tin-copper system, the nickel content in the thickness of the solder material should correspond to the gradient trend of the copper content, and the nickel addition not only can reduce the Cu content in the tin-copper-nickel system 6 Sn 5 And Cu 3 The growth rate of intermetallic compounds such as Sn, etc. improves the reliability of the interconnection of welding spots, and can also reduce the thermal expansion coefficient of the intermetallic compounds, and increase the thermal matching of the whole welding spot and a device or a substrate with low thermal expansion coefficient, such as a silicon, silicon carbide or gallium nitride chip, aluminum nitride, silicon nitride or aluminum oxide substrate.
Aiming at the preparation of the brazing filler metal, a vapor deposition method such as magnetron sputtering and the like is adopted, two or three sputtering cathode targets of pure tin and X (X can be pure copper, pure nickel or other copper-containing or nickel-containing alloys) are selected, and the concentration gradient is manufactured by controlling the deposition rate of each target in the deposition process.
Aiming at the preparation of the brazing filler metal, methods such as wet deposition, electroplating and the like are selected, and a gantry rack plating multi-groove continuous electroplating line or horizontal continuous electroplating line mode is selected. When a gantry hanging plating line is selected, a plurality of sub-tank bodies (for example, 10 sub-tank bodies) are arranged, alloy plating liquid medicine is adopted in each tank body, the concentration of each metal ion of the liquid medicine is regulated and controlled in sequence, and a deposited alloy layer forms a component gradient. For example, for a tin-copper system, the first bath solution has a copper content of 7.60wt.% and the second bath solution has a copper content of 6.76wt.%, the remainder being, in order, 5.91wt.%,5.07wt.%,4.22wt.%,3.38wt.%,2.54wt.%,1.69wt.%,0.85wt.%,0wt.%. Similarly, when a horizontal continuous plating line is selected, the metal ion concentration of the chemical liquid in each stage is made to be gradient. The anode uses an insoluble anode, such as yttrium titanium mesh, to maintain the metal concentration ratio of the liquid medicine during use.
Example 2:
the gradient solder layer composition is designed as a binary or multi-component zinc-based alloy system, such as zinc-aluminum binary alloys and zinc-tin binary alloys, and their respective multi-component alloys. For example, a zinc-aluminum system, preferably with an aluminum content of 6wt.% or more, the aluminum content of the solder alloy decreases with increasing distance from the self-propagating multilayer film along the thickness direction of the solder, so that the melting point of the alloy is about 660 ℃ at the near self-propagating multilayer film (aluminum content of 100 wt.%), and about 381 ℃ at the far multilayer film (aluminum content of 6 wt.%). In addition, for example, the zinc-tin system, preferably has a tin content of ≦ 91.2wt.%, and the alloy has a melting point of about 420 ℃ near the self-propagating multilayer film end (tin content of 0 wt.%), and about 196 ℃ away from the self-propagating multilayer film (tin content of 91.2 wt.%).
For the preparation of the brazing filler metal, a vapor deposition method such as magnetron sputtering and the like is selected, two sputtering cathode targets of pure zinc and X (X can be pure aluminum, pure tin or other alloy elements) are adopted, and the concentration gradient is manufactured by controlling the deposition rate of each target in the deposition process.
Aiming at the preparation of the brazing filler metal, methods such as wet deposition, electroplating and the like are selected, and a gantry rack plating multi-groove continuous electroplating line or horizontal continuous electroplating line mode is selected. When a gantry hanging plating line is selected, a plurality of sub-tank bodies (for example, 10 sub-tank bodies) are arranged, alloy plating liquid medicine is adopted in each tank body, the concentration of each metal ion of the liquid medicine is sequentially regulated, the component gradient is formed on the deposited alloy layer, and when a horizontal continuous plating line is selected, the concentration of the metal ion of the liquid medicine in each section forms a gradient. The anode uses an insoluble anode, such as yttrium titanium mesh, to maintain the metal concentration ratio of the liquid medicine during use. For zinc-aluminum systems, because aluminum ions cannot be electrodeposited in conventional aqueous solutions, organic molten salts (such as alkyl imidazoie halide, alkylaryl ammonium chloride salts, or alkyl pyridine halide systems) or organic solvent solutions (such as tetrahydrofuran, diethyl ether, or toluene systems) are used as the electrodeposition electrolyte to ensure the electroreduction of aluminum metal.
Example 3:
the graded solder layer composition is designed as a binary or multicomponent gold-based alloy system, such as gold-silicon, gold-germanium and gold-tin binary alloys. For example, a gold-tin system, preferably with a tin content of 20wt.% or less, the tin content of the solder alloy increases with increasing distance from the self-propagating multilayer film along the thickness direction of the solder, so that the melting point of the alloy is less than or equal to 1064 ℃ near the self-propagating multilayer film (tin content is more than or equal to 0 wt.%), and about 278 ℃ away from the self-propagating multilayer film end (tin content is 20 wt.%).
