WO2003096389A2 - Zur wenigstens teilweisen beschichtung mit einer substanz bestimmter metallgegenstand - Google Patents
Zur wenigstens teilweisen beschichtung mit einer substanz bestimmter metallgegenstand Download PDFInfo
- Publication number
- WO2003096389A2 WO2003096389A2 PCT/DE2003/001529 DE0301529W WO03096389A2 WO 2003096389 A2 WO2003096389 A2 WO 2003096389A2 DE 0301529 W DE0301529 W DE 0301529W WO 03096389 A2 WO03096389 A2 WO 03096389A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- nanopores
- surface section
- reduction
- oxidation
- Prior art date
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- 229910010293 ceramic material Inorganic materials 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims description 57
- 230000003647 oxidation Effects 0.000 claims description 56
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- 150000004706 metal oxides Chemical class 0.000 claims description 51
- 229910044991 metal oxide Inorganic materials 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 38
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- 239000000919 ceramic Substances 0.000 claims description 19
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- 239000012298 atmosphere Substances 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
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- 238000000576 coating method Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
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- 238000011049 filling Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
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- 229910000679 solder Inorganic materials 0.000 abstract description 7
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- 238000009713 electroplating Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76886—Modifying permanently or temporarily the pattern or the conductivity of conductive members, e.g. formation of alloys, reduction of contact resistances
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- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
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- H01L23/528—Geometry or layout of the interconnection structure
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
Definitions
- Metal object intended for at least partial coating with a substance.
- the invention relates to an object intended for at least partial coating with a substance and to devices in which the metal object is used in accordance with the type of the independent claims. Furthermore, the invention relates to a method for producing such a metal object.
- metal objects in particular connection, support or line components for an electronic component with their macroscopically smooth surfaces are to be coated with a substance, in particular made of plastic, ceramic or glass
- adhesion promoters are galvanically deposited on the macroscopically smooth surfaces of the metal objects, which form dendrites and thus one Provide teeth between the metal object and the substance.
- a disadvantage of these electrodeposited adhesive layers is that such an adhesive layer forms two further boundary layers or phase transitions, namely an interface between the smooth, unchanged metal surface and a further interface between the dendritic adhesive layer and the substance to be applied.
- this preparation of the metal surface has the disadvantage that the adhesive layer is applied with the aid of a wet process and thus contamination of components of the electroplating bath is inevitable. Such contaminations can increase the lifespan of such an adhesive layer. ten and thus reduce the lifespan of the electronic components.
- macroscopically smooth surfaces of metal objects are understood to mean surfaces that have at least one polishing quality.
- Metal objects of this type with polished surfaces are used, in particular, in electronic components as connection, support or line components, with further noble metal layers often being deposited on the polished surfaces in order to realize bonded connections and soldered connections thereon.
- these macroscopically smooth surfaces turn into rough surfaces which are partially covered with dendrites of the bonding agent or grinding pits or etching pits.
- the macroscopically smooth surface areas which are to represent contact pads, bond fingers or other components, must be protected from roughening.
- the object of the invention is to create a metal object intended for at least partial connection with a substance, which does not have any additional adhesion-promoting materials in order to enable a mechanically intensive connection of its surface with a further substance.
- the macroscopically smooth surface of the metal object should be preserved.
- a metal object intended for at least partial coating with a substance, in particular connection, support or line components for an electronic component which has macroscopically smooth surface sections.
- a plurality of multi-curved open nanopores emerging on the surface section in question are provided in an area of at least one surface section.
- Such microscopic nanopores advantageously promote the mechanical connection of the metal object with a substance, but macroscopically the surface section or the entire surface of the metal object remains smooth and flat.
- microscopic is understood to mean dimensions that can only be detected and measured under an electron microscope.
- an advantage of this metal object is that any substances, in particular glass, ceramic and plastic, can be anchored in the nanopores, this anchoring taking place three-dimensionally due to the multiple curvature of the nanopores, thus ensuring reliable adhesion and positive connection of the substance to the metal object.
- the object according to the invention has the advantage that a macroscopically smooth surface is retained despite the nanopores, so that finishing or coating of the surface sections, bonding, soldering and other techniques in which smooth surfaces of a metal object are a prerequisite remain possible .
