CN103484840A - Activating agent for preparation of embedded film resistor, preparation method of embedded film resistor and embedded film resistor - Google Patents
Activating agent for preparation of embedded film resistor, preparation method of embedded film resistor and embedded film resistor Download PDFInfo
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- CN103484840A CN103484840A CN201310398877.6A CN201310398877A CN103484840A CN 103484840 A CN103484840 A CN 103484840A CN 201310398877 A CN201310398877 A CN 201310398877A CN 103484840 A CN103484840 A CN 103484840A
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Abstract
The invention relates to an activating agent for preparation of an embedded film resistor, a preparation method of the embedded film resistor and the embedded film resistor. The activating agent for preparation of an embedded film resistor comprises water, zinc sulfate, DL-sodium malate and zinc powder, wherein the concentration of the zinc sulfate is 20-200 g/L; the concentration of the DL-sodium malate is 10-50 g/L; and the concentration of the zinc powder is 5-30 g/L. The activating agent is free of chlorine and palladium. Experiments prove that after a substrate is activated by using the activating agent, a nickel-phosphorus film can be formed on the substrate at a low temperature through chemical plating, the energy consumption is low, and no chlorine is introduced into the chemical plating solution, thereby ensuring the stability of the plating solution. The activation performed by using the activating agent is beneficial to lower the preparation cost of the embedded film resistor; and ensuring the stability of the plating solution is beneficial to ensure the quality of the nickel-phosphorus film, thereby ensuring that the embedded film resistor has favorable property.
Description
Technical field
The present invention relates to the electronically materials and component technical field, particularly relate to preparation method and the embed type sheet resistance of a kind of activator for the preparation of the embed type sheet resistance, embed type sheet resistance.
Background technology
Along with unicircuit is highly integrated, the development of densification, and the development of digital data transmission high frequency and high speed, require printed circuit board (PCB) (PCB) towards miniaturization, lighting future development.The embedded resistors technology can be saved a large amount of PCB surface-area is installed, thereby can increase wiring degree of freedom and the integration density of PCB.Therefore, the embedded resistors technology will become the encapsulation technology of following main flow, and the embed type sheet resistance becomes the focus of current research.
At present, be mainly with alloys such as nickel-chromium (Ni-Cr) or nickel-phosphorus (Ni-P) for burying the resistance material, adopt the method for magnetron sputtering or electroless plating to prepare the embed type sheet resistance.With magnetically controlled sputter method, compare, the cost of chemical plating is lower and be beneficial to scale operation, but the method for the standby embed type film resistance of current chemically plating need to be used the precious metal sensitizing such as palladium (Pd) and carry out chemical plating on high temperature.For example, use the Pd of chloride ion-containing as activator, carry out plated film at the temperature of 90 ± 2 ℃.So not only increase production cost, also may make in plating solution to bring into chlorion, caused the unstable of plating solution.At higher temperature, the steam of generation is to environment on every side in addition.
Summary of the invention
Based on this, be necessary to provide a kind of activator for the preparation of the embed type sheet resistance that does not contain chlorine and palladium.
Further, provide a kind of preparation method of embed type sheet resistance and the embed type sheet resistance prepared by the method.
A kind of activator for the preparation of the embed type sheet resistance, comprise water, zinc sulfate, DL-sodium malate and zinc powder, wherein, the concentration that the concentration that described sulfuric acid zinc concentration is 20～200g/L, described DL-sodium malate is 10～50 g/L, described zinc powder is 5～30g/L.
A kind of preparation method of embed type sheet resistance, comprise the steps:
Substrate is provided;
With the above-mentioned activator for the preparation of the embed type sheet resistance, described substrate is activated the substrate after being activated;
Prepare nickel phosphorus film on the surface of the substrate of employing electroless plating method after described activation, obtain being laminated with the substrate of nickel phosphorus film;
PCB substrate and the described substrate that is laminated with nickel phosphorus film are carried out to pressing, and make described nickel phosphorus pellicular cascade on described PCB substrate; And
Described substrate and nickel phosphorus film are carried out to etching, obtain the embed type sheet resistance.
In embodiment, before the step described substrate activated with the above-mentioned activator for the preparation of the embed type sheet resistance, be included on described substrate and stick photosensory membrane, the step of then being exposed therein.
In embodiment, on described substrate, stick photosensory membrane therein, after then being exposed, also comprise the step that described substrate is washed before the step described substrate activated with the above-mentioned activator for the preparation of the embed type sheet resistance.
In embodiment, the step of described washing is for first being washed with washing composition, then the sulphuric acid soln that is 5% by mass concentration carries out pickling therein.
In embodiment, described substrate is Copper Foil therein, and described Copper Foil has relative shiny surface and uneven surface, and described nickel phosphorus pellicular cascade is on the uneven surface of described Copper Foil.
