WO2019131433A1 - Film métallique, composant électronique pourvu d'un film métallique et procédé de production de film métallique - Google Patents

Film métallique, composant électronique pourvu d'un film métallique et procédé de production de film métallique Download PDF

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Publication number
WO2019131433A1
WO2019131433A1 PCT/JP2018/046979 JP2018046979W WO2019131433A1 WO 2019131433 A1 WO2019131433 A1 WO 2019131433A1 JP 2018046979 W JP2018046979 W JP 2018046979W WO 2019131433 A1 WO2019131433 A1 WO 2019131433A1
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Prior art keywords
nickel
film
phosphorus
metal film
crystalline
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PCT/JP2018/046979
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English (en)
Japanese (ja)
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慎治 竹岡
弘幸 榎並
白石　憲一
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パナソニックＩｐマネジメント株式会社
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Publication of WO2019131433A1 publication Critical patent/WO2019131433A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers

Definitions

  • the present disclosure relates to a metal film, an electronic component including the metal film, and a method of manufacturing the metal film. More specifically, the present disclosure relates to a metal film suitable for alloying solder or the like to an electronic component, an electronic component including the metal film, and a method of manufacturing the metal film.
  • the nickel-phosphorus film is alloyed with solder or the like.
  • the alloy contains tin, an intermetallic compound which is a reaction product of the nickel of the nickel-phosphorus film and the tin of the alloy may be formed. Then, due to this intermetallic compound, the bond between the electronic component and the substrate is likely to be reduced.
  • Patent Document 1 proposes that the surface of a nickel-phosphorus film is covered with an electroless metal plating layer made of palladium to suppress the formation of intermetallic compounds during alloying.
  • Patent Document 1 since it is necessary to increase the number of steps for forming the electroless metal plating layer, it is conceivable that the complexity in manufacturing and the manufacturing cost increase.
  • the object of the present disclosure is to provide a metal film capable of suppressing the formation of an intermetallic compound consisting of nickel of a nickel-phosphorus film and tin of an alloy even if the nickel-phosphorus film is alloyed, an electronic component comprising a metal film, And providing a method of producing a metal film.
  • the metal film according to the present disclosure includes a nickel-phosphorus film in which crystalline Ni is dispersed.
  • An electronic component according to the present disclosure includes the metal film and a component body, and the metal film is located on the surface of the component body.
  • a method of producing a metal film according to the present disclosure comprises subjecting an amorphous film containing nickel and phosphorus to a heat treatment to reform the amorphous film into a nickel-phosphorus film in which crystalline Ni is dispersed. Including.
  • the formation of an intermetallic compound composed of nickel of the nickel-phosphorus film and tin of the alloy can be suppressed.
  • FIG. 1 shows a photograph of an example of a metal film according to an embodiment of the present disclosure taken with a transmission electron microscope.
  • FIG. 2A is a cross-sectional photograph of the distribution of tin taken with a scanning electron microscope employing energy dispersive X-ray spectroscopy in an embodiment in which a solder is bonded to the metal film.
  • FIG. 2B is a cross-sectional photograph of the distribution of nickel taken with the scanning electron microscope in the above embodiment.
  • FIG. 2C is, in the above embodiment, a cross-sectional photograph of the distribution of phosphorus taken by the scanning electron microscope.
  • FIG. 1 shows a photograph of an example of a metal film according to an embodiment of the present disclosure taken with a transmission electron microscope.
  • FIG. 2A is a cross-sectional photograph of the distribution of tin taken with a scanning electron microscope employing energy dispersive X-ray spectroscopy in an embodiment in which a solder is bonded to the metal film.
  • FIG. 2B is
  • FIG. 3A is a cross-sectional photograph of the distribution of tin taken with a scanning electron microscope as described above in a mode in which a solder is bonded to an amorphous film according to a first comparative example of the present disclosure.
  • FIG. 3B is a cross-sectional photograph of the distribution of nickel taken with the scanning electron microscope in the above embodiment.
  • FIG. 3C is a cross-sectional photograph of the distribution of phosphorus taken with the scanning electron microscope in the above embodiment.
  • FIG. 5A is a schematic cross-sectional view showing an example of a method of manufacturing a metal film according to an embodiment of the present disclosure.
  • FIG. 5B is a schematic cross-sectional view showing an example of the manufacturing method of the same.
  • FIG. 6 is a curve diagram showing, as an example, the results of differential thermal analysis on an amorphous film having a phosphorus concentration of 15 atm%, according to one embodiment of the present disclosure.
  • FIG. 7A is a third comparative example of the present disclosure, and in the aspect in which a solder is bonded to a metal film formed by heating the amorphous film at 320 ° C., the distribution of tin is measured by the scanning electron microscope. It is a cross-sectional photograph taken.
  • FIG. 7B is a cross-sectional photograph of the distribution of nickel taken with the scanning electron microscope in the above embodiment.
