CN103540799B - Embedded resistor alloy material, embedded resistor film and preparation method thereof - Google Patents
Embedded resistor alloy material, embedded resistor film and preparation method thereof Download PDFInfo
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- CN103540799B CN103540799B CN201310530701.1A CN201310530701A CN103540799B CN 103540799 B CN103540799 B CN 103540799B CN 201310530701 A CN201310530701 A CN 201310530701A CN 103540799 B CN103540799 B CN 103540799B
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Abstract
The present invention relates to a kind of embedded resistor alloy material, embedded resistor film and preparation method thereof.This embedded resistor alloy material by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.This embed type alloy material is made embedded resistor film, our experiments show that, this embedded resistor film has good solidity to corrosion, thermostability and ageing resistance.
Description
Technical field
The present invention relates to electronic material and encapsulation technology field, particularly relate to a kind of embedded resistor alloy material, embedded resistor film and preparation method thereof.
Background technology
The electronic products such as computer, mobile phone, digital camera are popularized rapidly in recent years, and the aspect such as performance, price, light and handy portability of people to these electronic products also proposes more and more higher requirement.Assemble these electronic products to need to use a large amount of passive elements such as electric capacity, resistance, inductance, and its quantity is far more than active parts such as chips, the typical proportions value of the quantity of passive element and active part is 20:1, and in some radio products, the number ratio of both ratios is even up to 50:1.A large amount of passive element as with traditional discrete formula encapsulation, be both unfavorable for miniaturization and the portability of electronic product, also can cause printed circuit board (pcb) complex structure, circuit performance reduce, need throw huge fund exploitation efficiently pick up put element machinery etc. problem.
Carry out passive element integrated, such as, use PCB embed type passive element technology then can solve the problem.PCB imbed component package encapsulate with traditional discrete formula compared with there is a lot of advantage, as: PCB surface can be reduced in a large number and amass, reduce electronic product volume and weight, improve product portability; Shorten wiring distance, reduce parasitic inductance and electromagnetic interference, improve product electric property; Reduce solder joint and PCB complicacy, improve product reliability; Reduce PCB design cost, sealed in unit input and passive element cost etc.
Resistance is as one of three large passive element, critical role is occupied in electronic product, embed type sheet resistance is realized at 20 century 70s by Ohmega company the earliest, will Ni-P resistance film will be clipped between Copper Foil and semicure media substrate (FR-4), after etching, be then laminated into PCB inside.The companies such as current Ohmega, Shipley, Gould, DuPont have the alloy firms such as Ni-P, Ni-Cr and bury the appearance of resistance material commodity, and the alloy firms such as these Ni-P, Ni-Cr bury resistance material and are used widely in electronic product.But the solidity to corrosion of these materials, thermostability and ageing resistance are also poor, the space promoted is also had to apply widely to obtain.
Summary of the invention
Based on this, be necessary to provide a kind of embedded resistor alloy material, to prepare the good embedded resistor film of solidity to corrosion, thermostability and ageing resistance.
Further, a kind of embedded resistor film and preparation method thereof is provided.
A kind of embedded resistor alloy material, by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
A kind of embedded resistor film, the element of described embedded resistor film by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
Wherein in an embodiment, the thickness of described embedded resistor film is 500 nanometer ~ 5000 nanometers.
A preparation method for embedded resistor film, comprises the steps:
Substrate is provided, described substrate is activated; And
Described substrate after activation is put into chemical plating fluid and carries out plated film, the surface of described substrate is formed embedded resistor film, and the element of described embedded resistor film by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
Wherein in an embodiment, describedly described substrate after activation is put into before chemical plating fluid carries out the step of plated film, also comprise the step of described substrate being carried out to oil removing, describedly to the step that described substrate carries out oil removing be: clean described substrate with organic solvent, the more described substrate after cleaning is soaked in basic solution.
Wherein in an embodiment, described organic solvent is acetone or gasoline, and described basic solution is the aqueous solution containing sodium hydroxide, sodium carbonate and sodium phosphate.
Wherein in an embodiment, after oil removing is carried out to described substrate, describedly described substrate is put into before chemical plating fluid carries out the step of plated film, also comprise the step of described substrate being carried out to pickling.
Wherein in an embodiment, the described step that described substrate is carried out activating be described substrate is put into temperature be 20 DEG C ~ 60 DEG C activator soak 1 minute ~ 10 minutes.
