CN109989083A - Pretreating process is electroplated in the super roughening lead frame of one kind - Google Patents
Pretreating process is electroplated in the super roughening lead frame of one kind Download PDFInfo
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- CN109989083A CN109989083A CN201910347487.3A CN201910347487A CN109989083A CN 109989083 A CN109989083 A CN 109989083A CN 201910347487 A CN201910347487 A CN 201910347487A CN 109989083 A CN109989083 A CN 109989083A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses the super roughening lead frames of one kind, and pretreating process is electroplated, and includes the following steps: step 1: carrying out spray process to lead frame using organic acid coarsening solution；Step 2: after spray process, being washed using ultrapure adverse current, carry out immersion treatment using the hydrochloric acid solution of 2%-5%, the corrosion product of lead frame copper material surface black can be dissolved, and highlight the color of copper, be washed using ultrapure adverse current, and level-one roughening is completed；Step 3: carry out secondary roughening using acid copper plating solution, lead frame is cathode, and stainless steel plate is that anode carries out electro-coppering, carries out electric current adjustment with pulse rectifier when electro-coppering, current-mode using 8: 2 positive and negative pulse current system.
Description
Technical field
The present invention relates to lead frames, and preconditioning technique field is electroplated, and in particular to the super roughening lead frame plating of one kind is pre-
Treatment process.
Background technique
IC lead frame is used as chip carrier, and keeps chip interior electric by lead key and (bonding gold thread or copper wire)
Road is the important component of semiconductor packages by pin and exterior PC B circuit connection on lead frame.In complete IC package
In body, lead frame plays fixed chip, transfer circuit signal, provides heat dissipation path, while playing protection to chip circuit structure
Effect.Because the reliability step of integrated circuit is often determined by Multiple factors, but the packaging technology pair of IC chip
The requirement of lead frame is with regard to relatively high, and the performance of lead frame plays leading role for promoting MSL reliability step.Closely
The reliability of more and more semiconductor packages customer requirement IC chips must reach MSL1 grades of requirement over year, wherein
Crucial improvement is to improve the bond strength of lead frame and potting resin.From original angle, realize that raising chip can
Method by property is exactly to increase the roughness of lead frame surface, by mechanical interlocked principle to enhance lead frame substrate with
The binding force of potting resin avoids in MSL1 grades of reliability tests, and " popcorn effect " occur leads to lead frame and encapsulation
The failure mode of resin layering.
The lead frame surface treatment process of present comparative maturity mainly has microetch, copper face brown oxidation and plating roughening
Three kinds.Wherein microetch carving technology occurs earliest, and solution formula is simple, mainly based on common inorganic acid, such as dioxysulfate water
Type, it is at low cost.Microetch carving technology, which refers to, carries out surface microcorrosion to lead frame surface before plating, keeps original presentation fine
The copper foil surface of dimension shape shows the form that height rises and falls.Copper face brown oxidation technique refers to after the completion of plating, uses strong oxygen
Agent generates one layer of fine and close oxide layer in copper alloy surface, while it is thin in organic matter formation complex compound to generate one layer of copper
The binding force of film, film and plastic packaging material is greater than the binding force of copper and plastic packaging material.The solution formula that the technique uses is at present at the country
It is at high cost in space state, poor operability.In contrast, microetch process costs are low, are the traditional surface treatment sides of comparison
Method, but can not stability contorting, copper surface roughness changes over time can be increasing.And coppery brown oxidation technology
It is at high cost although good reliability, poor operability.A kind of last plating roughening process, only has two joint lead frames at present
Frame manufacturing enterprise has the technology, and the country is in space state in terms of the plating roughening process.Three kinds of roughening processes are being roughened
The phenomenon that taking into account is difficult in degree, cost and operability leads to cost and the unbalance problem of operability.
Summary of the invention
It is an object of the invention to: it is difficult on coarsening rate, cost and operability for above-mentioned three kinds of roughening processes
The phenomenon that take into account, leads to cost and the unbalance problem of operability, and the present invention provides a kind of super pre- place of roughening lead frame plating
Science and engineering skill.
The technical solution adopted by the invention is as follows:
Pretreating process is electroplated in the super roughening lead frame of one kind, includes the following steps:
Step 1: spray process being carried out to lead frame using organic acid coarsening solution；
Step 2: after spray process, washing using ultrapure adverse current, carried out at immersion using the hydrochloric acid solution of 2%-5%
Reason, the corrosion product of lead frame copper material surface black can be dissolved, and highlight the color of copper, be washed using ultrapure adverse current,
Complete level-one roughening:
Step 3: carrying out secondary roughening using acid copper plating solution, lead frame is cathode, and stainless steel plate is anode progress
Electro-coppering, carries out electric current adjustment with pulse rectifier when electro-coppering, and current-mode uses 8: 2 positive and negative pulse current system.
