WO2022267384A1 - 一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层 - Google Patents

一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层 Download PDF

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WO2022267384A1
WO2022267384A1 PCT/CN2021/137710 CN2021137710W WO2022267384A1 WO 2022267384 A1 WO2022267384 A1 WO 2022267384A1 CN 2021137710 W CN2021137710 W CN 2021137710W WO 2022267384 A1 WO2022267384 A1 WO 2022267384A1
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concentration
electroplating solution
salt
alloy
complexing agent
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French (fr)
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高丽茵
刘志权
孙蓉
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

Definitions

  • the present application relates to the technical field of electronic manufacturing, and in particular to an Fe-Ni-P alloy electroplating solution, an electrodeposition method of an Fe-Ni-P alloy coating, and an alloy coating.
  • Inductance is one of the most basic electronic components, and the power inductors, chokes, filters, etc. composed of it are indispensable and important components of electronic circuits. If the discrete passive components can be integrated through inductors, the size reduction of the final product will be dozens or even hundreds of times of what is usually expected today. Inductive applications require high saturation induction to increase its current handling capability, high resistivity to reduce eddy current losses, and low coercive force to reduce hysteresis losses.
  • the atomic magnetic moments of Fe (iron), Co (cobalt), and Ni (nickel) are 2.2 ⁇ B, 1.7 ⁇ B, and 0.6 ⁇ B, respectively.
  • Moment is close to that of pure iron. Since the wave functions of the 3d electrons of Fe, Co, and Ni overlap each other, the metals and alloys can be ferromagnetic through direct exchange, and the magnetic permeability after alloying is higher than that of pure metals. , so the soft magnetic alloy is generally based on one or two transition metals Fe, Co, Ni.
  • the existing Fe-Ni, Fe-Co binary and multi-element alloy soft magnetic materials can be obtained by electrodeposition, which is low in cost and high in preparation efficiency, but its resistivity is low.
  • the formulations of electroless Fe-Ni-P plating include systems using acetic acid (salt), citric acid (salt), glycine, etc. as complexing agents.
  • the above-mentioned complexing agents cannot effectively adjust the precipitation potential of each metal ion, resulting in insufficient polarization of the plating solution, severe hydrogen evolution reaction, and the final obtained Fe-Ni-P
  • the coating often has a large coercive force, and the surface of the Fe-Ni-P coating is relatively rough and the stress is large.
  • the technical problem mainly solved by this application is to provide a Fe-Ni-P alloy electroplating solution, an electrodeposition method of Fe-Ni-P alloy coating and an alloy coating, by adding citric acid (salt) and nitrilotriacetic acid to the electroplating solution (Salt) as a double complexing agent can solve the problem of high coercive force of Fe-Ni-P coating.
  • the first technical scheme that the application adopts is to provide a kind of Fe-Ni-P alloy electroplating solution, comprise main salt, complexing agent and water, complexing agent comprises double complexing agent, double complexing agent Including citric acid and nitrilotriacetic acid, or citric acid and nitrilotriacetic acid salt, or citrate and nitrilotriacetic acid, or citrate and nitrilotriacetic acid salt; of double complexing agents, nitrilotriacetic acid or nitrilotriacetic acid
  • the ratio of the concentration of acetate to the concentration of citric acid or citrate is 0.5 ⁇ 5; wherein, the concentration of citric acid or citrate is 0.01 ⁇ 0.5mol/L, and the concentration of nitrilotriacetic acid or nitrilotriacetate 0.01 ⁇ 0.5mol/L.
  • the electroplating solution also includes rare earth elements; wherein, the rare earth elements include rare earth salts or rare earth oxides, and the concentration of the rare earth salts or rare earth oxides is 0.25 ⁇ 0.4g/L; the rare earth elements are La, Ce, Pr, Nd, Pm, One or two of Sm, Eu, Gd and Tb.
  • the main salt includes ferrous salt, nickel salt and hypophosphite; wherein, the concentration of ferrous salt is 0.01 ⁇ 0.5mol/L, the concentration of nickel salt is 0.01 ⁇ 0.5mol/L, and the concentration of hypophosphite 0.01 ⁇ 0.3mol/L.
  • the ferrous salt includes FeSO 4 and/or FeCl 2
  • the nickel salt includes one or both of NiSO 4 , Ni (NH 2 SO 3 ) 2 and NiCl 2
  • the hypophosphite includes NaH 2 PO 2 .
  • the electroplating solution further includes antioxidant, brightener and wetting agent; wherein, the concentration of antioxidant is 0.01 ⁇ 5g/L, the concentration of brightener is 0.01 ⁇ 5g/L, and the concentration of wetting agent is 0.01 ⁇ 5g/L. L; wherein, the antioxidant includes ascorbic acid, the brightener includes sodium saccharin or butynediol, and the wetting agent includes sodium lauryl sulfate.
  • the second technical solution adopted by the present application is to provide a method for electrodeposition of Fe-Ni-P alloy coating, comprising: obtaining Fe-Ni-P alloy electroplating solution, the electroplating solution includes main salt, complexing complexing agent including double complexing agent, double complexing agent including citric acid and nitrilotriacetic acid, or citric acid and nitrilotriacetic acid salt, or citrate and nitrilotriacetic acid, or citrate and ammonia Triacetate; in the double complexing agent, the ratio of the concentration of nitrilotriacetic acid or nitrilotriacetate to the concentration of citric acid or citrate is 0.5 ⁇ 5; wherein the concentration of citric acid or citrate is 0.01 ⁇ 0.5mol/L, the concentration of nitrilotriacetic acid or nitrilotriacetic acid salt is 0.01 ⁇ 0.5mol/L; obtain the substrate that has been surface treated;
  • the substrate includes a block or film of metal material, a PCB circuit board, and a silicon wafer sputtered with a thin metal layer.
  • the content of each element in the Fe-Ni-P alloy coating is adjusted by changing the content of the main salt in the electroplating solution, the content of the complexing agent and any one or several of the process parameters in the electrodeposition process; wherein, the process Parameters include current density, voltage, pH of the plating solution, and temperature of the plating solution.
  • the voltage under the constant voltage control condition is 0.7-4.0V
  • the current density under the constant current condition is 2.0 ⁇ 9.0A/dm 2
  • the pH value of the electroplating solution is controlled at 2 ⁇ 5
  • the temperature of the electroplating solution is controlled at 45 ⁇ 60°C.
  • the third technical solution adopted by the present application is to provide a Fe-Ni-P alloy coating, which is made by the above-mentioned electrodeposition method, and the alloy coating includes Fe, Ni and P ;
  • the application provides a Fe-Ni-P alloy electroplating solution, an electrodeposition method of the Fe-Ni-P alloy coating and an alloy coating, by adding citric acid to the electroplating solution (salt) and nitrilotriacetic acid (salt) as a double complexing agent, using the double complexing agent and metal ions to form more stable complex ions that can exist in the solution, can adjust the precipitation potential of each metal ion in the electroplating solution,
  • the degree of electrochemical polarization of the plating solution is greatly increased, so that the prepared coating has a low degree of disorder and fewer internal structural defects, thereby reducing the coercive force of the Fe-Ni-P alloy coating, and obtaining a coating with a bright surface and a fine structure.
  • Fig. 1 is the schematic flow sheet of an embodiment of the electrodeposition method of Fe-Ni-P alloy coating of the present application
  • Fig. 2 is the surface topography figure of coating in the embodiment 1 ⁇ 5 of the present application and comparative example 1;
  • Fig. 3 is the component analysis result figure of coating in the embodiment 1 ⁇ 5 of the present application and comparative example 1;
  • Fig. 4 is the hysteresis loop schematic diagram of coating in embodiment 3 of the present application.
  • Fig. 5 is the comparative schematic diagram of the hysteresis loop of the coating in Example 6 of the present application and the hysteresis loop of the coating in Comparative Example 2;
  • FIG. 6 is a schematic diagram comparing the hysteresis loop of the coating in Example 6 of the present application with the hysteresis loop of the coating in Comparative Example 3.