- the metal surface is first oxidized and then the resulting metal oxide layer is reduced, so that the material in the area of the surface section with nanopores is identical to the material of the metal object.
- both the oxidation and the reduction of the metal object can be carried out in dry processes, with no contamination of foreign substances remaining in the nanopores. As a result, highly pure metallic surfaces are formed which can be mechanically bonded directly to the substance to be applied.
- a reduction in the metal oxide layer can be set in such a way that a metal object for at least partial coating with a substance is formed which has a buried metal oxide layer.
- the metal object has a solid metal core which has at least one porous macroscopically flat metal layer region in the region of at least one surface section.
- the metal layer area has the material of the metal core and, on the other hand, it shows multi-curved open nanopores. These nanopores emerge from the surface of the metal layer area.
- a pore-free buried layer of metal oxide is arranged between the metal layer area with nanopores and the solid metal core.
- This three-layered structure made of metal with nanopores, non-porous metal oxide and non-porous metal core has the advantage that the buried layer of metal oxide forms an electrically insulating layer, so that when electrically conductive substances are applied, these layers of the metal core of the metal object are electrically insulated.
- the surface section with nanopores can be arranged adjacent to a non-porous metal surface.
- a non-porous metal surface Such structures and geometries are possible if the oxidation and reduction process are only limited to the surface sections of the metal object that are to be mechanically connected to a substance.
- the surface section with nanopores can also be surrounded by a non-porous metal oxide surface.
- the entire surface is first oxidized and only reduced on the surface sections on which nanopores are to be formed.
- the metal object according to the invention is particularly suitable for improving through contacts made of metal, the through contacts leading through glass, ceramic or plastic.
- the through contact made of metal in the form of flat conductors or lead wires can have a surface in its through contact area. Chen section with a plurality of multiply curved and emerging on the surface section concerned open nanopores. In the case of through-contact, these nanopores are filled with the substance to be connected, such as glass, ceramic or plastic, so that the substance is closely interlocked with the metal via despite macroscopically smooth surface areas.
- a further embodiment of the invention provides that such a via has copper or a copper alloy as the metal object. Copper or copper alloys are preferred for such through contacts mechanically connected to glass, ceramic or plastic, since they have a low electrical resistance. However, the thermal expansion coefficient of copper or copper alloys cannot be adapted to the substance as desired, so that in further embodiments of the invention metal objects made of chromium / nickel / iron alloys are used as vias, especially since nickel-iron alloys in particular depend on the composition different expansion coefficients of the substances can be adjusted.
- a plurality of metal objects such as flat conductor ends, inner flat conductors or chip islands on which semiconductor chips are arranged, are to be connected to a plastic housing compound of an electronic component.
- the metal objects have macroscopically smooth surface sections, wherein in the area of at least one surface section a multiplicity of open nanopores which are curved and emerge on the relevant surface section are provided and which are filled with plastic housing compound which is to be mechanically connected to the metal objects. So you can Realize an electronic component in which the metallic objects or metal components are not to be coated with an additional adhesion promoter layer or adhesive layer, so that no additional material that could reduce the service life of the component is introduced into the overall structure. Rather, only the metals required for the metal objects are used and are directly connected to the plastic housing compound without further additives.
- the object according to the invention can also be used in electronic components with a plastic housing and a semiconductor chip which has metallic conductor tracks.
- the semiconductor chip is sealed on its active top side against external influences with a passivation layer made of ceramic.
- This ceramic layer lies partly on smooth, metallic conductor tracks, the ceramic layer in particular having silicon nitride.
- this ceramic layer made of silicon nitride also on the macroscopically smooth surface sections of the conductor tracks, in the area of at least one of the surface sections a multiplicity of open nanopores which emerge on the relevant surface section of the conductor track can be provided.
- These nano-pores are filled in this embodiment of the invention with a ceramic mass, and hence the conductor paths and 'the ceramic composition are closely connected to each other mechanically.
- metallic chip islands These chip islands have macroscopically smooth surface sections to which the semiconductor chip is to be electrically connected.
- a Conductive adhesive used between the semiconductor chip and the macroscopically smooth surface of the chip island.
- the mechanical connection between the conductive adhesive and the chip island can be intensified if a multiplicity of multi-curved open nanopores emerging on the surface section in question is provided.