Further, organic coarsening solution main component described in step 1 includes formic acid, copper chloride, sodium chloride, ammonium chloride, second
Diamines, citrate, tartrate, it is ultrapure water that the organic acid coarsening solution, which prepares the water that solution uses, the machine acid roughening
Cu in liquid2+Ion concentration is 15-30g/L, and formic acid accounts for the 5%-15% of total solution volume ratio, and sodium chloride and ammonium chloride content are respectively
8%-10%, citrate and tartrate content are respectively 0.5%-2%, and wherein formic acid is for providing required for corrosion metal
Hydrogen ion and formation buffer solution system, make the pH value of etching solution keep relative stability；Ethylenediamine is used for and copper ion or Asia
Copper ion is complexed to form complex compound, participates in corrosion reaction, and keep the stabilization of etching solution；It is micro- when in coarsening solution without copper ion
Erosion speed is very slow, and microetch depth as shallow, Copper dichloride dihydrate makes microetch speed tend towards stability；Sodium chloride and ammonium chloride are for controlling erosion
Speed is carved, etching efficiency is improved.
Further, the spray pressure of the coarsening solution of machine acid described in step 1 requires between 0.15-0.2MPa, the roughening of machine acid
The treatment temperature of liquid maintains 20-40 DEG C, and the time for spraying roughening controls between 15-90s.
Further, the main component of acid copper plating solution described in step 3 includes sulfuric acid, copper sulphate, titanium sulfate, wolframic acid
Sodium, Cu2+Ion concentration is 15-25g/L, and sulfuric acid content 100-120g/L, sulfuric acid Ti content is 0.5-1.5g/L, sodium tungstate
Content is 0.05-0.15g/L；Wherein Ti2+Cu can be effectively improved2+In the deposition morphology of lead frame surface, reactive ion and
The absorption of non-reactive ion will affect Cu2+In the speed of separating out of cathode surface, and influence crystalline orientation and the coating cause of copper ion
Density, by influencing the deposition process of copper ion to effective very high surface roughness.Current density is higher, copper ion deposition speed
Degree is faster, and corresponding current density is higher, and crystalline particle size is smaller, and surface roughness raising is less, and copper ion deposition velocity is got over
Slowly, corresponding current density is higher, and crystalline particle size is larger, and surface roughness is obviously improved.
Further, step 3 electroplating process uses air stirring, and current density is controlled in 30-50A/dm2, in electroplating process
Bath filter pump need to be increased, continuously recycled, washed after electroplating processes using three ultrapure adverse currents.
Further, stainless steel plate described in step 3 is 304 stainless steel plates of mesh, thickness 0.2-0.6mm.
Further, which can carry out selectivity according to the different of coarsening rate
Setting, can be roughened with 1 organic acid of cancellation step and step 2 hydrochloric acid cleans, and carry out step 3 acid copper-plating technique only to be roughened；Or
3 acid copper-plating technique of person's cancellation step is roughened using the roughening of step 1 organic acid and the cleaning of step 2 hydrochloric acid.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. acid copper-plating is big using sulfuric acid, the plating crystalline particle of copper sulphate system itself, and depends on material surface protrusion
The principle of position preferential crystallization carries out second time electroplating roughening；
2. sulfuric acid and copper sulphate are plating solution foundational system, copper ion is higher, and crystallization rate is faster, and dendrite morphology is more obvious.
Titanium sulfate is crystallographic orientation agent, plate surface roughness can be improved, current density is higher, and dendrite morphology is more obvious.Sodium tungstate
Addition can control grain size, so that crystallite dimension is tended to be uniform；
3. can control etching speed by using sodium chloride and ammonium chloride, etching efficiency is improved；
4. can have as hydroxyl hydroxy acid salt compound as ion sequestering agent by using tartrate and citrate
The Fe that the masking of effect is generated when handling copper alloy2+, Ni2+Equal foreign ions, maintain coarsening solution to stablize；
5. the roughening scheme is roughened before copper pre-plating with organic acid, hydrochloric acid cleaning and acid copper-plating are roughened three technology generations
For the pickling processes in traditional handicraft, operability is good, at low cost, and surface roughness Ra makes up current line up to 0.5 micron
Three kinds of roughening processes are difficult to take into account on coarsening rate, cost and operability the unbalance of cost and operability in industry.
