Bi-Layer Nanoparticle Adhesion Film
20180166369 ยท 2018-06-14
Inventors
Cpc classification
H01L2224/48465
ELECTRICITY
H01L23/3142
ELECTRICITY
H01L2924/00012
ELECTRICITY
H01L2224/131
ELECTRICITY
H01L2224/8369
ELECTRICITY
H01L2924/18301
ELECTRICITY
B32B3/08
PERFORMING OPERATIONS; TRANSPORTING
H01L2224/8169
ELECTRICITY
H01L2224/131
ELECTRICITY
H01L2924/00
ELECTRICITY
H01L2924/00
ELECTRICITY
H01L2224/816
ELECTRICITY
B32B2255/28
PERFORMING OPERATIONS; TRANSPORTING
H01L2924/00014
ELECTRICITY
H01L2224/83687
ELECTRICITY
H01L2224/836
ELECTRICITY
H01L21/4821
ELECTRICITY
H01L2224/81687
ELECTRICITY
H01L2924/00014
ELECTRICITY
H01L2924/00012
ELECTRICITY
B32B7/10
PERFORMING OPERATIONS; TRANSPORTING
B32B15/20
PERFORMING OPERATIONS; TRANSPORTING
H01L24/73
ELECTRICITY
H01L2224/48465
ELECTRICITY
International classification
B32B7/10
PERFORMING OPERATIONS; TRANSPORTING
H01L21/48
ELECTRICITY
Abstract
A device comprises a substrate) of a first material with a surface, which is modified by depositing a bi-layer nanoparticle film. The film includes a nanoparticle layer of a second material on top of and in contact with surface, and a nanoparticle layer of a third material on top of and in contact with the nanoparticle layer of the second material. The nanoparticles of the third material adhere to the nanoparticles of the second material. The substrate region adjoining surface comprises an admixture of the second material in the first material. A fourth material contacts and chemically/mechanically bonds to the nanoparticle layer of the third material.
Claims
1. A device comprising: a substrate of a first material, the substrate having a surface; a nanoparticle layer of a second material on top of and in contact with the surface of the substrate, a substrate region adjoining the substrate surface comprising an admixture of the second material in the first material; a nanoparticle layer of a third material on top of and in contact with the nanoparticle layer of the second material, the nanoparticles of the third material adhering to the nanoparticles of the second material; and a package of a fourth material, the fourth material contacted to, and bonded to, the nanoparticle layer of the third material, the fourth material filling any voids in the layer of third material.
2. The device of claim 1 wherein the substrate of the first material is a laminated substrate including metallic regions.
3. The device of claim 1 wherein the substrate of the first material is one or more surfaces on a metallic leadframe.
4. The device of claim 3 wherein the first material of the metallic leadframe is selected from a group including copper, copper alloys, aluminum, aluminum alloys, iron-nickel alloys, and Kovar.
5. The device of claim 4 wherein the metallic leadframe further includes plated layers selected from a group including nickel, palladium, gold, and tin.
6. The device of claim 1 wherein the fourth material includes a polymeric compound such as an epoxy-based molding compound.
7. The device of claim 1 wherein the second material is selected from a group including metals, metal oxides, oxides, and ceramics.
8. The device of claim 1 wherein the third material is selected from a group including polymers, oxides, ceramics, metals, and metal oxides.
9. The device of claim 1 wherein the adhering of the nanoparticles of the third material to the nanoparticles of the second material is based on intermolecular forces between the nanoparticles.
10. The device of claim 1 wherein the bonding of the fourth material to the nanoparticle layer of the third material is based on intermingling of the fourth material with the third material.
11. The device of claim 1 wherein the bonding of the fourth material to the nanoparticle layer of the third material is based on chemical bonding.