  • FIG. 8A is a schematic cross-sectional view showing an example of an electronic component according to an embodiment of the present disclosure.
  • FIG. 8B is a schematic cross-sectional view showing another example of the electronic component according to the embodiment of the present disclosure.
  • the metal film 1 according to the present embodiment includes a nickel-phosphorus film 1a as shown in FIG.
  • the nickel-phosphorus film 1a contains a plurality of crystalline Ni (hereinafter, crystalline nickel) 12.
  • the nickel-phosphorus film 1a further contains an amorphous structure 13 containing nickel and phosphorus.
  • the amorphous structure 13 fills the space between the adjacent crystalline nickels 12 and is in contact with the outer surface of each crystalline nickel 12.
  • the amorphous structure 13 is formed in a lattice, and crystalline nickel 12 is embedded in each lattice.
  • the total volume of the crystalline nickel 12 is larger than the total volume of the amorphous structure 13.
  • Crystalline nickel 12 is dispersed in the form of particles in the nickel-phosphorus film 1a.
  • the shape of crystalline nickel 12 is spherical.
  • the average particle diameter of such crystalline nickel 12 is preferably 3 nm or more.
  • the average particle size is 3 nm or more, the crystalline nickel 12 can easily maintain its crystal structure in the nickel-phosphorus film 1a.
  • the particle diameter of crystalline nickel 12 is 3 nm, the number of nickel atoms located on the outer surface of crystalline nickel 12 is 50% with respect to the total number 100% of nickel atoms contained in crystalline nickel 12;
  • the number of nickel atoms located inside 12 is 50%.
  • the average particle size is more preferably 5 nm or more.
  • the upper limit of the average particle size is not particularly limited as long as crystalline nickel 12 is dispersed in the nickel-phosphorus film 1a.
  • the average particle size may be, for example, 7 nm or less.
  • the average particle size is an average value of particle sizes measured for crystalline nickel 12 with a transmission electron microscope.
  • the nickel-phosphorus film 1a is a heat-treated product of an amorphous film (AL) containing nickel and phosphorus as described later.
  • A amorphous film
  • nickel is crystallized in the amorphous film (AL).
  • Such crystalline nickel 12 can contain phosphorus up to the solid solution limit as long as its crystalline structure can be maintained.
  • crystalline nickel 12 can contain 1 atm% or less of phosphorus.
  • the crystalline nickel 12 may not contain phosphorus.
  • the nickel-phosphorus film 1 a may contain more crystalline nickel 12 than crystalline Ni 3 P.
  • the crystalline Ni 3 P may be a minor component, and the crystalline nickel 12 may be a major component.
  • the nickel-phosphorus film 1a does not contain crystalline Ni 3 P.
  • the phosphorus concentration in the amorphous tissue 13 is higher than the phosphorus concentration of the amorphous film (AL). Further, even if the phosphorus concentration in the amorphous structure 13 increases with the generation and growth of the crystalline nickel 12, the amount of phosphorus in the nickel-phosphorus film 1a is the same as that of the amorphous film (AL). That is, the average phosphorus concentration (PC1) in the nickel-phosphorus film 1a is the same as the phosphorus concentration (PC2) of the amorphous film (AL).
  • the phosphorus concentration (PC2) is in the range of not less than 12.5 atm% and not more than 25 atm%.
  • the average phosphorus concentration (PC1) is also in the range of not less than 12.5 atm% and not more than 25 atm%.
  • the average phosphorus concentration (PC1) and the phosphorus concentration (PC2) may be 20 atm% or less.
  • the nickel concentration (NC) of the amorphous film (AL) may be in the range of 75 atm% to 87.5 atm%.
  • the nickel concentration (NC) may be 80 atm% or more.
  • the amorphous film (AL) contains nickel and phosphorus, and the phosphorus concentration (PC2) may be in the range of 12.5 atm% or more and 25 atm% or less, and may be any amorphous film. .
  • PC2 phosphorus concentration
  • the structure of the nickel-phosphorus film 1a can be sufficiently and clearly specified by this method.
  • the impossible and unpractical circumstances regarding the nickel-phosphorus film 1a will be described below.
  • the phosphorus concentration (PC3) in the amorphous structure 13 increases with the generation and growth of crystalline nickel 12, as described above.
  • the size and growth rate of each crystalline nickel 12 depend on the concentration of nickel around it. Therefore, the phosphorus concentration (PC3) tends to be uneven in the amorphous tissue 13.
  • the phosphorus concentration (PC3) is measured by a scanning electron microscope or the like adopting energy dispersive X-ray spectroscopy, the phosphorus concentration (PC3) is likely to differ depending on the measurement position. Therefore, even if the phosphorus concentration (PC3) is higher than the phosphorus concentration (PC2) with the generation and growth of crystalline nickel 12, the composition of the amorphous tissue 13, particularly the phosphorus concentration (PC3) is sufficiently specified. It is impossible.
