CN102438404A - Preparation method of embedded resistor for printed circuit board - Google Patents
Preparation method of embedded resistor for printed circuit board Download PDFInfo
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- CN102438404A CN102438404A CN2011102336738A CN201110233673A CN102438404A CN 102438404 A CN102438404 A CN 102438404A CN 2011102336738 A CN2011102336738 A CN 2011102336738A CN 201110233673 A CN201110233673 A CN 201110233673A CN 102438404 A CN102438404 A CN 102438404A
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- printed circuit
- resistance
- circuit board
- potting formula
- formula resistance
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Abstract
The invention relates to a preparation method of an embedded resistor for a printed circuit board, belonging to the technical field of electronic materials and elements, which comprises the following steps of: carrying out stannous chloride sensitization, hydrolisis and palladium chloride activation to the imaging printed circuit board, carrying out dry film sticking, exposure imaging and dry film removing, and exposing an embedded type resistor manufacture area; carrying out chemical plating in the embedded resistor manufacture area to obtain a Ni-p alloy embedded type resistor with a porous structure; and carrying out hot quenching and tempering to a Ni-p alloy material with the porous structure to obtain the embedded resistor, wherein chemical plating solution contains 5-50 grams of NiSO4 or NiCl2, 5-50 grams of NaHPO2, 2-25 grams of buffer, 1milligram of potassium iodide stabilizer, 5-50 grams of complexing agent and 1-80 grams of resistance value regulator at each cubic dm, the PH value is between 2.5-5.0, and the temperature is 60-95 DEG C. The embedded resistor for the printed circuit, prepared by the invention, has the characteristics of large square resistance, stable resistance value and good radiation property, the manufacture process is simple, can be compatible with the manufacture process of the common printed circuit, and is easy to popularize in printed circuit enterprises.
Description
Technical field
The invention belongs to electronic material and components and parts technical field, particularly a kind of preparation method of used for printed circuit board potting formula resistance.
Background technology
Along with the develop rapidly of electronic industry, when carrying out high-frequency signal or high digital data transmission in consumption electronic product such as high level computer and the equipment such as communicate by letter, all be to realize usually through characteristic value in the strict control transmission line and corresponding passive component.But these big flux matched passive components have occupied a large amount of area and the spaces of printed circuit board.Through with the passive component potting to printed circuit board, can make the area of circuit board dwindle about 40% than the area of the circuit board that adopts surface mounting technology (SMT) to make.Potting resistance is as one of three big passive devices, each large-scale research institute both at home and abroad, and enterprise and colleges and universities have all launched a large amount of research.
The preparation of potting formula resistance is that printed circuit board enterprise merges with the printed board manufacture craft through the preparation flow with resistance, realizes from material, design, technology, to a series of operation processes such as tests.There are companies such as Du Pont, MacDermid Incorporated in the main mechanism that realizes.The regional low-temperature sintering that E.I.Du Pont Company uses barium titanate ceramic to make resistance at needs is made resistance, makes the printed circuit board circuit through operations such as exposure, development, etchings then.This method can obtain higher resistance, and square resistance can reach thousands of ohms, even the number megohm, but complex technical process, resistance is difficult to control.MacDermid Incorporated company makes the printed circuit board circuit through operations such as exposure imaging etchings, makes potting resistance through operations such as sensitization, activation, pad pasting, exposure imaging, chemical Ni-P plating resistance materials then.This process and printed board manufacture craft amalgamation are good, enterprise's easy master, and also the resistance of making is stable, low price, and weak point is resistance material square resistance too little (the thick square resistance of 1 μ m is no more than 5 Ω).(list of references [1] Richard Ulrich.Embedded Resistors and Capacitors for Organic-Based SOP [J] .IEEE Transaction on Advanced Packaging, 2004, Vol.27 (2): 326～331; [2] Kimmo
Embedded Resistors in Printed Wiring Boards [C] .9
ThInt ' l Symposium on Advanced Packaging Materials.2004, pp.220～229; [3] John Felten; Richard Snogren; Jiming Zhou.Embedded Ceramic Resistors and Capacitors in PWB:Process and Performance.http: //www2.dupont.com/). in " Integrated Passive Component Technology " book that [4] IEEE publishes 11～12,15～16 pages).
Summary of the invention
The present invention provides a kind of preparation method of used for printed circuit board potting formula resistance; This method is used for reference MacDermid Incorporated company potting formula resistance manufacture craft, through toward chemical plating fluid in, add the resistance conditioning agent make compactness preferably nickel-phosphorus alloy form porous material and carry out hot modifier treatment and obtain the potting formula resistance that resistance is stablized, thermal diffusivity is good.Compare the potting formula resistance that MacDermid Incorporated company makes; Side's resistance of the potting formula resistance that the present invention is prepared has improved an one magnitude; And manufacture craft is simple, compatible mutually with existing printed circuit board manufacture craft, grasped and realization by ordinary printed circuit board making enterprise easily.