  • FIG. 6 is a schematic diagram comparing the hysteresis loop of the coating in Example 6 of the present application with the hysteresis loop of the coating in Comparative Example 3.
  • Inductance is one of the most basic electronic components, and the power inductors, chokes, filters, etc. composed of it are indispensable and important components of electronic circuits. If the discrete passive components can be integrated through inductors, the size reduction of the final product will be dozens or even hundreds of times of what is usually expected today. Inductive applications require high saturation induction to increase its current handling capability, high resistivity to reduce eddy current losses, and low coercive force to reduce hysteresis losses.
  • the atomic magnetic moments of Fe, Co, and Ni are 2.2 ⁇ B, 1.7 ⁇ B, and 0.6 ⁇ B, respectively.
  • the atomic magnetic moments of Fe-Co and Fe-Ni alloys are close to those of pure iron. Since the wave functions of the 3d electrons of Fe, Co, and Ni overlap each other, the metals and alloys can be ferromagnetic through direct exchange, and the magnetic permeability after alloying is higher than that of pure metals. , so the soft magnetic alloy is generally based on one or two transition metals Fe, Co, Ni.
  • the existing Fe-Ni, Fe-Co binary and multi-element alloy soft magnetic materials can be obtained by electrodeposition, which is low in cost and high in preparation efficiency, but its resistivity is low.
  • the formulations of electroless Fe-Ni-P plating include systems using acetic acid (salt), citric acid (salt), glycine, etc. as complexing agents.
  • the above-mentioned complexing agents cannot effectively adjust the precipitation potential of each metal ion, resulting in insufficient polarization of the plating solution, severe hydrogen evolution reaction, and the final obtained Fe-Ni-P
  • the coating often has a large coercive force, and the surface of the Fe-Ni-P coating is relatively rough and the stress is large.
  • the application provides a Fe-Ni-P alloy electroplating solution, an electrodeposition method of Fe-Ni-P alloy coating and an alloy coating, by adding citric acid (salt) and nitrilotriacetic acid in the electroplating solution as bis
  • the complexing agent can solve the problem of high coercive force of Fe-Ni-P coating.
  • the double complexing agent and metal ions form more stable complexed ions that can exist in the solution, and adjust the electroplating process.
  • the precipitation potential of each metal ion in the solution can greatly increase the electrochemical polarization degree of the plating solution, so that the prepared coating has a lower degree of disorder and fewer internal structural defects, thereby reducing the coercive force of the Fe-Ni-P alloy coating , to obtain a bright surface and a fine-grained coating.
  • the Fe-Ni-P alloy electroplating solution provided by the application includes main salt, complexing agent and water, the complexing agent includes double complexing agent, and double complexing agent includes citric acid (C 6 H 8 O 7 , Citric Acid , CA) and nitrilotriacetic acid (N(CH 2 COOH) 3 , Nitrilo triacetic acid, NTA), or citric acid and nitrilotriacetic acid, or citrate and nitrilotriacetic acid, or citrate and nitrilotriethyl salt; in the double complexing agent, the ratio of the concentration of nitrilotriacetic acid or nitrilotriacetic acid salt to the concentration of citric acid or citrate is 0.5 ⁇ 5; wherein, the concentration of citric acid or citrate is 0.01 ⁇ 0.5 mol/L, the concentration of nitrilotriacetic acid or nitrilotriacetic acid salt is 0.01 ⁇ 0.5mol/L.
  • the citrate includes sodium citrate (C 6 H 5 Na 3 O 7 ).
  • the double complexing agent can perform better complexation with metal ions.
  • the higher the concentration of nitrilotriacetic acid or nitrilotriacetic acid salt the higher the content of Fe in the final alloy coating and the higher the saturation magnetic induction.
  • the main salt includes ferrous salt, nickel salt and hypophosphite; wherein, the concentration of ferrous salt is 0.01-0.5mol/L, the concentration of nickel salt is 0.01-0.5mol/L, and the concentration of hypophosphite The concentration of salt is 0.01 ⁇ 0.3mol/L.
  • ferrous salt includes FeSO 4 (ferrous sulfate) and/or FeCl 2 (ferrous chloride)
  • nickel salt includes NiSO 4 (nickel sulfate), Ni (NH 2 SO 3 ) 2 (nickel sulfamate) and One or both of NiCl 2 (nickel chloride)
  • hypophosphites include NaH 2 PO 2 (sodium hypophosphite).
  • doping the non-metallic element P on the basis of the Fe-Ni alloy can increase the resistivity of the alloy coating. Since the co-deposition potential of Fe-Ni-P alloy is relatively negative, citric acid (salt) and nitrilotriacetic acid are added as double complexing agents in the electroplating solution, and the double complexing agent can be used to form complex ions with metal ions.
  • the ions are more stable than the previous metal ions, which can make it more difficult for the metal to deposit out of the solution, thereby adjusting the precipitation potential of each metal ion in the electroplating solution, increasing the electrochemical polarization of the plating solution, and making the generated tissue More delicate to further generate Fe-Ni-P alloy coatings with lower disorder and fewer internal structural defects, and low coercive force usually benefits from lower disorder of the coating and fewer internal structural defects.
  • the electroplating solution further includes an antioxidant, a brightener and a wetting agent; wherein, the concentration of the antioxidant is 0.01 to 5 g/L, the concentration of the brightener is 0.01 to 5 g/L, and the concentration of the wetting agent is 0.01 ⁇ 5g/L;
  • antioxidants include ascorbic acid
  • brighteners include sodium saccharin or butynediol
  • wetting agents include sodium lauryl sulfate.
  • the electroplating solution also includes H 3 BO 3 (boric acid), wherein the concentration of H 3 BO 3 is 0.25 ⁇ 1 mol/L.
  • H 3 BO 3 boric acid
  • boric acid as a buffer, can suppress the change of the pH value of the electroplating solution during electroplating.
  • the electroplating solution also includes rare earth elements (RE); wherein, the rare earth elements include rare earth salts or rare earth oxides, and the concentration of the rare earth salts or rare earth oxides is 0.25 ⁇ 0.4g/L; the rare earth elements are La (lanthanum ), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (uranium), Gd (gadolinium) and Tb (terbium).
  • the rare earth elements include rare earth salts or rare earth oxides, and the concentration of the rare earth salts or rare earth oxides is 0.25 ⁇ 0.4g/L; the rare earth elements are La (lanthanum ), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (uranium), Gd (gadolinium) and Tb (terbium).
  • adding an appropriate amount of rare earth elements can increase the polarization of the plating solution.
  • this embodiment adds citric acid (salt) and nitrilotriacetic acid (salt) as double complexing agents to the electroplating solution, and utilizes double complexing agents and metal ions to form more stable metal ions that can exist in the solution.
  • complex ions which can adjust the precipitation potential of each metal ion in the electroplating solution, greatly increase the degree of electrochemical polarization of the plating solution, make the prepared coating less disordered and have fewer internal structural defects, thereby reducing the Fe-Ni-
  • the coercive force of the P alloy coating can be used to obtain a coating with a bright surface and a fine structure.
  • the electroplating solution system in this embodiment is simple, high in stability, low in the concentration of each component, and has the advantages of low cost and easy promotion, it can be widely used in the fields of microelectronics and semiconductor functional devices.
  • the present application provides an electrodeposition method of Fe-Ni-P alloy coating.
  • FIG. 1 is a schematic flowchart of an embodiment of an electrodeposition method of Fe—Ni—P alloy coating in the present application. As shown in Figure 1, in this embodiment, the method includes:
  • electroplating solution includes main salt, complexing agent and water
  • complexing agent includes double complexing agent
  • double complexing agent includes citric acid and nitrilotriacetic acid, or citric acid and ammonia triacetate, or citrate and nitrilotriacetic acid, or citrate and nitrilotriacetate
  • the concentration of nitrilotriacetic acid or nitrilotriacetate in the double complexing agent was the same as that of citric acid or citrate
  • the concentration ratio is 0.5 ⁇ 5; wherein, the concentration of citric acid or citrate is 0.01 ⁇ 0.5mol/L, and the concentration of nitrilotriacetic acid or nitrilotriacetic acid salt is 0.01 ⁇ 0.5mol/L.