  • crystalline nickel is dispersed on any substrate, and then any thin film is formed, such as vapor deposition and sputtering.
  • any thin film is formed, such as vapor deposition and sputtering.
  • the substrate is disposed with its treated surface directed downward or laterally. For this reason, it is impractical to retain crystalline nickel on the substrate during deposition of the amorphous mixture, even if the crystalline nickel is sprayed onto the substrate.
  • the nickel-phosphorus film 1 a constitutes the surface layer of the metal film 1. Therefore, the surface of the nickel-phosphorus film 1 a constitutes the exposed surface of the metal film 1.
  • the nickel-phosphorus film 1a can be joined to the alloy 2 containing tin as shown in FIGS. 2A to 2C. Do. In this case, the alloy 2 is heated and melted to be joined to the nickel-phosphorus film 1a.
  • the amorphous structure 13 makes it difficult for the nickel of the nickel-phosphorus film 1a and the tin of the alloy 2 to be mixed. For this reason, it can be made difficult to form the intermetallic compound which consists of nickel and tin. Specifically, since nickel has high affinity to phosphorus, phosphorus in the amorphous tissue 13 suppresses the reaction between nickel and tin. That is, since the phosphorus concentration (PC3) is increased by the generation of crystalline nickel 12, the amorphous structure 13 can suppress the reaction between nickel and tin.
  • PC3 phosphorus concentration
  • the reaction between nickel and tin is suppressed, the nickel of the nickel-phosphorus film 1a and the tin of the alloy 2 are less likely to be mixed, and the formation of the intermetallic compound is easily suppressed.
  • the metal film 1 after being bonded to the alloy 2 can be made less brittle.
  • the layer of the intermetallic compound is in the nickel-phosphorus film 1a or in an alloy with the nickel-phosphorus film 1a. It may be formed between two. Particularly preferably, no layer of intermetallic compound is formed. That is, the thickness of the layer of intermetallic compound is 0 ⁇ m.
  • FIGS. 2A to 2C show an embodiment in which alloy 2 is dissolved and joined in a nickel-phosphorus film 1a having an average phosphorus concentration (PC1) of 15 atm% and a thickness of 3 ⁇ m.
  • PC1 average phosphorus concentration
  • FIG. 2B the position corresponding to the surface of the alloy 2 of FIG. 2A (the surface of the part where the tin distribution is deep) is shown by a dotted line. From the result of FIG. 2B, in the thickness direction of the nickel-phosphorus film 1a, since there is no thick distribution of nickel from the dotted line to the alloy 2 side, the formation of the intermetallic compound is suppressed to such an extent that it can not be confirmed by a scanning electron microscope There is.
  • FIG. 1A the position corresponding to the surface of the alloy 2 of FIG. 2A (the surface of the part where the tin distribution is deep) is shown by a dotted line. From the result of FIG. 2B, in the thickness direction of the nickel-phosphorus film 1a, since there
  • the boundary of the part where the phosphorus distribution is dark is indicated by a dotted line. From the result of FIG. 2C, since the thickness H1 of the portion where the phosphorus distribution is deep is 3 ⁇ m, the thickness of the nickel-phosphorus film 1a is maintained even if the alloy 2 is bonded to the nickel-phosphorus film 1a.
  • an amorphous film 3 containing nickel and phosphorus having a concentration of 15 atm% is employed instead of the nickel-phosphorus film 1 a, and an amorphous film 3 ⁇ m in thickness is used.
  • membrane 3 and joined it is shown.
  • FIG. 3B the position corresponding to the surface of the part where the tin distribution is deep in FIG. 3A is shown by a dotted line. From the results of FIG. 3B, in the thickness direction of the amorphous film 3, a thick distribution of nickel is shown from the dotted line on the side of the alloy 2 with a thickness H2 of about 3 ⁇ m.
  • the boundary of the portion where the phosphorus distribution is dark is indicated by a dotted line. From the result of FIG. 3C, the thickness H3 of the part where the phosphorus distribution is deep is 5 ⁇ m. Therefore, when the alloy 2 is bonded to the amorphous film 3, the nickel of the amorphous film 3 and the tin of the alloy 2 are mixed to easily form an intermetallic compound. Therefore, the thickness of the amorphous film 3 after joining with the alloy 2 is larger than that before joining.
  • the second comparative example of FIG. 4 shows the result of annealing at 220 ° C. of the product obtained by bonding the amorphous film 3 of each phosphorus concentration (15 atm%, 23 atm%) with the alloy 2.
  • the thickness of the intermetallic compound Ni 3 Sn 4
  • the thickness of the intermetallic compound is 2.5 ⁇ m with an annealing time of about 10 minutes.
  • the nickel-phosphorus film 1a is a film obtained by modifying an amorphous film (AL) containing nickel and phosphorus by heat treatment.
  • the amorphous film 3 of the second comparative example does not have a crystal structure, and the film quality tends to be unstable.
