Structure with conductive feature and method of forming same

Information

  • Patent Grant
  • 12211809
  • Patent Number
    12,211,809
  • Date Filed
    Wednesday, December 29, 2021
    3 years ago
  • Date Issued
    Tuesday, January 28, 2025
    5 days ago
Abstract
An element is disclosed. The element can include a non-conductive structure having a non-conductive bonding surface, a cavity at least partially extending through a portion of a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive pad disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. An average size of the grains at the bonding surface is smaller than an average size of the grains adjacent the bottom side of the cavity. The conductive pad can include a crystal structure with grains oriented along a 111 crystal plane. The element can be bonded to another element to form a bonded structure. The element and the other element can be directly bonded to one another without an intervening adhesive.
Description
BACKGROUND
Field of the Invention

The field relates to structures with features, such as surface contact pads, and methods for forming the same, and in particular to structures with conductive features having engineered metal grains, methods for forming the same and for directly bonding such features to conductive features on other elements.


Description of the Related Art

Semiconductor elements, such as integrated device dies or chips, may be mounted or stacked on other elements. For example, a semiconductor element can be mounted to a carrier, such as a package substrate, an interposer, a reconstituted wafer or element, etc. As another example, a semiconductor element can be stacked on top of another semiconductor element, e.g., a first integrated device die can be stacked on a second integrated device die. Each of the semiconductor elements can have conductive pads for mechanically and electrically bonding the semiconductor elements to one another. There is a continuing need for improved methods for forming the conduct pads.





BRIEF DESCRIPTION OF THE DRAWINGS

Specific implementations will now be described with reference to the following drawings, which are provided by way of example, and not limitation.



FIG. 1 illustrates a schematic cross-sectional view of an element, according to an embodiment.



FIG. 2A shows a step in a manufacturing process for forming the element illustrated in FIG. 1, according to an embodiment.



FIG. 2B shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2C shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2D shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2E shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2F shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2G shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 2H illustrates a schematic cross-sectional view of the element being in contact with another element.



FIG. 2I illustrates a schematic cross-sectional view of a bonded structure.



FIG. 3A shows a step in another manufacturing process for forming the element illustrated in FIG. 1, according to an embodiment.



FIG. 3B shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 3C shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 3D shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 3E shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 3F shows another step in the manufacturing process for forming the element illustrated in FIG. 1.



FIG. 3G shows another step in the manufacturing process for forming the element illustrated in FIG. 1.





DETAILED DESCRIPTION

The present disclosure describes methods of engineering metallic grain structures for conductive pads in microelectronic elements. Such engineering can be advantageous for direct metal bonding, such as direct hybrid bonding. For example, two or more semiconductor elements (such as integrated device dies, wafers, etc.) may be stacked on or bonded to one another to form a bonded structure. Conductive contact pads of one element may be electrically connected to corresponding conductive contact pads of another element. Any suitable number of elements can be stacked in the bonded structure. The methods and bond pad structures described herein can be useful in other contexts as well.


In some embodiments, the elements are directly bonded to one another without an adhesive. In various embodiments, a non-conductive (e.g., semiconductor or inorganic dielectric) material of a first element can be directly bonded to a corresponding non-conductive (e.g., semiconductor or inorganic dielectric) field region of a second element without an adhesive. In various embodiments, a conductive region (e.g., a metal pad) of the first element can be directly bonded to a corresponding conductive region (e.g., a metal pad) of the second element without an adhesive. The non-conductive material can be referred to as a nonconductive bonding region or bonding layer of the first element. In some embodiments, the non-conductive material of the first element can be directly bonded to the corresponding non-conductive material of the second element using bonding techniques without an adhesive using the direct bonding techniques disclosed at least in U.S. Pat. Nos. 9,564,414; 9,391,143; and 10,434,749, the entire contents of each of which are incorporated by reference herein in their entirety and for all purposes. In other applications, in a bonded structure, a non-conductive material of a first element can be directly bonded to a conductive material of a second element, such that a conductive material of the first element is intimately mated with a non-conductive material of the second element. Suitable dielectric materials for direct bonding include but are not limited to inorganic dielectrics, such as silicon oxide, silicon nitride, or silicon oxynitride, or can include carbon, such as silicon carbide, silicon oxycarbonitride, silicon carbonitride or diamond-like carbon. Such carbon-containing ceramic materials can be considered inorganic, despite the inclusion of carbon. Additional examples of hybrid direct bonding may be found throughout U.S. Pat. No. 11,056,390, the entire contents of which are incorporated by reference herein in their entirety and for all purposes.


In various embodiments, direct bonds can be formed without an intervening adhesive. For example, semiconductor or dielectric bonding surfaces can be polished to a high degree of smoothness. The bonding surfaces can be cleaned and exposed to a plasma to activate the surfaces. In some embodiments, the surfaces can be terminated with a species after activation or during activation (e.g., during the plasma processes). Without being limited by theory, in some embodiments, the activation process can be performed to break chemical bonds at the bonding surface, and the termination process can provide additional chemical species at the bonding surface that improves the bonding energy during direct bonding. In some embodiments, the activation and termination are provided in the same step, e.g., a plasma or wet etchant to activate and terminate the surfaces. In other embodiments, the bonding surface can be terminated in a separate treatment to provide the additional species for direct bonding. In various embodiments, the terminating species can comprise nitrogen. Further, in some embodiments, the bonding surfaces can be exposed to fluorine. For example, there may be one or multiple fluorine peaks near layer and/or bonding interfaces. Thus, in the directly bonded structures, the bonding interface between two non-conductive materials can comprise a very smooth interface with higher nitrogen content and/or fluorine peaks at the bonding interface. Additional examples of activation and/or termination treatments may be found throughout U.S. Pat. Nos. 9,564,414; 9,391,143; and 10,434,749, the entire contents of each of which are incorporated by reference herein in their entirety and for all purposes.


In various embodiments, conductive contact pads of the first element can also be directly bonded to corresponding conductive contact pads of the second element. For example, a direct hybrid bonding technique can be used to provide conductor-to-conductor direct bonds along a bond interface that includes covalently direct bonded dielectric-to-dielectric surfaces, prepared as described above. In various embodiments, the conductor-to-conductor (e.g., contact pad to contact pad) direct bonds and the dielectric-to-dielectric hybrid bonds can be formed using the direct bonding techniques disclosed at least in U.S. Pat. Nos. 9,716,033 and 9,852,988, the entire contents of each of which are incorporated by reference herein in their entirety and for all purposes. The bond structures described herein can also be useful for direct metal bonding without non-conductive region bonding, or for other bonding techniques.


In some embodiments, inorganic dielectric bonding surfaces can be prepared and directly bonded to one another without an intervening adhesive as explained above. Conductive contact pads (which may be surrounded by nonconductive dielectric field regions) may also directly bond to one another without an intervening adhesive. In some embodiments, the respective contact pads can be recessed below exterior (e.g., upper) surfaces of the dielectric field or nonconductive bonding regions, for example, recessed by less than 30 nm, less than 20 nm, less than 15 nm, or less than 10 nm, for example, recessed in a range of 2 nm to 20 nm, or in a range of 4 nm to 10 nm. The nonconductive bonding regions can be directly bonded to one another without an adhesive at room temperature in some embodiments and, subsequently, the bonded structure can be annealed. Upon annealing, the contact pads can expand with respect to the nonconductive bonding regions and contact one another to form a metal-to-metal direct bond. Beneficially, the use of hybrid bonding techniques, such as Direct Bond Interconnect, or DBI®, available commercially from Xperi of San Jose, CA, can enable high density of pads connected across the direct bond interface (e.g., small or fine pitches for regular arrays). In various embodiments, the contact pads can comprise copper or copper alloys, although other metals may be suitable.


Thus, in direct bonding processes, a first element can be directly bonded to a second element without an intervening adhesive. In some arrangements, the first element can comprise a singulated element, such as a singulated integrated device die. In other arrangements, the first element can comprise a carrier or substrate (e.g., a wafer) that includes a plurality (e.g., tens, hundreds, or more) of device regions that, when singulated, form a plurality of integrated device dies. Similarly, the second element can comprise a singulated element, such as a singulated integrated device die. In other arrangements, the second element can comprise a carrier or substrate (e.g., a wafer).


As explained herein, the first and second elements can be directly bonded to one another without an adhesive, which is different from a deposition process. The first and second elements can accordingly comprise non-deposited elements. Further, directly bonded structures, unlike deposited layers, can include a defect region along the bond interface in which nanovoids are present. The nanovoids may be formed due to activation of the bonding surfaces (e.g., exposure to a plasma). As explained above, the bond interface can include concentration of materials from the activation. For example, in embodiments that utilize a nitrogen plasma for activation, a nitrogen peak can be formed at the bond interface. In embodiments that utilize an oxygen plasma for activation, an oxygen peak can be formed at the bond interface. In some embodiments, the bond interface can comprise a nitrogen-terminated inorganic non-conductive material, such as nitrogen-terminated silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, silicon oxycarbonitride, etc. Thus, the surface of the bonding layer can comprise silicon nitride, silicon oxynitride, silicon oxycarbonitride, or silicon carbonitride, with levels of nitrogen present at the bonding interface that are indicative of nitrogen termination of at least one of the elements prior to direct bonding. In some embodiments, nitrogen and nitrogen related moieties may not be present at the bonding interface. As explained herein, the direct bond can comprise a covalent bond, which is stronger than van Der Waals bonds. The bonding layers can also comprise polished surfaces that are planarized to a high degree of smoothness.


In various embodiments, the metal-to-metal bonds between the contact pads can be joined such that copper grains grow into each other across the bond interface. In some embodiments, the copper can have grains oriented vertically along the 111 crystal plane for improved copper diffusion across the bond interface. In some embodiments, the misorientation of 111 crystal plane in the conductive material may be in a range of ±30° with respect to the vertical direction from the surface of the conductive material. In some embodiments, the crystal misorientation can be in a range of ±20°, or in a range of ±15°, with respect to the vertical direction. The bond interface can extend substantially entirely to at least a portion of the bonded contact pads, such that there is substantially no gap between the nonconductive bonding regions at or near the bonded contact pads. In some embodiments, a barrier layer may be provided under the contact pads (e.g., which may include copper). In other embodiments, however, there may be no barrier layer under the contact pads, for example, as described in US 2019/0096741, which is incorporated by reference herein in its entirety and for all purposes.


Annealing temperatures and annealing durations for forming the metal-to-metal direct bond can affect the consumption of thermal budget by the annealing. It may be desirable to lower the annealing temperature and/or annealing duration to minimize consumption of the thermal (energy) budget. Surface diffusion of atoms along the 111 crystal plane (<111>) can be 3 to 4 orders of magnitude faster than along the 100 or 110 crystal planes. Also, a metal (e.g., Cu) with grains oriented along a 111 crystal plane can have a higher surface mobility as compared to conventional back end of line (BEOL) copper. Further, low-temperature direct metal-to-metal bonding is enabled by creep on the 111 planes of Cu. Therefore, it can be advantageous to have the 111 crystal plane on the bonding surface in order to shorten the annealing time and/or reduce the annealing temperature for direct bonding (e.g., direct hybrid bonding). The advantage to have the 111 crystal plane can be pronounced especially at lower temperatures because the metal surface diffusion (e.g., Cu surface diffusion) also slows down when the annealing temperature is reduced. Accordingly, in various embodiments disclosed herein, a crystal structure can have grains oriented vertically along the 111 crystal plane to enhance metal diffusion (e.g., copper diffusion) during direct bonding.


A metal layer can be formed with a process selected to plate a copper (Cu) layer having Cu in the 111 crystal orientation at or near the bonding surface of the conductive layer or bonding pad. The Cu layer may be deposited from a non-superfilling or super-filling electroplating bath, for example, with plating chemistry selected to optimize efficient filling of voids or embedded cavities (e.g., vias, trenches) in the substrate, rather than to optimize the direct metal-to-metal bonding to occur during direct hybrid bonding. Subsequent metal treatment, described hereinbelow, can facilitate subsequent bonding such that any desirable plating chemistry can be employed to optimize for other considerations, such as filling noted above. The microstructure (e.g., a grain size) of the deposited or coated metal layer is typically less than 50 nm and may need to be stabilized, for example by an annealing step (at temperature typically lower than 300° C.). After the plated metal stabilization step, the coated metal can be planarized by CMP methods to remove unwanted materials (excess plated metal, barrier layer, and/or portion of the non-conductive layer) to form the planar bond surface. The bonding surface can include a planar non-conductive portion that surrounds an adequately dispersed planar conductive portion.


Various embodiments disclosed herein relate to forming an element with a conductive pad that has a direct bonding surface having a 111 crystal plane orientation independent of plating chemistry. The direct bonding surface can have a cold worked surface with nano-grains that is independent of a metal coating method such as electroplating, electroless, physical vapor deposition (PVD) amongst others. Therefore, various embodiments disclosed herein provide greater flexibility for the design of plating processes and/or more efficient conductive material filling, as compared to conventional plating processes tuned for forming a 111 crystal plane orientation. In some embodiments, the conductive pad (e.g., plated Cu in a damascene cavity) can be treated by a cold work process at room temperature and/or below room temperature. In some embodiments, the surface of the coated conductive material including the conductive pad can be treated by way of peening in which the conductive pad is bombarded with a stream of particles, such as metal, glass, or ceramic. In some embodiments, the cold work process may comprise, for example, cold rolling a coated conductive material to reduce the grain size of the coated conductive material. A lubricating fluid with and/or without colloidal particles may be used in the cold rolling process. In some embodiments, grain boundaries of the deformed grains of conductive pad can comprise subgrains, high angle grain boundaries, twins massive dislocations and/or dislocation networks. In some embodiments, nano-spaced nano-twinned grains and/or nano-laminates can be formed within the conductive pad.