Technical scheme of the present invention is following:
A kind of preparation method of used for printed circuit board potting formula resistance, as shown in Figure 4, may further comprise the steps:
Step 1: printed circuit figureization.
Adopt the printed circuit manufacture craft to produce circuitous pattern, obtain patterned printed circuit board on medium copper-clad plate surface;
Step 2: stannous chloride sensitization, hydrolysis.
Graphical printed circuit board is soaked in carries out sensitization in the stannous chloride aqueous solution; After the sensitization graphical printed circuit board is soaked in the deionized water and is hydrolyzed, be slightly soluble in the tin salt gelling material Sn of water at media substrate surface deposition one deck of graphical printed circuit board
2(OH)
3Cl.
Step 3: palladium bichloride activation.
With the media substrate surface deposition Sn
2(OH)
3The graphical printed circuit board of Cl is soaked in palladium bichloride (PdCl
2) in the aqueous solution, make Sn
2(OH)
3Cl is with the Pd in the palladium chloride solution
2+Ion is reduced into the Pd atom and is deposited on the media substrate surface of graphical printed circuit board, assembles the center thereby form the electroless deposition thing.
Step 4: dry film is pasted on the graphical printed circuit board surface after handling through step 3, removes the dry film that needs to make potting formula resistance region after use resistance pattern mask exposure, the development, exposes potting formula resistance and makes regional.
Step 5: chemical plating potting formula resistance.
Make the zone at potting formula resistance and carry out chemical plating, obtain the nickel-phosphorus alloy potting formula resistance of loose structure, wherein the used every liter of volume of plating bath of chemical plating contains NiSO
4Or NiCl
25～50 grams, NaHPO
25～50 grams, pH value buffer 2～25 grams, 1 milligram of KI stabilizer, complexing agent 5～50 grams and resistance conditioning agent 1～80 gram; Adopting the pH value conditioning agent to regulate pH value when the plating bath preparation is accomplished is between 2.5～5.0, maintains the temperature between 60～95 ℃ in the plating bath use.
Step 6: potting formula resistance heat modifier treatment.
Under 150～300 ℃ of temperature, the nickel-phosphorus alloy potting formula resistance of step 5 gained loose structure was heat-treated more than 30 minutes, obtain the stable potting formula resistance of resistance.
Need to prove: 1) because tin element has polyvalent cation, so preparation SnCl
2During the aqueous solution, need to add certain concentrated hydrochloric acid to prevent SnCl
2Sn in the aqueous solution
2+Be oxidized to Sn
4+2) because PdCl
2Be insoluble in water, so preparation PdCl
2During the aqueous solution, need to add certain concentrated hydrochloric acid to increase PdCl
2Dissolubility.
In the technique scheme: said pH value buffer is sodium acetate or potassium acetate, and role is the scope that constant plating bath pH value is being set; Said complexing agent is one or more in citric acid, succinic acid, thiocarbamide, DL malic acid or the lactic acid, and role is with complexing Ni
2+, the Ni of release fixed amount in the chemical plating process
2+Said resistance conditioning agent is one or more in manganese sulfate, manganese chloride or the manganese nitrate, and role is that the Ni-P alloy that makes chemical plating form forms porous type; Said pH value conditioning agent is one or more in ammoniacal liquor, NaOH or the potassium hydroxide, regulates pH value to needed acidity.
Make the nickel-phosphorus alloy material form loose structure (as shown in Figure 1) through adding the resistance conditioning agent in the plating bath, thereby improve the resistivity of resistive layer material; In the chemical plating process, the Ni in the plating bath
2+Thereby can on particulate, deposit the stability that reduces plating bath, behind the adding KI stabilizer, the KI stabilizer can combine with the particulate in the plating bath, stops Ni
2+On particulate, deposit, thus the stability of raising plating bath; Resistive layer material square resistance is along with the content of resistance conditioning agent in the electroplate liquid formulation increases and increases.
The used for printed circuit board potting formula resistance that the present invention does preparation has loose structure; Contain Ni80%～97%, contain P3%～20%; Have square resistance big (the thick square resistance of 1 μ m can reach 100 Ω), resistance is stable and the characteristics of thermal diffusivity good (resistance material of the loose structure thermal diffusivity than the resistance material that does not have loose structure in theory is good); And manufacture craft is simple, can be compatible mutually with the ordinary printed process for manufacturing circuit board, be easy at the printed circuit business enterprise expand.