Therein in embodiment, the step described substrate activated with the above-mentioned activator for the preparation of the embed type sheet resistance is specially: the above-mentioned activator for the preparation of the embed type sheet resistance is remained on to 20 ℃～60 ℃, more described substrate is placed in to activator that described temperature is 20 ℃～60 ℃ soaks 1 minute～10 minutes.
Therein in embodiment, prepare nickel phosphorus film on the surface of the substrate of described employing electroless plating method after described activation, the step that obtains being laminated with the substrate of nickel phosphorus film is specially: it is that 20 ℃～90 ℃ chemical plating fluids are processed 0.5 minute～5 minutes that the substrate after described activation is put into to temperature.
In embodiment, every liter of described chemical plating fluid contains single nickel salt 5～80 grams, ortho phosphorous acid hydrogen sodium 5～80 grams, buffer reagent 10～80 grams, 1～5 milligram of stablizer and complexing agent 10～80 grams therein.
Therein in embodiment, described PCB substrate and the described substrate that is laminated with nickel phosphorus film are carried out to pressing, and the step of described nickel phosphorus pellicular cascade on described PCB substrate is specially: the described substrate that is laminated with nickel phosphorus film is positioned on described PCB substrate, and make described nickel phosphorus pellicular cascade on described PCB substrate, prepreg is held between described nickel phosphorus film and PCB substrate again, vacuumize, after thermal treatment by the described substrate attaching of nickel phosphorus film that is laminated with on described PCB substrate.
Therein in embodiment, described heat treated step is insulation 1 hour under 100 ℃～140 ℃, then insulation 1 hour under 140 ℃～180 ℃.
Therein in embodiment, the described step that described substrate and nickel phosphorus film are carried out to etching comprises:
Adopt the first etching liquid to carry out etching to described substrate and nickel phosphorus film; And
Adopt the second etching liquid to carry out etching to described substrate.
Therein in embodiment, the mixed aqueous solution that described the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the mixed aqueous solution that described the second etching liquid is cupric chloride, ammonium chloride and ammoniacal liquor.
A kind of embed type sheet resistance prepared by above-mentioned preparation method.
The above-mentioned activator for the preparation of the embed type sheet resistance does not contain the precious metal palladium that chlorine and price are high, the experiment proved that, after adopting this activator to be activated substrate, chemically plating nickel phosphorus film on substrate at a lower temperature, energy consumption is lower, and in chemical plating fluid, do not introduce chlorine, guaranteed the stability of plating solution.Use above-mentioned activator to be activated, be conducive to reduce the preparation cost of embed type sheet resistance, and, due to the stability that has guaranteed plating solution, be conducive to guarantee the quality of nickel phosphorus film, thereby guarantee that the embed type sheet resistance has performance preferably.
The accompanying drawing explanation
The preparation method's of the embed type sheet resistance that Fig. 1 is an embodiment schema;
The preparation method's that Fig. 2 is the embed type sheet resistance shown in Fig. 1 schematic diagram;
The EDS figure of the nickel phosphorus film that Fig. 3 is embodiment 1;
The SEM figure of the nickel phosphorus film that Fig. 4 is embodiment 1;
The SEM figure of another multiplying power of the nickel phosphorus film that Fig. 5 is embodiment 1;
Temperature coefficient of resistance (TCR) curve of the embed type sheet resistance that Fig. 6 is embodiment 1 and embodiment 2;
The SEM figure of the nickel phosphorus film that Fig. 7 is embodiment 3.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subject to the restriction of following public concrete enforcement.
The activator for the preparation of the embed type sheet resistance of one embodiment, comprise water, zinc sulfate (ZnSO
4), DL-sodium malate and zinc powder.
Wherein, zinc sulfate and DL-sodium malate are dissolved in the water, and zinc powder is scattered in water.The concentration that the concentration that the sulfuric acid zinc concentration is 20～200g/L, DL-sodium malate is 10～50g/L, zinc powder is 5～30g/L.
The higher precious metal palladium with respect to price, the price of zinc sulfate, DL-sodium malate and zinc powder is lower, makes this price for the preparation of the activator of embed type sheet resistance lower, is conducive to reduce the preparation cost of embed type sheet resistance.
And the above-mentioned activator for the preparation of the embed type sheet resistance does not contain chlorine, after using this activator activation substrate, when carrying out chemically plating, chlorion can not introduced to chemical plating fluid, can guarantee the stability of chemical plating fluid.
Our experiments show that, after adopting this activator to be activated substrate, chemically plating nickel phosphorus film on substrate at a lower temperature, energy consumption is lower.And, because the temperature of plated film is lower, the steam of generation is less, environmental pollution is less.
Refer to Fig. 1, the preparation method of the embed type sheet resistance of an embodiment, comprise the steps:
Step S110: substrate is provided.
Please consult Fig. 2, substrate 10 can, for Copper Foil, aluminium foil or aluminum magnesium alloy etc., be preferably Copper Foil simultaneously.Copper Foil has relative shiny surface and uneven surface.As the surperficial smoother of other substrates, need roughening treatment is carried out in one of them surface of substrate, to improve the sticking power of subsequent chemistry coating.