- the conductive adhesive is now also mechanically connected to the metallic chip island by filling up the curved nanopores.
- the nanopores in such a metal object have an average diameter D of 10 nm to 300 nm.
- the average density of the nanopores on the surface of the metal object is such that the macroscopically smooth surface is not disturbed by the nanopores and also not warped or collapsing.
- the depth of the nanopores is between 0.1 and 10 micrometers. If a pore-free buried layer of metal oxide is provided, its thickness d can be between 0.1 micrometers and 3 micrometers.
- a method for producing a metal object for at least partially mechanical connection with a substance has the following method steps.
- a partial oxidation of the metal object is performed to form a metal oxide layer on a surface portion of the metal object.
- the metal oxide layer is then reduced to a porous structure with multi-curved open nanopores emerging from the surface section. Based on the heterogeneous kinetics in this oxide layer reduction, the metal surface that is created again remains with a corresponding nano-porosity.
- This structure forms as a sponge structure on the surface of the metal object, since the molar volume of the metal oxides after the oxidation is generally greater than that of the corresponding metals.
- the dimensions and the number of pores can be freely set by means of the parameters "oxidation rate, oxide thickness, reduction rate" as well as by cyclic oxidation and reduction and re-oxidation and reduction.
- the system parameters such as oxidation / reduction temperature and oxidation / reduction can be set
- the time and the partial pressure of the oxygen component of the oxidizing atmosphere can be varied in the oxidation step, and the partial pressure of the reducing medium in the reduction step can also be varied metals are stable produced, which also form stable oxides, that is, their oxides do not evaporate.
- these oxides must be reducible at a temperature below the melting temperature of the metals with a reducing medium such as hydrogen. Therefore copper and copper alloys as well as nickel / chrome / iron alloys can be used.
- the reduction of the metal oxide layer cannot take place completely, so that a buried metal oxide layer remains on the surface of the metal object as an intermediate layer.
- the reduction of the metal oxide layer can only; limited to certain surface sections, so that the surface section made of metal with nanopores is surrounded by a pore-free metal oxide layer.
- a protective layer is applied to the areas that are not to be reduced.
- the oxidation is carried out in an oxygen-containing, dry atmosphere with an oxygen content of 20 to 100% by volume.
- the oxidation temperature depends on the type of metal object. Dry oxidation has the advantage that it forms very dense, but slowly growing layers. Such a dry oxidation ensures at the same time that the later reduced areas form a coherent metal skeleton that has a smooth surface macroscopically.
- the oxidation of the metal surface can also be carried out in a moist, oxygen-containing atmosphere, the relative humidity being between 60 and 95% and the oxygen content being 20 to 98% by volume.
- the moist oxidation proceeds faster than the dry oxidation, since the water molecules are significantly smaller than the oxygen molecules and their rate of diffusion through the oxide layers already formed is greater than with the dry oxidation. While the dry oxidation for a copper object or a copper alloy object can be carried out at temperatures between 300 and 600 ° C for 10 to 20 minutes, a lower temperature range between 300 and 500 ° C is sufficient for a moist oxidation. The oxidation process of wet oxidation of copper or a copper alloy only takes between 5 and 10 minutes.
- the lower temperature range of the moist oxidation has the advantage that the metal surfaces of an electronic component can also be produced after a semiconductor chip has been applied to the chip island and after the semiconductor chip has been wire-bonded to the corresponding inner flat conductor ends. To do this, only the semiconductor chip has to withstand the thermal stress, but is not contaminated by additional chemicals, as is the case when electroplating adhesive layers.
- the exposed surface sections of the various metal components can be provided with nanopores by means of oxidation and reduction, so that an intensive connection can be made with a plastic housing compound to be subsequently applied.
- the reaction temperature or oxidation temperature for metal objects made of chromium / nickel / iron alloys is between 500 and 900 ° C. This means that much higher oxidation temperatures are to be used for such metal objects than for copper alloys.
- Such wires made of these metal alloys are used, however, for through-contact through glasses and ceramics, since their thermal expansion coefficient can be adapted to the expansion coefficients of glasses and ceramics.
- mechanical anchoring and connection with the glasses and ceramics has been a problem that has been solved with the present invention.