In some embodiments, a texture gradient and a grain-size gradient within the conductive pad can be formed by the cold work process. For example, smaller grains and/or a lower percentage of 111 oriented crystals can be achieved near the surface of the pad as compared to deeper within the pad. The cold worked coated conductive material or layers deform plastically. Most of the mechanical energy expended in the deformation process can be converted into heat and the remainder can be stored in the deformed structure with the creation of lattice imperfections. The lattice imperfections can include fine grains, high angle grain boundaries, mechanical twins and/or nano-twins, dislocations, vacancies etc. In the deformed conductive layer (pads and traces), the dominant contribution to the stored energy of the cold work process can be the energy associated with the formation of the additional lattice imperfections present relative to those in an undeformed portion of the annealed conductive layer. The deformation process can induce residual compressive stress in the conductive pad. This residual compressive stress may vary from the surface of the pad to the bottom of the pad. Depending on the energy imparted to the metal in the cold working process, upper portions of the pad may have a higher residual stress compared to the lower portions of the pad.


Various embodiments disclosed herein allows for relatively low temperature annealing for metal-to-metal direct bonding while being independent of electroplating baths, electroplating methods and/or other conductive layer coating or forming method. In some embodiments, stored energy in a portion of the cold-worked conductive layer can contribute to enabling a relatively low temperature annealing. In some embodiments, the annealing temperature for bonding can be, for example, between about 50° C. and about 250° C., between about 100° C. and about 200° C., 125° C. and about 170° C. or between about 50° C. and about 180° C. Depending on the annealing temperature or temperatures, the annealing time may range between 45 minutes to 180 minutes. The annealing time may increase when the annealing temperature is lower. However, the embodiments disclosed herein can still lower consumption of the thermal (energy) budget relative to conventional structures, such that anneal durations can remain low despite lower anneal temperatures.



FIG. 1 illustrates a schematic cross-sectional view of an element 1, according to an embodiment. The element 1 can comprise a semiconductor element, either before singulation, such as a semiconductor substrate or wafer, or after singulation, such as an interposer, electronic component, integrated circuit (IC) die or chip. The element 1 can include a substrate 10 (e.g., bulk semiconductor material), a non-conductive layer (e.g., a dielectric layer 12, such as silicon oxide or other low k material) over the substrate 10, a conductive pad 14 disposed in a cavity 16 formed in the dielectric layer 12, and a barrier layer 18 disposed between the dielectric layer 12 and the conductive pad 14. While for simplicity a single dielectric layer 12 is illustrated, the skilled artisan will understand that the dielectric layer 12 and conductive pad 14 can comprise part of a back-end-of-line (BEOL) structure or redistribution layer (RDL) structure over a BEOL structure, which typically includes vias and trenches or traces (not shown). In some embodiment, the conductive pad or via or trace may comprise an alloy of copper, nickel, gold, or other metal alloys.


In some embodiments, the substrate 10 can comprise a semiconductor substrate or wafer. In some embodiments, the substrate 10 can comprise a glass substrate, a dielectric substrate, or a ceramic substrate.


The dielectric layer 12 can comprise a relatively low k (e.g., k<4) dielectric material. In some embodiments, the dielectric layer 12 can comprise an inorganic material. The dielectric layer 12 can have a lower side 12a that faces the substrate 10 and an upper side 12b opposite the lower side 12a. The upper side 12b can define a bonding surface of the dielectric layer 12, and can thus include, for example, a higher concentration of nitrogen and/or fluorine compared to the bulk material of the layer, as described above. In some embodiments, the bonding surface at the upper side can be defined by a barrier or etch stop layer (not shown) over the low k dielectric layer 12. The dielectric layer 12 can have the cavity 16 that at least partially extends through a thickness of the dielectric layer 12 from the upper side 12b. The cavity 16 has a bottom side 20 and sidewalls 22.


The conductive pad 14 can have a lower side 14a that faces the bottom side 20 of the cavity and an upper side 14b opposite the lower side 14a. The upper side 14b can define a bonding surface of the conductive pad 14. The conductive pad 14 can comprise a metal such as copper (Cu). The conductive pad 14 can comprise copper with grains oriented along a 111 crystal plane. In some embodiments, the conductive pad 14 can comprise a cold worked or mechanically or optically deformed pad.


Sizes of the grains 24 in the element 1 can vary in deformed conductive pads 14. A size of the grain 24 used herein may refer the maximum dimension of the grain 24. In some embodiments, the grains 24 at or near the upper side 14b can be smaller on average than the grains 24 at or near the lower side 14a. In some embodiments, the grains can have a small grain region 26 at or near the upper side 14b of the conductive pad 14 and a large grain region 28 at or near the lower side 14a of the conductive pad 14. In some embodiments, the small grain region 26 can be arbitrarily selected to be a region of the conductive pad 14 from the upper side 14b to 1000 nm deep into the conductive pad 14 for a shallow conductive pad 14, or to 3000 nm in a deeper conductive pad 14 (e.g., pads of thickness greater than 5000 nm), for purposes of comparing grain sizes above and below this level. In some embodiments, an average grain size in the small grain region 26 at or near the upper side 14b can be about 10 nanometers (nm) to 200 nm, or about 30 nm to 200 nm. In some embodiments, an average grain size in the large grain region 28 at or near the lower side 14a can be about 0.5 microns (μm) to 5 μm. In some embodiments the average grain size can vary depending on the width and depth of the conductive pad 14. In some embodiments, the average size of the grain 24 at or near the lower side 14a can be at least five times greater than the average size of the grains 24 at or near the upper side 14b. For example, the average size of the grain 24 at or near the lower side 14a can be about 3 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, or 40 to 100, times greater than the average size of the grains 24 at or near the upper side 14b of the deformed conductive pad 14. In some embodiments, the grains 24 can have graded grain sizes through the depth of the conductive pad 14 as a result of the gradation of lattice imperfections from the upper side 14b to the lower side 14a. In some embodiments, the conductive pad 14 can be measurably harder at or near the upper side 14b than at or near the lower side 14a. In some embodiments, the average size of 3 contiguous grains 24 at or near the lower side 14a can be about 3 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, or 40 to 100, times greater than the average size of 3 contiguous grains 24 at or near the upper side 14b of the deformed conductive pad 14. Similarly, the average grain size of 2 contiguous grains 24 at or near the upper side 14b of the deformed conductive pad 14 can be at least 2 times smaller than the average of 2 contiguous grain in an interconnect layer below the barrier layer 18 (not shown) of the deformed conductive pad 14. In some embodiments, at a higher determined deformation of the coated conductive layer, the grain size of 3 contiguous grains 24 near the upper side 14b of the conductive pad 14 and lower side 14a of the conductive pad 14 are similar, and can be at least 3 times smaller than grain size at corresponding locations in undeformed conductive pads 14.


Upon thermal annealing after cold working, such as during bonding the conductive pad 14 to another conductive pad of another element, to release the stored energy in the deformed conductive pad 14 (deformed due to compressive stress induced by mechanical or optical peening) and to enhance grain recovery and growth, the recovered grains of the upper side 14b region of the conductive pad 14 can be larger than the recovered grains of the lower side 14a region beneath (see FIG. 2I). The grain sizes at the upper side 14b can exceed the sizes at the lower side 14a to produce a reversed gradient from that just after the cold working process. Similarly the grain sizes at the upper side 14b can exceed the sizes of an interconnect layer below the barrier layer 18 (not shown) of the deformed conductive pad 14.


In some embodiments, the upper side 14b of the conductive pad 14 can be recessed below the upper side 12b of the dielectric layer 12. For example, the upper side 14b of the conductive pad 14 can be recessed below the upper side 12b of the dielectric layer 12 by less than about 30 nm, less than about 20 nm, less than about 15 nm, or less than about 10 nm. For example, the upper side 14b of the conductive pad 14 can be recessed below the upper side 12b of the dielectric layer 12 in a range of 2 nm to 20 nm, or in a range of 4 nm to 15 nm.


The barrier layer 18 can comprise, for example, a dielectric barrier layer, such as silicon nitride, silicon oxynitride, silicon carbonitride, diamond-like carbon, etc. The barrier layer 18 can comprise a conductive barrier, such as a metal nitride (e.g., Ta, TiN, TaN, WN, and their various combinations etc.). For example, a conductive barrier layer 18 can be deposited over the bottom side 20 and the sidewalls 22 of the cavity 16. A non-conductive barrier layer 18 may be formed on the sidewalls 22, and not at the bottom side 20 of the cavity 16. In some embodiments, the non-conductive barrier layer 18 may be discontinuous over the bottom side 20 of the cavity 16. The barrier layer 18 can intervene between the dielectric layer 12 and the conductive pad 14.



FIGS. 2A-2G show stages in a manufacturing process for forming the element 1 illustrated in FIG. 1, according to an embodiment. FIG. 2H shows the element 1 being in contact with another element (a second element 2), and FIG. 2I shows a bonded structure 3 that include the element 1 and the second element 2.


In FIG. 2A, a dielectric layer 12 is provided over a substrate 10. A cavity 16 is selectively formed in the dielectric layer 12, including an upper surface 12b. The cavity 16, shown with a bottom surface 20 and sidewall surfaces 22, can extend through at least a portion of a thickness of the dielectric layer 12. The cavity 16 can be formed by way of masking and etching or drilling. The cavity 16 can comprise a damascene cavity that is formed with damascene processes. The cavity 16 may comprise a thru substrate cavity (TSC) such as a through silicon via (TSV) or a through glass via (TGV). In some embodiments, the cavity 16 may be formed to be in contact with an embedded interconnect structure such as a BEOL or RDL layer (not shown).


In FIG. 2B, a barrier layer 18 can be provided on the upper surface 12b of the dielectric layer, the sidewalls 22 of the cavity 16, and the bottom surface 20 of the cavity 16. As mentioned earlier the barrier layer 18 may be a non-conductive material formed on the upper surface 12b of the dielectric layer, the sidewalls 22 of the cavity 16, and not at the bottom surface 20 of the cavity 16. A seed layer 30 can be provided on the barrier layer 18 over these same surfaces. In some embodiments, a conductive via or vias or one or more traces (not shown) contacting the barrier layer 18 may be disposed beneath the lower surface 20 of the cavity 16.


In FIG. 2C, a conductive material 32 can be provided in the cavity 16 and over the upper side 12b of the dielectric layer 12. In some embodiments, the conductive material can comprise metal, such as copper (Cu), and can be provided, for example, by plating or other known methods. In some embodiment, the conductive material 32 may comprise an alloy of copper, nickel, gold, or other metal alloys. The conductive material 32 can have a lower side 32a and an upper side 32b. Advantageously, the plating methods and additives can be optimized for efficiently filling the cavity 16, which may be just one of many vias and/or trenches across the substrate, and which can have high aspect ratios. In some embodiments, the conductive material 32 can comprise an electroplating coating formed at or below room temperature. The room temperature can be defined as temperatures in a range of, for example, 20° C. to 35° C. The plated metal of the conductive material 32 can have grain sizes in a range of between 10 nm to 100 nm, or 30 nm to 100 nm in the as-plated state.


In FIG. 2D, the conductive material 32 can be annealed at a temperature between room temperature and 250° C. In some embodiment, some electroplated copper films with low interstitial and non-interstitial impurities can form large grains at room temperatures due to room temperature grain growth phenomenon. The annealing process can stabilize the microstructure (e.g., a grain size) of grains 24 in the conductive material 32. The annealing process can form relatively large grains 24 in the conductive material 32. For relatively large pads greater than 5 microns across, the grain size of the conductive material after annealing can be in a range of, for example, 0.3 microns to 3 microns. For conductive traces with width less than 1 microns, the grain structure may exhibit a bamboo type grain structure extending along the trace axes.


In FIG. 2E, the conductive material 32 can be treated with a cold work process. The cold work process can take place at room temperature and/or below room temperature. For example, the substrate temperature during the cold work process may range from −196° C. (77K), the temperature of liquid nitrogen, to about 30° C. or 50° C., or from 0° C. to about 25° C., and in one example at about ambient clean room temperature. The conductive material 32 can be treated from the upper side 32b. In some embodiments, the conductive material 21 can be treated with a strain hardening process. For example, the conductive material 32 can be treated by a shot peening process, cold rolling or laser peening process to induce plastic deformation in the conductive material 32. As noted above, shot peening can include bombardment by particles, such as metal, sand, glass, or ceramic. For example, the mechanical peening may include bombarding the surface (e.g., the upper side 32b) of the conductive material 32 with ceramic or steel shots. For example, s diameter of the shots may range between 0.1 mm and 2 mm, a velocity of the shots can be between 1 to 5 meters per second, and a bombardment time can be between 30 s to 180 s. In some embodiments, the substrate 10 may rotate between 10 to 60 rpm and preferably between 15 to 45 rpm during the peening operation. In some embodiments, the element 1 can be static during the peening operation. The plastic deformation can induce residual compressive stresses in the grains 24 at the surface and below the surface of the conductive material 32 and/or tensile stresses at an interior or bulk of the conductive material 32. The conductive material 32 after the cold work process can have stored energy from compressive residual stress. In some embodiments, a portion of the conductive material 32 at or near the upper side 32b can have higher stored energy from the cold work process than the lower side 32a. In some embodiment, the conductive material 32 can be uniformly deformed from the top surface 32b to the bottom surface 32a, including a portion of the conductive material 32 at the bottom of the cavity 20 adjacent to the barrier layer 18. The conductive material 32 may be heavily deformed such that it is challenging to distinguish the individual metal grains because of the massive structural defects such as stacking faults, mechanical twins, slips, vacancies, and/or dislocation networks induced by the deformation process. As a result of the structural defects and very small grain sizes (e.g., 5 nm to 30 nm), it may be challenging to index the individual grains 24 for their orientation. Regardless of the method of applying compressive force or forces to the conductive material 32, the applied force should degrade the substrate 1. Degrading the element 1 may, for example, comprise applying excessive force so as to induce delamination of the barrier layer 18 or induce defects or cracks in the dielectric layer 12 and/or the substrate 10. The stored energy can contribute to achieving a relatively low temperature annealing bonding (see FIG. 2I).