Aiming at the preparation of the brazing filler metal, a vapor deposition method such as magnetron sputtering and the like is selected, two sputtering cathode targets of pure tin and pure gold are adopted, and the concentration gradient is manufactured by controlling the deposition rate of each target in the deposition process.
For the preparation of the brazing filler metal, wet deposition methods such as electroplating and the like can be selected, and a gantry rack plating multi-groove continuous electroplating line or horizontal continuous electroplating line mode is selected. When a gantry hanging plating line is selected, a plurality of sub-tank bodies (for example, 10 sub-tank bodies) are arranged, alloy plating liquid medicine is adopted in each tank body, the concentration of each metal ion of the liquid medicine is regulated and controlled in sequence, and a deposited alloy layer forms a component gradient. Similarly, when a horizontal continuous plating line is selected, the metal ion concentration of the chemical liquid in each stage is made to be gradient. The anode uses an insoluble anode, such as yttrium titanium mesh, to maintain the metal concentration ratio of the liquid medicine during use. For gold-tin systems, the use of tin rich components (tin content ≧ 30 wt.%) is not recommended to reduce the risk of solder joint embrittlement. The self-propagating gold-tin brazing sandwich structure has good wettability for the bonding pad which is finally finished to be a gold layer.
Example 4:
the gradient solder layer composition is designed as binary or multi-element bismuth-based alloy systems, such as bismuth-silver, bismuth-copper and bismuth-zinc binary alloys, and their respective multi-element alloys. For bismuth-silver systems, the bismuth content is preferably less than or equal to 97.5wt.%, and the bismuth content of the solder alloy increases with increasing distance from the self-propagating multilayer film along the thickness direction of the solder, so that the melting point of the alloy is less than or equal to 962 ℃ near the self-propagating multilayer film (bismuth content is more than or equal to 0 wt.%), and about 271 ℃ at the far multilayer film end (bismuth content is 97.5 wt.%).
Aiming at the preparation of the brazing filler metal, a vapor deposition method such as magnetron sputtering and the like is selected, two sputtering cathode targets of pure bismuth and pure silver are adopted, and the concentration gradient is manufactured by controlling the deposition rate of each target in the deposition process.
For the preparation of the brazing filler metal, wet deposition methods such as electroplating and the like can be selected, and a gantry rack plating multi-groove continuous electroplating line or horizontal continuous electroplating line mode is selected. When a gantry hanging plating line is selected, a plurality of sub-tank bodies (for example, 10 sub-tank bodies) are arranged, alloy plating liquid medicine is adopted in each tank body, the concentration of each metal ion of the liquid medicine is regulated and controlled in sequence, and a deposited alloy layer forms a component gradient. Similarly, when a horizontal continuous plating line is selected, the metal ion concentration of the chemical liquid in each stage is made to be gradient. The anode uses an insoluble anode, such as yttrium titanium mesh, to maintain the metal concentration ratio of the liquid medicine during use.
According to the above embodiment, the highest instantaneous temperature near the multilayer film in the solder layer can be controlled by adjusting the self-propagating multilayer film system, the thickness and the total thickness of each layer, and the highest instantaneous temperature at the far multilayer film end of the solder layer, namely the contact temperature of the brazing instantaneous device/bonding pad, can be controlled by regulating the alloy system, the composition gradient and the thickness of the solder layer. The contact temperature for different solder alloy systems exhibits different temperature range, for example 196 ℃ for zinc-tin, 232 ℃ for tin-copper and tin-nickel, 271 ℃ for bismuth-silver, 278 ℃ for gold-tin and 381 ℃ for zinc-aluminum. And selecting a proper brazing filler metal sandwich structure according to the heat-resistant threshold temperature of the device, so that the brazing process step can be completed by the brazing filler metal with a higher melting point through a lower environment processing temperature.