- an oxide layer between 0.1 and 10 microns thick will grow on the metal object.
- this thickness can be set in a targeted manner by means of the oxidation parameters, temperature, time and the oxidation atmosphere, and by choosing a suitable metal material. With this oxide layer thickness, the depths of the different nanopores can thus be defined in advance.
- the reduction is carried out in an atmosphere containing hydrogen.
- the temperature of the reduction is between 300 and 500 ° C for copper oxide layers.
- the reduction temperatures are correspondingly higher for oxide layers based on chromium / nickel / iron alloys.
- Dia in, forming gas, hydrazine and / or formaldehyde can be used as hydrogen-containing components in the reduction atmosphere.
- by performing oxidation several times and reduction an enlargement and deepening of the nanopores can be achieved.
- the following method steps are to be carried out.
- First of all, at least some of the metal components of the electronic component are oxidized, which are to be packaged in a plastic housing compound.
- these partially oxidized metallic components are reduced to form multi-curved nanopores, which emerge from correspondingly reduced surface sections of the components.
- the material of the housing like the plastic housing compound, can penetrate into these open pores and can be firmly anchored to the mechanical components, so that the electronic component has a longer service life.
- the semiconductor chip can be specially prepared with the method according to the invention in order to apply a passivation layer on the active surface of the semiconductor chip in a moisture-resistant manner.
- the metallic conductor tracks on the active upper side of the semiconductor chip are at least partially oxidized and then these partially oxidized metallic conductor tracks are reduced to form multiply curved nanopores, the nanopores emerging from correspondingly reduced surface sections of the conductor tracks.
- the passivation layer made of polyimide, silicon carbide, silicon dioxide or silicon nitride is then introduced into the open nanopores, so that the surfaces of the semiconductor chip which have conductor tracks are protected by filling these nanopores with the material of the passivation layer and the danger the delamination of the passivation layer from the active top side of the semiconductor chip is reduced for such electronic components.
- the adhesion of polymers to macroscopically smooth metal surfaces is characterized on the one hand by a chemical bond between the metal oxides present on the metal surfaces and a functional group of the organic molecule of the polymer.
- these binding forces are extremely weak and are based on a Van der Waal "interaction.
- the adhesion to clean and smoothly polished metal surfaces is extremely poor.
- high adhesion is achieved through a rough surface structure, which is achieved with the aid of galvanically deposited adhesive layers
- Adhesive layers of this type have the disadvantage, however, that they introduce impurities and contaminants into the overall structure and concept, which can considerably reduce the lifespan of electronic components, in particular with semiconductor chips.
- the metal object according to the invention has metal surfaces with pores on a nanometer scale.
- the corresponding metal is first thermally oxidized to an oxide thickness between 0.1 and 10 micrometers, preferably between 1 and 5 micrometers.
- the present metal oxide is then thermally reduced in a mixture of nitrogen and hydrogen, such as a forming gas which contains 5% hydrogen. Based on the heterogeneous kinetics in the oxide layer reduction, the metal surface that is created again remains with a corresponding nanometer porosity.
- This metal structure offers itself as a kind of sponge structure on the substrate surface because the molar volume of the metal loxide is generally larger than that of the corresponding metals.
- the dimensions and the number of pores can be freely set by means of the parameters “oxide speed, oxide thickness, reduction speed” and by cyclic oxidizing-reducing-oxidizing-reducing.
- the system parameters such as oxidation / reduction temperature and time as well as the partial pressure of oxygen in the oxidation step and the partial pressure of hydrogen in the reduction step to achieve a given oxidation thickness and thus a given pore depth of the nanopores.
- all metals that form stable oxides and their oxides below the melting temperature of the metal with hydrogen can be used for this process can be reduced.
- FIG. 1 shows a schematic cross section through part of a metal object
- Figure 2 shows a schematic cross section through a
- FIG. 3 shows a schematic cross section through part of a metal object after reduction of the metal oxide to metal with nanopores in the metal structure
- FIG. 4 shows a schematic cross section through part of a metal object mechanically connected to a substance
- FIGS. 5 to 7 show schematic cross sections through part of a metal object after method steps for producing a metal object with a buried oxide layer
- characters 8 to 10 show schematic cross sections through a part of a metal object after method steps for producing a surface section with nanopores
- 11 to 13 show schematic cross sections through part of a metal object after method steps for producing a surface section with nanopores surrounded by a pore-free metal oxide layer in a metal matrix
- FIGS. 14 to 16 show schematic cross sections through part of a metal object after method steps for producing an isolated surface section with nanopores in a metal matrix.