FIG. 2F shows the grains 24 after the treatment in FIG. 2E. Sizes of the grains 24 in the conductive material 32 can vary. In some embodiments, the grains 24 at or near the upper side 32b can be smaller than the grains 24 at or near the lower side 32a. In some embodiments, an average size of the grains 24 at or near the upper side 32b can be about 10 nanometers (nm) to 200 nm, or about 50 nm to 200 nm. In some embodiments, an average size of the grains 24 at or near the lower side 32a or at the interior of the cavity can be about 0.5 microns (μm) to 1 μm. In some embodiments, the average size of the grains 24 at or near the lower side 32a can be at least about five times greater than the average size of the grains 24 at or near the upper side 32b. For example, the average size of the grain 24 at or near the lower side 32a can be about 10 to 100, 20 to 100, 30 to 100, 40 to 100, or 40 to 100, times greater than the average size of the grains 24 at or near the upper side 32b. In some embodiments, because of the top to bottom variation in the compressive residual stress in the conductive material, the grains 24 can have gradient grain sizes. For example, the grain sizes of the grains 24 can gradually increase from the upper side 32b to the lower side 32a or in the interior of the conductive cavity or layer. In some embodiments, the conductive material 32 can be harder at or near the upper side 32b than at or near the lower side 32a. As compared to the deeper or bulk material near the lower side 32a, the conductive material 32 near the upper side 32b can have a lower percentage of grains 24 with vertically oriented 111 crystal planes and comparatively higher percentage of 220 crystal planes (<220>) from the deformation process. In some embodiments, especially when laser peening method is applied to the conductive material 32, the cold working of the conductive layer can be sufficiently deep, such that the smaller grains at the upper surface 32b are similar to those at lower side 32a or at the interior of the cavity.


In some applications, the conductive material 32 may comprise a portion of a through substrate pad (not shown), such as a through-silicon via (TSV) or through-glass via (TGV). Here, a portion of the conductive material 32 at or near the upper surface 32b may exhibit lattice imperfections from the cold working step.


In FIG. 2G, the element 1 is formed and prepared for direct bonding, such as by a high degree of polishing and activation (e.g., nitrogen termination). At least a portion of the conductive material 32 can be removed, such as by polishing. Portions of the barrier layer 18 and the seed layer 30 can also be removed. Although the slurry chemistry for chemical mechanical planarization (CM) can be selective to stop on the dielectric layer 12, a portion of the dielectric layer 12 can also be removed to form a bonding surface. The bonding surface can include highly polished surfaces of the non-conductive layer 12b and the upper surface 14b of the planar conductive material. In some embodiments, the portions of the conductive material, barrier layer 18, seed layer 30, and the dielectric layer 12 can be removed by polishing, such as chemical mechanical polishing (CMP), in one or multiple stages with one or multiple different slurry compositions to form the bonding surface. The upper side 12b of the dielectric layer 12 can be polished to a high degree of smoothness to prepare for direct bonding, followed by very slight etching and/or surface activation, such as by exposure to nitrogen-containing plasma. The activated bonding surface is cleaned with a suitable solvent such as deionized water (DI) water to remove unwanted particles. The cleaned surface may be spun dried to remove cleaning solvent residues prior to a bonding operation and subsequent annealing step.


In some embodiments, the highly polished bonding surfaces of the non-conductive layer 12b and the upper surface 14b of the planar conductive material of the substrate 10 may be coated with a protective layer (not shown), typically with an organic resist layer. The coated substrate can be mounted on a dicing frame for singulation. The singulation process may be formed by any known process, for example, saw dicing, laser singulation, reactive ion etching (RIE), wet etching or any suitable combination of these singulation steps. Regardless of the singulation step, the protective layer and singulation particulates can be cleaned off from the singulated dies and from the dicing frame. The bonding surfaces of the cleaned dies may ashed to remove unwanted organic residues and cleaned for direct bonding to another prepared bonding surface of another substrate. In some embodiments, the cleaned bonding surface of the singulated dies may be activated by known methods, cleaned of unwanted particles and material prior to directly bonding the bonding surfaces of the activated die to another prepared bonding surface of a second substrate. The bonded elements can be annealed to mechanically and electrically interconnect the opposing conductive pads of the bonded substrates (see FIG. 2I). In some embodiments, the second substrate with bonded singulated dies may further be singulated to form directly bonded die stacks.


Sizes of the grains 24 in the element 1 can vary. In some embodiments, the grains 24 at or near the upper side 14b can be smaller on average than the grains 24 at or near the lower side 14a. In some embodiments, the grains can have a small grain region at or near the upper side 14b of the conductive pad 14 and a large grain region at or near the lower side 14a of the conductive pad 14. In some embodiments, the small grain region can be a region of the conductive pad 14 from the upper side 14b to 1000 nm, or to 3000 nm for a deeper pad, into the conductive pad 14. In some embodiments, an average size of the grains 24 in the small grain region at or near the upper side 14b can be about 10 nanometers (nm) to 200 nm, or about 30 nm to 200 nm. In some embodiments, an average size of the grain 24 in the large grain region at or near the lower side 14a can be about 0.2 microns (μm) to 1 μm, or 0.2 μm to 0.5 μm. In some embodiments, the average size of the grain 24 at or near the lower side 14a can be at least five times greater than the average size of the grains 24 at or near the upper side 14b. For example, the average size of the grain 24 at or near the lower side 14a can be about 10 to 100, 20 to 100, 30 to 100, 40 to 100, or 40 to 100, times greater than the average size of the grains 24 at or near the upper side 14b. In some embodiments, the grains 24 can have gradient grain sizes. For example, the grain sizes of the grains 24 can gradually increase from the upper side 14b to the lower side 14a. In some embodiments, the conductive pad 14 can be harder at or near the upper side 14b than at or near the lower side 14a. In some embodiments, the cold working of the conductive pad 14 is sufficiently deep such that an average size of the smaller grains at or near the upper surface 14b is similar to an average size of the grains at or near lower side 14a or at the interior of the cavity.


In FIG. 2H, the element 1 is brought into contact with the second element 2. In some embodiments, the second element can comprise an identical or generally similar element as the element 1. In some embodiments, the second element 2 can comprise a carrier, such as a package substrate, an interposer, a reconstituted wafer or element, etc. In some embodiments, the second element 2 can also be prepared for direct bonding as in element 1. A dashed line shown in FIG. 2H indicates a bond interface 56 between the element 1 and the second element 2. The second element 2 can include a second substrate 50, a second dielectric layer 52, and a second conductive pad 54. The conductive pad 54 can have grains 64. In some embodiments, upon contacting the dielectric layer 12 and the second dielectric layer 52, the dielectric layers 12 and 52 can bond to one another. In some embodiments, the dielectric layer 12 and the second dielectric layer 52 can be bonded to one another directly without an intervening adhesive. The dielectric layer 12 and the second dielectric layer 52 can be directly bonded at room temperature without external pressure. Although not shown in FIG. 2H, the conductive pads 14, 54 can be recessed from the surfaces of the dielectric layers 12, 52, respectively, at the time of contact, such that a small gap is present between the opposing bond pads 14, 54 or other conductive elements at the surface.


In FIG. 2I, the conductive pad 14 and the second conductive pad 54 are bonded to one another. In some embodiments, the conductive pad 14 and the second conductive pad 54 can be bonded to one another directly without an intervening adhesive. The bonded structure can be annealed. Upon annealing, the conductive pads 14, 54 can expand and contact one another to form a metal-to-metal direct bond. A dashed line shown in FIG. 2I indicates the bond interface 56 between the element 1 and the second element 2.


As described above, prior to anneal, the crystal structure of the conductive material 32 can have grains 24 including a lower percentage of vertically oriented 111 crystal planes near the interface, as compared to the bottom regions of the conductive pads 14, 54. The conductive pad 14 after the cold work process in FIGS. 2G and 2H has stored energy in the cold worked conductive pad 14. The cold worked conductive pad 14 may comprise very fine non-oriented grain sizes (with massive lattice imperfections, high angle grain boundaries, twins, dislocations, vacancies etc.) exhibiting high creep in the pad 14. The combination of higher creep and grain stored energy can enable the bridging of the recess between the pads 14 and 54. at relatively low temperature annealing. Therefore, the conductive pads 14, 54 can be sufficiently bonded to one another directly with a relatively low temperature and/or short anneal. In some embodiments, the conductive pad 14 and the second conductive pads 54 can be annealed at a temperature less than 250° C., less than 200° C., or less than 150° C., for example about 100° C. to 250° C., about 125° C. to 200° C., or about 125° C. to 180° C.


After the conductive pad 14 and the second conductive pad 54 are annealed and bonded, the grain sizes can change relative to before bonding. In some embodiments, a size of a grain 24, 64 at or near the bonding interface 56 can be on average more than about 1.2 or 2 times larger than a size of a grain 24 at or near the lower side 14a of the conductive pad 14. For example, the size of a grain 24, 64 at or near the bonding interface 56 can be on average more than about 2 to 10, 2 to 7, 2 to 5, 1.2 to 10, 1.2 to 7, or 1.2 to 5 times larger than a size of a grain 24 at or near the lower side 14a of the conductive pad 14. In some embodiment, a grain size of the grain 24, 64 at or near the bonding interface 56 may be at least 20% to 50% larger than a grain size of the grain 24 at or near the lower side 14a of the conductive pad 14.


In some embodiments, an average dimension of the grains 24, 64 at the bonding interface 56 is about 3 to 8 times, 3 to 6 times, 4 to 8 times, or 4 to 6 times greater than an average dimension of the grains 24 closer to the lower side 14a of the conductive pad 14. In some embodiments, the grains 24, 64 at or near the bonding interface of the bonded conductive pads 14, 54 can have a higher percentage of 111 planes and annealing twins than that of the grains 24 at or near the lower side 14a of the conductive pad 14. The stored energy in the surface grain structure facilitates greater grain growth and re-orientation during the anneal for bonding, as compared to deeper parts of the pad structure that are less affected by the cold working process.



FIGS. 3A-3G show steps in a manufacturing process for forming the element 1 illustrated in FIG. 1, according to another embodiment. The process illustrated in FIGS. 3A-3G is different from the process illustrated in FIGS. 2A-2G in that the conductive material 32 is thinned prior to peening in the process illustrated in FIGS. 2A-2G. The components shown in FIGS. 3A-3G can be the same as or generally similar to like components shown in FIGS. 1-2I, and like reference numerals are used to refer to like parts.


In FIG. 3A, a dielectric layer 12 is provided over a substrate 10. A cavity 16 is formed in the dielectric layer 12. The cavity 16 can extend through at least a portion of a thickness of the dielectric layer 12. The cavity 16 can be formed by way of selective etching or drilling. The cavity 16 can comprise a damascene cavity that is formed with damascene processes. In FIG. 3A, an insulating or conductive barrier layer 18 can be provided on an upper side 12b of the dielectric layer 12, sidewalls 22 of the cavity 16, and the bottom side 20 of the cavity 16. A seed layer 30 can be provided on the barrier layer 18 over the same surfaces.


In FIG. 3B, a conductive material 32 can be provided in the cavity 16 and over the upper side 12b of the dielectric layer 12. In some embodiments, the conductive material can comprise metal, such as copper (Cu). The conductive material 32 can have a lower side 32a and an upper side 32b. As shown in FIG. 3C, the conductive material 32 can be annealed. The annealing process can stabilize the microstructure (e.g., grain structure) of grains 24 in the conductive material 32. The annealing process can form relatively large grains in the conductive material 32.


In FIG. 3D, the conductive material 32 can be thinned from the upper side 32b. In some embodiments, the conductive material 32 can be thinned by way of polishing, such as chemical mechanical polishing (CMP). FIG. 3D illustrates that a portion of the conductive material 32 is disposed on the upper side 12b of the dielectric layer 12. However, in some embodiments, the conductive material 32 positioned over the upper side 12b of the dielectric layer 12 can be removed completely and expose the barrier layer 18. In some other embodiments, the barrier layer 18 over the upper side 12b of the dielectric layer 12 can be removed completely and expose the upper side 12b of the dielectric layer 12.


In FIG. 3E, the conductive material 32 can be treated with a cold work process as described above with respect to FIG. 2E. The cold work process can take place at room temperature and/or below room temperature. For example, the substrate temperature during the cold work process may range from −196° C. (77K), the temperature of liquid nitrogen, to about 50° C., or from 0° C. to about 25° C., and in one example at about ambient clean room temperature. The conductive material 32 can be treated from the upper side 32b. In some embodiments, the conductive material 21 can be treated with a strain hardening process. For example, the conductive material 32 can be treated by a shot peening process or laser peening process to induce plastic deformation in the conductive material 32. As noted above, shot peening can include bombardment by particles, such as metal, sand, glass, or ceramic. The plastic deformation can induce residual compressive stresses in the grains 24 at a surface and below surface of the conductive material 32 and/or tensile stresses at an interior of the conductive material 32. As discussed herein, regardless of the method of applying compressive force or forces to the conductive material 32, the applied force should degrade the substrate 1. Degrading the element 1 may, for example, comprise applying excessive force so as to induce delamination of the barrier layer 18 for the surface of the substrate or induce defects or cracks in the dielectric layer 12 and/or the substrate 10.



FIG. 3F shows the grains 24 after the treatment in FIG. 3E. Sizes of the grains 24 in the conductive material 32 can vary. In some embodiments, the grains 24 at or near the upper side 32b can be smaller than the grains 24 at or near the lower side 32a. In some embodiments, an average size of the grains 24 at or near the upper side 32b can be about 5 nanometers (nm) to 200 nm, or about 30 nm to 200 nm. Depending upon the thickness of remaining metal over field regions (upper surface of the dielectric layer 12), an average size of the grain 24 at or near the lower side 32a can be about 0.5 microns (μm) to 3 μm or larger. In some embodiments, the average size of the grain 24 at or near the lower side 32a or in the regions of the bottom of the conductive pad can be at least about two times greater than the average size of the grains 24 at or near the upper side 32b to the average size of the grain 24 at or near the lower side 32a. For example, the average size of the grain 24 at or near the lower side 32a can be about 2 to 100, 20 to 100, 30 to 100, 40 to 100, or 40 to 100, times greater than the average size of the grains 24 at or near the upper side 32b. In some embodiments, the grains 24 can have 1 gradient grain sizes. For example, the grain sizes of the grains 24 can gradually increase from the upper side 32b to the lower side 32a. In some embodiments, the conductive material 32 can be harder at or near the upper side 32b than at or near the lower side 32a. Due to the plastic deformation, reduced grain sizes, increased lattice imperfections and a reduced percentage of 111 oriented crystal planes are left at or near the upper side 32b of the conductive pad 32. In some embodiments, due to the reduced thickness of the metal left by the planarization shown in FIG. 3E, the plastic deformation may extend from the upper side 32b of the conductive pad 32 to the lower side 32a of the conductive pads 32.