Description of drawings
Fig. 1 is the SEM figure of the prepared used for printed circuit board potting formula resistance material of the present invention.Can find out obviously that from Fig. 1 the used for printed circuit board potting formula resistance material that the present invention makes is a loose structure.
Fig. 2 is the EDS figure of the prepared used for printed circuit board potting formula resistance of the present invention.Abscissa is an energy, and unit is keV; Ordinate is an intensity, and unit is C/S; Ni, P are potting formula resistance material main component among the figure, and elements such as C, O, Al are the media substrate main component.
Fig. 3 is the content figure of the square resistance of the prepared used for printed circuit board potting formula resistance of the present invention with resistance conditioning agent (manganese sulfate).Abscissa is the content of manganese sulfate, and unit is g/L, and ordinate is the square resistance resistance, and unit is Ω.
Fig. 4 is the flow chart of used for printed circuit board potting formula resistance provided by the invention.
Specific embodiments
The contrast embodiment---the potting formula resistance preparation technology who adopts MacDermid Incorporated company to provide prepares potting formula resistance.
Use to give birth to that the epoxy glass fabric base material carries out porous resistance material deposition as the chemical plating insulated substrate in the thick single-side coated copper plate of 0.2mm that beneficial company produces.Detailed process is following:
(1) substrate alkaline degreasing:
The first step: the electrochemical deoiling solution with preparing, place thermostat water bath, regulating the water-bath preset temperature is 50-60 ℃;
Second step: after treating that temperature rises to preset temperature, the plating sample is put into except that oil solution, and will be held except that the beaker of oil solution and transfer in the supersonic wave cleaning machine ultrasonic cleaning 10min;
The 3rd step: after oil removing finishes, take out plating piece with deionized water with twice of plating sample wash after, put into the beaker of small amount of deionized water, ultrasonic cleaning 2min carries out next step operation once more.
Its degreasing fluid prescription is: NaOH 25g/L, sodium carbonate 30g/L, tertiary sodium phosphate 50g/L, additive a little.
(2) stannous chloride sensitization, hydrolysis:
Tellite behind the alkaline degreasing is soaked in sensitization in the stannous chloride aqueous solution, and the sensitization process conditions are:
Table 1 substrate sensitizing solution
| Stannous chloride (SnCl 2·2H 2O) | 40g/L |
| Concentrated hydrochloric acid | 100ml/L |
| Temperature | Room temperature |
| Time | 3.5min |
Substrate after the sensitization is placed 3min in the deionized water, and hydrolysis generates the tin salt gelling material Sn that is slightly soluble in water
2(OH)
3Cl is deposited on the substrate surface equably, as reducing agent when the activation processing the Pd in the activator
2+Ion is reduced into the Pd atom.
(3) palladium bichloride activation:
The substrate of sensitization, hydrolysis, deionized water is carried out reduction reaction, Sn in the immersion palladium chloride aqueous solution after cleaning
2+Ion is the Pd in the palladium chloride aqueous solution
2+Ion is reduced into the Pd atom, and the Pd atom is attached to the sedimental gathering center during as chemical plating on the substrate surface.Process conditions are:
Table 2 palladium bichloride activating solution
| Palladium bichloride | 0.1g/L |
| Concentrated hydrochloric acid | 10ml/L |
| Temperature | Room temperature |
| Time | 4min |
(4) chemical plating resistance material:
Substrate is placed in the plating bath, used water-bath to stablize bath temperature, its process conditions are following:
Table 3 substrate chemical plating porous resistance material process conditions (1)
| Nickelous sulfate | 30g/L |
| Inferior sodium phosphate | 40g/L |
| Complexing agent (citric acid) | 23.4g/L |
| PH value buffer (sodium acetate) | 10g/L |
| Complexing agent (succinic acid) | 10g/L |
| (water-bath) temperature | 90℃ |
| The pH value | 3.5 |
| The KI stabilizer | 1mg/L |
| Time | 15min |
The chemical plating resistance material reach 1 micron thickness intact after, use four point probe tester test square resistance, the square resistance resistance is 2.3 Ω.
(5) resistance material is placed 180 ℃ of heat treatment 30min, the resistive square resistance is 2.3 Ω.
Can find out that by above-mentioned contrast embodiment the prepared potting formula resistance of potting formula resistance preparation technology that adopts MacDermid Incorporated company to provide be that the resistance of 1 micron thick time side is very little at resistance material, and hot modifier treatment is invalid to resistance material.