  • the concentrations of the main salt, complexing agent and additives in the electroplating solution are selected.
  • the main salt includes ferrous salt, nickel salt and hypophosphite; wherein, the concentration of ferrous salt is 0.01 ⁇ 0.5mol/L, the concentration of nickel salt is 0.01 ⁇ 0.5mol/L, and the concentration of hypophosphite The concentration is 0.01 ⁇ 0.3mol/L; wherein, the ferrous salt includes FeSO 4 and/or FeCl 2 , the nickel salt includes one or both of NiSO 4 , Ni (NH 2 SO 3 ) 2 and NiCl 2 , and the subferrous Phosphates include NaH 2 PO 2 .
  • the selection and parameters of the double complexing agent are as described above.
  • Additives include antioxidants, brighteners and wetting agents; wherein, the concentration of antioxidants is 0.01 ⁇ 5g/L, the concentration of brighteners is 0.01 ⁇ 5g/L, and the concentration of wetting agents is 0.01 ⁇ 5g/L; among them, Antioxidants include ascorbic acid, brighteners include sodium saccharin or butynediol, and humectants include sodium lauryl sulfate.
  • boric acid is first dissolved in deionized water at 85° C., stirred and dissolved, and sodium hypophosphite, complexing agent, additives, etc. are added in sequence.
  • NaOH cannot be used to adjust the pH after adding ferrous salt and nickel salt to prevent precipitation.
  • boric acid is first dissolved in deionized water at 85° C., stirred and dissolved, and then rare earth elements, sodium hypophosphite, complexing agents, additives, etc. are added in sequence.
  • the base material includes a block or film of a metal material, a PCB circuit board, and a silicon wafer sputtered with a thin metal layer.
  • the metals include copper (Cu), titanium (Ti), aluminum (Al), tantalum (Ta), and titanium-tungsten alloy (Ti-W).
  • the surface treatment of the substrate can remove possible dust, grease, oxides, etc. Among them, reducing the washing of the substrate can remove grease; carrying out pickling on the substrate can remove oxides.
  • the steps of alkaline cleaning of the substrate are: cleaning the surface of the substrate with deionized water to remove dust; and then placing the substrate in a 50°C degreasing alkaline solution to clean the grease on the surface of the substrate.
  • the degreasing lye is a mixture of NaOH and Na 3 PO 4 (sodium phosphate), the concentration of NaOH is 10g/L, and the concentration of Na 3 PO 4 is 20g/L; Dry and set aside.
  • the steps of pickling the substrate are: cleaning the surface of the substrate with deionized water to remove dust; then placing the substrate in the pickling solution to remove the oxide layer on the surface of the substrate to achieve the purpose of surface activation.
  • the pickling solution is 5% HCl or dilute H 2 SO 4 (sulfuric acid); rinse with deionized water after pickling, and dry it for later use.
  • process parameters of electrodeposition need to be determined.
  • the process parameters include current density, voltage, pH value of the electroplating solution and temperature of the electroplating solution.
  • the cathode and anode materials required for electroplating are selected.
  • the cathode material is the substrate
  • the anode material is Fe-Ni alloy
  • the content of Fe in the Fe-Ni alloy is 70wt.%.
  • the anode material can also be pure iron balls and pure nickel balls, wherein the volume of pure iron balls accounts for 60-70%, which is not limited in this application. Specifically, when the anode materials are pure iron balls and pure nickel balls, it is necessary to put the anode balls into the titanium basket.
  • the substrate is immersed in the electroplating solution, and electroplating is performed under constant voltage or constant current conditions, and the agitation form of cathode swing and circulating spray of the plating solution is used during the electroplating process.
  • the content of each element in the Fe-Ni-P alloy coating can be adjusted.
  • the content is adjusted to obtain alloy coatings with different components.
  • adjusting the ratio of Fe, Ni, P, and RE components in the coating can achieve controllable adjustment of the thermal expansion coefficient, magnetic properties, and electrical properties of the thin film material.
  • the voltage under the constant voltage control condition is 0.7-4.0V
  • the current density under the constant current control condition is 2.0-9.0A/dm 2 .
  • control electroplating time is 5-60min.
  • the power supply is stopped immediately, the stirring is stopped, and the plating layer and the substrate are taken out. Since the electroplating solution is acidic, it is necessary to repeatedly rinse and transfer the plating layer with deionized water to remove the residual plating solution on the surface of the plating layer. After cleaning, dry the surface of the plating layer with compressed air.
  • this embodiment provides a plating solution system with citric acid (salt) and nitrilotriacetic acid (salt) as double complexing agents, which has a more obvious polarization effect, so that the disorder of the prepared coating can be lower And there are few internal structural defects, thereby reducing the coercive force of the Fe-Ni-P alloy coating, and obtaining a coating with a bright surface and a fine structure.
  • the electroplating solution system in this embodiment is simple, high in stability, low in the concentration of each component, and has the advantages of low cost and easy promotion, it can be widely used in the fields of microelectronics and semiconductor functional devices.
  • alloy coatings with different components can also be obtained to expand the application range of materials.
  • the present application provides an Fe-Ni-P alloy coating, which is made by the above-mentioned electrodeposition method.
  • the high resistivity is obtained by non-metallic elements, generally doped with 5 ⁇ 15% non-metallic element P, which can increase the resistivity by about 10 times.
  • the iron content of the alloy coating is relatively high, so the coating has a high saturation magnetic induction; due to the doping of a part of P, it also has a high resistivity.
  • this embodiment provides a plating solution system with citric acid (salt) and nitrilotriacetic acid (salt) as double complexing agents, which has a more obvious polarization effect, so that the prepared alloy coating can be highly saturated Magnetic induction intensity, high resistivity and low coercive force are required for magnetic core materials, and its comprehensive performance is excellent, which can be applied to related electroplated magnetic film applications such as advanced integrated circuit packaging and printed circuit board manufacturing.
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, N(CH 2 COOH) 3 is 0.01mol/L, Ascorbic acid is 5g/L, sodium saccharin is 2g/L, sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH value of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10min.
  • Fe-Ni alloy Fe70wt.%
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, N(CH 2 COOH) 3 is 0.05mol/L, Ascorbic acid is 5g/L, sodium saccharin is 2g/L, sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10 min.
  • Fe-Ni alloy Fe70wt.%
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, N(CH 2 COOH) 3 is 0.10mol/L, Ascorbic acid is 5g/L, sodium saccharin is 2g/L, sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH value of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10min.
  • Fe-Ni alloy Fe70wt.%
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, N(CH 2 COOH) 3 is 0.15mol/L, Ascorbic acid is 5g/L, sodium saccharin is 2g/L, sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH value of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10min.
  • Fe-Ni alloy Fe70wt.%
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, N(CH 2 COOH) 3 is 0.20mol/L, Ascorbic acid is 5g/L, sodium saccharin is 2g/L, sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH value of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10min.
  • Fe-Ni alloy Fe70wt.%
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.10mol/L, NiSO 4 6H 2 O is 0.10mol/L, NaH 2 PO 2 is 0.20mol/L, Nd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.25mol/L, C 6 H 8 O 7 is 0.05mol/L, ascorbic acid is 5g/L, sodium saccharin is 2g/L, Sodium lauryl sulfate is 1g/L, and the rest is water.
  • the wafer sputtered with the TiW seed layer was surface-treated and placed in the plating tank, using Fe-Ni alloy (Fe70wt.%) as the anode material, adjusting the pH value of the plating solution to 3, and controlling the temperature of the plating solution to 60 °C, the current density is controlled to be 3.0A/dm 2 , and the electroplating time is controlled to be 10min.