In FIG. 3G, the element 1 is formed. At least a portion of the conductive material 32 can be removed. Portions of the barrier layer 18 and the seed layer 30 can also be removed to form a highly polished planar bonding surface. A portion of the dielectric layer 12 can also be removed. In some embodiments, the portions of the conductive material, barrier layer 18, seed layer 30, and the dielectric layer 12 can be removed by polishing, such as chemical mechanical polishing (CMP) in one or multiple stages to form a highly polished bonding surface. The bonding surface comprising a planar top surface of the dielectric layer 12 and a planar polished surface of the conductive pad 14. The upper side 12b of the dielectric layer 12 can be polished to a high degree of smoothness and can be activated to prepare for direct bonding.


As described above with respect to FIGS. 2H and 2I, the structure shown in FIG. 3G can then be directly hybrid bonded to another element, which may or may not have received similar treatment. As also noted above with respect to FIGS. 2H and 2I, the prepared bonding surface can first be protected with a protective layer, such as an organic resist layer, for intervening singulation or other processing prior to bonding.


The conductive pad 14 after the cold work process in FIGS. 2E and 3E have stored energy in conductive pad 14. The stored energy can enable a relatively low temperature annealing for bonding the element (the first element 1) to another element (the second element 2). The conductive pads 14, 54 can be directly bonded to one another sufficiently with a relatively low temperature and/or a relatively short anneal duration. In some embodiments, the conductive pad 14 and the second conductive pad 54 can be annealed at a temperature less than 250° C., less than 200° C., or less than 150° C., for example about 100° C. to 250° C., or about 125° C. to 180° C.


After the conductive pad 14 and the second conductive pad 54 are annealed and bonded, the grain sizes can change relative to the grain sizes before bonding. In some embodiments, a size of a grain 24, 64 at or near the bonding interface 56 can be on average more than about 1.2 or 2 times larger than a size of a grain 24 at or near the lower side 14a of the conductive pad 14. For example, the size of a grain 24, 64 at or near the bonding interface can be on average more than about 2 to 10, 2 to 7, 2 to 5, 1.2 to 10, 1.2 to 7, or 1.2 to 5 times larger than a size of a grain 24, 64 at or near the lower side of the conductive pad 14, 54. In some embodiment, a grain size of the grain 24, 64 at or near the bonding interface may be at least 20% to 50% larger than a grain size of the grain 24, 64 at or near the lower side of the conductive pad 14, 54. In general, the larger the stored energy from the applied compressive force, the larger the grain size in the annealed bonded conductive pads.


In some embodiments, a third conductive material (not shown) may be disposed in a cavity 16 in the dielectric material 12, beneath the barrier layer 18 (see FIGS. 2B and 3A) as typical in multilayer BEOL or redistribution layer (RDL) within the element 1. After the bonding and annealing operation(s), as a result of the mechanical and thermal treatment(s) to the conductive material 32 in the cavity 16, an average size of the grain 24 in the regions of the conductive pad 32 of cavity 16 can be at least about 20% greater than the average size of the grains 24 of the third conductive material beneath the barrier layer 18 compared to a third conductive material that was exposed to only thermal treatment. For example, the average size of the grain 24 of conductive pad 32 can be about 1.2 to 20 times greater than the average size of the grains 24 of the third conductive material beneath the barrier layer 18 or subsequent conductive pads (not shown) beneath the third conductive pads.


Referring back to FIG. 2I, in some embodiment, after annealing the mechanically or optically cold worked conductive material, the annealed grains are elongated along a direction generally parallel to the dielectric bonding surface or the bonding surface of the conductive material. A horizontal dimension (length l) of a grain of the annealed conductive material 24 may be at least 20% larger than a vertical dimension (thickness t) of the same grain about a direction perpendicular to the dielectric bonding surface or the bonding surface of the conductive material. For example, the length of a grain of the conductive material generally parallel to the bonding interface can be, on average, more than about 1.5 to 10 times larger than the thickness of the grain in a direction generally perpendicular to the bonding interface. In some embodiment, the length of the columnar grain a bonded elements (e.g., the bonded elements 3 shown in FIG. 2I) may be at least 20% to 300% longer than the thickness of columnar grain of the conductive material in bonded element 3. In some embodiments, an aspect ratio of a grain (the maximum longitudinal dimension (length l) of a grain/the maximum perpendicular dimension (thickness t) of the same grain), can be greater than 1.2, 1.5, or 3.


In one aspect, an element is disclosed. The element can include a non-conductive structure that has a non-conductive bonding surface, a cavity that at least partially extends through a portion of a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive pad that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. An average size of the grains at the bonding surface is smaller than an average size of the grains that are adjacent the bottom side of the cavity.


In one embodiment, the non-conductive structure includes a dielectric layer. The non-conductive bonding surface of the non-conductive layer can be prepared for direct bonding.


The conductive bonding surface of the conductive pad can be prepared for direct bonding.


The conductive pad comprises can be a copper (Cu) pad.


The conductive pad can include a lower percentage of grains with 111 crystal planes at the bonding surface compared with adjacent to the bottom side.


The conductive pad can include a higher percentage of grains with 220 crystal planes at the bonding surface compared with adjacent to the bottom side


In one embodiment, the average size of the grains adjacent the bottom side of the cavity is at least 3 times greater than the average size of the grains at the bonding surface.


In one embodiment, the average size of the grains adjacent the bottom side of the cavity is at least 20 times greater than the average size of the grains at the bonding surface.


In one embodiment, the average size of the grains adjacent the bottom side of the cavity is between 0.2 microns (μm) to 1 μm.


In one embodiment, the average size of the grains at the bonding surface is between 30 nanometer (nm) to 200 nm.


In one embodiment, the element further includes a barrier layer disposed between the non-conductive layer and the conductive pad.


In one aspect, a bonded structure is disclosed. The bonded structure can include a first element that includes a non-conductive structure that has a non-conductive bonding surface, a cavity that extends at least partially through a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive pad that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. An average size of the grains at the bonding interface is at least 20% greater than an average size of the grains adjacent the bottom side of the cavity. The bonded structure can include a second element that has a second conductive pad. The conductive pad of the first element and the second conductive pad of the second element are directly bonded to one another without an intervening adhesive along a bonding interface.


In one embodiment, the second element further includes a second non-conductive structure that has a second non-conductive bonding surface that is directly bonded to the non-conductive bonding surface of the first element without an intervening adhesive.


In one embodiment, an average size of the grains at the bonding interface is at least 50% greater than an average size of the grains closer to the back side.


In one embodiment, an average size of the grains at the bonding interface is at least two times greater than an average size of the grains adjacent the bottom side of the cavity.


An average size of the grains at the bonding interface can be at least three times greater than an average size of the grains adjacent the bottom side of the cavity.


In one aspect, a method for forming an element is disclosed. The method can include providing a non-conductive structure that has a first side and a second side opposite the first side. The method can include forming a cavity in the non-conductive structure. The method can include providing a conductive material in the cavity and on a portion of the first side of the non-conductive layer. The conductive material has a lower side facing a bottom side of the cavity and an upper side opposite the lower side. The method can include cold working the upper side of the conductive material to modify a grain structure of the conductive material. The cold working is conducted between about −196° C. and 50° C. The method can include removing at least a portion of the conductive material to define a conductive pad that has a conductive bonding surface.


In one embodiment, the cold working includes mechanical peening or laser peening.


In one embodiment, the cold working includes bombarding the upper side of the conductive material with metal particles, glass particles, or ceramic particles.


In one embodiment, the cold working includes decreasing a percentage of 111 crystal planes in the conductive material.


The cold working includes inducing plastic deformation in the conductive material, and causing grain sizes of the conductive material at least at the upper side to be reduced compared to prior to the cold working.


In one embodiment, the cold working produces smaller grains sizes at the upper side of the conductive material compared to at the lower side of the conductive material.


In one embodiment, the method further includes annealing the conductive material to stabilize grain sizes of the conductive material prior to cold working.


In one embodiment, the removing includes at least partially removing the portion of the conductive material prior to cold working.


The method can further include preparing the conductive bonding surface of the conductive pad and the first side of the non-conductive structure for direct bonding.


In one embodiment, the method further includes providing a barrier layer between the non-conductive structure and the conductive material.


In one embodiment, a method for forming a bonded structure includes bonding the element to a second element having a second non-conductive structure and a second conductive pad.


The bonding can include directly bonding the non-conductive structure and the second non-conductive structure.


The bonding can further include annealing the conductive pad and the second conductive pad at a temperature between 50° C. and 250° C.


The annealing can include annealing the conductive pad and the second conductive pad at a temperature between 50° C. and 150° C.


The annealing the conductive pad and the second conductive pad can cause an average grain size of the conductive material at the upper side to be larger as compared to prior to the annealing.


The annealing the conductive pad and the second conductive pad can cause an average grain size of the conductive material at the upper side to be larger than an average grain size of the conductive material at the lower side.


In one aspect, an element is disclosed. The element can include a non-conductive structure that has a non-conductive bonding surface, a cavity that at least partially extends through a portion of a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive pad that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. The conductive pad includes a lower percentage of grains with vertically oriented 111 crystal planes at the bonding surface as compared with grains adjacent to the bottom side.


In one aspect, an element is disclosed. The element can include a non-conductive structure that has a non-conductive bonding surface, a cavity that at least partially extends through a portion of a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive feature that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive feature has a bonding surface and a back side opposite the bonding surface. An average size of grains in a portion of the conductive feature near the bonding surface is less than 200 nanometer (nm).


In one embodiment, the average size of the grains in the portion of the conductive feature near the bonding surface is at least 50 nm.


In one aspect, a bonded structure is disclosed. The bonded structure can include a first element that includes a non-conductive structure that has a non-conductive bonding surface, a cavity that extends at least partially through a thickness of the non-conductive structure from the non-conductive bonding surface, and a conductive pad that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. The conductive pad includes a crystal structure with grains oriented along a 111 crystal plane. An average grain size of the conductive pad at the bonding surface is greater than an average grain size of the conductive pad at the back side. The bonded structure can include a second element that has a second conductive pad. The conductive pad of the first element and the second conductive pad of the second element are directly bonded to one another without an intervening adhesive along a bonding interface.


In one aspect, a method for forming an element is disclosed. the method can include providing a non-conductive structure that has a first side and a second side opposite the first side. The method can include forming a cavity in the first side of the non-conductive structure. The method can include providing a conductive material in the cavity and over the first side of the non-conductive structure. The method can include increasing a grain size of the conductive material by thermal annealing. The method can include forming lattice imperfections in the annealed conductive material. The method can include forming a planar bonding surface comprising a non-conductive bonding surface and a conductive bonding surface. The conductive bonding surface includes the lattice imperfections.


In one embodiment, the method further includes providing a barrier layer between the non-conductive structure and the conductive material.


In one embodiment, the method further includes singulating the element on a dicing frame.


The method can further include providing a protective layer over the element and further cleaning off the protective layer particles from singulation from the bonding surface of the singulated element and the dicing frame.


The method can further include directly bonding a cleaned singulated element to a prepared bonding surface of a second substrate to form a bonded structure.


The method can further include annealing the bonded structure at a temperature below 200° C. to electrically bond the singulated element to the second substrate.


In one embodiment, the forming the lattice imperfections comprises cold working a surface of the annealed conductive material.


In one aspect, a bonded structure is disclosed. The bonded structure can include a first element that includes a non-conductive structure that has a non-conductive bonding surface, a cavity extending at least partially through a thickness of the nonconductive structure from the non-conductive bonding surface, and a conductive pad that is disposed in the cavity. The cavity has a bottom side and a sidewall. The conductive pad has a bonding surface and a back side opposite the bonding surface. The conductive pad includes a longitudinal columnar grain structure oriented generally parallel to the non-conductive bonding surface. The bonded structure can include a second element that has a second conductive pad. The conductive pad of the first element and the second conductive pad of the second element are directly bonded to one another without an intervening adhesive along a bonding interface.


In one aspect, a bonded structure is disclosed. the bonded structure can include a first element that includes a planar conductive structure embedded in the surface of a non-conductive material that has a non-conductive bonding surface. The conductive structure has a longitudinal columnar grain structure oriented generally parallel to the non-conductive bonding surface. The bonded structure can include a second element that has a planar bonding surface. The bonding surface of the first element and the second element are directly bonded to one another without an intervening adhesive along a bonding interface.


In one aspect, a bonded structure is disclosed. The bonded structure can include a first element that includes a first conductive feature and a first non-conductive region. the bonded structure can include a second element that includes a second conductive feature that is directly bonded to the first conductive feature without an intervening adhesive and a second non-conductive region that is bonded to the first non-conductive region. The bonded first and second conductive features include grains. Each grain of the grains has a length along an bonding interface between the first and second element and a thickness perpendicular to the bonding interface. The grains have an average length that is at least 1.5 times larger than an average thickness of the grains.[0069] Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise,” “comprising,” “include,” “including” and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to.” The word “coupled”, as generally used herein, refers to two or more elements that may be either directly connected, or connected by way of one or more intermediate elements. Likewise, the word “connected”, as generally used herein, refers to two or more elements that may be either directly connected, or connected by way of one or more intermediate elements. Additionally, the words “herein,” “above,” “below,” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of this application. Moreover, as used herein, when a first element is described as being “on” or “over” a second element, the first element may be directly on or over the second element, such that the first and second elements directly contact, or the first element may be indirectly on or over the second element such that one or more elements intervene between the first and second elements. Where the context permits, words in the above Detailed Description using the singular or plural number may also include the plural or singular number respectively. The word “or” in reference to a list of two or more items, that word covers all of the following interpretations of the word: any of the items in the list, all of the items in the list, and any combination of the items in the list.


Moreover, conditional language used herein, such as, among others, “can,” “could,” “might,” “may,” “e.g.,” “for example,” “such as” and the like, unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or states. Thus, such conditional language is not generally intended to imply that features, elements and/or states are in any way required for one or more embodiments.


While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel apparatus, methods, and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the disclosure. For example, while blocks are presented in a given arrangement, alternative embodiments may perform similar functionalities with different components and/or circuit topologies, and some blocks may be deleted, moved, added, subdivided, combined, and/or modified. Each of these blocks may be implemented in a variety of different ways. Any suitable combination of the elements and acts of the various embodiments described above can be combined to provide further embodiments. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure.