  • crystalline nickel 12 is formed by heat treatment of the amorphous film (AL).
  • the film quality of the nickel-phosphorus film 1a is stabilized, and the increase of the phosphorus concentration in the amorphous structure 13 is considered to suppress the formation of the intermetallic compound.
  • the average phosphorus concentration in the amorphous tissue 13 is considered to be much higher than 23 atm%.
  • the alloy 2 according to the present embodiment only needs to contain tin and can be melted and joined to the nickel-phosphorus film 1a, and the specific aspect of the alloy 2 is not particularly limited.
  • the alloy 2 is, for example, a solder.
  • the alloy 2 may be any solder containing tin.
  • the solder may be lead free solder. Examples of lead-free solders include Sn-Sb, Sn-Cu, Sn-Cu-Ag, Sn-Ag, Sn-Ag-Cu, Sn-Ag-Bi-Cu, Sn-In-Ag-Bi, and Sn-Zn. , Sn-Zn-Bi, Sn-Bi, and Sn-In.
  • the nickel-phosphorus film 1a is a thin film having a structure in which crystalline nickel 12 is dispersed, and may have a thickness that can withstand bonding with the alloy 2.
  • the thickness of the nickel-phosphorus film 1a is particularly It is not limited.
  • the thickness of the nickel-phosphorus film 1a is, for example, in the range of 1 ⁇ m to 7 ⁇ m.
  • the thickness of the nickel-phosphorus film 1a is the same as the thickness of the amorphous film (AL).
  • the metal film 1 may further include one or more other metal layers if the surface layer is a nickel-phosphorus film 1a.
  • This metal layer can be composed of any metal material such as nickel, nickel-boron, iridium and the like. Also, the metal film 1 may be composed of only the nickel-phosphorus film 1a.
  • the method for producing a metal film according to the present embodiment is a method for producing the metal film 1.
  • the amorphous film 5 containing nickel and phosphorus is heat-treated to form an amorphous nickel-phosphorus film 1a in which crystalline nickel 12 is dispersed. It comprises modifying the quality membrane 5.
  • the amorphous film 5 is the above-mentioned amorphous film (AL). As shown in FIG. 5A, the amorphous film 5 is formed on the surface of the base 6, for example, the component body of the electronic component, with its one surface exposed. In this case, the amorphous film 5 may be in contact with the substrate 6. After the formation of the amorphous film 5, the amorphous film 5 is heat-treated to be reformed into a nickel-phosphorus film 1a. In this case, the nickel-phosphorus film 1a may be in contact with the substrate 6. Further, when the amorphous film 5 is modified, nickel atoms in the amorphous film 5 are aggregated to form crystalline nickel 12.
  • the phosphorus concentration (PC3) in the amorphous tissue 13 is higher than the phosphorus concentration (PC2) of the amorphous film 5 before heating.
  • the amorphous film 5 is heat-treated at a temperature at which nickel in the amorphous film 5 is crystallized.
  • the crystallization temperature of nickel is a temperature lower than the crystallization temperature of Ni 3 P as shown in FIG.
  • an amorphous film 5 may be heat treated at a temperature between peak (P1) and peak (P2). That is, the amorphous film 5 may be heat-treated at a temperature at which the amount of generation of crystalline nickel 12 is larger than the amount of generation of crystalline Ni 3 P.
  • the example of FIG. 6 shows the result of differential thermal analysis of the amorphous film 5 having a phosphorus concentration (PC2) of 15 atm%. The results in FIG. 6 indicate that crystalline nickel 12 is generated at a heating temperature of 150 ° C.
  • the generation of crystalline Ni 3 P is most accelerated at a heating temperature of 320 ° C.
  • the peak temperature of the peak (P2) tends to shift to a lower temperature side as the phosphorus concentration in the amorphous film 5 before heating is higher. For this reason, when the crystalline Ni 3 P is not generated at the time of reforming the amorphous film 5, the amorphous film 5 is heat-treated with the temperature at which the crystalline Ni 3 P is not generated as the upper limit.
  • the amorphous film 5 is heat-treated in vacuum or in an inert gas.
  • the amorphous film 5 is heat-treated, for example, in a chamber.
  • Inert gases include, for example, nitrogen and argon.
  • the heating time of the amorphous film 5 is appropriately set as long as the nickel-phosphorus film 1a can be formed.
  • the heating time of the amorphous film 5 is, for example, in the range of 0.5 hours or more and 24 hours or less.
  • the nickel-phosphorus of FIG. 1 is obtained by heat treating the amorphous film 5 having a phosphorus concentration (PC2) of 15 atm% and a thickness of 3 ⁇ m in nitrogen gas at 220 ° C. for 1 hour.
  • PC2 phosphorus concentration
  • An embodiment is shown in which the film 1a is formed, and the alloy 2 is dissolved and bonded to the nickel-phosphorus film 1a. From the results of FIGS. 2A to 2C, even when the alloy 2 is bonded to the nickel-phosphorus film 1a, the thickness of the nickel-phosphorus film 1a is maintained.