  • Fe-Ni alloy Fe70wt.%
  • Fig. 2 is the surface topography figure of coating in the embodiment 1 ⁇ 5 of the present application and comparative example 1
  • Fig. 3 is the coating in embodiment 1 ⁇ 5 of the present application and comparative example 1 Composition analysis result graph. It can be seen from Figure 2 and Figure 3 that only the content of nitrilotriacetic acid is changed, and other conditions remain unchanged. When the content of nitrilotriacetic acid increases from 0mol/L to 0.20mol/L, the surface of the coating changes from having defects to no obvious defects.
  • the brightness of the coating is gradually improved, and the microstructure is more detailed; at the same time, the content of Fe in the alloy coating increases from 12wt.% to 80wt.%, and the content of Ni decreases from 70wt.% to 5wt.%, indicating that the composition of the coating is adjusted by nitrilotriacetic acid
  • the content of Fe can be adjusted within a wide range, and the higher the nitrilotriacetic acid content, the higher the Fe content.
  • Example 3 when nitrilotriacetic acid is 0.15mol/L, the coating composition is Fe76.80wt.%, Ni10.85wt.%, P12.35wt.%. Obtain the hysteresis loop of the coating in Example 3. Specifically, please refer to FIG. 4 , which is a schematic diagram of the hysteresis loop of the coating in Example 3 of the present application.
  • the saturation magnetic induction of the coating is 1.3T, and the coercive force is 0.8Oe, indicating that when the content of Fe is higher, the saturation magnetic induction of the coating is higher, and it also shows that nitrilotriacetic acid is added to the plating solution to form After the double complexing agent, the coercive force of the coating is lower.
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.50mol/L, NiSO 4 6H 2 O is 0.50mol/L, NaH 2 PO 2 is 0.01mol/L, Gd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.50mol/L, C 6 H 8 O 7 is 0.20mol/L, N(CH 2 COOH) 3 is 0.20mol/L, Ascorbic acid is 5g/L, sodium saccharin is 5g/L, sodium lauryl sulfate is 5g/L, and the rest is water.
  • the wafer sputtered with Ti/Cu seed layer into the plating tank after surface treatment use pure iron balls and pure nickel balls (pure iron balls account for 60 ⁇ 70% of the volume) as anode materials, adjust the plating solution
  • the pH value is 5, the temperature of the electroplating solution is controlled to be 45° C., the current density is controlled to be 6.0 A/dm 2 , and the electroplating time is controlled to be 20 minutes.
  • Fe-Ni-P alloy electroplating solution is obtained, wherein, the composition and concentration of the electroplating solution are as follows: FeSO 4 7H 2 O is 0.50 mol/L, NiSO 4 6H 2 O is 0.50 mol/L, H 3 BO 3 is 0.50mol/L, ascorbic acid 5g/L, sodium saccharin 5g/L, sodium lauryl sulfate 5g/L, and the rest is water.
  • the wafer sputtered with Ti/Cu seed layer into the plating tank after surface treatment use pure iron balls and pure nickel balls (pure iron balls account for 60 ⁇ 70% of the volume) as anode materials, adjust the plating solution
  • the pH value is 5, the temperature of the electroplating solution is controlled to be 45° C., the current density is controlled to be 6.0 A/dm 2 , and the electroplating time is controlled to be 20 minutes.
  • Fe-Ni-P alloy electroplating solution wherein, the composition and concentration of electroplating solution are as follows: FeSO 4 7H 2 O is 0.50mol/L, NiSO 4 6H 2 O is 0.50mol/L, NaH 2 PO 2 is 0.01mol/L, Gd 2 O 3 is 0.25g/L, H 3 BO 3 is 0.50mol/L, C 6 H 8 O 7 is 0.20mol/L, ascorbic acid is 5g/L, sodium saccharin is 5g/L, Sodium lauryl sulfate is 5g/L, and the rest is water.
  • the wafer sputtered with Ti/Cu seed layer into the plating tank after surface treatment use pure iron balls and pure nickel balls (pure iron balls account for 60 ⁇ 70% of the volume) as anode materials, adjust the plating solution
  • the pH value is 5, the temperature of the electroplating solution is controlled to be 45° C., the current density is controlled to be 6.0 A/dm 2 , and the electroplating time is controlled to be 20 minutes.
  • the composition of the coating in Example 2 is Fe 50wt.%, Ni 50wt.%;
  • the composition of the coating in Comparative Example 3 is Fe 33wt.%, Ni 54wt.%, P 11wt.%, Gd 2wt.%.
  • Fig. 5 is a comparative schematic diagram of the hysteresis loop of the coating in Example 6 of the present application and the hysteresis loop of the coating in Comparative Example 2.
  • Fig. 6 is a schematic diagram of the hysteresis loop in Example 6 of the present application.
  • the saturation magnetic induction of the coating in Example 6 is 1.5T, and the coercive force is 0.6Oe.
  • adding citric acid and nitrilotriacetic acid as a double complexing agent can greatly increase the polarization of the plating solution, and obtain a higher saturation while obtaining a Fe-Ni-P co-deposited film. Magnetic induction, and reduced coercive force.
  • the saturation magnetic induction of the coating in Comparative Example 3 is 1.1T, and the coercive force is 7Oe, showing that when doping sodium hypophosphite on the basis of the iron-nickel plating solution, only citric acid is added as a complexing agent, Even if rare earth elements are added, the polarization of the plating solution cannot be greatly increased, and the content of Fe in the coating is also low, resulting in low saturation magnetic induction and high coercive force of the obtained Fe-Ni-P co-deposited film.
  • Example 6 and Comparative Examples 2 and 3 observe the surface appearance of the coating in Example 6 and Comparative Examples 2 and 3 under a microscope, and find that the surface of the coating in Example 6 and Comparative Example 2 is bright without obvious defects, while the surface of the coating in Comparative Example 3 is whitish And there are cracks, indicating that when doping sodium hypophosphite on the basis of iron-nickel plating solution, adding citric acid and nitrilotriacetic acid as double complexing agents can make the prepared coating have low disorder and internal structural defects.
  • this application adds citric acid (salt) and nitrilotriacetic acid (salt) as double complexing agents to the electroplating solution, and utilizes double complexing agents and metal ions to form more stable metal ions that can exist in the solution.
  • Complex ions can adjust the precipitation potential of each metal ion in the electroplating solution, greatly increase the electrochemical polarization of the plating solution, make the prepared coating less disordered and have fewer internal structural defects, thereby reducing Fe-Ni-P
  • the coercive force of the alloy coating can be used to obtain a coating with a bright surface and a fine structure.
  • the electroplating solution system in this embodiment is simple, high in stability, low in the concentration of each component, and has the advantages of low cost and easy promotion, it can be widely used in the fields of microelectronics and semiconductor functional devices.