At first substrate 10 is cut into to the size needed, then on the shiny surface of substrate 10, sticks the photosensory membrane (not shown), and exposed, in subsequent chemistry plated film step, to protect substrate.
By the alkaline stain remover washing composition that is mixed with soluble in water, and washing composition is heated to 30 ℃～60 ℃, then substrate 10 is placed in to the washing composition supersound process 1 minute～10 minutes that temperature is 30 ℃～60 ℃, to remove the greasy dirt on substrate 10 surfaces.
In washing composition, supersound process, after 1 minute～10 minutes, is taken out with washed with de-ionized water substrate 10.Then the sulphuric acid soln that the mass concentration that substrate 10 is placed in to normal temperature is 5% soaks 1 minute～10 minutes, after taking out, uses washed with de-ionized water, standby.
Be to remove the oxide film on substrate 10 surfaces, oxide skin and corrosion product by the purpose of carrying out again pickling after detergent washing, to avoid oxide film, oxide skin and corrosion product, the nickel phosphorus film of follow-up preparation produced to detrimentally affect.
Step S120: with the above-mentioned activator for the preparation of the embed type sheet resistance, substrate is activated the substrate after being activated.
By above-mentioned for the preparation of the activator of embed type sheet resistance remain on 20 ℃～60 ℃, the substrate 10 after washing is placed in to the activator that temperature is 20 ℃～60 ℃ and soaks 1 minute～10 minutes, then take out and use washed with de-ionized water.
After overactivation, on the surface relative with photosensory membrane of substrate 10, deposit the zinc layer.
Step S130: prepare nickel phosphorus film on the surface of the substrate of employing electroless plating method after activation, obtain being laminated with the substrate of nickel phosphorus film.
Chemical plating fluid be take water as solvent.Every liter of chemical plating fluid contains single nickel salt (NiSO
4) 5～80 grams, ortho phosphorous acid hydrogen sodium (NaH
2pO
2) 5～80 grams, buffer reagent 10～80 grams, 1～5 milligram of stablizer and complexing agent 10～80 grams.
Wherein, buffer reagent is preferably sodium-acetate or Potassium ethanoate, for the pH value that maintains chemical plating fluid in the scope of setting.
Stablizer is preferably thiocarbamide.
Complexing agent is preferably at least one in Trisodium Citrate, DL-sodium malate and lactic acid.The effect of complexing agent is complex ni-ion, discharges the nickel ion of fixed amount in the electroless plating process.
During use, at first by pH adjusting agent, the pH value of chemical plating fluid is adjusted to 1～12.PH adjusting agent is preferably at least one in ammoniacal liquor, dilute sulphuric acid, sodium hydroxide and potassium hydroxide.
Preferably, every liter of chemical plating fluid also comprises 10g ammonium chloride.Use this chemical plating fluid that contains ammonium chloride to carry out electroless plating, can carry out at normal temperatures, energy consumption is low, and environmental protection.
It is that 20 ℃～90 ℃ chemical plating fluids are processed 0.5 minute～5 minutes that substrate after activation is put into to temperature.The zinc of substrate surface at first with chemical plating fluid in nickel ion generation replacement(metathesis)reaction, reaction formula is shown in following formula (1), newborn nickel form the surface that next step electroless plating provides autocatalysis, the electronics that nickel ion has obtained providing from inferior sodium phosphate, be reduced sticking power in the surface of newborn nickel dam.
Newborn nickel has katalysis, and water and the reaction of Hypophosporous Acid, 50 root have produced and be adsorbed on the lip-deep atomic hydrogen of autocatalysis, and reaction formula is shown in following formula (2); The hydrogen of surface adsorption on the autocatalysis surface reduced nickel and the reduction phosphorus process, reaction formula is shown in respectively following formula (3) and (4); In reduced nickel-phosphorus, the hydrogen of atomic state is combined into hydrogen and separates out.
（1）Zn+Ni
2+→Ni+Zn
2+；
(2) H
2pO
2 -+ H
2o → HPO
3 2-+ H
++ 2H
absorption;
(3) Ni
2++ 2H
absorption→ Ni+2H
+;
(4) H
2pO
2 -+ H
++ H
absorption -→ 2H
2o+P;
(5) 2H
absorption+ 2e
-→ H
2.
Through above-mentioned reaction (1)～(5), form and be laminated in the nickel phosphorus film 20 on substrate.
Step S140: PCB substrate and the substrate that is laminated with nickel phosphorus film are carried out to pressing, and make nickel phosphorus pellicular cascade on the PCB substrate.
Remove the photosensory membrane on substrate 10, then with washed with de-ionized water substrate 10 and after drying, the substrate 10 that is laminated with nickel phosphorus film 20 is positioned on PCB substrate 30, and nickel phosphorus film 20 is laminated on PCB substrate 30, the prepreg (not shown) is held between nickel phosphorus film 20 and PCB substrate 30 again, vacuumize, thermal treatment, maintenance pressure is 10MPa, PCB substrate 30 and the substrate 10 that is laminated with nickel phosphorus film 20 are carried out to pressing, the substrate 10 that is laminated with nickel phosphorus film 20 is fitted on PCB substrate 30.