- Figure 1 shows a schematic cross section through part of a metal object.
- This metal object has a macroscopically smooth surface 3, which forms a metal surface 9 which is still non-porous.
- FIG. 2 shows a schematic cross section through part of a metal object after its surface has been oxidized. This creates a metal oxide layer 12 with a pore-free metal oxide surface 10, which covers the surface of the depicted part of the metal object.
- the thickness V of the metal oxide layer is greater than the depth of the amount of metal used in the oxidation of the non-porous metal surface 9, as is shown in FIG. 1, since the molar volume of the metal oxide is generally greater than that of the corresponding metal.
- the oxidation is achieved by the Metal object is placed in an oxidation furnace with an oxygen content between 20 and 100 vol.%, The object can already oxidize in air at correspondingly high temperatures.
- the oxidation temperature in the oxidation furnace for a metal object made of copper or a copper alloy is set between 300 and 600 ° C for 5 to 20 minutes.
- the higher temperature and the longer time are required for dry oxidation, and the shorter time and the lower temperature can be achieved by moist oxidation.
- the reaction atmosphere is operated with a relative humidity between 60 to 95% and with temperatures between 300 and 500 ° C.
- the thickness V of the oxide layer is between 0.1 and 10 micrometers and can be precisely controlled by adjusting the oxidation parameters.
- FIG. 3 shows a schematic cross section through part of a metal object after reduction of the metal oxide layer 12 to metal with nanopores in the metal structure. Due to the heterogeneous kinetics of this oxide layer reduction, the metal surface that is created again remains with a corresponding porosity of nanopores. The nanopores are open towards the top. The diameter of the nanopores D is between 10 and 300 nanometers. The limit or depth t of the nanopores is determined by the depth V of the metal oxide layer 12 shown in FIG. 2. With complete reduction of the metal oxide layer 12 shown in FIG. 2, a macroscopically smooth surface 3 made of metal with nanopores 5 which extend to the surface and have a depth of t is achieved.
- the reduction itself is carried out in a atmosphere of 300 to 500 ° C for the reduction of copper or copper alloys.
- Hydrogen-containing components are used for the reduction.
- Forming gas with 5% hydrogen content can be used or diamine, a compound between nitrogen and hydrogen, can be used. It is also possible to use hydrazine or formaldehyde for hydrogen reduction in a corresponding reduction furnace.
- FIG. 4 shows a schematic cross section through part of a metal object connected to a substance.
- 'Such metal objects are preferably components of an electronic component having a semiconductor chip.
- the metal object 2 shown here illustrates the inner end of a flat conductor of an electronic component and the substance 1 in this example of FIG. 4 is a plastic housing compound in which the flat conductor and other metallic components of the electronic component, such as bond wires and chip islands, are embedded ,
- the nanopores 5 in the surface of the metal object 2 achieve a tight interlocking interlocking while maintaining a macroscopically smooth surface 3 of the metal object 2. Furthermore, no chemicals are required to implement this combination.
- FIGS. 5 to 7 show schematic cross sections through part of a metal object 2 after method steps for producing a metal object 2 with buried metal oxide layer 8. In this production method, the procedure is the same as in the first three FIGS. 1 to 3, but the reduction is ended earlier than would be necessary for a complete reduction of the metal oxide layer 12 shown in FIG. 6.
- a buried oxide layer 8 as shown in FIG. 7 can thus be formed, which has an insulating effect and is particularly suitable if conductor tracks of a semiconductor chip are to be provided with a passivation layer made of ceramic or polyimide.
- FIG. 5 again shows a schematic cross section through part of a metal object.
- This metal object has a macroscopically smooth surface 3, which forms a metal surface 9 which is still non-porous.
- FIG. 6 again shows a schematic cross section through part of a metal object after its surface has been oxidized. This creates a metal oxide layer 12 which covers a pore-free metal core 6.