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Abstract

本申请公开了一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层，属于电子制造技术领域。该电镀液包括主盐、络合剂以及水，络合剂包括双络合剂，双络合剂包括柠檬酸和氨三乙酸，或柠檬酸和氨三乙酸盐，或柠檬酸盐和氨三乙酸，或柠檬酸盐和氨三乙酸盐；双络合剂中，氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5；其中，柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，氨三乙酸或氨三乙酸盐的浓度为0.01~0.5mol/L。本申请通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，能够增加镀液的电化学极化程度，使制备的Fe-Ni-P合金镀层的矫顽力较低，镀层表面光亮、组织细致，可应用于微电子领域以及半导体功能器件等领域。

Description

一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层 技术领域
本申请涉及电子制造技术领域，特别是涉及一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层。
 背景技术
电感是最基本的电子元器件之一，由其构成的功率电感器、扼流器、滤波器等是电子电路必不可少的重要元件。若能通过电感将分立的无源元件实现集成，最终产品的尺寸缩小幅度将是现在通常预计的几十倍乃至上百倍。电感应用需要较高的饱和磁感应强度以提高其电流处理能力、高的电阻率以减少涡流损耗以及低的矫顽力以减少磁滞损耗。
Fe（铁）、Co（钴）、Ni（镍）原子磁矩分别为2.2µB、1.7µB、0.6µB，在含铁量较高的成分范围内，Fe-Co、Fe-Ni合金的原子磁矩与纯铁接近。由于Fe、Co、Ni的3d电子的波函数存在相互交叠的现象，通过直接交换作用能够使其金属及合金表现为铁磁性，且合金化后的磁导率比纯金属的磁导率高，因而软磁合金大体是以过渡金属Fe、Co、Ni的一种或两种为基的。
 技术问题
目前已有的Fe-Ni、Fe-Co二元及多元合金软磁材料可以以电沉积方式获得，成本低且制备效率高，但是其电阻率较低，为进一步增加Fe-Ni合金的电阻率，通常掺杂非金属元素P。现有技术中，化学镀Fe-Ni-P的配方有分别以醋酸(盐)、柠檬酸(盐) 、甘氨酸等为络合剂的体系。然而，大多Fe-Ni-P合金由于共沉积电位较负，上述络合剂无法有效调节各金属离子的析出电位，导致镀液极化程度不够，析氢反应剧烈，最终获得的Fe-Ni-P镀层往往矫顽力较大，Fe-Ni-P镀层表面较为粗糙且应力较大。
 技术解决方案
本申请主要解决的技术问题是提供一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层，通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，能够解决Fe-Ni-P镀层矫顽力较大的问题。
为解决上述技术问题，本申请采用的第一技术方案是提供一种Fe-Ni-P合金电镀液，包括主盐、络合剂以及水，络合剂包括双络合剂，双络合剂包括柠檬酸和氨三乙酸，或柠檬酸和氨三乙酸盐，或柠檬酸盐和氨三乙酸，或柠檬酸盐和氨三乙酸盐；双络合剂中，氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5；其中，柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，氨三乙酸或氨三乙酸盐的浓度为0.01~0.5mol/L。
其中，电镀液还包括稀土元素；其中，稀土元素包括稀土盐或稀土氧化物，稀土盐或稀土氧化物的浓度为0.25~0.4g/L；稀土元素为La、Ce、Pr、Nd、Pm、Sm、Eu、Gd和Tb中的一种或两种。
其中，主盐包括亚铁盐、镍盐以及次亚磷酸盐；其中，亚铁盐的浓度为0.01~0.5mol/L，镍盐的浓度为0.01~0.5mol/L，次亚磷酸盐的浓度为0.01~0.3mol/L。
其中，亚铁盐包括FeSO 4和/或FeCl 2，镍盐包括NiSO 4、Ni (NH 2SO 3) 2以及NiCl 2中的一种或两种，次亚磷酸盐包括NaH 2PO 2。
其中，电镀液进一步包括抗氧化剂、光亮剂以及润湿剂；其中，抗氧化剂的浓度为0.01~5g/L，光亮剂的浓度为0.01~5g/L，润湿剂的浓度为0.01~5g/L；其中，抗氧化剂包括抗坏血酸，光亮剂包括糖精钠或丁炔二醇，润湿剂包括十二烷基硫酸钠。
为解决上述技术问题，本申请采用的第二技术方案是提供一种Fe-Ni-P合金镀层的电沉积方法，包括：获取Fe-Ni-P合金电镀液，电镀液包括主盐、络合剂以及水，络合剂包括双络合剂，双络合剂包括柠檬酸和氨三乙酸，或柠檬酸和氨三乙酸盐，或柠檬酸盐和氨三乙酸，或柠檬酸盐和氨三乙酸盐；双络合剂中，氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5；其中，柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，氨三乙酸或氨三乙酸盐的浓度为0.01~0.5mol/L；获取已进行表面处理的基材；将基材浸入电镀液中，在恒电压条件或恒电流条件下进行电镀，以在基材上沉积合金镀层。
其中，基材包括金属材料的块体或薄膜、PCB线路板以及溅射有金属薄层的硅片。
其中，Fe-Ni-P合金镀层中各元素的含量通过更改电镀液中主盐的含量、络合剂的含量和电沉积过程中的工艺参数中任意一项或几项进行调节；其中，工艺参数包括电流密度、电压、电镀液的pH值以及电镀液的温度。
其中，控制恒电压条件下的电压为0.7 -4.0V，控制恒电流条件下的电流密度为2.0~9.0A/dm 2，控制电镀液的pH值为2~5，控制电镀液的温度为45~60℃。
为解决上述技术问题，本申请采用的第三技术方案是提供一种Fe-Ni-P合金镀层，该Fe-Ni-P合金镀层由上述电沉积方法制成，合金镀层包括Fe、Ni以及P；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，其余为P；或，合金镀层包括Fe、Ni、P以及稀土元素；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，稀土元素>0~2%，其余为P。
 有益效果
本申请的有益效果是：区别于现有技术，本申请提供一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层，通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，利用双络合剂与金属离子形成更加稳定的能在溶液中存在的络合离子，能够调整电镀液中各金属离子的析出电位，大幅增加镀液的电化学极化程度，使制备的镀层无序度较低且内部结构缺陷较少，从而降低Fe-Ni-P合金镀层的矫顽力，获得表面光亮、组织细致的镀层。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请Fe-Ni-P合金镀层的电沉积方法一实施方式的流程示意图；
图2是本申请实施例1~5以及对比例1中镀层的表面形貌图；
图3是本申请实施例1~5以及对比例1中镀层的成分分析结果图；
图4是本申请实施例3中镀层的磁滞回线示意图；
图5是本申请实施例6中镀层的磁滞回线与对比例2中镀层的磁滞回线的对比示意图；
图6是本申请实施例6中镀层的磁滞回线与对比例3中镀层的磁滞回线的对比示意图。
 本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，均属于本申请保护的范围。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上文清楚地表示其他含义，“多种”一般包含至少两种，但是不排除包含至少一种的情况。
应当理解，本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