Wherein in an embodiment, often liter of described activator comprises: 20 ~ 120 grams, zinc sulfate, DL-sodium malate 10 ~ 50 grams and zinc powder 5 ~ 30 grams.
Wherein in an embodiment, often liter of described chemical plating fluid comprises: single nickel salt 5 ~ 80 grams, inferior sodium phosphate 5 ~ 80 grams, Sodium orthomolybdate 0.1 ~ 10 gram, buffer reagent 10 ~ 80 grams, stablizer 1 ~ 5 milligram and complexing agent 10 ~ 80 grams.
Wherein in an embodiment, described by activation after described substrate put into the step that chemical plating fluid carries out plated film, the temperature of described chemical plating fluid is 60 DEG C ~ 90 DEG C, and the time of plated film is 1 ~ 30 minute.
Wherein in an embodiment, the pH value of described chemical plating fluid is 7 ~ 12.
Above-mentioned embedded resistor alloy material, by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.This embed type alloy material is made embedded resistor film, our experiments show that, this embedded resistor film has good solidity to corrosion, thermostability and ageing resistance.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the embedded resistor film of an embodiment;
Fig. 2 is the EDX figure of embedded resistor film prepared by embodiment 1;
Fig. 3 is that the uneven surface of the Copper Foil of embodiment 1 is schemed carrying out the SEM before electroless plating;
Fig. 4 is the SEM figure of embedded resistor film prepared by embodiment 1;
Fig. 5 is the SEM picture of another multiplying power of embedded resistor film prepared by embodiment 1;
Fig. 6 is the EDX figure of embedded resistor film prepared by comparative example 1;
Fig. 7 is the SEM figure of another multiplying power of embedded resistor film prepared by embodiment 1;
Fig. 8 is the SEM figure of embedded resistor film prepared by comparative example 1;
Fig. 9 is the solidity to corrosion test curve of the embedded resistor film of embodiment 1 preparation and the embedded resistor film of comparative example 1 preparation;
Figure 10 is the temperature coefficient of resistance curve of the embedded resistor film of embodiment 1 preparation and the embedded resistor film of comparative example 1 preparation;
Figure 11 is the ageing resistance curve of the embedded resistor film of embodiment 2 preparation and the embedded resistor film of comparative example 2 preparation.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The embedded resistor alloy material of one embodiment, by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
This embedded resistor alloy material is adopted to prepare embedded resistor film, our experiments show that, this embedded resistor film is compared with the embedded resistor film adopting existing nickel-phosphorus alloy material to prepare, there is good thermostability, ageing resistance, solidity to corrosion and film uniformity, and sheet resistance value is comparatively large, can be widely used in electronic product.
A kind of embedded resistor film, its element by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
This embedded resistor film has good thermostability, ageing resistance, solidity to corrosion and film uniformity, and has larger sheet resistance value, can be widely used in electronic product.
Preferably, the thickness of this embedded resistor film is 500 nanometer ~ 5000 nanometers.
Refer to Fig. 1, the preparation method of the embedded resistor film of an embodiment, comprises the steps:
Step S110: provide substrate, activates substrate.
Substrate can be Copper Foil, aluminium foil or aluminum magnesium alloy etc., is preferably Copper Foil.Preferably on the uneven surface of Copper Foil, form embedded resistor film.
First substrate is activated, with substrate surface deposition embedded resistor alloy material after activation, form the embedded resistor film be laminated on substrate surface.
Preferably, substrate is put into temperature be 20 DEG C ~ 60 DEG C activator soak 1 minute ~ 10 minutes, to activate the surface of substrate.
Activator preferably adopts often liter of activator containing 20 ~ 120 grams, zinc sulfate, DL-sodium malate 10 ~ 50 grams and zinc powder 5 ~ 30 grams.
After adopting above-mentioned activator to activate, the deposited on silicon of substrate has zinc layers.Zinc and follow-up chemical plating fluid react, and to generate autocatalysis surface, form embedded resistor film.
Be appreciated that in other embodiments, Palladous chloride activator also can be adopted to activate substrate.But adopt above-mentioned activator to activate substrate, chlorion can not be introduced in subsequent chemistry plating solution, thus chlorion can be avoided to cause the phenomenon of chemical plating fluid instability, be conducive to the quality improving embedded resistor film.
Preferably, before substrate is activated, comprise the step of substrate being carried out to oil removing.