  • a nickel-phosphorus film 1a is formed by the same procedure as described above except that the amorphous film 5 is heat-treated at 150 ° C., 185 ° C., 220 ° C., or 255 ° C., and the alloy 2 is bonded to the nickel-phosphorus film 1a. Even if this is done, the thickness of the nickel-phosphorus film 1a is maintained.
  • the amorphous film 5 having a phosphorus concentration (PC2) of 15 atm% and a thickness of 3 ⁇ m is heat-treated at 320 ° C. in nitrogen gas for 1 hour.
  • a nickel-phosphorus film 1b in which Ni 3 P is generated is formed.
  • the alloy 2 is melted and joined to the nickel-phosphorus film 1b.
  • FIG. 7B the position corresponding to the surface of the part where tin distribution is thick is shown by a dotted line in FIG. 7A. From the results of FIG.
  • a thick distribution of nickel is shown with a thickness H4 of about 3 ⁇ m from the dotted line to the alloy 2 side in the thickness direction of the nickel-phosphorus film 1b. That is, when the alloy 2 is bonded to the nickel-phosphorus film 1b, the nickel of the nickel-phosphorus film 1b and the tin of the alloy 2 are easily mixed. As a result, the reaction between nickel and tin is facilitated, and the intermetallic compound is easily formed. Further, when the amorphous film 5 by reformed to generate a crystalline Ni 3 P, Ni - in phosphorus film 1b, is considered a layer of crystalline Ni 3 P is present. For this reason, the phosphorus concentration in the surface layer of the nickel-phosphorus film 1b is lower than the phosphorus concentration (PC2), which is considered to result in the formation of an intermetallic compound.
  • PC2 phosphorus concentration
  • the amorphous film 5 according to the present embodiment is a thin film as long as it can be reformed into the nickel-phosphorus film 1a at a temperature at which nickel is crystallized, and the thickness of the amorphous film 5 is not particularly limited.
  • the thickness of the amorphous film 5 is, for example, in the range of 1 ⁇ m to 7 ⁇ m.
  • the amorphous film 5 can be formed by any thin film formation method such as vapor deposition, sputtering, electrolytic plating, and electroless plating.
  • the surface of the metal film 1 is a nickel-phosphorus film 1a
  • one or a plurality of other metal layers may be formed between the nickel-phosphorus film 1a and the base 6.
  • This metal layer can be formed by any thin film formation method such as vapor deposition, sputtering, electrolytic plating, and electroless plating.
  • the metal film 1 may be composed of only the nickel-phosphorus film 1a. That is, the nickel-phosphorus film 1a may be formed in contact with the substrate 6.
  • FIGS. 8A to 8B an electronic component according to an embodiment will be described with reference to FIGS. 8A to 8B.
  • the same reference numerals are given to configurations overlapping with the description of the metal film 1 and the description of the manufacturing method of the metal film 1, and the description thereof is omitted. That is, in the present embodiment, the description of the metal film 1 and the description of the method of manufacturing the metal film 1 can be referred to.
  • the base 6 is a component body of the electronic component 10.
  • the electronic component 10 is equipped with the metal film 1 and the component main body 6 like FIG. 8A.
  • the metal film 1 is located on the surface of the component body 6.
  • the metal film 1 may be in contact with the component body 6.
  • the surface layer of the metal film 1 is the nickel-phosphorus film 1a as described above. For this reason, even if the alloy 2 is dissolved in the nickel-phosphorus film 1a and then joined, the nickel of the nickel-phosphorus film 1a and the tin of the alloy 2 become difficult to be mixed, so that the intermetallic compound can be hardly generated.
  • the component body 6 has a first end 61 and a second end 62.
  • the second end 62 is an end of the component body 6 at a position different from the first end 61.
  • the second end 62 is an end located opposite to the first end 61 in one cross section of the component body 6.
  • metal films 1 and 1 are formed on the first end 61 and the second end 62, respectively.
  • the metal film 1 is connected to the first conductor 71 by the alloy 2.
  • the metal film 1 is connected to the second conductor 72 with the alloy 2 on the side of the second end 62 of the component body 6.
  • the first end 61 and the second end 62 may be in contact with the metal film 1, 1 respectively.
  • the electronic component 10 may or may not include the first conductor 71 and the second conductor 72.
  • the electronic component 10 may have the metal film 1, the alloy 2, and the first conductor 61 at the first end 61 along the thickness direction of the component body 6. It has a structure in which one conductor 71 is stacked in this order. Furthermore, the electronic component 10 also has a structure in which the metal film 1, the alloy 2, and the second conductor 72 are laminated in this order at the second end 62 along the thickness direction of the component body 6.
  • the metal film 1 on the first end 61 side is connected to the first conductor 71 on the substrate with the alloy 2, and the second end 62 side
  • the metal film 1 is connected by an alloy 2 to a second conductor 72 on the substrate.