应当理解，本文中使用的术语“包括”、“包含”或者其他任何变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
电感是最基本的电子元器件之一，由其构成的功率电感器、扼流器、滤波器等是电子电路必不可少的重要元件。若能通过电感将分立的无源元件实现集成，最终产品的尺寸缩小幅度将是现在通常预计的几十倍乃至上百倍。电感应用需要较高的饱和磁感应强度以提高其电流处理能力、高的电阻率以减少涡流损耗以及低的矫顽力以减少磁滞损耗。
Fe、Co、Ni原子磁矩分别为2.2µB、1.7µB、0.6µB，在含铁量较高的成分范围内，Fe-Co、Fe-Ni合金的原子磁矩与纯铁接近。由于Fe、Co、Ni的3d电子的波函数存在相互交叠的现象，通过直接交换作用能够使其金属及合金表现为铁磁性，且合金化后的磁导率比纯金属的磁导率高，因而软磁合金大体是以过渡金属Fe、Co、Ni的一种或两种为基的。
目前已有的Fe-Ni、Fe-Co二元及多元合金软磁材料可以以电沉积方式获得，成本低且制备效率高，但是其电阻率较低，为进一步增加Fe-Ni合金的电阻率，通常掺杂非金属元素P。现有技术中，化学镀Fe-Ni-P的配方有分别以醋酸(盐)、柠檬酸(盐) 、甘氨酸等为络合剂的体系。然而，大多Fe-Ni-P合金由于共沉积电位较负，上述络合剂无法有效调节各金属离子的析出电位，导致镀液极化程度不够，析氢反应剧烈，最终获得的Fe-Ni-P镀层往往矫顽力较大，Fe-Ni-P镀层表面较为粗糙且应力较大。
基于上述情况，本申请提供一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层，通过在电镀液中加入柠檬酸（盐）和氨三乙酸作为双络合剂，能够解决Fe-Ni-P镀层矫顽力较大的问题。
本申请通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，利用双络合剂与金属离子形成更加稳定的能在溶液中存在的络合离子，调整电镀液中各金属离子的析出电位，能够大幅增加镀液的电化学极化程度，使制备的镀层无序度较低且内部结构缺陷较少，从而降低Fe-Ni-P合金镀层的矫顽力，获得表面光亮、组织细致的镀层。
下面结合附图和实施方式对本申请进行详细说明。
本申请所提供的Fe-Ni-P合金电镀液，包括主盐、络合剂以及水，络合剂包括双络合剂，双络合剂包括柠檬酸（C 6H 8O 7，Citric Acid，CA）和氨三乙酸（N(CH 2COOH) 3，Nitrilo triacetic acid，NTA），或柠檬酸和氨三乙酸盐，或柠檬酸盐和氨三乙酸，或柠檬酸盐和氨三乙酸盐；双络合剂中，氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5；其中，柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，氨三乙酸或氨三乙酸盐的浓度为0.01~0.5mol/L。
其中，柠檬酸盐包括柠檬酸钠（C 6H 5Na 3O 7）。
具体地，当氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5时，双络合剂能够与金属离子起到较好的络合作用。且氨三乙酸或氨三乙酸盐的浓度越高，最终形成的合金镀层中Fe的含量越高，饱和磁感应强度越高。
本实施方式中，主盐包括亚铁盐、镍盐以及次亚磷酸盐；其中，亚铁盐的浓度为0.01~0.5mol/L，镍盐的浓度为0.01~0.5mol/L，次亚磷酸盐的浓度为0.01~0.3mol/L。
其中，亚铁盐包括FeSO 4（硫酸亚铁）和/或FeCl 2（氯化亚铁），镍盐包括NiSO 4（硫酸镍）、Ni (NH 2SO 3) 2（氨基磺酸镍）以及NiCl 2（氯化镍）中的一种或两种，次亚磷酸盐包括NaH 2PO 2（次亚磷酸钠）。
具体地，在Fe-Ni合金的基础上掺杂非金属元素P，能够提高合金镀层的电阻率。由于Fe-Ni-P合金的共沉积电位较负，在电镀液中加入柠檬酸（盐）和氨三乙酸作为双络合剂，可利用双络合剂与金属离子形成络合离子，络合离子比之前金属离子的存在形式更加稳定，能够使得金属更难从溶液中沉积出来，从而调整了电镀液中各金属离子的析出电位，增大了镀液的电化学极化，使生成的组织更加细腻，以进一步生成无序度较低且内部结构缺陷较少的Fe-Ni-P合金镀层，而低矫顽力通常得益于镀层无序度较低、内部结构缺陷较少。
本实施方式中，电镀液进一步包括抗氧化剂、光亮剂以及润湿剂；其中，抗氧化剂的浓度为0.01~5g/L，光亮剂的浓度为0.01~5g/L，润湿剂的浓度为0.01~5g/L；其中，抗氧化剂包括抗坏血酸，光亮剂包括糖精钠或丁炔二醇，润湿剂包括十二烷基硫酸钠。
其中，电镀液还包括H 3BO 3（硼酸），其中，H 3BO 3的浓度为0.25~1mol/L。具体地，硼酸作为缓冲剂，在电镀中能抑制电镀液pH值的变化。
在其他实施方式中，电镀液还包括稀土元素（RE）；其中，稀土元素包括稀土盐或稀土氧化物，稀土盐或稀土氧化物的浓度为0.25~0.4g/L；稀土元素为La（镧）、Ce（铈）、Pr（镨）、Nd（钕）、Pm（钷）、Sm（钐）、Eu（铀）、Gd（钆）和Tb（铽）中的一种或两种。
具体地，添加适量的稀土元素，可以增加镀液极化。
区别于现有技术，本实施方式通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，利用双络合剂与金属离子形成更加稳定的能在溶液中存在的络合离子，能够调整电镀液中各金属离子的析出电位，大幅增加镀液的电化学极化程度，使制备的镀层无序度较低且内部结构缺陷较少，从而降低Fe-Ni-P合金镀层的矫顽力，获得表面光亮、组织细致的镀层。进一步地，由于本实施方式中的电镀液体系简单、稳定性高、各组分浓度低，还具有成本较低、易于推广的优点，能够广泛应用于微电子领域以及半导体功能器件等领域。
对应地，本申请提供了一种Fe-Ni-P合金镀层的电沉积方法。
请参阅图1，图1是本申请Fe-Ni-P合金镀层的电沉积方法一实施方式的流程示意图。如图1所示，在本实施方式中，该方法包括：
S11：获取Fe-Ni-P合金电镀液，电镀液包括主盐、络合剂以及水，络合剂包括双络合剂，双络合剂包括柠檬酸和氨三乙酸，或柠檬酸和氨三乙酸盐，或柠檬酸盐和氨三乙酸，或柠檬酸盐和氨三乙酸盐；双络合剂中，氨三乙酸或氨三乙酸盐的浓度与柠檬酸或柠檬酸盐的浓度之比为0.5~5；其中，柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，氨三乙酸或氨三乙酸盐的浓度为0.01~0.5mol/L。
本实施方式中，首先选择电镀液中主盐、络合剂以及添加剂的浓度。具体地，主盐包括亚铁盐、镍盐以及次亚磷酸盐；其中，亚铁盐的浓度为0.01~0.5mol/L，镍盐的浓度为0.01~0.5mol/L，次亚磷酸盐的浓度为0.01~0.3mol/L；其中，亚铁盐包括FeSO 4和/或FeCl 2，镍盐包括NiSO 4、Ni (NH 2SO 3) 2以及NiCl 2中的一种或两种，次亚磷酸盐包括NaH 2PO 2。双络合剂的选择及参数如上所述。添加剂包括抗氧化剂、光亮剂以及润湿剂；其中，抗氧化剂的浓度为0.01~5g/L，光亮剂的浓度为0.01~5g/L，润湿剂的浓度为0.01~5g/L；其中，抗氧化剂包括抗坏血酸，光亮剂包括糖精钠或丁炔二醇，润湿剂包括十二烷基硫酸钠。
本实施方式中，先将硼酸溶于85℃的去离子水中，搅拌溶解，依次加入次亚磷酸钠、络合剂、添加剂等。使用NaOH（氢氧化钠）以及HCl（盐酸）将所得的混合溶液的pH值调节至2~5后，加入亚铁盐以及镍盐；使用HCl微调pH后，将混合溶液倒入容量瓶中定容，以获取Fe-Ni-P合金电镀液。
其中，加入亚铁盐、镍盐后不可用NaOH调节pH，以防沉淀。
进一步地，调整电镀液的温度，控制电镀液的温度为45~60℃。
在其他实施方式中，先将硼酸溶于85℃的去离子水中，搅拌溶解，依次加入稀土元素、次亚磷酸钠、络合剂、添加剂等。使用NaOH（氢氧化钠）以及HCl（盐酸）将所得的混合溶液的pH值调节至2~5后，加入亚铁盐以及镍盐；使用HCl微调pH后，将混合溶液倒入容量瓶中定容，以获取Fe-Ni-P-RE合金电镀液。
S12：获取已进行表面处理的基材。