12. A method for substrate modification comprising: providing a substrate of a first material, the substrate having a first surface; additively depositing onto the first substrate a layer of a solvent paste including nanoparticles of a second material; applying energy to the first solvent paste to increase the temperature to sinter together the nanoparticles of the second material and concurrently for diffusing the second material into a substrate region adjoining the first surface; additively depositing onto the sintered nanoparticles of the second material a layer of a second solvent paste, the second solvent paste including nanoparticles of a third material; and applying energy to the second solvent paste to increase the temperature to solidify the nanoparticles of the third material, the solidified nanoparticles of the third material adhering to the sintered nanoparticles of the second material, thereby forming a bi-layer nanoparticle film.
13. The method of claim 12 wherein the substrate is selected from a group including metallic substrates, metallic leadframes used for semiconductor devices, and laminated substrates including metallic layers alternating with insulating layers.
14. The method of claim 12 wherein the first material is selected from a group including copper, copper alloys, aluminum, aluminum alloys, iron-nickel alloys, and Kovar.
15. The method of claim 14 wherein the first material includes a plated layer of a metal selected from a group including tin, silver, nickel, palladium, and gold.
16. The method of claim 12 wherein the method of additively depositing is selected from a group including screen printing, flexographic printing, gravure printing, dip coating, spray coating, and inkjet printing comprising piezoelectric, thermal, acoustic, and electrostatic inkjet printing.
17. The method of claim 12 wherein the second material is selected from a group including metals, metal oxides, oxides, and ceramics.
18. The method of claim 12 wherein the third material is selected from a group including polymers, oxides, ceramics, metals, and metal oxides.
19. The method of claim 12 wherein the energy for sintering the second nanoparticles is selected from a group including thermal energy, photonic energy, electromagnetic energy, and chemical energy.
20. A method for substrate modification comprising: providing a first material; additively depositing on a surface of the first material a layer of a solvent paste comprising a semi-homogeneous mixture of: nanoparticles of a second material bondable to the first material by interdiffusion; and nanoparticles of a third material adhering to the second material and bondable to a fourth material chemically and mechanically; applying energy to increase the temperature for sintering together the nanoparticles of the second and the third materials, forming a sintered nanoparticle layer, and concurrently for diffusing second material into a region adjoining the surface of the first material; and bringing the fourth material in contact with the sintered nanoparticle layer, thereby bonding the fourth material to the nanoparticles of the third material.
21. A method for enhancing adhesion of packaged semiconductor devices, comprising: providing a substrate of a first material, the substrate having a first surface; additively depositing onto the first surface a layer of a first solvent paste, the first solvent paste including nanoparticles of a second material; applying energy to the first solvent paste to increase the temperature of the first solvent paste to sinter together the nanoparticles of the second material and concurrently for diffusing the second material into a substrate region adjoining the first surface; additively depositing onto the sintered nanoparticles of the second material a layer of a second solvent paste, the second solvent paste including nanoparticles of a third material; applying energy to the second solvent paste to increase the temperature of the second solvent paste to solidify the nanoparticles of the third material, the solidified nanoparticles of the third material adhering to the sintered nanoparticles of the second material, thereby forming a bi-layer nanoparticle film; and encapsulating the bi-layer nanoparticle film and at least portions of the substrate in a fourth material, the fourth material chemically bondable to the solidified nanoparticles of the third material.
22. The method of claim 21 wherein the substrate is a metallic leadframe for use in semiconductor devices with the first material selected from a group including copper, copper alloys, aluminum, aluminum alloys, iron-nickel alloys, and Kovar.
23. The method of claim 22 wherein the first material includes a plated layer of a metal selected from a group including tin, silver, nickel, palladium, and gold.
24. The method of claim 21 wherein the second material is selected from a group including metals, metal oxides, oxides, and ceramics.
25. The method of claim 21 wherein the third material is selected from a group including polymers, oxides, ceramics, metals, and metal oxides.
26. The method of claim 21 further including, before the process of encapsulating, the process of assembling a semiconductor chip on the substrate so that the chip will be positioned inside the package after the process of encapsulating.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] In an embodiment of the invention, a method for enhancing the adhesion and mechanical bonding between diverse materials is described. The method comprises the formation and anchoring of an additive adhesion film composed of two superimposed (or alternatively, intermeshed) nanoparticle layers between the materials.