  • the first conductor 71 may have conductivity, and a specific aspect of the first conductor 71 is not particularly limited.
  • the shape of the first conductor 71 is, for example, a thin film.
  • any thin film forming method such as vapor deposition, sputtering, electrolytic plating, and electroless plating can be adopted.
  • As a material which comprises the 1st conductor 71 copper, nickel, platinum, and gold are mentioned, for example.
  • the 2nd conductor 72 should just have conductivity, and the specific mode of the 2nd conductor 72 is not specifically limited.
  • the shape of the second conductor 72 is, for example, a thin film.
  • any thin film forming method such as vapor deposition, sputtering, electrolytic plating, and electroless plating can be adopted.
  • As a material which comprises the 2nd conductor 72 copper, nickel, platinum, and gold are mentioned, for example.
  • the component main body 6 should just be applicable to arbitrary electric devices, and the specific aspect of the component main body 6 is not specifically limited.
  • the component main body 6 is a main body in any electronic component such as, for example, a diode, a capacitor, a resistor, and a thermoelectric conversion element.
  • the component body 6 may include a semiconductor.
  • the electronic component 10 may be a thermoelectric conversion element 10 p as shown in FIG. 8B.
  • the thermoelectric conversion element 10p is supplied with a direct current to function, and thereby, a temperature difference can be generated on both sides of the thermoelectric conversion element 10p.
  • the thermoelectric conversion element 10p can generate electric power by converting the temperature difference (difference in thermal energy) on both sides thereof into electric power energy.
  • the component body 6 When the electronic component 10 is the thermoelectric conversion element 10 p, the component body 6 includes a semiconductor. Specifically, the component body 6 includes a P-type semiconductor 6a and an N-type semiconductor 6b. The P-type semiconductors 6a and the N-type semiconductors 6b are alternately arranged and connected in series along the direction in which electricity flows in the thermoelectric conversion element 10p.
  • the P-type semiconductor 6 a has a first end 601 and a second end 602 opposite to the first end 601 in the thickness direction of the P-type semiconductor 6 a.
  • the metal film 1, the alloy 2, and the first conductor 71 are stacked in this order at the first end 601. Furthermore, the metal film 1, the alloy 2, and the second conductor 72 are stacked in this order on the second end 602.
  • the first end 601 and the second end 602 may be in contact with the metal film 1, 1 respectively.
  • the N-type semiconductor 6 b has a first end 611 and a second end 612 located on the opposite side of the first end 611 in the thickness direction of the N-type semiconductor 6 b.
  • the metal film 1, the alloy 2, and the first conductor 71 are stacked in this order at the first end 611.
  • the metal film 1, the alloy 2, and the second conductor 72 are stacked in this order.
  • the first end 611 and the second end 612 may be in contact with the metal film 1, 1 respectively.
  • Each of the P-type semiconductor 6a and the N-type semiconductor 6b includes a semiconductor.
  • the semiconductor preferably forms an ohmic contact with the metal film 1, particularly nickel in the nickel-phosphorus film 1a.
  • the work function of the portion of the metal film 1 in contact with the semiconductor becomes less susceptible to the influence of tin. That is, the Schottky contact between the semiconductor, the tin, and the intermetallic compound composed of tin and nickel is less likely to occur, and the electrical resistance due to the intermetallic compound may be less likely to occur.
  • the first conductor 71 and the second conductor 72 When there is a temperature difference between the first conductor 71 and the second conductor 72, one of the first conductor 71 and the second conductor 72 has a high temperature, and the remaining conductors have a low temperature.
  • the first conductor 71 has a high temperature
  • the formation of the intermetallic compound can be suppressed in each of the metal film 1 at the first end 601 and the metal film 1 at the first end 611. For this reason, even if the first conductor 71 is continued at a high temperature, the formation of the intermetallic compound is likely to be continuously suppressed.
  • the formation of the intermetallic compound can be suppressed in each of the metal film 1 at the second end 602 and the metal film 1 at the second end 612. For this reason, even if the second conductor 72 is continued at a high temperature, the formation of the intermetallic compound is likely to be continuously suppressed.
  • the electric resistance caused by the intermetallic compound is less likely to occur, and the power generation efficiency of the thermoelectric conversion element 10 p can be improved.
  • thermoelectric conversion element 10p is a Peltier element
  • suppressing the formation of the intermetallic compound with the high temperature metal film 1 makes it difficult to cause an electrical resistance due to the intermetallic compound, so the first conductor 71 and the first conductor 71 A more accurate temperature difference can be obtained between the two conductors 72.
  • Examples of the semiconductor included in the N-type semiconductor 6 b include BiTe-based semiconductors such as Bi 2 Te 3 . If N-type semiconductor 6b comprises a semiconductor Bi 2 Te 3, the electron affinity of the semiconductor Bi 2 Te 3 is 5.14EV.