Claims
  • 1. An element comprising: a non-conductive structure having a non-conductive bonding surface;a cavity at least partially extending through a portion of a thickness of the non-conductive structure from the non-conductive bonding surface, the cavity having a bottom side and a sidewall; anda conductive pad disposed in the cavity, the conductive pad having a bonding surface and a back side opposite the bonding surface, wherein the bonding surface of the conductive pad is recessed below the non-conductive bonding surface and wherein_an average size of grains of the conductive pad at the bonding surface being smaller than an average size of the grains adjacent the bottom side of the cavity.
  • 2. The element of claim 1, wherein the non-conductive structure comprises a dielectric layer, and the non-conductive bonding surface of the non-conductive structure is prepared for direct bonding.
  • 3. The element of claim 2, wherein the conductive pad is a copper (Cu) pad.
  • 4. The element of claim 3, wherein the conductive pad includes a lower percentage of grains with vertically-oriented 111 crystal planes at the bonding surface compared with adjacent to the bottom side.
  • 5. The element of claim 3, wherein the conductive pad includes a higher percentage of grains with vertically-oriented 220 crystal planes at the bonding surface compared with adjacent to the bottom side.
  • 6. The element of claim 1, wherein the average size of the grains adjacent the bottom side of the cavity is at least 3 times greater than the average size of the grains at the bonding surface.
  • 7. The element of claim 1, wherein the average size of the grains adjacent the bottom side of the cavity is at least 20 times greater than the average size of the grains at the bonding surface.
  • 8. The element of claim 1, wherein the average size of the grains adjacent the bottom side of the cavity is between 0.2 microns (μm) to 1 μm.
  • 9. The element of claim 1, wherein the average size of the grains at the bonding surface is between 30 nanometer (nm) to 200 nm.
  • 10. The element of claim 1, further comprising a barrier layer disposed between the non-conductive structure and the conductive pad.
  • 11. A bonded structure comprising: a first element including; a non-conductive structure having a non-conductive bonding surface;a cavity extending at least partially through a thickness of the non-conductive structure from the non-conductive bonding surface, the cavity having a bottom side and a sidewall; anda conductive pad disposed in the cavity, the conductive pad having a bonding surface and a back side opposite the bonding surface, wherein an average size of grains of the conductive pad at the bonding surface is different than an average size of the grains adjacent the bottom side of the cavity; anda second element having a second conductive pad,wherein the conductive pad of the first element and the second conductive pad of the second element are directly bonded to one another without an intervening adhesive along a bonding interface, wherein the second element comprises a second non-conductive bonding surface, wherein the non-conductive bonding surface is directly bonded to the second non-conductive bonding surface, and wherein at least one of the non-conductive bonding surface and the second non-conductive bonding surface comprises an activated bonding surface.
  • 12. The bonded structure of claim 11, wherein the second non-conductive bonding surface is directly bonded to the non-conductive bonding surface without an intervening adhesive.
  • 13. The bonded structure of claim 11, wherein the average size of the grains at the bonding interface is at least 50% greater than the average size of the grains adjacent the bottom side of the cavity.
  • 14. The bonded structure of claim 11, wherein the average size of the grains at the bonding interface is at least two times greater than the average size of the grains adjacent the bottom side of the cavity.
  • 15. The bonded structure of claim 14, wherein the average size of the grains at the bonding interface is at least three times greater than the average size of the grains adjacent the bottom side of the cavity.
  • 16. The bonded structure of claim 11, wherein the average size of the grains of the conductive pad at the bonding surface is at least 20% different than the average size of the grains adjacent the bottom side of the cavity.
  • 17. The bonded structure of claim 16, wherein the average size of the grains of the conductive pad at the bonding surface is at least 20% greater than the average size of the grains adjacent the bottom side of the cavity.
  • 18. The bonded structure of claim 11, wherein the activated bonding surface comprises a plasma-activated bonding surface.
  • 19. The bonded structure of claim 11, wherein the activated bonding surface comprises an amount of nitrogen that is indicative of nitrogen termination.
  • 20. The bonded structure of claim 11, wherein the activated bonding surface comprises a nitrogen-terminated inorganic non-conductive material.
  • 21. The bonded structure of claim 11, wherein the non-conductive bonding surface is directly bonded to the second non-conductive bonding surface with a covalent bond.
  • 22. A method for forming an element, the method comprising: providing a non-conductive structure having a first side and a second side opposite the first side;forming a cavity in the non-conductive structure;providing a conductive material in the cavity and on a portion of the first side of the non-conductive structure, the conductive material having a lower side facing a bottom side of the cavity and an upper side opposite the lower side;cold working the upper side of the conductive material to modify a grain structure of the conductive material, wherein the cold working is conducted between about −196° C. and 50° C.; andremoving at least a portion of the conductive material to define a conductive pad having a conductive bonding surface.
  • 23. The method of claim 22, wherein the cold working comprises mechanical peening or laser peening.
  • 24. The method of claim 22, wherein the cold working comprises bombarding the upper side of the conductive material with metal particles, glass particles, or ceramic particles.
  • 25. The method of claim 22, wherein the cold working comprises decreasing a percentage of 111 crystal planes in the conductive material.
  • 26. The method of claim 25, wherein the cold working comprises inducing plastic deformation in the conductive material, and causing grain sizes of the conductive material at least at the upper side to be reduced compared to prior to the cold working.
  • 27. The method of claim 22, wherein the cold working produces smaller grains sizes at the upper side of the conductive material compared to at the lower side of the conductive material.
  • 28. The method of claim 22, further comprising annealing the conductive material to stabilize grain sizes of the conductive material prior to cold working.
  • 29. The method of claim 22, further comprising preparing the conductive bonding surface of the conductive pad and the first side of the non-conductive structure for direct bonding.
  • 30. A method for forming a bonded structure, the method comprising bonding the element of claim 22 to a second element having a second non-conductive structure and a second conductive pad.
  • 31. The method of claim 30, wherein the bonding comprises directly bonding the non-conductive structure and the second non-conductive structure.
  • 32. The method of claim 31, wherein the bonding further comprises annealing the conductive pad and the second conductive pad at a temperature between 50°° C. and 250° C.
  • 33. The method of claim 32, wherein annealing the conductive pad and the second conductive pad causes an average grain size of the conductive material at the upper side to be larger as compared to prior to the annealing.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 63/132,334, filed Dec. 30, 2020, titled “STRUCTURE WITH CONDUCTIVE FEATURE AND METHOD OF FORMING SAME,” the entire contents of each of which are hereby incorporated herein by reference.