本实施方式中，基材包括金属材料的块体或薄膜、PCB线路板以及溅射有金属薄层的硅片。
其中，金属包括铜（Cu）、钛（Ti）、铝（Al）、钽（Ta）、钛钨合金（Ti-W）。
在基材上电沉积合金镀层前，对基体进行表面处理，能够去除可能存在的灰尘、油脂、氧化物等。其中，对基底进行减洗，可去除油脂；对基底进行酸洗，可去除氧化物。
具体地，基底碱洗的步骤为：使用去离子水清洗基底表面，以去除灰尘；再将基底置于50℃除油碱液中，以清洗基底表面的油脂。其中，除油碱液为NaOH和Na 3PO 4（磷酸钠）的混合液，NaOH的浓度为10g/L，Na 3PO 4的浓度为20g/L；碱洗后使用去离子水冲洗，吹干备用。
基底酸洗的步骤为：使用去离子水清洗基底表面，以去除灰尘；再将基底置于酸洗液中，以去除基底表面的氧化层，实现表面活化的目的。其中，酸洗液为5%的HCl或稀H 2SO 4（硫酸）；酸洗后用去离子水冲洗，吹干备用。
S13：将基材浸入电镀液中，在恒电压条件或恒电流条件下进行电镀，以在基材上沉积合金镀层。
本实施方式中，在进行电镀前，需要确定电沉积的工艺参数。其中，工艺参数包括电流密度、电压、电镀液的pH值以及电镀液的温度。
例如，选择某一电流密度，根据需要电镀的表面积，计算施加的电流。若有不需电镀部分，可用光刻胶、树脂覆盖或进行其他绝缘处理。
进一步地，选择电镀所需的阴极、阳极材料。其中，阴极材料即为基底，阳极材料为Fe-Ni合金，Fe-Ni合金中Fe的含量为70wt.%。
在其他实施方式中，阳极材料还可以为纯铁球和纯镍球，其中，纯铁球的体积占比60~70%，本申请对此不作限定。具体地，当阳极材料为纯铁球和纯镍球时，需要将阳极球装入钛篮。
进一步地，将基材浸入电镀液中，在恒电压条件或恒电流条件下进行电镀，并在电镀过程中使用阴极摆动以及镀液循环喷流的搅拌形式。
本实施方式中，通过更改电镀液中主盐的含量、络合剂的含量和电沉积过程中的工艺参数中任意一项或几项，均可以对Fe-Ni-P合金镀层中各元素的含量进行调节，以得到不同组分的合金镀层。具体地，调节镀层中Fe、Ni、P以及RE组分的比例，可以实现对薄膜材料热膨胀系数、磁性能以及电性能的可控调节。
其中，控制恒电压条件下的电压为0.7 -4.0V，控制恒电流条件下的电流密度为2.0~9.0A/dm 2。
其中，控制电镀时间为5-60min。
进一步地，在电镀时间结束后，立刻停止通电，停止搅拌，取出镀层及基底。由于电镀液为酸性，故需要用去离子水反复冲洗移镀层，以去除镀层表面的残余镀液，清洗完成后用压缩空气吹干镀层表面。
区别于现有技术，本实施方式通过提供极化效果更加明显的以柠檬酸（盐）和氨三乙酸（盐）为双络合剂的镀液体系，能够使制备的镀层无序度较低且内部结构缺陷较少，从而降低Fe-Ni-P合金镀层的矫顽力，获得表面光亮、组织细致的镀层。进一步地，由于本实施方式中的电镀液体系简单、稳定性高、各组分浓度低，还具有成本较低、易于推广的优点，能够广泛应用于微电子领域以及半导体功能器件等领域。此外，通过更改电镀液中主盐的含量、络合剂的含量和电沉积过程中的工艺参数中任意一项或几项，还能够得到不同组分的合金镀层，以扩大材料的使用范围。
对应地，本申请提供了一种Fe-Ni-P合金镀层，该合金镀层由上述电沉积方法制成。
本实施方式中，Fe-Ni-P合金镀层包括Fe、Ni以及P；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，其余为P；或，合金镀层包括Fe、Ni、P以及稀土元素；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，稀土元素>0~2%，其余为P。
具体地，Fe-Ni-P合金镀层中铁含量越高，其饱和磁感应强度越高。而高电阻率是通过非金属元素获得，一般掺杂5~15%非金属元素P，可将电阻率提高10倍左右。
本实施方式中，合金镀层的铁含量较高，故镀层具有高饱和磁感应强度；由于掺杂了部分P，还兼具有高电阻率。
更重要的是，由于电镀时使用了极化效果更加明显的以柠檬酸（盐）和氨三乙酸为双络合剂的镀液体系，因而制备的合金镀层的矫顽力较低。
区别于现有技术，本实施方式通过提供极化效果更加明显的以柠檬酸（盐）和氨三乙酸（盐）为双络合剂的镀液体系，能够使制得的合金镀层兼顾高饱和磁感应强度、高电阻率以及低矫顽力的磁芯材料要求，其综合性能优异，能够适用于先进集成电路封装以及印制线路板制造等相关电镀磁性薄膜应用领域。
为便于对本申请实施例进行理解，本申请提供了以下非限制性实施例，对本申请作进一步的详细说明。
实施例1
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，N(CH 2COOH) 3为0.01mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
实施例2
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，N(CH 2COOH) 3为0.05mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
实施例3
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，N(CH 2COOH) 3为0.10mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
实施例4
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，N(CH 2COOH) 3为0.15mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
实施例5
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，N(CH 2COOH) 3为0.20mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
对比例1
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.10mol/L，NiSO 4·6H 2O为0.10mol/L，NaH 2PO 2为0.20mol/L，Nd 2O 3为0.25g/L，H 3BO 3为0.25mol/L，C 6H 8O 7为0.05mol/L，抗坏血酸为5g/L，糖精钠为2g/L，十二烷基硫酸钠为1g/L，其余为水。将溅射有TiW种子层的晶圆进行表面处理后置于镀槽中，使用Fe-Ni合金（Fe70wt.%）作为阳极材料，调节镀液的pH值为3，控制电镀液的温度为60℃，控制电流密度为3.0A/dm 2，控制电镀时间为10min。
用电镜观察实施例1~5以及对比例1中镀层的表面形貌，以及测试实施例1~5以及对比例1中镀层的成分。
具体地，请参阅图2与图3，图2是本申请实施例1~5以及对比例1中镀层的表面形貌图，图3是本申请实施例1~5以及对比例1中镀层的成分分析结果图。由图2、图3可以看出，仅改变氨三乙酸的含量，其他条件不变，当氨三乙酸含量从0mol/L增加至0.20mol/L时，镀层表面从有缺陷至无明显缺陷，表明镀层的光亮性逐渐提升，组织结构更细致；同时合金镀层中Fe含量从12wt.%提升至80wt.%，Ni含量从70wt.%下降至5wt.%，表明镀层的成分通过调节氨三乙酸的含量可以在较大范围内调整，且氨三乙酸的含量越高，Fe的含量越高。
进一步地，实施例3中，当氨三乙酸为0.15mol/L时，镀层成分为Fe76.80wt.%，Ni10.85wt.%，P12.35wt.%。获取实施例3中镀层的磁滞回线。具体地，请参阅图4，图4是本申请实施例3中镀层的磁滞回线示意图。如图4所示，该镀层的饱和磁感应强度为1.3T，矫顽力为0.8Oe，表明Fe的含量较高时，镀层的饱和磁感应强度较高，同时还表明镀液中加入氨三乙酸形成双络合剂后，镀层的矫顽力较低。
实施例6