Specific embodiments 1
Epoxy glass fabric base material material is as the chemical plating insulated substrate in the living beneficial 0.2mm single-side coated copper plate of use, and on contrast embodiment step (1)～(3) basis, step (4) is used following process conditions:
Table 3 substrate chemical plating porous resistance material process conditions (2)
| Nickelous sulfate | 30g/L |
| Inferior sodium phosphate | 30g/L |
| Complexing agent (citric acid) | 25g/L |
| PH value buffer (sodium acetate) | 10g/L |
| Resistance conditioning agent (manganese sulfate) | 20g/L |
| (water-bath) temperature | 90℃ |
| The pH value | 3.5 |
| The KI stabilizer | 1mg/L |
| Time | 15min |
The chemical plating resistance material reach 1 micron thickness intact after, use that square resistance is 525 Ω after the four point probe tester test chemical plating, the back is heat-treated 10min 150 ℃ of temperature to resistance material, obtaining square resistance is 108 Ω; Re-use 180 ℃ of temperature resistance material is handled 30min, obtaining square resistance is 95 Ω; At 180 ℃ of heat treatment 60min, obtaining square resistance is 93 Ω again.
Can find out from above-mentioned specific embodiments 1; Adopting the prepared potting formula resistance of the preparation method of used for printed circuit board potting formula resistance provided by the invention is that side's resistance of the 1 micron thick time side resistance potting formula resistance more prepared than the potting formula resistance preparation technology who adopts MacDermid Incorporated company to provide is much bigger at resistance material; And after hot modifier treatment, resistance is stablized (180 ℃ of heat treatment deviations are in 6%).Use normal temperature, pressure to be 140N/cm
2To material lamination 20min, obtaining the square resistance resistance is 105 Ω, explains that lamination is very little to side's resistance influence of the prepared potting formula resistance of the present invention.The potting formula resistance junction of using the adhesive tape method to detect the present invention's preparation is simultaneously made a concerted effort, and the result shows that adhesion is good.
Specific embodiments 2
Use living beneficial 0.2mm copper-clad plate to be base material, on its circuit, form potting formula resistance.Its preparation flow is following:
1) printed circuit board is produced printed circuit copper wire figure through exposure, development, etching and striping.
2) carry out stannous chloride sensitization, palladium bichloride activation according to step (1)～(3) in the contrast embodiment at the printed circuit board that contains the figure circuit, assemble the center to form the electroless deposition thing.
3) on printed circuit board, paste dry film, use the resistance pattern mask exposure, dry film is removed in the zone that needs are made resistance in the back of developing, in order to next step chemical plating porous type resistance material.
4) the middle MnSO of step (4) in the modification 1
4The resistance conditioning agent is 10g/L, and sedimentation time is 10min, and other technological parameters are constant, at printed circuit board presumptive area deposition potting formula resistance.
5) resistance is placed 180 ℃ of hot modifier treatment 30min, obtain the stable potting formula resistance of resistance.
Use the resistance at universal instrument test potting resistance two ends, the resistance that contains 1 square is 20 Ω, and the resistance that contains 8 squares is 110 Ω, and the resistance that contains 10 squares is 155 Ω.
Claims (5)
1. the preparation method of a used for printed circuit board potting formula resistance may further comprise the steps:
Step 1: printed circuit figureization;
Adopt the printed circuit manufacture craft to produce circuitous pattern, obtain patterned printed circuit board on medium copper-clad plate surface;
Step 2: stannous chloride sensitization, hydrolysis;
Graphical printed circuit board is soaked in carries out sensitization in the stannous chloride aqueous solution; After the sensitization graphical printed circuit board is soaked in the deionized water and is hydrolyzed, be slightly soluble in the tin salt gelling material Sn of water at media substrate surface deposition one deck of graphical printed circuit board
2(OH)
3Cl;
Step 3: palladium bichloride activation;
With the media substrate surface deposition Sn
2(OH)
3The graphical printed circuit board of Cl is soaked in the palladium chloride solution, makes Sn
2(OH)
3Cl is with the Pd in the palladium chloride solution
2+Ion is reduced into the Pd atom and is deposited on the media substrate surface of graphical printed circuit board, assembles the center thereby form the electroless deposition thing;
Step 4: dry film is pasted on the graphical printed circuit board surface after handling through step 3, removes the dry film that needs to make potting formula resistance region after use resistance pattern mask exposure, the development, exposes potting formula resistance and makes regional;
Step 5: chemical plating potting formula resistance;
Make the zone at potting formula resistance and carry out chemical plating, obtain the nickel-phosphorus alloy potting formula resistance of loose structure, wherein the used every liter of volume of plating bath of chemical plating contains NiSO
4Or NiCl25～50 restrain, NaHPO
25～50 grams, buffer 2～25 grams, 1 milligram of KI stabilizer, complexing agent 5～50 grams and resistance conditioning agent 1～80 gram, it is between 2.5～5.0 that plating bath adopts the pH value conditioning agent to regulate pH value, bath temperature is between 60～95 ℃;
Step 6: potting formula resistance heat modifier treatment;
Under 150～300 ℃ of temperature, the nickel-phosphorus alloy potting formula resistance of step 5 gained loose structure was heat-treated more than 30 minutes, obtain the stable potting formula resistance of resistance.