Preferably, heat treated step is to be incubated 1 hour under 100 ℃～140 ℃, be incubated 1 hour again under 140 ℃～180 ℃, substrate 10 and the tight pressing of PCB substrate 30 will be laminated with nickel phosphorus film 20, make the substrate 10 that is laminated with nickel phosphorus film 20 fit tightly the surface at PCB substrate 30.
Step S150: substrate and nickel phosphorus film are carried out to etching, obtain the embed type sheet resistance.
Etching comprises employing the first etching liquid to substrate 10 and nickel phosphorus film 20 carries out etching and adopt the second etching liquid substrate 10 to be carried out to the step of etching.With the second etching liquid, to substrate 10, carry out secondarily etched.
The mixed aqueous solution that the first etching liquid is Sulfothiorine and anhydrous cupric sulfate.Preferably, the concentration of Sulfothiorine is 20g/L, and the concentration of anhydrous cupric sulfate is 30g/L.
The mixed aqueous solution that the second etching liquid is cupric chloride, ammonium chloride and ammoniacal liquor.Preferably, the concentration of cupric chloride is 30g/L, and the concentration of ammonium chloride is 45g/L, and it is 1～12 that the add-on of ammoniacal liquor makes the pH value of this second etching liquid.Preferred pH value is 9.
At first, on the surface at substrate 10 away from nickel phosphorus film 20, stick photosensory membrane, then with the first film paper, exposed, develop.The first film paper has the consistent pattern of the required Resistance model for prediction of this step.After development, sample is soaked 5 minutes～10 minutes in the first etching liquid, substrate 10 partial etchings are fallen and nickel phosphorus film 20 partial etchings are fallen, stay the square unfashioned resistance sample that buries.
Above-mentioned sample, by washed with de-ionized water and after drying, is sticked to photosensory membrane on the surface at substrate 10 away from nickel phosphorus film 20, then with the second film paper, exposed, develop.The second film paper has the final required consistent pattern of Resistance model for prediction.To put into the second etching liquid with the sample after the first etching liquid etching and soak 5 minutes～10 minutes, etch away with the substrate 10 by unnecessary, but not affect the integrity of coating, obtain embedded resistor, as shown in Figure 2.
Preferably, in etching process, the temperature of the second etching liquid remains on 30 ℃～60 ℃.
The preparation method of above-mentioned embed type sheet resistance adopts the above-mentioned activator for the preparation of the embed type sheet resistance that does not contain chlorine and palladium to be activated substrate, make and follow-uply can at lower temperature, carry out plated film, energy consumption is low, and preparation technology is simple, preparation cost is low.Preparation-obtained embed type sheet resistance has advantages of that square resistance can regulate and control, resistance temperature factor temperature.
And, because adopted activator does not contain chlorine, can not introduce chlorion in chemical plating fluid, guaranteed the stability of plating solution, be conducive to guarantee the quality of nickel phosphorus film, prepare the embed type sheet resistance of better performances.
And, because electroless plating is carried out at lower temperature, the steam of generation is less, environmental pollution is few.
The embed type sheet resistance prepared by above-mentioned preparation method of one embodiment.Owing to using the above-mentioned activator that does not contain chlorine to be activated substrate in preparation process, guaranteed the temperature of plating solution, make the quality of this nickel phosphorus film higher, be conducive to improve the performance of embed type sheet resistance.
And because above-mentioned activator does not contain expensive palladium, price is lower, can improve the preparation cost of embed type sheet resistance, is conducive to reduce the cost of embed type sheet resistance.
Below by specific embodiment, further set forth.