[0022] An application of the process flow shown in
[0023] When the substrate is a leadframe (see
[0024] A leadframe provides a stable support pad (1001 in
[0025] It is important that leadframe characteristics facilitate reliable adhesion to an attached chip and to packaging compounds (1070 in
[0026] Referring to the process flow of
[0027] Nanoparticles 302 may be selected from a group including metals, metal oxides, oxides, and ceramics. The metals may include gold, silver, copper, aluminum, tin, zinc, and bismuth. Metal oxides may include copper oxide, which, as a mixture of cupric and cuprous oxide with a varying ratio, is known to offer better chemical adhesion to molding compounds than copper.
[0028] During step 103 of the process flow of
[0029] The equipment for depositing the solvent paste includes a computer-controlled inkjet printer with a moving syringe 210 with nozzle 211, from which discrete drops 310 of the paste are released. Automated inkjet printers can be selected from a number of commercially available printers. Alternatively, a customized inkjet printer can be designed to work for specific pastes. Alternatively, any additive method can be used including inkjet printing, screen printing, gravure printing, dip coating, spray coating, and many others.
[0030] As stated, the deposited layer 200 may extend along the lateral dimensions of the substrate 201, or may include, as depicted in
[0031] During step 104 of the process flow of
[0032] Concurrent with the sintering of the nanoparticles 402 of the second material, some second material is diffusing by atomic interdiffusion into the first material of the region adjoining the surface 201a (first surface) of substrate 201. In
[0033] After the sintering process, the liquid network structure 402 of second material is solidified to create a solid layer 400 of second material 402. Since the hardened network structure 400 remains at the substrate surface as a solid layer, the nanoparticles 402 of the second material are structural nanoparticles.
[0034] During the process step 105 of the process flow shown in
[0035] In conjunction with the selection of the nanoparticles of the second material, the nanoparticles of the third material are selected so that they are operable to have adhesion to the nanoparticles of the second material. Due to intermolecular forces, the nanoparticles of the third material cling to the nanoparticles of the second material. In a related effect, an increase of surface tension, or surface energy, causes an increase of adhesion and wetting to a surface.
[0036] When surfaces of nanoparticles are treated so that the treated nanoparticles are enabled to perform certain desired functions, such treatment is referred to as functionalization. For example, if nanoparticles are desired to stay separate from each other, they can be treated with ligands (they are functionalized) to prevent coagulation. In the example described in
[0037] The cores of other nanoparticles may have hydrophilic ligand molecules attached to the core surface. Examples include mercaptoacetic acid (MAA), mercaptopropionic acid (MPA), mercaptoundecanoic acid (MUA), mercaptosuccinic acid (MSA), dihydrolipic acid (DHLA), bis-sulphonated triphenylphosphine (mPEG.sub.5-SH, mPEG.sub.45-SH), and short peptide of sequence CALNN. Ligand molecules such as inert molecular chains attached on the surface of the core can stabilize the nanoparticles against aggregation, while other ligand molecules attached on the surface can enhance the adhesion to objects.
[0038] As an example, for promoting covalent bonding of copper oxide (both CuO and Cu.sub.2O) nanoparticles, molecules of siloxane, silane, or the amine-group may be attached to the core surface to functionalize copper oxide nanoparticles.
[0039] For some applications, adhesion between the layer of the third material and the layer of the second material can be achieved, when the third material is the same chemical element as the second material but has different porosity or a different compound formulation leading to a different surface function. As an example, the third material may be a compound of the amine group or the silane group of the same element as the second material or the third material may belong to a different oxide formulation, for example CuO vs. Cu.sub.2O. As another example, the material density may be different, or the size or density of the porosity (regular vs. random configuration). As yet another example, the third material may have a different diffusion characteristic into solids along grain boundaries or lattice defects.