  • the work function of nickel is 5.15 eV on average, and this work function has a width of 5.04 to 5.35 eV depending on the plane orientation.
  • the work function of tin is 4.42 eV. That is, the electron affinity of the semiconductor Bi 2 Te 3 is about the same as the work function of nickel in the metal film 1, and both form an ohmic contact.
  • the semiconductor contained in the P-type semiconductor 6a include BiTe-based semiconductor such as Bi 0.5 Sb 1.5 Te 3.
  • P-type semiconductor 6a comprises a semiconductor Bi 0.5 Sb 1.5 Te 3
  • the electron affinity of the semiconductor Bi 0.5 Sb 1.5 Te 3 is 4.50EV
  • the band gap energy is 0.20 eV.
  • the sum of the electron affinity and the band gap energy of the semiconductor Bi 0.5 Sb 1.5 Te 3 is 4.70 eV.
  • the work function of nickel is 5.15 eV on average, and this work function has a width of 5.04 to 5.35 eV depending on the plane orientation.
  • the work function of tin is 4.42 eV.
  • the sum of the electron affinity and the band gap energy needs to be smaller than the work function of the metal film.
  • the sum of the electron affinity and the band gap energy of the semiconductor Bi 0.5 Sb 1.5 Te 3 is 0.45 eV smaller than the work function of nickel, and both form an ohmic contact.
  • the work function of tin contained in alloy 2 is smaller than the sum of the electron affinity and the band gap energy of the semiconductor Bi 0.5 Sb 1.5 Te 3 .
  • the metal film 1 can suppress the diffusion of tin in the alloy 2. Therefore, the work function of the metal film 1 is less susceptible to the influence of tin in the portion where the P-type semiconductor 6a and the metal film 1 are in contact. That is, it the semiconductor Bi 0.5 Sb 1.5 Te 3, tin and, since the Schottky contact between the intermetallic compound of tin and nickel is less likely to occur, less likely to cause an electrical resistance due to the intermetallic compound.
  • thermoelectric conversion elements When connecting the P-type semiconductor 6a and the N-type semiconductor 6b in series, the same procedure as any of the thermoelectric conversion elements can be adopted.
  • one of the first conductor 71 and the second conductor 72 is divided between the P-type semiconductor 6a and the N-type semiconductor 6b, and the remaining conductors are the P-type semiconductor 6a and the N-type The semiconductor 6b is connected.
  • the first embodiment includes the nickel-phosphorus film (1a) which is the metal film (1) and in which the crystalline Ni (12) is dispersed.
  • the nickel-phosphorus film (1a) is applied with the alloy (2), formation of an intermetallic compound consisting of nickel of the nickel-phosphorus film (1a) and tin of the alloy (2) Can be suppressed.
  • a second aspect is the metal film (1) of the first aspect, wherein the nickel-phosphorus film (1a) contains crystalline Ni (12) more than crystalline Ni 3 P.
  • the formation of an intermetallic compound consisting of the nickel of the nickel-phosphorus film (1a) and the tin of the alloy (2) can be suppressed.
  • a third aspect is the metal film (1) of the second aspect, wherein the nickel-phosphorus film (1a) does not contain crystalline Ni 3 P.
  • a fourth aspect is the metal film (1) according to any one of the first to third aspects, wherein the average particle diameter of the crystalline Ni (12) is 3 nm or more.
  • the crystalline nickel (12) can easily maintain the crystalline structure in the nickel-phosphorus film (1a).
  • a fifth aspect is the metal film (1) according to any one of the first to fourth aspects, wherein the average phosphorus concentration in the nickel-phosphorus film (1a) is at least 12.5 atm% and at most 25 atm%. It is in the range.
  • the formation of an intermetallic compound consisting of the nickel of the nickel-phosphorus film (1a) and the tin of the alloy (2) can be suppressed.
  • the sixth aspect is the metal film (1) according to any one of the first to fifth aspects, wherein the nickel-phosphorus film (1a) is capable of bonding to an alloy (2) containing tin. Membrane.
  • a seventh aspect is an electronic component (10), including the metal film (1) of any one of the first to sixth aspects and a component body (6).
  • the metal film (1) is located on the surface of the component body (6).
  • the seventh aspect even if the nickel-phosphorus film (1a) is alloyed (2), an intermetallic compound composed of nickel of the nickel-phosphorus film (1a) and tin of the alloy (2) is formed. Can be suppressed.
  • An eighth aspect is the electronic component (10) of the seventh aspect, wherein the component body (6) includes a semiconductor.
  • the semiconductor forms an ohmic contact with the nickel in the metal film (1).
  • the Schottky contact between the semiconductor, the tin, and the intermetallic compound made of tin and nickel can be hardly caused, the electric resistance caused by the intermetallic compound can be hardly generated.
  • a ninth aspect is a method for producing a metal film (1), wherein the amorphous film (5) containing nickel and phosphorus is subjected to a heat treatment to form a nickel-phosphorus film in which crystalline Ni (12) is dispersed.