2. the preparation method of used for printed circuit board potting formula resistance according to claim 1 is characterized in that, complexing agent described in the step 5 is one or more in citric acid, succinic acid, thiocarbamide, DL malic acid or the lactic acid.
3. the preparation method of used for printed circuit board potting formula resistance according to claim 1 is characterized in that, the conditioning agent of resistance described in the step 5 is one or more in manganese sulfate, manganese chloride or the manganese nitrate.
4. the preparation method of used for printed circuit board potting formula resistance according to claim 1 is characterized in that, the conditioning agent of pH value described in the step 5 is one or more in ammoniacal liquor, NaOH or the potassium hydroxide.
5. the preparation method of used for printed circuit board potting formula resistance according to claim 1 is characterized in that the buffer of pH value described in the step 5 is sodium acetate or potassium acetate.
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|---|---|---|---|
| CN2011102336738A CN102438404A (en) | 2011-08-16 | 2011-08-16 | Preparation method of embedded resistor for printed circuit board |
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|---|---|---|---|
| CN2011102336738A CN102438404A (en) | 2011-08-16 | 2011-08-16 | Preparation method of embedded resistor for printed circuit board |
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| CN102438404A true CN102438404A (en) | 2012-05-02 |
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ID=45986199
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106572601A (en) * | 2016-10-19 | 2017-04-19 | 衢州顺络电路板有限公司 | Printed circuit board with porous structure resistance layer, and manufacturing method for printed circuit board |
| CN110389257A (en) * | 2019-08-29 | 2019-10-29 | 电子科技大学 | A kind of production method for the integrating device and embedded resistors that embedded resistors are monitored online |
| 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 |
| CN111295044A (en) * | 2018-12-06 | 2020-06-16 | 庆鼎精密电子（淮安）有限公司 | Method for manufacturing embedded resistor |
| CN111458328A (en) * | 2020-04-26 | 2020-07-28 | 电子科技大学 | Method for detecting distribution of residual copper layer of printed circuit board |
| CN114783712A (en) * | 2022-04-27 | 2022-07-22 | 电子科技大学 | Method for preparing high-resistance embedded resistor by chemically doping carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827848A (en) * | 2006-04-05 | 2006-09-06 | 南昌大学 | Process for coarsening-free chemical plating of nickel-phosphor alloy on optical fiber surface and chemical plating solution thereof |
| US20100181207A1 (en) * | 2009-01-20 | 2010-07-22 | Sung-Ling Su | Method For Fabricating Embedded Thin Film Resistors Of Printed Circuit Board |
-
2011
- 2011-08-16 CN CN2011102336738A patent/CN102438404A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827848A (en) * | 2006-04-05 | 2006-09-06 | 南昌大学 | Process for coarsening-free chemical plating of nickel-phosphor alloy on optical fiber surface and chemical plating solution thereof |
| US20100181207A1 (en) * | 2009-01-20 | 2010-07-22 | Sung-Ling Su | Method For Fabricating Embedded Thin Film Resistors Of Printed Circuit Board |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106572601A (en) * | 2016-10-19 | 2017-04-19 | 衢州顺络电路板有限公司 | Printed circuit board with porous structure resistance layer, and manufacturing method for printed circuit board |
| 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 |
| CN111295044A (en) * | 2018-12-06 | 2020-06-16 | 庆鼎精密电子（淮安）有限公司 | Method for manufacturing embedded resistor |
| CN110389257A (en) * | 2019-08-29 | 2019-10-29 | 电子科技大学 | A kind of production method for the integrating device and embedded resistors that embedded resistors are monitored online |
| CN111458328A (en) * | 2020-04-26 | 2020-07-28 | 电子科技大学 | Method for detecting distribution of residual copper layer of printed circuit board |
| CN114783712A (en) * | 2022-04-27 | 2022-07-22 | 电子科技大学 | Method for preparing high-resistance embedded resistor by chemically doping carbon |
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Application publication date: 20120502 |