Detailed description of the invention
This practical invention will illustrate by example and with reference to the appended drawing, in which:
Fig. 1 is organic acid coarsening solution roughening effect diagram of the present invention；
Fig. 2 is acid copper plating solution roughening effect diagram of the present invention；
Fig. 3 is conventional lead frame plating process:
Fig. 4 is lead frame plating process of the present invention.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
It elaborates below with reference to Fig. 1, Fig. 2, Fig. 3 and Fig. 4 to the present invention.
Embodiment 1
Pretreating process is electroplated in the super roughening lead frame of one kind, includes the following steps:
Step 1: prepare organic acid coarsening solution, organic coarsening solution main component include formic acid, copper chloride, sodium chloride,
Ammonium chloride, ethylenediamine, citrate, tartrate, the water that proportion solution uses are ultrapure water；In the organic acid coarsening solution
Cu2+Ion concentration is 15g/L, and formic acid accounts for the 5% of total solution volume ratio, and sodium chloride and ammonium chloride content are respectively 8%, citrate
It is respectively 0.5% with tartrate content；Then spray process is carried out to lead frame using organic acid coarsening solution, the spray makes
Spray process is carried out with fan nozzle, using transmission belt conveying products, the organic acid coarsening solution spray pressure requirement is
Between 0.15MPa, organic acid coarsening solution treatment temperature maintains 20 DEG C, and the time for spraying roughening controls in 15s；
Step 2: after spray process, washing using three ultrapure adverse currents, carried out at immersion using 2% hydrochloric acid solution
Reason, the corrosion product of lead frame copper material surface black can be dissolved, and the color of copper be highlighted, using three ultrapure counter-flow waters
It washes, completes level-one roughening；
Step 3: carrying out secondary roughening using acid copper plating solution, lead frame is cathode, and stainless steel plate is anode, described
Stainless steel plate is 304 stainless steel plate of mesh, and thickness 0.2mm, the main component of the acid copper plating solution includes sulfuric acid, sulfuric acid
Copper, titanium sulfate, sodium tungstate, Cu2+Ion concentration is 15g/L, and sulfuric acid content 100g/L, sulfuric acid Ti content is 0.5g/L, wolframic acid
Sodium content is 0.05g/L；Wherein Ti2+Cu can be effectively improved2+In the deposition morphology of lead frame surface, reactive ion and non-
The absorption of reactive ion will affect Cu2+In the speed of separating out of cathode surface, and influence the crystalline orientation and plated layer compact of copper ion
Degree, by influencing the deposition process of copper ion to effective very high surface roughness.Current density is higher, copper ion deposition velocity
Faster, corresponding current density is higher, and crystalline particle size is smaller, and surface roughness raising is less, and copper ion deposition velocity is slower,
Corresponding current density is higher, and crystalline particle size is larger, and surface roughness is obviously improved.It is carried out when electro-coppering with pulse rectifier
Electric current adjustment, current-mode use 8: 2 positive and negative pulse current system.Required electric current is adjusted according to the area of lead frame
It is whole.After acid copper-plating is roughened, rough surface can improve 50% on the basis of level-one is roughened again.Electroplating process uses empty
Gas agitating, current density control are needed to increase bath filter pump in 30A/dm2, electroplating process, continuously be recycled.Electroplating processes
It is washed afterwards using three ultrapure adverse currents.
The roughening scheme operability is good, and at low cost, surface roughness Ra is up to 0.4 micron.