Embodiment 1
Prepare the embed type sheet resistance
1, the Copper Foil of 8cm * 4cm is provided, and Copper Foil has relative shiny surface and uneven surface, sticks photosensory membrane exposure on the shiny surface of Copper Foil;
2, take washing powder 10g, add deionized water 400ml, be configured for the washing composition of oil removing.The Copper Foil of step 1 is put into to washing composition, and supersound process 10min, then take out and use washed with de-ionized water;
3, measure the 20ml vitriol oil, be configured to the dilute sulphuric acid that massfraction is 5%, the Copper Foil that step 2 is handled well is put into this dilute sulphuric acid, and then pickling 10min takes out and use washed with de-ionized water;
4, taking 35g zinc sulfate, 3.5gDL-sodium malate and 5g zinc powder adds in deionized water, be mixed with the activator of 200mL for the preparation of the embed type sheet resistance, this activator is heated to 40 ℃, then the Copper Foil of step 3 being handled well is put into this activator and is soaked 10 minutes, then uses washed with de-ionized water;
5, taking 15.00g inferior sodium phosphate, 12.50g single nickel salt 10.00g Trisodium Citrate, 10.00g sodium-acetate and 0.5mg thiocarbamide is dissolved in deionized water, be made into 500ml solution, with dilute sulphuric acid, regulate pH=5, plating solution is stirred to 1h, then be put in thermostat water bath, be heated to 88 ℃, the Copper Foil that step 4 is handled well is put into this solution, plating 30 seconds, plated with nickel phosphorus film on the uneven surface of Copper Foil, obtain being laminated with the Copper Foil of nickel phosphorus film, then take out and use washed with de-ionized water, dry;
6, the sample of step 5 being handled well is placed on the PCB substrate, make nickel phosphorus pellicular cascade on the PCB substrate, then pressing from both sides prepreg between PCB substrate and nickel phosphorus film, put into tabletting machine, vacuumized, under 120 ℃, insulation is incubated one hour under one hour, 150 ℃, keeps pressure at 10MP
a, the Copper Foil and the PCB substrate that are laminated with nickel phosphorus film are pressed together, then naturally cooling;
7, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the first film paper, exposing and developing, the sample of step 6 is soaked 5 minutes in the first etching liquid, then take out and use washed with de-ionized water; Wherein, the mixed aqueous solution that the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the concentration of Sulfothiorine is 20g/L, the concentration of anhydrous cupric sulfate is 30g/L;
8, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the second film paper, exposing and developing, the sample of step 7 is soaked 5 minutes in the second etching liquid, then take out with washed with de-ionized water, oven dry, obtain the embed type film; Wherein, the mixed aqueous solution that the second etching liquid is cupric chloride, ammonium chloride and ammoniacal liquor, the concentration of anhydrous cupric sulfate is 30g/L, and the concentration of ammonium chloride is 45g/L, and it is 9 that the add-on of ammoniacal liquor makes the pH value of this second etching liquid.
The activator for the preparation of the embed type sheet resistance of embodiment 1 and the component of chemical plating fluid see the following form 1.
Table 1
The EDS figure of the nickel phosphorus film that Fig. 3 is embodiment 1.Can be drawn atomic percent and the mass percent of nickel and phosphorus by Fig. 3, see the following form 2.
Table 2
The SEM figure of the nickel phosphorus film that Fig. 4 is embodiment 1, wherein, magnification is 60000 times, and operating distance is 6.1mm, and high pressure is 10.00KV, and detector is ETD.As seen from Figure 4, the thickness of nickel phosphorus film is probably 1 micron.
The SEM figure of another multiplying power of the nickel phosphorus film that Fig. 5 is embodiment 1, wherein, magnification is 8000 times, and operating distance is 5.6mm, and high pressure is 5.00KV, and detector is ETD.As seen from Figure 5, the surface of coating is almost the same with the Copper Foil rough surface morphology, uneven.
Embodiment 2
Prepare the embed type sheet resistance
1, the Copper Foil of 8cm * 4cm is provided, and Copper Foil has relative shiny surface and uneven surface, sticks photosensory membrane exposure on the shiny surface of Copper Foil;
2, take washing powder 10g, add deionized water 400ml, be configured for the washing composition of oil removing.The Copper Foil of step 1 is put into to washing composition, and supersound process 10min, then take out and use washed with de-ionized water;
3, measure the 20ml vitriol oil, be configured to the dilute sulphuric acid that massfraction is 5%, the Copper Foil that step 2 is handled well is put into this dilute sulphuric acid, and then pickling 10min takes out and use washed with de-ionized water;
4, taking 35g zinc sulfate, 3.5gDL-sodium malate and 5g zinc powder adds in deionized water, be mixed with the activator of 200mL for the preparation of the embed type sheet resistance, this activator is heated to 40 ℃, then the Copper Foil of step 3 being handled well is put into this activator and is soaked 10 minutes, then uses washed with de-ionized water;
5, taking 10.04g inferior sodium phosphate, 10.07g single nickel salt, 10.00g ammonium chloride, 8.00g Trisodium Citrate, 8.00g sodium-acetate and 0.5mg thiocarbamide is dissolved in deionized water, be made into 400ml solution, regulate pH=8 with dilute sulphuric acid, plating solution is stirred to 1h, at normal temperatures, the Copper Foil that step 4 is handled well is put into this solution, plating 1 minute, plated with nickel phosphorus film on the uneven surface of Copper Foil, obtain being laminated with the Copper Foil of nickel phosphorus film, then take out and use washed with de-ionized water, dry;
6, the sample of step 5 being handled well is placed on the PCB substrate, make nickel phosphorus pellicular cascade on the PCB substrate, then pressing from both sides prepreg between PCB substrate and nickel phosphorus film, put into tabletting machine, vacuumized, under 120 ℃, insulation is incubated one hour under one hour, 150 ℃, keeps pressure at 10MPa, the Copper Foil and the PCB substrate that are laminated with nickel phosphorus film are pressed together, then naturally cooling;
7, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the first film paper, exposing and developing, the sample of step 6 is soaked 10 minutes in the first etching liquid, then take out and use washed with de-ionized water; Wherein, the mixed aqueous solution that the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the concentration of Sulfothiorine is 20g/L, the concentration of anhydrous cupric sulfate is 30g/L;
8, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the second film paper, exposing and developing, the sample of step 7 is soaked 10 minutes in the second etching liquid, then take out with washed with de-ionized water, oven dry, obtain the embed type film; Wherein, the mixed aqueous solution that the second etching liquid is anhydrous cupric sulfate, ammonium chloride and ammoniacal liquor, the concentration of cupric chloride is 30g/L, and the concentration of ammonium chloride is 45g/L, and it is 9 that the add-on of ammoniacal liquor makes the pH value of this second etching liquid.