- FIG. 7 shows a schematic cross section through the metal object after incomplete reduction of the metal oxide layer 12 shown in FIG. 6.
- Three layer regions are formed. Firstly, a metal layer region 7 with nanopores 5, this metal layer region 7 having the same material as the solid metal core 6, while the buried metal oxide layer 8 is arranged between the metal core 6 and the metal layer region 7 and has a thickness d. The thickness d can be adjusted by adjusting the duration and the temperature of the reduction phase.
- FIGS. 8 to 10 show schematic cross sections through a part of a metal object after method steps for producing a surface section with nanopores.
- FIG. 8 shows a cross section through a pore-free solid metal core 6, which is covered on its smooth upper side 3 by a mask 13, so that only one surface section 14 is oxidized.
- FIG. 9 shows the cross section through the metal object after the oxidation and after the mask 13 has been removed. This results in an elevation in the surface section 14 due to the oxidation and the increase in volume of the metal oxide relative to the metal core 6.
- FIG. 10 shows the metal object after reduction of the oxide layer produced in FIG. 9, the elevation being retained, but the resulting reduced metal structure has nanopores 5.
- This surface section with nanopores 5 is suitable for mechanically connecting the metal object at this point, for example an external contact area of a metal structure, to a further material, such as an external contact or solder ball.
- FIGS. 11 to 13 show schematic cross sections through part of a metal object after method steps for producing a surface section with nanopores surrounded by a pore-free metal oxide layer in a metal matrix.
- FIG. 11 again shows a schematic cross section through part of a metal object.
- This metal object, a metal core 6, has a macroscopically smooth surface 3, which forms a metal surface 9 which is still non-porous.
- FIG. 12 again shows a schematic cross section through part of a metal object after its entire surface has been oxidized. This creates a metal oxide layer 12 which covers a pore-free metal core 6. This metal oxide layer is partially covered with a mask 13, so that only the surface area 14 can be reduced.
- a metal object prepared in this way has insulation surfaces in the form of metal oxide surfaces 12 and surface sections 14 which are conductive and additionally have nanopores, so that a further substance can be mechanically connected to this surface.
- Such a structure is particularly suitable for the application of external contacts in the form of solder balls, since a solder stop layer is automatically realized by the surrounding metal oxide layer 12, while an ideal anchoring of the solder ball to the external contact area is possible in the area of the nanopores.
- FIGS. 14 to 16 show schematic cross sections through part of a metal object after method steps for producing an isolated surface section with nanopores in a metal matrix.
- FIG. 14 again shows a schematic cross section through part of a metal object.
- This metal object has a macroscopically smooth surface 3, which forms a still non-porous metal surface 9.
- FIG. 15 again shows a schematic cross section through part of a metal object after its entire surface has been oxidized. This creates a metal oxide layer 12 which covers a pore-free metal core 6. This metal oxide layer is then covered by a mask 13, which releases a surface section 14 for a reduction.
- FIG. 16 shows a schematic cross section through part of a metal object after the reduction of the surface section 14. The reduction was stopped prematurely in this exemplary embodiment, so that a metal layer region with nanopores is formed, which is surrounded all around by a metal oxide layer 12 and also by the solid metal core 6 is insulated by a buried metal oxide layer 8. What is special about this structure is that it creates a metal structure in a metal oxide that has the same metal material as the solid metal core 6.