First on a surface of substrate, protective membrane is sticked, to protect substrate.Oil removing is carried out to the surface relative with protective membrane of substrate.
First the substrate organic solvent sticking protective membrane is cleaned; then the substrate after cleaning is soaked in basic solution; the grease that removing substrate surface may exist; water is evenly spread out at substrate surface; with the component making subsequent chemistry plating solution preferably reactive deposition on a surface of the substrate, form the good embedded resistor film of thickness evenness.
Organic solvent is preferably acetone or gasoline.Basic solution is preferably containing sodium hydroxide (NaOH), sodium carbonate (Na
2cO
3) and sodium phosphate (Na
3pO
4) the aqueous solution.Preferably, in basic solution, the concentration of sodium hydroxide is 20 ~ 50g/L, and the concentration of sodium carbonate is 20 ~ 50g/L, and the concentration of sodium phosphate is 20 ~ 50g/L.
Preferably, be soak 1 ~ 10 minute in the basic solution of 30 DEG C ~ 60 DEG C, to ensure the grease removing substrate surface completely in temperature.
After oil removing is carried out to substrate, preferably, before substrate is activated, also comprise the step of substrate being carried out to pickling.Preferably, the substrate after oil removing is put into massfraction be 5% dilute sulphuric acid carry out pickling 1 ~ 5 minute.
The object of carrying out pickling is oxide film and the corrosion product of removing substrate surface, produces detrimentally affect to avoid oxide film and corrosion product to the embedded resistor film of follow-up preparation.
Step S120: the substrate after activation is put into chemical plating fluid and carries out plated film, form embedded resistor film on a surface of the substrate, the element of embedded resistor film by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
Chemical plating fluid is the solution comprising nickel source, molybdenum source and phosphorus source.Preferably, often liter of chemical plating fluid comprises single nickel salt (NiSO
4) 5 ~ 80 grams, inferior sodium phosphate (NaH
2pO
4) 5 ~ 80 grams, Sodium orthomolybdate (Na
2moO
42H
2o) 0.1 ~ 10 gram, buffer reagent 10 ~ 80 grams, stablizer 1 ~ 5 milligram and complexing agent 10 ~ 80 grams.
Preferably, above-mentioned chemical plating fluid also comprises pH adjusting agent.PH adjusting agent is 7 ~ 12 for regulating the pH value of chemical plating fluid.PH adjusting agent is preferably sodium hydroxide or dilute sulphuric acid.
Single nickel salt as nickel source and the molybdate (Na as molybdenum source
2moO
42H
2not only O) be the main salt of alloy, provide nickel and molybdenum, inferior sodium phosphate provides phosphorus as reductive agent.
In electroless plating reaction process, can produce by product hydrogen ion, hydrogen ion can cause the pH value of chemical plating fluid to decline.Buffer reagent is used for the pH value stablizing chemical plating fluid, makes the pH value of chemical plating fluid maintain in normal range, with the speed of stable electroless plating and the quality ensureing coating.
Preferably, buffer reagent is sodium-acetate (CH
3oONa).The concentration of sodium-acetate is preferably 10 ~ 40g/L.
When using above-mentioned chemical plating fluid to carry out plated film, the zinc of the substrate surface after activation first with the nickel ion generation replacement(metathesis)reaction in chemical plating fluid: Zn+Ni
2+→ Ni+Zn
2+, newborn nickel be formed as the surface that next step electroless plating provides autocatalysis, nickel ion obtains provides electronics from inferior sodium phosphate, is reduced sticking power in the surface of newborn nickel dam.Sodium orthomolybdate and inferior sodium phosphate generation redox reaction, make molybdenum deposit the surface with newborn nickel dam, final formation nickel-molybdenum-phosphorus film.
Chemical plating fluid is a thermodynamic unstable system, and reduction reaction occurs the place usually beyond substrate surface.When producing some in chemical plating fluid and having the activity core of catalytic effect, chemical plating fluid easily produces fierce self-catalyzed reaction and causes chemical plating fluid to be scrapped the same day.Stablizer is used for stablizing chemical plating fluid.Stablizer is preferentially adsorbed on activity core surface, suppresses self-catalyzed reaction, thus stablizes chemical plating fluid, the reduction of nickel ion is only occurred on the surface of substrate, thus extends the work-ing life of chemical plating fluid.
Stablizer is preferably thiocarbamide.