The activator for the preparation of the embed type sheet resistance of embodiment 2 and the component of chemical plating fluid see the following form 3.
Table 3
Temperature coefficient of resistance (TCR) curve of the embed type sheet resistance that Fig. 6 is embodiment 1 and embodiment 2.As can be seen from Figure 6, the embed type sheet resistance of embodiment 1 and embodiment 2 varies with temperature very little, and resistance is highly stable.
Embodiment 3
Prepare the embed type sheet resistance
1, the Copper Foil of 8cm * 4cm is provided, and Copper Foil has relative shiny surface and uneven surface, sticks photosensory membrane exposure on the uneven surface of Copper Foil;
2, take washing powder 10g, add deionized water 400ml, be configured for the washing composition of oil removing.The Copper Foil of step 1 is put into to washing composition, and supersound process 10min, then take out and use washed with de-ionized water;
3, measure the 20ml vitriol oil, be configured to the dilute sulphuric acid that massfraction is 5%, the Copper Foil that step 2 is handled well is put into this dilute sulphuric acid, and then pickling 10min takes out and use washed with de-ionized water;
4, taking 35g zinc sulfate, 3.5gDL-sodium malate and 5g zinc powder adds in deionized water, be mixed with the activator of 200mL for the preparation of the embed type sheet resistance, this activator is heated to 40 ℃, then the Copper Foil of step 3 being handled well is put into this activator and is soaked 10 minutes, then uses washed with de-ionized water;
5, taking 15.00g inferior sodium phosphate, 12.50g single nickel salt, 10.00g ammonium chloride, 8.00g Trisodium Citrate, 8.00g sodium-acetate and 0.0005g thiocarbamide is dissolved in deionized water, be made into 400ml solution, regulate pH=8 with sodium hydroxide, plating solution is stirred to 1h, then be put in thermostat water bath, be heated to 88 ℃, the Copper Foil that step 4 is handled well is put into this solution, plating 1min, plated with nickel phosphorus film on the shiny surface of Copper Foil, obtain being laminated with the Copper Foil of nickel phosphorus film, then take out and use washed with de-ionized water, dry;
6, the sample of step 5 being handled well is placed on the PCB substrate, make nickel phosphorus pellicular cascade on the PCB substrate, then pressing from both sides prepreg between PCB substrate and nickel phosphorus film, put into tabletting machine, vacuumized, under 120 ℃, insulation is incubated one hour under one hour, 150 ℃, keeps pressure at 10MPa, the Copper Foil and the PCB substrate that are laminated with nickel phosphorus film are pressed together, then naturally cooling;
7, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the first film paper, exposing and developing, the sample of step 6 is soaked 5 minutes in the first etching liquid, then take out and use washed with de-ionized water; Wherein, the mixed aqueous solution that the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the concentration of Sulfothiorine is 20g/L, the concentration of anhydrous cupric sulfate is 30g/L;
8, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the second film paper, exposing and developing, the sample of step 7 is soaked 5 minutes in the second etching liquid, then take out with washed with de-ionized water, oven dry, obtain the embed type film; Wherein, the mixed aqueous solution that the second etching liquid is anhydrous cupric sulfate, ammonium chloride and ammoniacal liquor, the concentration of cupric chloride is 30g/L, and the concentration of ammonium chloride is 45g/L, and it is 9 that the add-on of ammoniacal liquor makes the pH value of this second etching liquid.
The activator for the preparation of the embed type sheet resistance of embodiment 3 and the component of chemical plating fluid see the following form 4.
Table 4
The SEM figure of the nickel phosphorus film that Fig. 7 is embodiment 3, wherein, magnification is 8000 times, and operating distance is 5.5mm, and high pressure is 5.00KV, and detector is ETD.As seen from Figure 7, by nickel phosphorus thin-film-coating, on the shiny surface of Copper Foil, the surface of resulting nickel phosphorus film is also more smooth, consistent with the smooth surface of Copper Foil.
By Fig. 5 and Fig. 7 contrast, can be found out, form nickel phosphorus film on the uneven surface of Copper Foil, the surface of nickel phosphorus film is comparatively coarse, and when with the PCB substrate, carrying out pressing, the uneven surface of nickel phosphorus film and the sticking power of PCB substrate are higher.