US Referenced Citations (703)
Number Name Date Kind
3214827 Phohofsky Nov 1965 A
3766439 Isaacson Oct 1973 A
3775844 Parks Dec 1973 A
3873889 Leyba Mar 1975 A
4225900 Ciccio et al. Sep 1980 A
4567543 Miniet Jan 1986 A
4576543 Kuchyt et al. Mar 1986 A
4695870 Patraw Sep 1987 A
4716049 Patraw Dec 1987 A
4781601 Kuhl et al. Nov 1988 A
4804132 DiFrancesco Feb 1989 A
4818728 Rai et al. Apr 1989 A
4902600 Tamagawa et al. Feb 1990 A
4924353 Patraw May 1990 A
4939568 Kato et al. Jul 1990 A
4941033 Kishida Jul 1990 A
4975079 Beaman et al. Dec 1990 A
4982265 Watanabe et al. Jan 1991 A
4991290 MacKay Feb 1991 A
4998665 Hayashi Mar 1991 A
5046238 Daigle et al. Sep 1991 A
5068714 Seipler Nov 1991 A
5083697 DiFrancesco Jan 1992 A
5087585 Hayashi Feb 1992 A
5116456 Nestor May 1992 A
5116459 Kordus et al. May 1992 A
5117282 Salatino May 1992 A
5130779 Agarwala et al. Jul 1992 A
5138438 Masayuki et al. Aug 1992 A
5148265 Khandros et al. Sep 1992 A
5148266 Khandros et al. Sep 1992 A
5172303 Bemardoni et al. Dec 1992 A
5189505 Bartelink Feb 1993 A
5196726 Nishiguchi et al. Mar 1993 A
5198888 Sugano et al. Mar 1993 A
5214308 Nishiguchi et al. May 1993 A
5220448 Vogel et al. Jun 1993 A
5220488 Denes Jun 1993 A
5222014 Lin Jun 1993 A
5224023 Smith et al. Jun 1993 A
5236118 Bower et al. Aug 1993 A
5247423 Lin et al. Sep 1993 A
5251806 Agarwala et al. Oct 1993 A
5281852 Normington Jan 1994 A
5313416 Kimura May 1994 A
5322593 Hasegawa et al. Jun 1994 A
5324892 Granier et al. Jun 1994 A
5334804 Love et al. Aug 1994 A
5334875 Sugano et al. Aug 1994 A
5341564 Akhavain et al. Aug 1994 A
5345205 Kornrumpf Sep 1994 A
5347159 Khandros et al. Sep 1994 A
5390844 DiStefano et al. Feb 1995 A
5394303 Yamaji Feb 1995 A
5397916 Normington Mar 1995 A
5397997 Tuckerman et al. Mar 1995 A
5398863 Grube et al. Mar 1995 A
5409865 Kamezos Apr 1995 A
5413952 Pages et al. May 1995 A
5422435 Takiar et al. Jun 1995 A
5426563 Moresco et al. Jun 1995 A
5440171 Miyano et al. Aug 1995 A
5442235 Parrillo et al. Aug 1995 A
5448511 Paurus et al. Sep 1995 A
5454160 Nickel Oct 1995 A
5455390 DiStefano et al. Oct 1995 A
5455740 Burns Oct 1995 A
5457879 Gurtler et al. Oct 1995 A
5466635 Lynch et al. Nov 1995 A
5479318 Burns Dec 1995 A
5489749 DiStefano et al. Feb 1996 A
5489804 Pasch Feb 1996 A
5491302 DiStefano et al. Feb 1996 A
5501003 Bernstein Mar 1996 A
5503704 Bower et al. Apr 1996 A
5516727 Broom May 1996 A
5518964 DiStefano et al. May 1996 A
5536909 DiStefano et al. Jul 1996 A
5539153 Schwiebert et al. Jul 1996 A
5541525 Wood et al. Jul 1996 A
5552963 Burns Sep 1996 A
5587342 Lin et al. Dec 1996 A
5610431 Martin Mar 1997 A
5615824 Fjelstad et al. Apr 1997 A
5640052 Tsukamoto Jun 1997 A
5646446 Nicewarner, Jr. et al. Jul 1997 A
5656550 Tsuji et al. Aug 1997 A
5659952 Kovac et al. Aug 1997 A
5679977 Khandros et al. Oct 1997 A
5689091 Hamzehdoost et al. Nov 1997 A
5696406 Ueno Dec 1997 A
5717556 Yanagida Feb 1998 A
5731709 Pastore et al. Mar 1998 A
5734199 Kawakita et al. Mar 1998 A
5739585 Akram et al. Apr 1998 A
5753536 Sugiyama et al. May 1998 A
5762845 Crumly Jun 1998 A
5771555 Eda et al. Jun 1998 A
5776797 Nicewarner, Jr. et al. Jul 1998 A
5777386 Higashi et al. Jul 1998 A
5786271 Ohida et al. Jul 1998 A
5789815 Tessier et al. Aug 1998 A
5798286 Faraci et al. Aug 1998 A
5802699 Fjelstad et al. Sep 1998 A
5805422 Otake et al. Sep 1998 A
5811982 Beaman et al. Sep 1998 A
5821692 Rogers et al. Oct 1998 A
5854507 Miremadi et al. Dec 1998 A
5861666 Bellaar Jan 1999 A
5866942 Suzuki et al. Feb 1999 A
5956234 Mueller Sep 1999 A
5973391 Bischoff et al. Oct 1999 A
5980270 Fjelstad et al. Nov 1999 A
5985692 Poenisch et al. Nov 1999 A
5985739 Plettner et al. Nov 1999 A
5998808 Matsushita Dec 1999 A
6001671 Fjelstad Dec 1999 A
6008126 Leedy Dec 1999 A
6032359 Carroll Mar 2000 A
6052287 Palmer et al. Apr 2000 A
6054756 DiStefano et al. Apr 2000 A
6059984 Cohen et al. May 2000 A
6061245 Ingraham et al. May 2000 A
6063968 Hubner et al. May 2000 A
6071761 Jacobs Jun 2000 A
6080640 Gardner et al. Jun 2000 A
6097096 Gardner et al. Aug 2000 A
6117784 Uzoh Sep 2000 A
6123825 Uzoh et al. Sep 2000 A
6147000 You et al. Nov 2000 A
6157075 Karavakis et al. Dec 2000 A
6175159 Sasaki et al. Jan 2001 B1
6177636 Fjelstad et al. Jan 2001 B1
6202297 Faraci et al. Mar 2001 B1
6216941 Yokoyama et al. Apr 2001 B1
6217972 Beroz et al. Apr 2001 B1
6218302 Braeckelmann et al. Apr 2001 B1
6229220 Saitoh et al. May 2001 B1
6232150 Lin et al. May 2001 B1
6235996 Farooq et al. May 2001 B1
6258625 Brofman et al. Jul 2001 B1
6259160 Lopatin et al. Jul 2001 B1
6265775 Seyyedy Jul 2001 B1
6297072 Tilmans et al. Oct 2001 B1
6300679 Mukerji et al. Oct 2001 B1
6307260 Smith et al. Oct 2001 B1
6316786 Mueller et al. Nov 2001 B1
6322903 Siniaguine et al. Nov 2001 B1
6326555 McCormack et al. Dec 2001 B1
6329594 Sturcken Dec 2001 B1
6330272 Lomp Dec 2001 B1
6332270 Beaman et al. Dec 2001 B2
6333120 DeHaven et al. Dec 2001 B1
6333206 Ito et al. Dec 2001 B1
6335571 Capote et al. Jan 2002 B1
6348709 Graettinger et al. Feb 2002 B1
6358627 Benenati et al. Mar 2002 B2
6362525 Rahim Mar 2002 B1
6374770 Lee Apr 2002 B1
6396155 Nukiwa et al. May 2002 B1
6409904 Uzoh et al. Jun 2002 B1
6423640 Lee et al. Jul 2002 B1
6455785 Sakurai et al. Sep 2002 B1
6458411 Goossen et al. Oct 2002 B1
6465892 Suga Oct 2002 B1
6469394 Wong et al. Oct 2002 B1
6495914 Sekine et al. Dec 2002 B1
6514847 Ohsawa et al. Feb 2003 B1
6515355 Jiang et al. Feb 2003 B1
6522018 Tay et al. Feb 2003 B1
6528894 Akram et al. Mar 2003 B1
6545228 Hashimoto Apr 2003 B2
6550666 Chew et al. Apr 2003 B2
6552436 Burnette et al. Apr 2003 B2
6555917 Heo Apr 2003 B1
6555918 Masuda et al. Apr 2003 B2
6560117 Moon May 2003 B2
6578754 Tung Jun 2003 B1
6579744 Jiang Jun 2003 B1
6583515 James et al. Jun 2003 B1
6589813 Park Jul 2003 B1
6589870 Katoh et al. Jul 2003 B1
6592109 Yamaguchi et al. Jul 2003 B2
6600224 Farquhar et al. Jul 2003 B1
6624003 Rice Sep 2003 B1
6624653 Cram Sep 2003 B1
6627814 Stark Sep 2003 B1
6632377 Brusic et al. Oct 2003 B1
6647310 Yi et al. Nov 2003 B1
6648213 Patterson et al. Nov 2003 B1
6660564 Brady Dec 2003 B2
6664637 Jimarez et al. Dec 2003 B2
6667225 Hau-Riege et al. Dec 2003 B2
6681982 Tung Jan 2004 B2
6734539 Degani et al. May 2004 B2
6734556 Shibata May 2004 B2
6767819 Lutz Jul 2004 B2
6782610 Lijima et al. Aug 2004 B1
6815252 Pendse Nov 2004 B2
6822336 Kurita Nov 2004 B2
6828686 Park Dec 2004 B2
6837979 Uzoh et al. Jan 2005 B2
6852564 Ohuchi et al. Feb 2005 B2
6864585 Enquist Mar 2005 B2
6869750 Zhang et al. Mar 2005 B2
6870274 Huang et al. Mar 2005 B2
6875638 Yoneda et al. Apr 2005 B2
6887769 Kellar et al. May 2005 B2
6888255 Murtuza et al. May 2005 B2
6902869 Appelt et al. Jun 2005 B2
6902987 Tong et al. Jun 2005 B1
6906418 Hiatt et al. Jun 2005 B2
6908027 Tolchinsky et al. Jun 2005 B2
6909194 Farnworth et al. Jun 2005 B2
6956165 Hata et al. Oct 2005 B1
6962835 Tong et al. Nov 2005 B2
6965166 Hikita et al. Nov 2005 B2
6974769 Basol et al. Dec 2005 B2
6992379 Alcoe et al. Jan 2006 B2
6995044 Yoneda et al. Feb 2006 B2
6995469 Hatakeyama Feb 2006 B2
7043831 Farnworth et al. May 2006 B1
7045453 Canaperi et al. May 2006 B2
7078811 Suga Jul 2006 B2
7105980 Abbott et al. Sep 2006 B2
7109063 Jiang Sep 2006 B2
7115495 Wark et al. Oct 2006 B2
7125789 Tellkamp et al. Oct 2006 B2
7126212 Enquist et al. Oct 2006 B2
7176043 Haba et al. Feb 2007 B2
7183190 Saijo et al. Feb 2007 B2
7193423 Dalton et al. Mar 2007 B1
7214887 Higashida et al. May 2007 B2
7238919 Kaneko et al. Jul 2007 B2
7247508 Higashitani et al. Jul 2007 B2
7354798 Pogge et al. Apr 2008 B2
7361285 Kim Apr 2008 B2
7382049 Ho et al. Jun 2008 B2
7449099 Mayer et al. Nov 2008 B1
7485968 Enquist et al. Feb 2009 B2
7569935 Fan Aug 2009 B1
7598613 Tanida et al. Oct 2009 B2
7745943 Haba et al. Jun 2010 B2
7750488 Patti et al. Jul 2010 B2
7803693 Trezza Sep 2010 B2
7829265 Kitada et al. Nov 2010 B2
7901989 Haba et al. Mar 2011 B2
7911805 Haba Mar 2011 B2
7998335 Feeney et al. Aug 2011 B2
8039966 Yang et al. Oct 2011 B2
8101858 Hannour et al. Jan 2012 B2
8115310 Masumoto et al. Feb 2012 B2
8168532 Haneda et al. May 2012 B2
8183127 Patti et al. May 2012 B2
8241961 Kim et al. Aug 2012 B2
8242600 Yang et al. Aug 2012 B2
8314007 Vaufredaz Nov 2012 B2
8349635 Gan et al. Jan 2013 B1
8377798 Peng et al. Feb 2013 B2
8435421 Keleher et al. May 2013 B2
8441131 Ryan May 2013 B2
8476146 Chen et al. Jul 2013 B2
8476165 Trickett et al. Jul 2013 B2
8482132 Yang et al. Jul 2013 B2
8501537 Sadaka et al. Aug 2013 B2
8524533 Tong et al. Sep 2013 B2
8580607 Haba Nov 2013 B2
8620164 Heck et al. Dec 2013 B2
8647987 Yang et al. Feb 2014 B2
8697493 Sadaka Apr 2014 B2
8716105 Sadaka et al. May 2014 B2
8728934 Uzho et al. May 2014 B2
8802538 Liu Aug 2014 B1
8809123 Liu et al. Aug 2014 B2
8841002 Tong Sep 2014 B2
8988299 Kam et al. Mar 2015 B2
9000600 Uzoh et al. Apr 2015 B2
9028755 Itoh May 2015 B2
9093350 Endo et al. Jul 2015 B2
9123703 Uzoh et al. Sep 2015 B2
9142517 Liu et al. Sep 2015 B2
9147650 Hagimoto et al. Sep 2015 B2
9171756 Enquist et al. Oct 2015 B2
9184125 Enquist et al. Nov 2015 B2
9224704 Landru Dec 2015 B2
9230941 Chen et al. Jan 2016 B2
9257399 Kuang et al. Feb 2016 B2
9269612 Chen et al. Feb 2016 B2
9299736 Chen et al. Mar 2016 B2
9312229 Chen et al. Apr 2016 B2
9318385 Uzoh et al. Apr 2016 B2
9331149 Tong et al. May 2016 B2
9337235 Chen et al. May 2016 B2
9343330 Brusic et al. May 2016 B2
9349669 Uzoh et al. May 2016 B2
9368866 Yu Jun 2016 B2
9385024 Tong et al. Jul 2016 B2
9394161 Cheng et al. Jul 2016 B2
9431368 Enquist et al. Aug 2016 B2
9433093 Uzoh Aug 2016 B2
9437572 Chen et al. Sep 2016 B2
9443796 Chou et al. Sep 2016 B2
9461007 Chun et al. Oct 2016 B2
9496239 Edelstein et al. Nov 2016 B1
9536848 England et al. Jan 2017 B2
9559081 Lai et al. Jan 2017 B1
9620481 Edelstein et al. Apr 2017 B2
9633971 Uzoh Apr 2017 B2
9656852 Cheng et al. May 2017 B2
9666573 Sukekawa May 2017 B1
9723716 Meinhold Aug 2017 B2
9728521 Tsai et al. Aug 2017 B2
9741620 Uzoh et al. Aug 2017 B2
9799587 Fujii et al. Oct 2017 B2
9852988 Enquist et al. Dec 2017 B2
9881882 Hsu et al. Jan 2018 B2
9893004 Yazdani Feb 2018 B2
9899442 Katkar Feb 2018 B2
9929050 Lin Mar 2018 B2
9941241 Edelstein et al. Apr 2018 B2
9941243 Kim et al. Apr 2018 B2
9953941 Enquist Apr 2018 B2
9960142 Chen et al. May 2018 B2
10002844 Wang et al. Jun 2018 B1
10026605 Doub et al. Jul 2018 B2
10075657 Fahim et al. Sep 2018 B2
10147641 Enquist et al. Dec 2018 B2
10204893 Uzoh et al. Feb 2019 B2
10262963 Enquist Apr 2019 B2
10269708 Enquist et al. Apr 2019 B2
10269756 Uzoh Apr 2019 B2
10276619 Kao et al. Apr 2019 B2
10276909 Huang et al. Apr 2019 B2
10314175 Sato et al. Jun 2019 B2
10418277 Cheng et al. Sep 2019 B2
10434749 Tong et al. Oct 2019 B2
10446456 Shen et al. Oct 2019 B2
10446487 Huang et al. Oct 2019 B2
10446532 Uzoh et al. Oct 2019 B2
10508030 Katkar et al. Dec 2019 B2
10515913 Katkar et al. Dec 2019 B2
10522499 Enquist et al. Dec 2019 B2
10535626 Uzoh et al. Jan 2020 B2
10707087 Uzoh et al. Jul 2020 B2
10721822 Sato et al. Jul 2020 B2
10784191 Huang et al. Sep 2020 B2
10790262 Uzoh et al. Sep 2020 B2
10840135 Uzoh Nov 2020 B2
10840205 Fountain, Jr. et al. Nov 2020 B2
10854578 Morein Dec 2020 B2
10879212 Uzoh et al. Dec 2020 B2
10886177 DeLaCruz et al. Jan 2021 B2
10886250 Uzoh Jan 2021 B2
10892246 Uzoh Jan 2021 B2
10908173 Yamasaki et al. Feb 2021 B2
10923408 Huang et al. Feb 2021 B2
10923413 DeLaCruz Feb 2021 B2
10937755 Shah et al. Mar 2021 B2
10950547 Mohammed et al. Mar 2021 B2
10964664 Mandalapu et al. Mar 2021 B2
10985133 Uzoh Apr 2021 B2
10991804 DeLaCruz et al. Apr 2021 B2
10998292 Lee et al. May 2021 B2
11004757 Katkar et al. May 2021 B2
11011494 Gao et al. May 2021 B2
11011503 Wang et al. May 2021 B2
11031285 Katkar et al. Jun 2021 B2
11056348 Theil Jul 2021 B2
11088099 Katkar et al. Aug 2021 B2
11127738 DeLaCruz et al. Sep 2021 B2
11158606 Gao et al. Oct 2021 B2
11171117 Gao et al. Nov 2021 B2
11176450 Teig et al. Nov 2021 B2
11244920 Uzoh Feb 2022 B2
11256004 Haba et al. Feb 2022 B2
11264357 DeLaCruz et al. Mar 2022 B1
11276676 Enquist et al. Mar 2022 B2
11329034 Tao et al. May 2022 B2
11348898 DeLaCruz et al. May 2022 B2
11355443 Huang et al. Jun 2022 B2
11515279 Uzoh et al. Nov 2022 B2
11769747 Sawada Sep 2023 B2
11973056 Uzoh Apr 2024 B2
12027487 Uzoh Jul 2024 B2
20010008309 Iijima et al. Jul 2001 A1