[0040] During step 106 of the process flow shown in
[0041] The equipment for the deposition includes a computer-controlled inkjet printer with a moving syringe 510 with nozzle 511, from which discrete drops 610 of the paste are discontinuously released. Automated inkjet printers can be selected from a number of commercially available printers. Alternatively, a customized inkjet printer can be designed to work for specific pastes. Alternatively, any additive method can be used including screen printing, gravure printing, flexographic printing, dip coating, spray coating, and inkjet printing comprising piezoelectric, thermal, acoustic and electrostatic inkjet printing.
[0042] As stated, the deposited layer 500 may extend along the lateral dimensions of the whole substrate 201, or may, as depicted in
[0043] During step 107 of the process flow shown in
[0044] With the nanoparticles of the third material sintered, solidified, and adhering to the sintered nanoparticles of the second material, a bi-layer nanoparticle film 520 is formed. The thickness 520a of bi-layer film 520 is preferably between about 0.1 m and 10 m.
[0045] During step 108 of the process flow shown in
[0046] After the compound has polymerized and cooled down to ambient temperature, the polymeric compound 701 in the package as well as in the pores/voids is hardened. After hardening of the plastic material, the polymeric-filled pores/voids represent an anchor of the package in the nanoparticle layer 500, giving strength to the interface of package (fourth material) and the bi-layer nanoparticle film (third material). In addition, as mentioned above, layer 500 has adhesion to nanoparticle layer 400, giving the bi-layer film strength. In turn, layer 400 is anchored in metallic substrate 201 by metal interdiffusion 402a, giving the interface of the bi-layer film to the substrate strength. As an overall result, the bi-layer nanoparticle film improves the adhesion between the plastic package 701 and the metallic substrate 201. Adhesion improvements of an order of magnitude have been measured.
[0047] In addition to mechanical adhesion between bodies, the overall adhesion between two different materials can be improved by chemical adhesion. Consequently, the nanoparticles of the second material and third material can be chosen to enhance chemical adhesion. As an example, copper oxide nanoparticles have better chemical bonding to polymeric molding compounds than gold nanoparticles.
[0048] Another embodiment of the invention is a nanoparticle layer as depicted in
[0049] The fabrication process for layer 800, as illustrated in
[0050] The method for adhesion improvement between two objects by a sintered semi-homogeneous nanoparticle layer of two nanoparticle materials begins by providing an object of a first material and an object of a fourth material. Then, a solvent paste is provided, which includes a semi-homogeneous mixture of nanoparticles of a second material and nanoparticles of a third material. The nanoparticles of the second material are able to form diffusion bonds to the first material by molecular diffusion into the surface-near region of the substrate made of the first material. The nanoparticles of the third material form adhesion bonds by intermolecular forces to the nanoparticles of the second material, and further form to the object of the fourth material chemical bonds due to electrical forces and/or mechanical bonds due to filling of pores/voids.
[0051] Using a computerized inkjet printing technique for the next process, a layer of the semi-homogeneous mixture of the solvent paste is additively deposited on the surface of the object of the first material. Energy is then applied to elevate the temperature for sintering together the nanoparticles of the second and the third materials, forming a sintered nanoparticle layer, and for concurrently diffusing second material into the region adjoining the surface of the object of the first material.
[0052] Next, the object of the fourth material is brought into contact with the sintered nanoparticle layer so that the chemical and/or mechanical bonding is actualized; the object of the fourth material is bonded to the nanoparticles of the third material.
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[0054] In
[0055] While this invention has been described in reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. As an example in semiconductor technology, the invention applies not only to active semiconductor devices with low and high pin counts, such as transistors and integrated circuits, but also to combinations of active and passive components on a leadframe pad.
[0056] As another example, the invention applies not only to silicon-based semiconductor devices, but also to devices using gallium arsenide, gallium nitride, silicon germanium, and any other semiconductor material employed in industry. The invention applies to leadframes with cantilevered leads and to QFN and SON type leadframes.
[0057] As another example, the invention applies, in addition to leadframes, to laminated substrates and any other substrate or support structure, which is to be bonded to a non-metallic body.
[0058] It is therefore intended that the appended claims encompass any such modifications or embodiments.