Comparative Examples 1
Prepare the embed type sheet resistance
1, the Copper Foil of 8cm * 4cm is provided, and Copper Foil has relative shiny surface and uneven surface, sticks photosensory membrane exposure on the shiny surface of Copper Foil;
2, take washing powder 10g, add deionized water 400ml, be configured for the washing composition of oil removing.The Copper Foil of step 1 is put into to washing composition, and supersound process 10min, then take out and use washed with de-ionized water;
3, measure the 20ml vitriol oil, be configured to the dilute sulphuric acid that massfraction is 5%, the Copper Foil that step 2 is handled well is put into this dilute sulphuric acid, and then pickling 10min takes out and use washed with de-ionized water;
4, the Copper Foil of step 3 being handled well is soaked in sensitization in stannous chloride solution, the mixed aqueous solution that sensitizing solution is tin protochloride and concentrated hydrochloric acid, and wherein, the concentration of tin protochloride is 40g/L, the concentration of concentrated hydrochloric acid is 100ml/L; Place at ambient temperature 3min, taking-up is with after washed with de-ionized water, put into the palladium activator, the mixed aqueous solution that the palladium activation solution is Palladous chloride and concentrated hydrochloric acid, wherein, the concentration of Palladous chloride is 0.1g/L, and the concentration of concentrated hydrochloric acid is 10ml/L, place at ambient temperature 4min, and then take out and use washed with de-ionized water;
5, taking 15.00g inferior sodium phosphate, 12.50g single nickel salt, 10.00g ammonium chloride, 8.00g Trisodium Citrate, 8.00g sodium-acetate and 0.0005g thiocarbamide is dissolved in deionized water, be made into 400ml solution, regulate pH=8 with sodium hydroxide, plating solution is stirred to 1h, then be put in thermostat water bath, be heated to 88 ℃, the Copper Foil that step 4 is handled well is put into this solution, plating 1min, plated with nickel phosphorus film on the uneven surface of Copper Foil, obtain being laminated with the Copper Foil of nickel phosphorus film, then take out and use washed with de-ionized water, dry;
6, the sample of step 5 being handled well is placed on the PCB substrate, make nickel phosphorus pellicular cascade on the PCB substrate, then pressing from both sides prepreg between PCB substrate and nickel phosphorus film, put into tabletting machine, vacuumized, under 120 ℃, insulation is incubated one hour under one hour, 150 ℃, keeps pressure at 10MPa, the Copper Foil and the PCB substrate that are laminated with nickel phosphorus film are pressed together, then naturally cooling;
7, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the first film paper, exposing and developing, the sample of step 6 is soaked 5 minutes in the first etching liquid, then take out and use washed with de-ionized water; Wherein, the mixed aqueous solution that the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the concentration of Sulfothiorine is 20g/L, the concentration of anhydrous cupric sulfate is 30g/L;
8, stick photosensory membrane at Copper Foil on the surface away from nickel phosphorus film, after then with the second film paper, exposing and developing, the sample of step 7 is soaked 5 minutes in the second etching liquid, then take out with washed with de-ionized water, oven dry, obtain the embed type film; Wherein, the mixed aqueous solution that the second etching liquid is anhydrous cupric sulfate, ammonium chloride and ammoniacal liquor, the concentration of anhydrous cupric sulfate is 30g/L, and the concentration of ammonium chloride is 45g/L, and it is 9 that the add-on of ammoniacal liquor makes the pH value of this second etching liquid.
Utilize the square resistance of the embed type sheet resistance of digital source ammeter test implementation example 1～3 and Comparative Examples 1, test result is in Table 5.
Table 5
By table 5, the square resistance of the embed type sheet resistance of embodiment 1～3 is large than Comparative Examples 1 all.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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 (14)
1. the activator for the preparation of the embed type sheet resistance, it is characterized in that, comprise water, zinc sulfate, DL-sodium malate and zinc powder, wherein, the concentration that the concentration that described sulfuric acid zinc concentration is 20～200g/L, described DL-sodium malate is 10～50g/L, described zinc powder is 5～30g/L.
2. the preparation method of an embed type sheet resistance, comprise the steps:
Substrate is provided;
With the activator for the preparation of the embed type sheet resistance as claimed in claim 1, described substrate is activated the substrate after being activated;
Prepare nickel phosphorus film on the surface of the substrate of employing electroless plating method after described activation, obtain being laminated with the substrate of nickel phosphorus film;
PCB substrate and the described substrate that is laminated with nickel phosphorus film are carried out to pressing, and make described nickel phosphorus pellicular cascade on described PCB substrate; And
Described substrate and nickel phosphorus film are carried out to etching, obtain the embed type sheet resistance.
3. the preparation method of embed type sheet resistance according to claim 2, it is characterized in that, be included on described substrate and stick photosensory membrane, the step of then being exposed before the step described substrate activated with the activator for the preparation of the embed type sheet resistance as claimed in claim 1.