  • (1a) includes modifying the amorphous film (5).
  • the ninth aspect even if the nickel-phosphorus film (1a) is alloyed (2), an intermetallic compound composed of nickel of the nickel-phosphorus film (1a) and tin of the alloy (2) is produced. Can be suppressed.
  • a tenth aspect is the method for producing a metal film (1) according to the ninth aspect, wherein in the amorphous film (5), the generation amount of crystalline Ni (12) becomes larger than the generation amount of crystalline Ni 3 P Heat treated at temperature.
  • An eleventh aspect is the method for producing a metal film (1) according to the tenth aspect, wherein the amorphous film (5) is heat-treated at a temperature at which crystalline Ni 3 P is not generated.
  • the alloy (2) is attached to the nickel-phosphorus film (1a), formation of an intermetallic compound consisting of nickel of the nickel-phosphorus film (1a) and tin of the alloy (2) Can be suppressed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'objectif de la présente invention est de fournir un film métallique qui permet d'empêcher la formation d'un composé intermétallique lorsqu'un film de nickel-phosphore est brasé avec un alliage, ledit composé intermétallique étant formé de nickel dans le film de nickel-phosphore et d'étain dans l'alliage. Un film métallique (1) comprend un film de nickel-phosphore (1a) dans lequel du Ni cristallin (12) est dispersé.
PCT/JP2018/046979 2017-12-26 2018-12-20 Film métallique, composant électronique pourvu d'un film métallique et procédé de production de film métallique WO2019131433A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021139034A (ja) * 2020-02-29 2021-09-16 廣志 西口 複合材料、複合材料を用いた水素容器及び複合材料の製造方法

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JPS5852832A (ja) * 1981-09-25 1983-03-29 Hitachi Ltd 半導体装置
JPS60130801A (ja) * 1983-12-19 1985-07-12 トヨタ自動車株式会社 正特性サ−ミスタ
JPH0472075A (ja) * 1990-07-10 1992-03-06 Mitsubishi Electric Corp 耐摩耗・耐食性膜の製法
JPH09223312A (ja) * 1996-02-19 1997-08-26 Nippon Micro Coating Kk 表面にアモルファス−ニッケル−リンから成る被膜層を形成して成る被加工物の加工方法
JPH1096084A (ja) * 1996-09-20 1998-04-14 Taiho Kogyo Co Ltd 摺動部材の表面処理方法
JP2001196646A (ja) * 2000-01-17 2001-07-19 Aisin Seiki Co Ltd 熱電デバイス
JP2007308802A (ja) * 2006-05-19 2007-11-29 Ching Ho マグネシウム合金基板におけるニッケル系積層構造の作成方法、該方法による表面処理マグネシウム合金物及び該方法に用いる清浄溶液と表面処理溶液
JP2008150226A (ja) * 2006-12-14 2008-07-03 Toshiba Mach Co Ltd ガラス成形用金型の製造方法
JP2011246739A (ja) * 2010-05-24 2011-12-08 Toyota Motor Corp ステンレス鋼材へのめっき方法及びそのめっき材

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Publication number Priority date Publication date Assignee Title
JPS5852832A (ja) * 1981-09-25 1983-03-29 Hitachi Ltd 半導体装置
JPS60130801A (ja) * 1983-12-19 1985-07-12 トヨタ自動車株式会社 正特性サ−ミスタ
JPH0472075A (ja) * 1990-07-10 1992-03-06 Mitsubishi Electric Corp 耐摩耗・耐食性膜の製法
JPH09223312A (ja) * 1996-02-19 1997-08-26 Nippon Micro Coating Kk 表面にアモルファス−ニッケル−リンから成る被膜層を形成して成る被加工物の加工方法
JPH1096084A (ja) * 1996-09-20 1998-04-14 Taiho Kogyo Co Ltd 摺動部材の表面処理方法
JP2001196646A (ja) * 2000-01-17 2001-07-19 Aisin Seiki Co Ltd 熱電デバイス
JP2007308802A (ja) * 2006-05-19 2007-11-29 Ching Ho マグネシウム合金基板におけるニッケル系積層構造の作成方法、該方法による表面処理マグネシウム合金物及び該方法に用いる清浄溶液と表面処理溶液
JP2008150226A (ja) * 2006-12-14 2008-07-03 Toshiba Mach Co Ltd ガラス成形用金型の製造方法
JP2011246739A (ja) * 2010-05-24 2011-12-08 Toyota Motor Corp ステンレス鋼材へのめっき方法及びそのめっき材

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021139034A (ja) * 2020-02-29 2021-09-16 廣志 西口 複合材料、複合材料を用いた水素容器及び複合材料の製造方法
JP7434700B2 (ja) 2020-02-29 2024-02-21 廣志 西口 複合材料、複合材料を用いた水素容器及び複合材料の製造方法

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