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- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geometry (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03729885A EP1504466A2 (de) | 2002-05-14 | 2003-05-12 | Zur wenigstens teilweisen beschichtung mit einer substanz bestimmter metallgegenstand |
US10/986,372 US7384698B2 (en) | 2002-05-14 | 2004-11-12 | Metal article intended for at least partially coating with a substance and a method for producing the same |
US12/107,374 US8147621B2 (en) | 2002-05-14 | 2008-04-22 | Method for producing a metal article intended for at least partially coating with a substance |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10221503.0 | 2002-05-14 | ||
DE2002121503 DE10221503A1 (de) | 2002-05-14 | 2002-05-14 | Zur wenigstens teilweisen Beschichtung mit einer Substanz bestimmter Metallgegenstand |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/986,372 Continuation US7384698B2 (en) | 2002-05-14 | 2004-11-12 | Metal article intended for at least partially coating with a substance and a method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003096389A2 true WO2003096389A2 (de) | 2003-11-20 |
WO2003096389A3 WO2003096389A3 (de) | 2004-04-01 |
Family
ID=29285407
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/DE2003/001529 WO2003096389A2 (de) | 2002-05-14 | 2003-05-12 | Zur wenigstens teilweisen beschichtung mit einer substanz bestimmter metallgegenstand |
Country Status (4)
Country | Link |
---|---|
US (2) | US7384698B2 (de) |
EP (1) | EP1504466A2 (de) |
DE (1) | DE10221503A1 (de) |
WO (1) | WO2003096389A2 (de) |
Cited By (3)
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US7589403B2 (en) | 2005-04-29 | 2009-09-15 | Infineon Technologies Ag | Lead structure for a semiconductor component and method for producing the same |
US8178390B2 (en) | 2005-03-03 | 2012-05-15 | Infineon Technologies Ag | Semiconductor component and production method |
WO2017050702A1 (de) * | 2015-09-23 | 2017-03-30 | Siemens Aktiengesellschaft | Verfahren zur elektrischen isolierung eines elektrischen leiters insbesondere eines bauteilmoduls, leitermodul und bauteilmodul |
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US7060587B2 (en) * | 2004-02-02 | 2006-06-13 | Interuniversitair Microelektronica Centrum (Imec) | Method for forming macropores in a layer and products obtained thereof |
DE102004047510A1 (de) * | 2004-09-28 | 2006-04-13 | Infineon Technologies Ag | Halbleiterbauteil mit in Kunststoffgehäusemasse eingebetteten Halbleiterbauteilkomponenten |
DE102004049663B3 (de) * | 2004-10-11 | 2006-04-13 | Infineon Technologies Ag | Kunststoffgehäuse und Halbleiterbauteil mit derartigem Kunststoffgehäuse sowie Verfahren zur Herstellung derselben |
DE102005028704B4 (de) | 2005-06-20 | 2016-09-08 | Infineon Technologies Ag | Verfahren zur Herstellung eines Halbleiterbauteils mit in Kunststoffgehäusemasse eingebetteten Halbleiterbauteilkomponenten |
DE102005061248B4 (de) * | 2005-12-20 | 2007-09-20 | Infineon Technologies Ag | Systemträger mit in Kunststoffmasse einzubettenden Oberflächen, Verfahren zur Herstellung eines Systemträgers und Verwendung einer Schicht als Haftvermittlerschicht |
US7968144B2 (en) * | 2007-04-10 | 2011-06-28 | Siemens Energy, Inc. | System for applying a continuous surface layer on porous substructures of turbine airfoils |
WO2012054035A1 (en) * | 2010-10-21 | 2012-04-26 | Hewlett-Packard Development Company L.P. | Adhesion-promoting surface |
US20140273525A1 (en) * | 2013-03-13 | 2014-09-18 | Intermolecular, Inc. | Atomic Layer Deposition of Reduced-Leakage Post-Transition Metal Oxide Films |
JP6516399B2 (ja) * | 2013-10-25 | 2019-05-22 | セイコーインスツル株式会社 | 電子デバイス |
JP6481409B2 (ja) * | 2015-02-19 | 2019-03-13 | 三菱マテリアル株式会社 | パワーモジュール用基板及びパワーモジュール |
JP7373162B2 (ja) * | 2019-11-01 | 2023-11-02 | 国立研究開発法人産業技術総合研究所 | コネクタ及びその製造方法 |
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- 2003-05-12 EP EP03729885A patent/EP1504466A2/de not_active Withdrawn
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2004
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WO2017050702A1 (de) * | 2015-09-23 | 2017-03-30 | Siemens Aktiengesellschaft | Verfahren zur elektrischen isolierung eines elektrischen leiters insbesondere eines bauteilmoduls, leitermodul und bauteilmodul |
Also Published As
Publication number | Publication date |
---|---|
EP1504466A2 (de) | 2005-02-09 |
US7384698B2 (en) | 2008-06-10 |
US20050133910A1 (en) | 2005-06-23 |
US8147621B2 (en) | 2012-04-03 |
DE10221503A1 (de) | 2003-11-27 |
WO2003096389A3 (de) | 2004-04-01 |
US20080194063A1 (en) | 2008-08-14 |
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