4. the preparation method of embed type sheet resistance according to claim 3, it is characterized in that, stick photosensory membrane on described substrate, then, after being exposed, also comprise the step that described substrate is washed before the step described substrate activated with the activator for the preparation of the embed type sheet resistance as claimed in claim 1.
5. the preparation method of embed type sheet resistance according to claim 4, is characterized in that, the step of described washing is for first being washed with washing composition, then the sulphuric acid soln that is 5% by mass concentration carries out pickling.
6. the preparation method of embed type sheet resistance according to claim 2, is characterized in that, described substrate is Copper Foil, and described Copper Foil has relative shiny surface and uneven surface, and described nickel phosphorus pellicular cascade is on the uneven surface of described Copper Foil.
7. the preparation method of embed type sheet resistance according to claim 2, it is characterized in that, the step described substrate activated with the activator for the preparation of the embed type sheet resistance as claimed in claim 1 is specially: the activator for the preparation of the embed type sheet resistance as claimed in claim 1 is remained on to 20 ℃～60 ℃, more described substrate is placed in to activator that described temperature is 20 ℃～60 ℃ soaks 1 minute～10 minutes.
8. the preparation method of embed type sheet resistance according to claim 2, it is characterized in that, prepare nickel phosphorus film on the surface of the substrate of described employing electroless plating method after described activation, the step that obtains being laminated with the substrate of nickel phosphorus film is specially: it is that 20 ℃～90 ℃ chemical plating fluids are processed 0.5 minute～5 minutes that the substrate after described activation is put into to temperature.
9. the preparation method of embed type sheet resistance according to claim 8, it is characterized in that, every liter of described chemical plating fluid contains single nickel salt 5～80 grams, ortho phosphorous acid hydrogen sodium 5～80 grams, buffer reagent 10～80 grams, 1～5 milligram of stablizer and complexing agent 10～80 grams.
10. the preparation method of embed type sheet resistance according to claim 2, it is characterized in that, described PCB substrate and the described substrate that is laminated with nickel phosphorus film are carried out to pressing, and the step of described nickel phosphorus pellicular cascade on described PCB substrate is specially: the described substrate that is laminated with nickel phosphorus film is positioned on described PCB substrate, and make described nickel phosphorus pellicular cascade on described PCB substrate, again prepreg is held between described nickel phosphorus film and PCB substrate, vacuumize, after thermal treatment by the described substrate attaching of nickel phosphorus film that is laminated with on described PCB substrate.
11. the preparation method of embed type sheet resistance according to claim 10, is characterized in that, described heat treated step is to be incubated 1 hour under 100 ℃～140 ℃, then is incubated 1 hour under 140 ℃～180 ℃.
12. the preparation method of embed type sheet resistance according to claim 2, is characterized in that, the described step that described substrate and nickel phosphorus film are carried out to etching comprises:
Adopt the first etching liquid to carry out etching to described substrate and nickel phosphorus film; And
Adopt the second etching liquid to carry out etching to described substrate.
13. the preparation method of embed type sheet resistance according to claim 12, it is characterized in that, the mixed aqueous solution that described the first etching liquid is Sulfothiorine and anhydrous cupric sulfate, the mixed aqueous solution that described the second etching liquid is cupric chloride, ammonium chloride and ammoniacal liquor.
14. one kind prepares the embed type sheet resistance by the described preparation method of claim 2～13 any one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105695993A (en) * | 2016-02-04 | 2016-06-22 | 安捷利（番禺）电子实业有限公司 | Method for preparing embedded resistance copper foil |
| CN111246663A (en) * | 2018-11-28 | 2020-06-05 | 庆鼎精密电子（淮安）有限公司 | Embedded resistor structure and manufacturing method thereof |
| CN112055460A (en) * | 2020-09-01 | 2020-12-08 | 王川川 | Resistance material, copper-clad plate containing resistance layer and manufacturing method of printed circuit board |
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| JPH0711448A (en) * | 1993-06-29 | 1995-01-13 | Ishihara Chem Co Ltd | Catalytic solution for electroless plating selective to copper-based material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695993A (en) * | 2016-02-04 | 2016-06-22 | 安捷利（番禺）电子实业有限公司 | Method for preparing embedded resistance copper foil |
| CN105695993B (en) * | 2016-02-04 | 2018-07-06 | 安捷利（番禺）电子实业有限公司 | A kind of preparation method of embedded resistor copper foil |
| CN111246663A (en) * | 2018-11-28 | 2020-06-05 | 庆鼎精密电子（淮安）有限公司 | Embedded resistor structure and manufacturing method thereof |
| CN112055460A (en) * | 2020-09-01 | 2020-12-08 | 王川川 | Resistance material, copper-clad plate containing resistance layer and manufacturing method of printed circuit board |
| CN112055460B (en) * | 2020-09-01 | 2022-12-06 | 王川川 | Resistance material, copper-clad plate containing resistance layer and manufacturing method of printed circuit board |
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| CN103484840B (en) | 2015-11-18 |
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