Complexing agent for outside the concentration of the metal ion of reaction, can also control to generate precipitation by metallic ion, improve the stability of chemical plating fluid, extend the work-ing life of chemical plating fluid for controlling.
Complexing agent is preferably Trisodium Citrate (CH
3oONa).The concentration of Trisodium Citrate is preferably 10 ~ 40g/L.
Preferably, chemical plating fluid is heated to 60 DEG C ~ 90 DEG C, it is that 60 DEG C ~ 90 DEG C chemical plating fluids carry out electroless plating 1 ~ 30 minute that the substrate successively through oil removing, pickling and activation is placed in temperature.
Carry out electroless plating after 1 ~ 30 minute, take out in sample chemically plating solution, use deionized water rinsing post-drying, the surface relative with protective membrane of substrate forms embedded resistor film.The element of this embedded resistor film by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%.
The preparation method of above-mentioned embedded resistor film, corrosion resisting property is good, Heat stability is good and the good embedded resistor film of ageing resistance to adopt the method for electroless plating to be formed on substrate.The preparation method of this embedded resistor film, technique is simple, can chemically plating embedded resistor film on substrate at a lower temperature, and energy consumption is lower.Further, because the temperature of plated film is lower, the steam of generation is less, and environmental pollution is less.
After substrate is prepared embedded resistor film; by this sample pressure on a printed circuit; carry out pad pasting protection and etch away unnecessary substrate and embedded resistor film; and then pasting protective film etch away sections substrate; obtain the embedded resistor with electrode; and then another layer printed circuit board is pressed on embedded resistor, obtain the embedded resistor device be embedded between double-layer printing circuit board.Owing to using above-mentioned embedded resistor film, the better performances of this embedded resistor device.
Prepare alloy target material by the proportioning of above-mentioned embedded resistor alloy material, adopt magnetron sputtering technique to sputter this alloy target material on substrate, also can prepare and be laminated in embedded resistor film on substrate.
Set forth further below by way of specific embodiment.
Embodiment 1
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 50 DEG C basic solution soak 5 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of sodium phosphate is 30g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 5 minutes, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 40 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 10 minutes, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 24g, DL-sodium malate 3.5g and zinc powder 5g;
4, the sample that step 3 obtains is put into temperature is 88 DEG C, pH value be 8 500mL chemical plating fluid plating 3 minutes, then taking-up washed with de-ionized water is also dried, and prepares the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains: single nickel salt 12.50g, inferior sodium phosphate 15.00g, Sodium orthomolybdate 0.10g, Trisodium Citrate 10.00g/L, sodium-acetate 10.00g/L and thiocarbamide 5mg; With sodium hydroxide, the pH value of chemical plating fluid is adjusted to 8.The element of this embedded resistor film comprises Ni, P and Mo, by mass percentage, nickel accounts for 96.4%, molybdenum account for 0.7% and phosphorus account for 2.9%.
Fig. 2 is the EDX figure of embedded resistor film prepared by embodiment 1.As seen from Figure 2, the element of this embedded resistor film comprises Ni, P and Mo.
Fig. 3 is that the uneven surface of the Copper Foil of embodiment 1 is schemed carrying out the SEM before electroless plating.Fig. 4 is the SEM picture of embedded resistor film prepared by embodiment 1.Comparison diagram 3 and Fig. 4 can find out, on the uneven surface of substrate, the compactness of the embedded resistor film that chemical plating is formed is better.
Fig. 5 is the SEM picture of another multiplying power of embedded resistor film prepared by embodiment 1.As seen from Figure 5, the thickness of the embedded resistor film that embodiment 1 is coated with is 2.361 microns, and thickness is very even.
Embodiment 2
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 30 DEG C basic solution soak 10 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of sodium phosphate is 30g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 5 minutes, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 30 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 10 minutes, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 24g, DL-sodium malate 3.5g and zinc powder 5g;
4, the sample that step 3 obtains is put into temperature is 88 DEG C, pH value be 8 500mL chemical plating fluid plating 3 minutes, then taking-up washed with de-ionized water is also dried, and prepares the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains: single nickel salt 12.50g, inferior sodium phosphate 15.00g, Sodium orthomolybdate 0.50g, Trisodium Citrate 10.00g/L, sodium-acetate 10.00g/L and thiocarbamide 5mg; With sodium hydroxide, the pH value of chemical plating fluid is adjusted to 8; The element of embedded resistor film by mass percentage, comprises nickel 94.0%, molybdenum 0.8% and phosphorus 5.0%.