A self-propagating brazing sandwich structure is applied to bonding of large-area components, such as bonding of a power electronic device IGBT or MOSFET and a copper-clad ceramic gasket/base plate. Under the hot pressing condition, the soldering process is completed through the ignition triggering self-propagating reaction, for example, the first layer and the second layer of solder are both made of Sn-Cu alloy solder with the thickness of 20 microns, the composition of the far multilayer film end of the solder layer is Sn-0.9wt% Cu, the composition of the near multilayer film end is Sn-7.6 wt% Cu, the melting point gradient is from 227 ℃ to 415 ℃ from the far end to the near end, and the soldering sandwich structure is used for bonding 12mm × 9mm × 405 μmCi chips to the copper foil directly covered with the ceramic plate. FIG. 4 is an ultrasonic scanning microscope (SAM) image of a weld spot in the z-direction, the bond layer exhibiting high uniformity and low void fraction (< 3%). The chip shear force test shows that the initial shear strength value of the welding spot is 32.3MPa, the initial shear strength value is increased and then reduced along with the time change of aging treatment (Dry bake,155 ℃), and finally the initial shear strength value is stabilized at 31MPa, so that the reliability requirement of the welding spot is met. The shear test fracture plane is within the solder layer rather than at the interface of the self-propagating multilayer film and the solder or the interface of the solder and the device/backplane.
While the present disclosure has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present disclosure.
Claims (8)
1. The self-propagating brazing film is characterized by comprising a first brazing filler metal layer, a self-propagating multilayer film and a second brazing filler metal layer which are sequentially stacked, wherein the self-propagating multilayer film comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si and Al-CuO x The melting point of the first brazing filler metal layer and/or the second brazing filler metal layer is lower than the highest instantaneous reaction temperature of the self-propagating multilayer film; the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer are distributed in a gradient mode in a descending mode in the thickness direction far away from the self-propagating multilayer film.
2. The self-propagating brazing film according to claim 1, wherein the material of said first brazing material layer and/or said second brazing material layer comprises tin-based, gold-based, lead-based, silver-based, zinc-based, bismuth-based, indium-based, aluminum-based or copper-based alloy.
3. The self-propagating brazing film according to claim 2, wherein the material of the first brazing material layer and/or the second brazing material layer comprises one or two of binary or ternary tin-based, binary or ternary zinc-based, binary or ternary gold-based, binary or ternary bismuth-based alloys.
4. The self-propagating brazing film according to claim 2, wherein the melting point of the contact area of the first brazing filler metal layer and/or the second brazing filler metal layer and the self-propagating multilayer film is in the range of 1100-400 ℃; the melting point range of the welding interface area of the first brazing filler metal layer and/or the second brazing filler metal layer is 100-400 ℃.
5. The self-propagating brazing film according to claim 3, wherein the melting point of the contact area of the first brazing filler metal layer and/or the second brazing filler metal layer and the self-propagating multilayer film ranges from 1064 ℃ to 420 ℃, and the melting point of the welding interface area of the first brazing filler metal layer and/or the second brazing filler metal layer ranges from 196 ℃ to 381 ℃.
6. The preparation method of the self-propagating brazing film is characterized by comprising the following steps of:
selecting a substrate;
preparing a self-propagating multilayer film on the substrate, wherein the self-propagating multilayer film comprises Ti-Al, al-Ni, ti-Ni, ni-Si, nb-Si, al-CuO x One or more of Al-Pt thin films;
peeling the substrate;
respectively preparing a first brazing filler metal layer and/or a second brazing filler metal layer on the opposite surfaces of the self-propagating multilayer film; wherein the melting points of the first brazing filler metal layer and the second brazing filler metal layer are lower than the highest instantaneous reaction temperature of the self-propagating multilayer film; and controlling the components of the first brazing filler metal layer and/or the second brazing filler metal layer to be in gradient distribution along the thickness direction away from the self-propagating multilayer film by adopting dry deposition or wet deposition so as to obtain the gradient distribution of the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer in the thickness direction away from the self-propagating multilayer film, wherein the melting points of the first brazing filler metal layer and/or the second brazing filler metal layer are gradually reduced along the thickness direction away from the self-propagating multilayer film.
7. The method for preparing a self-propagating brazing film according to claim 6, wherein the material of the first brazing material layer and/or the second brazing material layer comprises tin-based, gold-based, lead-based, silver-based, zinc-based, bismuth-based, indium-based, aluminum-based or copper-based alloy.
8. The method according to claim 7, wherein the dry deposition comprises setting deposition rates of different targets; or, during the wet deposition, the concentration of the metal ion source in the electroplating liquid medicine component or the electroplating process parameter is set.
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| DE19714530A1 (en) * | 1997-04-08 | 1998-10-15 | Asea Brown Boveri | Process for soldering directionally solidified or single-crystal components |
| JP3772697B2 (en) * | 2001-06-15 | 2006-05-10 | 千住金属工業株式会社 | Lead-free solder ball and manufacturing method thereof |
| US6995084B2 (en) * | 2004-03-17 | 2006-02-07 | International Business Machines Corporation | Method for forming robust solder interconnect structures by reducing effects of seed layer underetching |
| WO2009003130A2 (en) * | 2007-06-26 | 2008-12-31 | Reactive Nanotechnologies, Inc. | Gasketless low-temperature hermetic sealing with solder |
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