20010030061 Yoneda Oct 2001 A1
20020000328 Motomura et al. Jan 2002 A1
20020003307 Suga Jan 2002 A1
20020025665 Juengling Feb 2002 A1
20020033412 Tung Mar 2002 A1
20020047208 Uzoh et al. Apr 2002 A1
20020056906 Kajiwara et al. May 2002 A1
20020074641 Towle et al. Jun 2002 A1
20020074670 Suga Jun 2002 A1
20020090756 Tago et al. Jul 2002 A1
20020094661 Enquist et al. Jul 2002 A1
20020125571 Corisis et al. Sep 2002 A1
20020153602 Tay et al. Oct 2002 A1
20020155661 Massingill et al. Oct 2002 A1
20020185735 Sakurai et al. Dec 2002 A1
20020190107 Shah et al. Dec 2002 A1
20030001286 Kajiwara et al. Jan 2003 A1
20030019568 Liu et al. Jan 2003 A1
20030075791 Shibata Apr 2003 A1
20030082846 Yoneda et al. May 2003 A1
20030092220 Akram May 2003 A1
20030094700 Aiba et al. May 2003 A1
20030107118 Pflughaupt et al. Jun 2003 A1
20030127734 Lee et al. Jul 2003 A1
20030132518 Castro Jul 2003 A1
20030157748 Kim et al. Aug 2003 A1
20030164540 Lee et al. Sep 2003 A1
20030189260 Tong et al. Oct 2003 A1
20030196833 Fujii et al. Oct 2003 A1
20030234453 Liu et al. Dec 2003 A1
20040031972 Pflughaupt et al. Feb 2004 A1
20040052390 Morales et al. Mar 2004 A1
20040052930 Basol et al. Mar 2004 A1
20040084414 Sakai et al. May 2004 A1
20040087057 Wang et al. May 2004 A1
20040126927 Lin et al. Jul 2004 A1
20040132533 Leifer Jul 2004 A1
20040135243 Aoyagi Jul 2004 A1
20040155358 Iijima Aug 2004 A1
20040173900 Chen et al. Sep 2004 A1
20040201096 Iijima et al. Oct 2004 A1
20040224441 Saito Nov 2004 A1
20040232533 Hatakeyama Nov 2004 A1
20040235603 Peck Nov 2004 A1
20040238492 Catabay et al. Dec 2004 A1
20040238936 Rumer et al. Dec 2004 A1
20040245213 Fukase et al. Dec 2004 A1
20040262778 Hua Dec 2004 A1
20050093164 Standing May 2005 A1
20050097727 Lijima et al. May 2005 A1
20050101136 Mori May 2005 A1
20050116326 Haba et al. Jun 2005 A1
20050121784 Standing Jun 2005 A1
20050124091 Fukase et al. Jun 2005 A1
20050133572 Brese et al. Jun 2005 A1
20050150684 Hashimoto Jul 2005 A1
20050194695 Lin et al. Sep 2005 A1
20050266670 Lin et al. Dec 2005 A1
20050274227 Aggarwal et al. Dec 2005 A1
20050284658 Kubota et al. Dec 2005 A1
20050285246 Haba et al. Dec 2005 A1
20060024950 Choi et al. Feb 2006 A1
20060055032 Chang et al. Mar 2006 A1
20060057945 Hsu et al. Mar 2006 A1
20060091538 Kabadi May 2006 A1
20060138647 Crisp et al. Jun 2006 A1
20060220197 Kobrinsky et al. Oct 2006 A1
20060220259 Chen et al. Oct 2006 A1
20060254502 Garrou et al. Nov 2006 A1
20070017090 Sakai et al. Jan 2007 A1
20070045869 Ho et al. Mar 2007 A1
20070096294 Ikeda et al. May 2007 A1
20070111386 Kim et al. May 2007 A1
20070138649 Knights Jun 2007 A1
20070141750 Iwasaki et al. Jun 2007 A1
20070164447 Ho et al. Jul 2007 A1
20070173900 Siegel et al. Jul 2007 A1
20070209199 Lijima et al. Sep 2007 A1
20070216012 Hozoji et al. Sep 2007 A1
20070230153 Tanida et al. Oct 2007 A1
20070232023 Tong et al. Oct 2007 A1
20070292988 Nakabayashi Dec 2007 A1
20080003402 Haba et al. Jan 2008 A1
20080067661 Kawabata Mar 2008 A1
20080073795 Kohl et al. Mar 2008 A1
20080122092 Hong May 2008 A1
20080138961 Lee Jun 2008 A1
20080145607 Kajiwara et al. Jun 2008 A1
20080220373 Choi et al. Sep 2008 A1
20080237053 Andricacos et al. Oct 2008 A1
20080251940 Lee et al. Oct 2008 A1
20080258299 Kang et al. Oct 2008 A1
20080268570 Shen et al. Oct 2008 A1
20090002964 Haba Jan 2009 A1
20090039507 Funaki Feb 2009 A1
20090039528 Haba et al. Feb 2009 A1
20090071707 Endo et al. Mar 2009 A1
20090071837 Fredenberg et al. Mar 2009 A1
20090091024 Zeng et al. Apr 2009 A1
20090115047 Haba et al. May 2009 A1
20090121348 Chang May 2009 A1
20090146303 Kwon Jun 2009 A1
20090148594 Moran et al. Jun 2009 A1
20090188706 Endo Jul 2009 A1
20090197408 Lehr et al. Aug 2009 A1
20090200668 Yang et al. Aug 2009 A1
20090243095 Fujita et al. Oct 2009 A1
20090294056 Yoshimura et al. Dec 2009 A1
20090302466 Shoji et al. Dec 2009 A1
20100006987 Murugan et al. Jan 2010 A1
20100044860 Haba et al. Feb 2010 A1
20100052189 Sakurai et al. Mar 2010 A1
20100093131 Maeda Apr 2010 A1
20100102452 Nakao Apr 2010 A1
20100164355 Son et al. Jul 2010 A1
20100255262 Chen et al. Oct 2010 A1
20100301485 Sekine et al. Dec 2010 A1
20100327443 Kim Dec 2010 A1
20110008632 Zheng et al. Jan 2011 A1
20110012263 Hata et al. Jan 2011 A1
20110074027 Kwon Mar 2011 A1
20110074040 Frank et al. Mar 2011 A1
20110084403 Yang et al. Apr 2011 A1
20110278063 Chen et al. Nov 2011 A1
20120025365 Haba Feb 2012 A1
20120042515 Shoji et al. Feb 2012 A1
20120211549 Yamakami et al. Aug 2012 A1
20120211894 Aoyagi Aug 2012 A1
20120212384 Kam et al. Aug 2012 A1
20120217165 Feng et al. Aug 2012 A1
20120248618 Akino Oct 2012 A1
20120273936 Uang et al. Nov 2012 A1
20120305298 Uang et al. Dec 2012 A1
20130009321 Kagawa et al. Jan 2013 A1
20130020704 Sadaka Jan 2013 A1
20130040451 Dragoi et al. Feb 2013 A1
20130099376 Haba Apr 2013 A1
20130136917 Dastoor et al. May 2013 A1
20130221527 Yang et al. Aug 2013 A1
20130252399 Leduc Sep 2013 A1
20130270328 Di Cioccio et al. Oct 2013 A1
20130320556 Liu et al. Dec 2013 A1
20140001636 Saito et al. Jan 2014 A1
20140007351 Cohen Jan 2014 A1
20140077351 Haba Mar 2014 A1
20140153210 Uzoh Jun 2014 A1
20140175655 Chen et al. Jun 2014 A1
20140191418 Cheng et al. Jul 2014 A1
20140225795 Yu Aug 2014 A1
20140231996 Fujisawa Aug 2014 A1
20140252635 Tran et al. Sep 2014 A1
20140264948 Chou et al. Sep 2014 A1
20140353828 Edelstein et al. Dec 2014 A1
20150014399 Ogashiwa et al. Jan 2015 A1
20150027755 Tsujimoto et al. Jan 2015 A1
20150064498 Tong Mar 2015 A1
20150108644 Kuang et al. Apr 2015 A1
20150206823 Lin et al. Jul 2015 A1
20150206840 Lin Jul 2015 A1
20150245474 Takahashi et al. Aug 2015 A1
20150279888 Chen et al. Oct 2015 A1
20150340269 Rivoire et al. Nov 2015 A1
20150357538 Hsing Chen et al. Dec 2015 A1
20150364434 Chen et al. Dec 2015 A1
20150380368 Momose et al. Dec 2015 A1
20160020183 Chuang et al. Jan 2016 A1
20160049384 Lu et al. Feb 2016 A1
20160133598 Baudin et al. May 2016 A1
20160168715 Ma et al. Jun 2016 A1
20160190103 Kabe et al. Jun 2016 A1
20160192496 Wang et al. Jun 2016 A1
20160247778 Katkar et al. Aug 2016 A1
20160276383 Chuang et al. Sep 2016 A1
20160343682 Kawasaki Nov 2016 A1
20170025381 Tsai Jan 2017 A1
20170047307 Uzoh Feb 2017 A1
20170069575 Haba et al. Mar 2017 A1
20170086320 Barber Mar 2017 A1
20170141079 Kao et al. May 2017 A1
20170194271 Hsu et al. Jul 2017 A1
20170271242 Lo Sep 2017 A1
20170330855 Tung et al. Nov 2017 A1
20170355040 Utsumi et al. Dec 2017 A1
20180151523 Chen et al. May 2018 A1
20180175012 Wu et al. Jun 2018 A1
20180182639 Uzoh et al. Jun 2018 A1
20180182665 Uzoh et al. Jun 2018 A1
20180182666 Uzoh et al. Jun 2018 A1
20180190580 Haba et al. Jul 2018 A1
20180190583 DeLaCruz et al. Jul 2018 A1
20180190876 Liu et al. Jul 2018 A1
20180219038 Gambino et al. Aug 2018 A1
20180273377 Katkar et al. Sep 2018 A1
20180295718 Uzoh et al. Oct 2018 A1
20180323177 Yu et al. Nov 2018 A1
20180323227 Zhang et al. Nov 2018 A1
20180331066 Uzoh et al. Nov 2018 A1
20180350674 Uzoh Dec 2018 A1
20190096741 Uzoh et al. Mar 2019 A1
20190115277 Yu et al. Apr 2019 A1
20190131277 Yang et al. May 2019 A1
20190198407 Huang et al. Jun 2019 A1
20190198409 Katkar et al. Jun 2019 A1
20190244909 Chiu Aug 2019 A1
20190265411 Huang et al. Aug 2019 A1
20190295954 Nomura et al. Sep 2019 A1
20190319007 Uzoh et al. Oct 2019 A1
20190333550 Fisch Oct 2019 A1
20190348336 Katkar et al. Nov 2019 A1
20190385935 Gao et al. Dec 2019 A1
20190385966 Gao et al. Dec 2019 A1
20190393086 Uzoh Dec 2019 A1
20200006280 Shah et al. Jan 2020 A1
20200013637 Haba Jan 2020 A1
20200013765 Fountain, Jr. et al. Jan 2020 A1
20200035641 Fountain, Jr. et al. Jan 2020 A1
20200075520 Gao et al. Mar 2020 A1
20200075534 Gao Mar 2020 A1
20200075553 DeLaCruz et al. Mar 2020 A1
20200098711 Choi Mar 2020 A1
20200126906 Uzoh et al. Apr 2020 A1
20200194396 Uzoh Jun 2020 A1
20200227367 Haba et al. Jul 2020 A1
20200243380 Uzoh et al. Jul 2020 A1
20200279821 Haba et al. Sep 2020 A1
20200294908 Haba et al. Sep 2020 A1
20200328162 Haba et al. Oct 2020 A1
20200328164 DeLaCruz et al. Oct 2020 A1
20200328165 DeLaCruz et al. Oct 2020 A1
20200335408 Gao et al. Oct 2020 A1
20200365575 Uzoh et al. Nov 2020 A1
20200371154 DeLaCruz et al. Nov 2020 A1
20200381389 Uzoh et al. Dec 2020 A1
20200395321 Katkar et al. Dec 2020 A1
20200411483 Uzoh et al. Dec 2020 A1
20210028136 Said et al. Jan 2021 A1
20210028144 Lu Jan 2021 A1
20210098411 Liff et al. Apr 2021 A1
20210098412 Haba et al. Apr 2021 A1
20210118864 DeLaCruz et al. Apr 2021 A1
20210143125 DeLaCruz et al. May 2021 A1
20210181510 Katkar et al. Jun 2021 A1
20210193603 Katkar et al. Jun 2021 A1
20210193624 DeLaCruz et al. Jun 2021 A1
20210193625 DeLaCruz et al. Jun 2021 A1
20210234070 Brueck et al. Jul 2021 A1
20210242152 Fountain, Jr. et al. Aug 2021 A1
20210296282 Gao et al. Sep 2021 A1
20210305202 Uzoh et al. Sep 2021 A1
20210335737 Katkar et al. Oct 2021 A1
20210366820 Uzoh Nov 2021 A1
20210407941 Haba Dec 2021 A1
20220077063 Haba Mar 2022 A1
20220077087 Haba Mar 2022 A1
20220130787 Uzoh Apr 2022 A1
20220139867 Uzoh May 2022 A1
20220139869 Gao et al. May 2022 A1
20220149002 Hou May 2022 A1
20220157752 Bourjot et al. May 2022 A1
20220165692 Uzoh et al. May 2022 A1
20220208650 Gao et al. Jun 2022 A1
20220208723 Katkar et al. Jun 2022 A1
20220246497 Fountain, Jr. et al. Aug 2022 A1
20220285303 Mirkarimi et al. Sep 2022 A1
20220319901 Suwito et al. Oct 2022 A1
20220320035 Uzoh et al. Oct 2022 A1
20220320036 Gao et al. Oct 2022 A1
20230005849 Chuang Jan 2023 A1
20230005850 Fountain, Jr. Jan 2023 A1
20230019869 Mirkarimi et al. Jan 2023 A1
20230036441 Haba et al. Feb 2023 A1
20230067677 Lee et al. Mar 2023 A1
20230069183 Haba Mar 2023 A1
20230100032 Haba et al. Mar 2023 A1
20230115122 Uzoh et al. Apr 2023 A1
20230122531 Uzoh Apr 2023 A1
20230123423 Gao et al. Apr 2023 A1
20230125395 Gao et al. Apr 2023 A1
20230130259 Haba et al. Apr 2023 A1
20230132632 Katkar et al. May 2023 A1
20230140107 Uzoh et al. May 2023 A1
20230142680 Guevara et al. May 2023 A1
20230154816 Haba et al. May 2023 A1
20230154828 Haba et al. May 2023 A1
20230187264 Uzoh et al. Jun 2023 A1
20230187317 Uzoh Jun 2023 A1
20230187412 Gao et al. Jun 2023 A1
20230197453 Fountain, Jr. et al. Jun 2023 A1
20230197496 Theil Jun 2023 A1
20230197559 Haba et al. Jun 2023 A1
20230197560 Katkar et al. Jun 2023 A1
20230197655 Theil et al. Jun 2023 A1
20230207402 Fountain, Jr. et al. Jun 2023 A1
20230207437 Haba Jun 2023 A1
20230207474 Uzoh et al. Jun 2023 A1
20230207514 Gao et al. Jun 2023 A1
20230215836 Haba et al. Jul 2023 A1
20230245950 Haba et al. Aug 2023 A1
20230268300 Uzoh et al. Aug 2023 A1
20230268307 Uzoh et al. Aug 2023 A1
20230299029 Theil et al. Sep 2023 A1
20230343734 Uzoh et al. Oct 2023 A1
20230360950 Gao Nov 2023 A1
20230361074 Uzoh et al. Nov 2023 A1
20230369136 Uzoh et al. Nov 2023 A1
20230375613 Haba et al. Nov 2023 A1
20240038702 Uzoh Feb 2024 A1
20240055407 Workman et al. Feb 2024 A1
20240079376 Suwito et al. Mar 2024 A1
20240105674 Uzoh et al. Mar 2024 A1
20240113059 Uzoh et al. Apr 2024 A1
20240213191 Theil et al. Jun 2024 A1
20240213210 Haba et al. Jun 2024 A1
20240217210 Zhao et al. Jul 2024 A1
20240222239 Gao et al. Jul 2024 A1
20240222315 Uzoh Jul 2024 A1
20240222319 Gao et al. Jul 2024 A1
20240266255 Haba et al. Aug 2024 A1
Foreign Referenced Citations (84)
Number Date Country
1112286 Nov 1995 CN
1942057 Apr 2007 CN
101002313 Jul 2007 CN
203013712 Jun 2013 CN
103531492 Jan 2014 CN
106711131 May 2017 CN
107256852 Sep 2019 CN
102006006825 Aug 2007 DE
0615283 Sep 1994 EP
1091406 Apr 2001 EP
1255295 Nov 2002 EP
1387402 Feb 2004 EP
1471570 Oct 2004 EP
1602749 Dec 2005 EP
54148484 Nov 1979 JP
57107501 Jul 1982 JP
62117346 May 1987 JP
63153889 Jun 1988 JP
64-086527 Mar 1989 JP
H04-151843 May 1992 JP
06268015 Sep 1994 JP
7211722 Aug 1995 JP
H08-31835 Feb 1996 JP
H10-013003 Jan 1998 JP
H10-125734 May 1998 JP
H11-087556 Mar 1999 JP
H11-97576 Apr 1999 JP
H11-111886 Apr 1999 JP
2000-100869 Apr 2000 JP
2000-183061 Jun 2000 JP
2000-277649 Oct 2000 JP
2001-118872 Apr 2001 JP
2001-244365 Sep 2001 JP
2002-016096 Jan 2002 JP
2002-043506 Feb 2002 JP
2002-124548 Apr 2002 JP
2002-261204 Sep 2002 JP
2002-313993 Oct 2002 JP
2002-313996 Oct 2002 JP
2002-353416 Dec 2002 JP
2002-359471 Dec 2002 JP
2003-007768 Jan 2003 JP
2003-037135 Feb 2003 JP
2003-051665 Feb 2003 JP