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.50mol/L，NiSO 4·6H 2O为0.50mol/L，NaH 2PO 2为0.01mol/L，Gd 2O 3为0.25g/L，H 3BO 3为0.50mol/L，C 6H 8O 7为0.20mol/L，N(CH 2COOH) 3为0.20mol/L，抗坏血酸为5g/L，糖精钠为5g/L，十二烷基硫酸钠为5g/L，其余为水。将溅射有Ti/Cu种子层的晶圆进行表面处理后置于镀槽中，使用纯铁球和纯镍球（纯铁球体积占比60~70%）作为阳极材料，调节镀液的pH值为5，控制电镀液的温度为45℃，控制电流密度为6.0A/dm 2，控制电镀时间为20min。
对比例2
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.50mol/L，NiSO 4·6H 2O为0.50mol/L，H 3BO 3为0.50mol/L，抗坏血酸为5g/L，糖精钠为5g/L，十二烷基硫酸钠为5g/L，其余为水。将溅射有Ti/Cu种子层的晶圆进行表面处理后置于镀槽中，使用纯铁球和纯镍球（纯铁球体积占比60~70%）作为阳极材料，调节镀液的pH值为5，控制电镀液的温度为45℃，控制电流密度为6.0A/dm 2，控制电镀时间为20min。
对比例3
获取Fe-Ni-P合金电镀液，其中，电镀液的组分及浓度如下：FeSO 4·7H 2O为0.50mol/L，NiSO 4·6H 2O为0.50mol/L，NaH 2PO 2为0.01mol/L，Gd 2O 3为0.25g/L，H 3BO 3为0.50mol/L，C 6H 8O 7为0.20mol/L，抗坏血酸为5g/L，糖精钠为5g/L，十二烷基硫酸钠为5g/L，其余为水。将溅射有Ti/Cu种子层的晶圆进行表面处理后置于镀槽中，使用纯铁球和纯镍球（纯铁球体积占比60~70%）作为阳极材料，调节镀液的pH值为5，控制电镀液的温度为45℃，控制电流密度为6.0A/dm 2，控制电镀时间为20min。
测试实施例6以及对比例2、3中镀层的成分，其中，实施例6中镀层的成分为Fe 80.14wt.%，Ni 9.36wt.%，P 10.30wt.%，Gd 0.20wt.%；对比例2中镀层的成分为Fe 50wt.%，Ni 50wt.%；对比例3中镀层的成分为Fe 33wt.%，Ni 54wt.%，P 11wt.%，Gd 2wt.%。
获取实施例6以及对比例2、3中镀层的磁滞回线并进行对比分析。具体地，请参阅图5与图6，图5是本申请实施例6中镀层的磁滞回线与对比例2中镀层的磁滞回线的对比示意图，图6是本申请实施例6中镀层的磁滞回线与对比例3中镀层的磁滞回线的对比示意图。
如图5所示，实施例6中镀层的饱和磁感应强度为1.5T，矫顽力为0.6Oe，对比例2中镀层的饱和磁感应强度为1.3T，矫顽力为2Oe，表明在铁镍镀液基础上掺杂次亚磷酸钠时，加入柠檬酸和氨三乙酸作为双络合剂，可以大幅增加镀液极化，在获得Fe-Ni-P共沉积薄膜的同时，获得较高的饱和磁感应强度，以及降低矫顽力。如图6所示，对比例3中镀层的饱和磁感应强度为1.1T，矫顽力为7Oe，表明在铁镍镀液基础上掺杂次亚磷酸钠时，仅加入柠檬酸作为络合剂，即使加入稀土元素，也无法大幅增加镀液极化，同时镀层中Fe的含量也较低，导致获得的Fe-Ni-P共沉积薄膜的饱和磁感应强度较低，而矫顽力较大。
进一步地，在显微镜下观察实施例6以及对比例2、3中镀层的表明形貌，发现实施例6以及对比例2中镀层的表面光亮，无明显缺陷，而对比例3中镀层表面发白且存在裂纹，表明在铁镍镀液基础上掺杂次亚磷酸钠时，加入柠檬酸和氨三乙酸作为双络合剂，能够使制备的镀层无序度较低且内部结构缺陷较少。
区别于现有技术，本申请通过在电镀液中加入柠檬酸（盐）和氨三乙酸（盐）作为双络合剂，利用双络合剂与金属离子形成更加稳定的能在溶液中存在的络合离子，能够调整电镀液中各金属离子的析出电位，大幅增加镀液的电化学极化程度，使制备的镀层无序度较低且内部结构缺陷较少，从而降低Fe-Ni-P合金镀层的矫顽力，获得表面光亮、组织细致的镀层。进一步地，由于本实施方式中的电镀液体系简单、稳定性高、各组分浓度低，还具有成本较低、易于推广的优点，能够广泛应用于微电子领域以及半导体功能器件等领域。
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (10)

  1. 一种Fe-Ni-P合金电镀液，包括主盐、络合剂以及水，其特征在于，所述络合剂包括双络合剂，所述双络合剂包括柠檬酸和氨三乙酸，或所述柠檬酸和氨三乙酸盐，或柠檬酸盐和所述氨三乙酸，或所述柠檬酸盐和所述氨三乙酸盐；所述双络合剂中，所述氨三乙酸或所述氨三乙酸盐的浓度与所述柠檬酸或所述柠檬酸盐的浓度之比为0.5~5；其中，所述柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，所述氨三乙酸或所述氨三乙酸盐的浓度为0.01~0.5mol/L。
  2. 根据权利要求1所述的Fe-Ni-P合金电镀液，其特征在于，所述电镀液还包括稀土元素；其中，所述稀土元素包括稀土盐或稀土氧化物，所述稀土盐或稀土氧化物的浓度为0.25~0.4g/L；所述稀土元素为La、Ce、Pr、Nd、Pm、Sm、Eu、Gd和Tb中的一种或两种。
  3. 根据权利要求1或2所述的Fe-Ni-P合金电镀液，其特征在于，所述主盐包括亚铁盐、镍盐以及次亚磷酸盐；其中，所述亚铁盐的浓度为0.01~0.5mol/L，所述镍盐的浓度为0.01~0.5mol/L，所述次亚磷酸盐的浓度为0.01~0.3mol/L。
  4. 根据权利要求3所述的Fe-Ni-P合金电镀液，其特征在于，所述亚铁盐包括FeSO 4和/或FeCl 2，所述镍盐包括NiSO 4、Ni (NH 2SO 3) 2以及NiCl 2中的一种或两种，所述次亚磷酸盐包括NaH 2PO 2。
  5. 根据权利要求4所述的Fe-Ni-P合金电镀液，其特征在于，所述电镀液进一步包括抗氧化剂、光亮剂以及润湿剂；其中，所述抗氧化剂的浓度为0.01~5g/L，所述光亮剂的浓度为0.01~5g/L，所述润湿剂的浓度为0.01~5g/L；其中，所述抗氧化剂包括抗坏血酸，所述光亮剂包括糖精钠或丁炔二醇，所述润湿剂包括十二烷基硫酸钠。
  6. 一种Fe-Ni-P合金镀层的电沉积方法，其特征在于，包括：
    获取Fe-Ni-P合金电镀液，所述电镀液包括主盐、络合剂以及水，所述络合剂包括双络合剂，所述双络合剂包括柠檬酸和氨三乙酸，或所述柠檬酸和氨三乙酸盐，或柠檬酸盐和所述氨三乙酸，或所述柠檬酸盐和所述氨三乙酸盐；所述双络合剂中，所述氨三乙酸或所述氨三乙酸盐的浓度与所述柠檬酸或所述柠檬酸盐的浓度之比为0.5~5；其中，所述柠檬酸或柠檬酸盐的浓度为0.01~0.5mol/L，所述氨三乙酸或所述氨三乙酸盐的浓度为0.01~0.5mol/L；
    获取已进行表面处理的基材；
    将所述基材浸入所述电镀液中，在恒电压条件或恒电流条件下进行电镀，以在所述基材上沉积所述合金镀层。
  7. 根据权利要求6所述的Fe-Ni-P合金镀层的电沉积方法，其特征在于，所述基材包括金属材料的块体或薄膜、PCB线路板以及溅射有金属薄层的硅片。
  8. 根据权利要求7所述的Fe-Ni-P合金镀层的电沉积方法，其特征在于，所述Fe-Ni-P合金镀层中各元素的含量通过更改所述电镀液中所述主盐的含量、所述络合剂的含量和电沉积过程中的工艺参数中任意一项或几项进行调节；其中，所述工艺参数包括所述电流密度、所述电压、所述电镀液的pH值以及所述电镀液的温度。
  9. 根据权利要求8所述的Fe-Ni-P合金镀层的电沉积方法，其特征在于，控制所述恒电压条件下的电压为0.7 -4.0V，控制所述恒电流条件下的电流密度为2.0~9.0A/dm 2，控制所述电镀液的pH值为2~5，控制所述电镀液的温度为45~60℃。
  10. 一种Fe-Ni-P合金镀层，其特征在于，所述Fe-Ni-P合金镀层由权利要求6~9任一项所述的电沉积方法制成，所述合金镀层包括Fe、Ni以及P；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，其余为P；
    或，所述合金镀层包括Fe、Ni、P以及稀土元素；其中，各元素重量百分含量为：Fe 10~85%，Ni 5~70%，Fe+Ni=70~95%，稀土元素>0~2%，其余为P。
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