Embodiment 3
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 30 DEG C basic solution soak 10 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 50g/L, and the concentration of sodium carbonate is 50g/L, and the concentration of sodium phosphate is 50g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 1 minute, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 60 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 1 minute, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 20g, DL-sodium malate 10g and zinc powder 6g;
4, the sample that step 3 obtains is put into temperature is 60 DEG C, pH value be 9 500mL chemical plating fluid plating 30 minutes, then taking-up washed with de-ionized water is also dried, and prepares the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains: single nickel salt 50g, inferior sodium phosphate 25.00g, Sodium orthomolybdate 5g, Trisodium Citrate 40.00g/L, sodium-acetate 20.00g/L and thiocarbamide 2mg; With sodium hydroxide, the pH value of chemical plating fluid is adjusted to 9; The element of embedded resistor film by mass percentage, comprises nickel 87%, molybdenum 4.8% and phosphorus 8.2%.
Embodiment 4
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 40 DEG C basic solution soak 6 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 20g/L, and the concentration of sodium carbonate is 20g/L, and the concentration of sodium phosphate is 20g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 1 minute, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 20 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 10 minutes, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 4g, DL-sodium malate 2.5g and zinc powder 1g;
4, the sample that step 3 obtains is put into temperature is 60 DEG C, pH value be 9 500mL chemical plating fluid plating 30 minutes, then taking-up washed with de-ionized water is also dried, and prepares the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains: single nickel salt 400g, inferior sodium phosphate 40.00g, Sodium orthomolybdate 3g, Trisodium Citrate 20.00g/L, sodium-acetate 20.00g/L and thiocarbamide 4mg; With sodium hydroxide, the pH value of chemical plating fluid is adjusted to 9; The element of embedded resistor film by mass percentage, comprises nickel 82.5%, molybdenum 6.5% and phosphorus 11%.
Comparative example 1
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 50 DEG C basic solution soak 5 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of sodium phosphate is 30g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 5 minutes, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 40 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 10 minutes, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 24g, DL-sodium malate 3.5g and zinc powder 5g;
4, the sample that step 3 obtains is put into temperature is 88 DEG C, the chemical plating fluid of 500mL carries out electroless plating 3 minutes, taking-up washed with de-ionized water, obtain the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains inferior sodium phosphate 15.00g, single nickel salt 12.50g, Trisodium Citrate 10.00g, sodium-acetate 10.00g and thiocarbamide 0.005g, and the pH value regulating chemical plating fluid with dilute sulphuric acid is 5; The element of embedded resistor film by mass percentage, comprises nickel 96.9% and phosphorus 3.1%.
Fig. 6 is the EDX figure of embedded resistor film prepared by comparative example 1.As seen from Figure 6, the element of this embedded resistor film comprises Ni and P.
Fig. 7 is the SEM figure of another multiplying power of embedded resistor film prepared by embodiment 1.Fig. 8 is the SEM figure of embedded resistor film prepared by comparative example 1.Comparison diagram 7 and Fig. 8, embedded resistor film prepared by embodiment 1 contains molybdenum element, still can keep higher compactness.
Measure the solidity to corrosion of the embedded resistor film (96.4%Ni-0.7%Mo-2.9%P) of embodiment 1 and the embedded resistor film (96.9%Ni-3.1%P) of comparative example 1.The embedded resistor film of embodiment 1 and the embedded resistor film of comparative example 1 are put into the dilute sulphuric acid that massfraction is 5%, measure the quality change in time of two kinds of embedded resistor films and chemical plating, and calculating the weightless quality than (the quality b of the quality a-time period coating of weightless ratio=original coating)/original coating a), measurement result is as shown in Figure 9.As seen from Figure 9, the embedded resistor film of embodiment 1 adds molybdenum element, and solidity to corrosion increases.
Measure the temperature coefficient of resistance of the embedded resistor film (96.4%Ni-0.7%Mo-2.9%P) of embodiment 1 and the embedded resistor film (96.9%Ni-3.1%P) of comparative example 1, measurement result as shown in Figure 10.As seen from Figure 10, the temperature coefficient of resistance of the embedded resistor film of embodiment 1 preparation is more stable under the high temperature conditions.Therefore, the better heat stability of the embedded resistor film of embodiment 1 preparation.