2003-092472 Mar 2003 JP
2003-124250 Apr 2003 JP
2004-128230 Apr 2004 JP
2004-221450 Aug 2004 JP
2004-273957 Sep 2004 JP
2004-342802 Dec 2004 JP
2004-349390 Dec 2004 JP
2005-026645 Jan 2005 JP
2005-032964 Feb 2005 JP
2005-045191 Feb 2005 JP
2005-072270 Mar 2005 JP
2005-093512 Apr 2005 JP
2005-123547 May 2005 JP
2005-216696 Aug 2005 JP
2005-243761 Sep 2005 JP
2005-285986 Oct 2005 JP
2006-005322 Jan 2006 JP
2007-023338 Feb 2007 JP
2007-129207 May 2007 JP
2007-242900 Sep 2007 JP
2007-266555 Oct 2007 JP
2009-177118 Jun 2009 JP
2010-521587 Jun 2010 JP
2013-033786 Feb 2013 JP
2016-21497 Feb 2016 JP
2018-129475 Aug 2018 JP
2018-160519 Oct 2018 JP
10-2008-0050129 Jun 2008 KR
10-2016-0066272 Jun 2016 KR
WO 2001041207 Jun 2001 WO
WO 2005043584 May 2005 WO
WO 2005122706 Dec 2005 WO
WO 2007069606 May 2007 WO
WO 2008000020 Jan 2008 WO
WO 2008076428 Jun 2008 WO
WO 2009017758 Feb 2009 WO
WO 2009020572 Feb 2009 WO
WO 2009021266 Feb 2009 WO
WO 2016136064 Sep 2016 WO
WO-2022147429 Jul 2022 WO
Non-Patent Literature Citations (55)
Entry
Akolkar, R., “Current status and advances in Damascene Electrodeposition,” Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry, 2017, 8 pages.
Che, F.X. et al., “Study on Cu protrusion of through-silicon via,” IEEE Transactions on Components, Packaging and Manufacturing Technology, May 2013, vol. 3, No. 5, pp. 732-739.
Dela Pena, Eden M. et al., “Electrodeposited copper using direct and pulse currents from electrolytes containing low concentration of additives,” School of Chemical and Process Engineering, University of Strathclyde, 2018 Surface and Coating Technology, 40 pages.
De Messemaeker, Joke et al., “Correlation between Cu microstructure and TSV Cu pumping,” 2014 Electronic Components & Technology Conference, pp. 613-619.
Di Cioccio, L. et al., “An overview of patterned metal/dielectric surface bonding: Mechanism, alignment and characterization,” Journal of The Electrochemical Society, 2011, vol. 158, No. 6, pp. P81-P86.
Ganesan, Kousik, “Capable copper electrodeposition process for integrated circuit—substrate packaging manufacturing,” A dissertation presented in partial fulfillment of the requirments for the degree Doctor of Philosophy, Arizona State University, May 2018, 320 pages. (2 parts).
Gondcharton, P. et al., “Kinetics of low temperature direct copper-copper bonding,” Microsyst Technol, 2015, vol. 21, pp. 995-1001.
Heryanto, A. et al., “Effect of copper TSV annealing on via protrustion for TSV wafer fabrication,” Journal of Electronic Materials, 2012, vol. 41, No. 9, pp. 2533-2542.
Hobbs, Anthony et al., “Evolution of grain and micro-void structure in electroplated copper interconnects,” Materials Transactions, 2002, vol. 43, No. 7, pp. 1629-1632.
Huang, Q., “Effects of impurity elements on isothermal grain growth of electroplated copper,” Journal of The Electrochemical Society, 2018, vol. 165, No. 7, pp. D251-D257.
Huang, Q., “Impurities in the electroplated sub-50 nm Cu lines: The effects of the plating additives,” Journal of the Electrochemical Society, 2014, vol. 161, No. 9, pp. D388-D394.
Jiang, T. et al., “Plasticity mechanism for copper extrusion in through-silicon vias for three-dimensional interconnects,” Applied Physics Letters, 2013, vol. 103, pp. 211906-1-211906-5.
Juang, Jing-Ye et al., “Copper-to-copper direct bonding on highly (111)-oriented nanotwinned copper in no-vacuum ambient,” Scientific Reports, Sep. 17, 2018, vol. 8, 11 pages.
Ker, Ming-Dou et al., “Fully process-compatible layout design on bond pad to improve wire bond reliability in CMOS Ics,” IEEE Transactions on Components and Packaging Technologies, Jun. 2002, vol. 25, No. 2, pp. 309-316.
Kim, Myung Jun et al., “Characteristics of pulse-reverse electrodeposited Cu thin film,” I. Effects of Anodic Step in the Absence of an Organic Additives, Journal of The Electrochemical Society, 2012, vol. 159, No. 9, pp. D538-D543.
Kim, Myung Jun et al., “Characteristics of pulse-reverse electrodeposited Cu thin film,” II. Effects of Organic Additives, Journal of The Electrochemical Society, 2012, vol. 159, No. 9, pp. D544-D548.
Liu, C. et al., “Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu,” Scientific Reports, May 12, 2015, 5:09734, pp. 1-11.
Liu, Chien-Min et al., “Effect of grain orientations of Cu seed layers on the growth of <111>-oriented nanotwinned Cu,” Scientific Reports, 2014, vol. 4, No. 6123, 4 pages.
Liu, Zi-Yu et al. “Detection and formation mechanism of micro-defects in ultrafine pitch Cu—Cu direct bonding,” Chin. Phys. B, 2016, vol. 25, No. 1, pp. 018103-1-018103-7.
Lu, L. et al., “Grain growth and strain release in nanocrystalline copper,” Journal of Applied Physics, vol. 89, Issue 11, pp. 6408.
Mendez, Julie Marie, “Characterization of copper electroplating and electropolishing processes for semiconductor interconnect metallization,” Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Department of Chemical Engineering, Case Western Reserve University, Aug. 2009, 140 pages.
Menk, L.A. et al., “Galvanostatic plating with a single additive electrolyte for bottom-up filling of copper in Mesoscale TSVs,” Microsystems and Engineering Sciences Applications (MESA) Complex, Sandia National Laboratories, Albuquerque, New Mexico, 2019 J. Electrochem. Soc. 166, 17 pages.
Moriceau, H. et al., “Overview of recent direct wafer bonding advances and applications,” Advances in Natural Sciences-Nanoscience and Nanotechnology, 2010, 11 pages.
Mott, D. et al., “Synthesis of size-controlled and shaped copper nanoparticles,” Langmuir, 2007, vol. 23, No. 10, pp. 5740-5745.
Nakanishi, H. et al., “Studies on SiO2—SiO2 bonding with hydrofluoric acid. Room temperature and low stress bonding technique for MEMS,” Sensors and Actuators, 2000, vol. 79, pp. 237-244.
Oberhammer, J. et al., “Sealing of adhesive bonded devices on wafer level,” Sensors and Actuators A, 2004, vol. 110, No. 1-3, pp. 407-412, see pp. 407-412, and Figures 1 (a)-1 (I), 6 pages.
Ortleb, Thomas et al., “Controlling macro and micro surface topography for a 45nm copper CMP process using a high resolution profiler,” Proc. of SPIE, 2008, vol. 6922, 11 pages.
Parthasaradhy, N.V., “Practical Electroplating Handbook,” 1989, Prentice-Hall, Inc., pp. 54-56.
Plobi, A. et al., “Wafer direct bonding: tailoring adhesion between brittle materials,” Materials Science and Engineering Review Journal, 1999, R25, 88 pages.
Saraswat, Stanford Presentation, Cu Interconnect slides, web page web.stanford.edu/class/ee311/NOTES/Cu_Interconnect_Slides.pdf, 19 pages.
Song, Xiaohui, “Atomic study of copper-copper bonding using nanoparticles,” Journal of Electronic Packaging, Jun. 2020, vol. 142, 5 pages.
Song, Xiaoning, “Microstructure and mechanical properties of electrodeposited copper films,” A thesis submitted to the College of Engineering and Physical Sciences of the University of Birmingham, 2011, web page etheses.bham.ac.uk/id/eprint/1764/, 111 pages.
Swingle, Karen D., “Nanograin Copper Deposition Using an Impinging Jet Electrode,” A Thesis submitted in partial satisfaction of the requirements of the degree of Master of Science, University of California, San Diego, 2013, 102 pages.
Takahashi, K. et al., “Transport phenomena that control electroplated copper filling of submicron vias and trenches,” Journal of The Electrochemical Society, 1999, vol. 146, No. 12, pp. 4499-4503.
Zheng, Z et al., “Study of grain size effect of Cu metallization on interfacial microstructures of solder joints,” Microelectronics Reliability, 2019, vol. 99, pp. 44-51.
International Search Report and Written Opinion for PCT/US2021/073169, dated Apr. 22, 2022, 9 pages.
Suga et al., “Bump-less interconnect for next generation system packaging,” Electronic Components and Technology Conference, 2001, IEEE, pp. 1003-1008.
Suga, T., “Feasibility of surface activated bonding for ultra-fine pitch interconnection—A new concept of bump-less direct bonding for system level packaging,” The University of Tokyo, Research Center for Science and Technology, 2000 Electronic Components and Technology Conference, 2000 IEEE, pp. 702-705.
Basol et al., “Electrochemical mechanical deposition (ECMDT technique for semiconductor interconnect applications,” Microelectronic Engineering, 2002, vol. 64, pp. 43-51.
Basol et al., “Planar copper plating and electropolishing techniques,” Chemical Engineering Communication, Jul. 2006, 14 pages.
Basol et al., “Study on the Mechanism of Electrochemical Mechanical Deposition of Copper Layers,” Nu Tool Inc., 1655 McCandless Drive, Milpitas, CA 95035, Electrochemical Processes in ULSI and MEMS, Proceedings of the International Symposium; Proceedings vol. 2004-17, pp. 155-160.
Bush, Steve, “Electronica: Automotive power modules from on Semi,” ElectronicsWeekly.com, indicating an Onsemi AR0820 product was to be demonstrated at a Nov. 2018 trade show, https://www.electronicsweekly.com/news/products/power-supplies/electronica-automotive-power-modules-semi-2018-11/ (published Nov. 8, 2018; downloaded Jul. 26, 2023).
Khan, Muhammed et al., “Damascene Process and Chemical Mechanical Planarization,”|http://www.ece.umd.edu/class/enee416/GroupActivities/Damascene%20Presentation.pdf, 25 pages.
Morrison, Jim et al., “Samsung Galaxy S7 Edge Teardown,” Tech Insights (posted Apr. 24, 2016), includes description of hybrid bonded Sony IMX260 dual-pixel sensor, https://www.techinsights.com/blog/samsung-galaxy-s7-edge-teardown, downloaded Jul. 11, 2023, 9 pages.
Onsemi AR0820 image, cross section of a CMOS image sensor product. The part in the image was shipped on Sep. 16, 2021. Applicant makes no representation that the partin the image is identical to the part identified in the separately submitted reference BUSH, Nov. 8, 2018, ElectronicsWeekly.com (“BUSH article”); however, the imaged part and the part shown in the BUSH article share the part number “ONSEMI AR0820.”.
Roy, A. et al., “Annealing effects on the surface properties of Cu—TiC thin films,” Materials Today: Proceedings, 2021, vol. 44, Part 1, pp. 170-175.
Sony IMX260 image, a first cross section of Sony product labeled IMX260, showing a hybrid bonded back side illuminated CMOS image sensor with a pad opening for a wire bond. The second image shows a second cross-section with peripheral probe and wire bond pads in the bonded structure. The part in the images was shipped in Apr. 2016. Applicant makes no representation that the part in the images is identical to the part identified in the separately submitted reference Morrison et al. (Tech Insights article dated Apr. 24, 2016), describing and showing a similar sensor product within the Samsung Galaxy S7; however the imaged part and the part shown in the Morrison et al. article share the part name “Sony IMX260 image.”
Zik, N. et al., “Thermally produced nano catalyst for biodiesel production: A review,” Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, 2018, vol. 52, Issue 2, pp. 139-147.
Definition of Pad, printout from Merriam-Webster, printed on Feb. 25, 2013.
Lau, John H., “Recent advances and trends in Cu—Cu hybrid bonding,” IEEE Transactions on Components, Packaging and Manufacturing Technology, Mar. 2023, vol. 13, No. 3, pp. 399-425.
Neo-Manhattan Technology, A Novel HDI Manufacturing Process, “High-density|interconnects for advanced flex substrates & 3-D package stacking,” IPC Flex & Chips Symposium, Tempe, AZ, Feb. 11-12, 2003.
North Corporation, “Processed intra-layer interconnection material for PWBs [Etched Copper Bump with Copper Foil],” NMBITM, Version 2001.6.
Paunovic, Milan et al., Modern Electroplating, Fifth Edition, 2010 Wiley & Sons, pp. 1-32.
Yamada, H. et al., “A fine pitch and high aspect ratio bump array for flip-chip interconnection,” Proceedings of the International Electronic Manufacturing Technology Symposium, Baltimore, USA, Sep. 28-30, 1992, New York, USA, IEEE, vol. SYMP.13, Sep. 28, 1992, pp. 288-292, XP010259441.
Yamada, H. et al., “A fine pitch and high aspect ratio bump fabrication process for flip-chip interconnection,” Proceedings of the Electronic Manufacturing Technology Symposium, Omiya, Japan, Dec. 4-6, 1995, New York, USA, IEEE, Dec. 4, 1995, pp. 121-124, XP010195564.
Related Publications (1)
Number Date Country
20220208702 A1 Jun 2022 US
Provisional Applications (1)
Number Date Country
63132334 Dec 2020 US