Comparative example 2
1, provide the Copper Foil with relative shiny surface and uneven surface as substrate, the shiny surface of Copper Foil stick protective membrane, by this Copper Foil acetone clean after put into temperature be 50 DEG C basic solution soak 5 minutes, take out, by washed with de-ionized water; Wherein, basic solution is the mixed aqueous solution of sodium hydroxide, sodium carbonate and sodium phosphate, and the concentration of sodium hydroxide is 30g/L, and the concentration of sodium carbonate is 30g/L, and the concentration of sodium phosphate is 30g/L;
2, it is carry out pickling in the dilute sulphuric acid of 5% 5 minutes, taking-up washed with de-ionized water that sample step 1 obtained immerses massfraction;
3, it is in the 200mL activator of 40 DEG C that sample step 2 obtained immerses temperature, leaves standstill and activates for 10 minutes, taking-up washed with de-ionized water; Wherein, 200mL activator contains zinc sulfate 24g, DL-sodium malate 3.5g and zinc powder 5g;
4, the sample that step 3 obtains is put into temperature is 88 DEG C, the chemical plating fluid of 500mL carries out electroless plating 3 minutes, taking-up washed with de-ionized water, obtain the embedded resistor film be laminated on Copper Foil.Wherein, often liter of chemical plating fluid contains inferior sodium phosphate 15.00g, single nickel salt 12.50g, Trisodium Citrate 10.00g, sodium-acetate 10.00g and thiocarbamide 0.005g, and the pH value regulating chemical plating fluid with dilute sulphuric acid is 5; The element of embedded resistor film by mass percentage, comprises nickel 95.1% and phosphorus 4.9%.
Measure the ageing resistance of the embedded resistor film (94.0%Ni-0.8%Mo-5.0%P) of embodiment 2 and the embedded resistor film (95.1%Ni-4.9%P) of comparative example 2.Place 15 days under temperature is 85 DEG C and humidity is the condition of 85, measure the resistance of the embedded resistor film of embodiment 2 and comparative example 2 every day, test result as shown in figure 11.As can see from Figure 11, the resistance to deterioration of the embedded resistor film of embodiment 2 is better than comparative example 2.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (6)
1. a preparation method for embedded resistor film, comprises the steps:
Substrate is provided, described substrate is activated; And
Described substrate after activation is put into chemical plating fluid and carries out plated film, the surface of described substrate is formed embedded resistor film, and the element of described embedded resistor film by mass percentage, comprises nickel 80 ~ 97%, molybdenum 0.1 ~ 8% and phosphorus 2 ~ 12%;
The described step that described substrate is carried out activating be described substrate is put into temperature be 20 DEG C ~ 60 DEG C activator soak 1 minute ~ 10 minutes;
Often liter of described activator comprises: 20 ~ 120 grams, zinc sulfate, DL-sodium malate 10 ~ 50 grams and zinc powder 5 ~ 30 grams;
Often liter of described chemical plating fluid comprises: single nickel salt 5 ~ 80 grams, inferior sodium phosphate 5 ~ 80 grams, Sodium orthomolybdate 0.1 ~ 10 gram, buffer reagent 10 ~ 80 grams, stablizer 1 ~ 5 milligram and complexing agent 10 ~ 80 grams.
2. the preparation method of embedded resistor film according to claim 1, it is characterized in that, describedly described substrate after activation is put into before chemical plating fluid carries out the step of plated film, also comprise the step of described substrate being carried out to oil removing, describedly to the step that described substrate carries out oil removing be: clean described substrate with organic solvent, the more described substrate after cleaning is soaked in basic solution.
3. the preparation method of embedded resistor film according to claim 2, is characterized in that, described organic solvent is acetone or gasoline, and described basic solution is the aqueous solution containing sodium hydroxide, sodium carbonate and sodium phosphate.
4. the preparation method of embedded resistor film according to claim 2, is characterized in that, after carrying out oil removing, is describedly put into by described substrate before chemical plating fluid carries out the step of plated film, also comprise the step of described substrate being carried out to pickling to described substrate.
5. the preparation method of embedded resistor film according to claim 1, it is characterized in that, described by activation after described substrate put into the step that chemical plating fluid carries out plated film, the temperature of described chemical plating fluid is 60 DEG C ~ 90 DEG C, and the time of plated film is 1 ~ 30 minute.
6. the preparation method of embedded resistor film according to claim 1, is characterized in that, the pH value of described chemical plating fluid is 7 ~ 12.
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