Embodiment 2
Pretreating process is electroplated in the super roughening lead frame of one kind, includes the following steps:
Step 1: prepare organic acid coarsening solution, organic coarsening solution main component include formic acid, copper chloride, sodium chloride,
Ammonium chloride, ethylenediamine, citrate, tartrate, the water that proportion solution uses is ultrapure water；In the organic acid coarsening solution
Cu2+Ion concentration is 22g/L, and formic acid accounts for the 10% of total solution volume ratio, and sodium chloride and ammonium chloride content are respectively 9%, citric acid
Salt and tartrate content are respectively 1.2%；Then spray process is carried out to lead frame using organic acid coarsening solution, it is described organic
Sour coarsening solution spray pressure requires between 0.17MPa, and organic acid coarsening solution treatment temperature maintains 30 DEG C, spray roughening when
Between control in 52s；
Step 2: it after spray process, is washed using ultrapure adverse current, carries out immersion treatment using 3.5% hydrochloric acid solution,
The corrosion product of lead frame copper material surface black can be dissolved, and highlight the color of copper, be washed using ultrapure adverse current, be completed
Level-one roughening:
Step 3: carrying out secondary roughening using acid copper plating solution, lead frame is cathode, and stainless steel plate is anode, described
Stainless steel plate is 304 stainless steel plate of mesh, and thickness 0.4mm, the main component of the acid copper plating solution includes sulfuric acid, sulfuric acid
Copper, titanium sulfate, sodium tungstate, Cu2+ ion concentration are 20g/L, and sulfuric acid content 110g/L, sulfuric acid Ti content is 1g/L, sodium tungstate
Content is 0.1g/L；Wherein Ti2+Cu can be effectively improved2+In the deposition morphology of lead frame surface, reactive ion and non-reaction
The absorption of ion will affect Cu2+In the speed of separating out of cathode surface, and the crystalline orientation and plated layer compact degree of copper ion are influenced, led to
The deposition process for influencing copper ion is crossed to effective very high surface roughness.Current density is higher, and copper ion deposition velocity is faster,
Corresponding current density is higher, and crystalline particle size is smaller, and surface roughness raising is less, and copper ion deposition velocity is slower, corresponding
Current density is higher, and crystalline particle size is larger, and surface roughness is obviously improved.Electric current is carried out with pulse rectifier when electro-coppering
Adjustment, current-mode use 8: 2 positive and negative pulse current system.Required electric current is adjusted according to the area of lead frame.
After acid copper-plating is roughened, rough surface can improve 50% on the basis of level-one is roughened again.Electroplating process uses air
Stirring, current density control are needed to increase bath filter pump in 40A/dm2, electroplating process, continuously be recycled.After electroplating processes
Using three ultrapure adverse current washings.
The roughening scheme operability is good, and at low cost, surface roughness Ra is up to 0.5 micron.
Embodiment 3
Pretreating process is electroplated in the super roughening lead frame of one kind, includes the following steps:
Step 1: prepare organic acid coarsening solution, organic coarsening solution main component include formic acid, copper chloride, sodium chloride,
Ammonium chloride, ethylenediamine, citrate, tartrate, Cu in the organic acid coarsening solution2+Ion concentration is 30g/L, and formic acid Zhan is total
It is 10% that the 15% of liquor capacity ratio, sodium chloride and ammonium chloride content, which account for, and citrate and tartrate content are 2%；
Then spray process is carried out to lead frame using organic acid coarsening solution, the organic acid coarsening solution spray pressure requirement is
Between 0.2MPa, organic acid coarsening solution treatment temperature maintains 40 DEG C, and the time for spraying roughening controls between 90s；
Step 2: after spray process, being washed using ultrapure adverse current, carry out immersion treatment using 5% hydrochloric acid solution, draw
The corrosion product of wire frame copper material surface black can be dissolved, and highlight the color of copper, be washed using ultrapure adverse current, be completed thick
Change.
The roughening scheme operability is good, and at low cost, surface roughness Ra is up to 0.2 micron.
Claims (7)
1. pretreating process is electroplated in the super roughening lead frame of one kind, which comprises the steps of:
Step 1: spray process being carried out to lead frame using organic acid coarsening solution；
Step 2: after spray process, being washed using ultrapure adverse current, immersion treatment is carried out using hydrochloric acid solution, using ultrapure inverse
Flowing water is washed, and level-one roughening is completed；
Step 3: carrying out secondary roughening using acid copper plating solution, lead frame is cathode, and stainless steel plate is anode, is electroplated
Copper carries out electric current adjustment with pulse rectifier when electro-coppering.
2. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that in step 1
Organic coarsening solution main component includes formic acid, copper chloride, sodium chloride, ammonium chloride, ethylenediamine, citrate, tartrate,
Cu in the machine acid coarsening solution2+Ion concentration is 15-30g/L, and formic acid accounts for the 5%-15% of total solution volume ratio, sodium chloride and chlorine
Changing ammonium content is respectively 8%-10%, and citrate and tartrate content are respectively 0.5%-2%.
3. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that in step 1
The spray pressure of the organic acid coarsening solution requires between 0.15-0.2MPa, and the treatment temperature of organic acid coarsening solution maintains
20-40 DEG C, the time for spraying roughening controls between 15-90s.
4. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that in step 3
The main component of the acid copper plating solution includes sulfuric acid, copper sulphate, titanium sulfate, sodium tungstate, Cu2+Ion concentration is 15-25g/
L, sulfuric acid content 100-120g/L, sulfuric acid Ti content are 0.5-1.5g/L, and wolframic acid sodium content is 0.05-0.15g/L.
5. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that step 3 electricity
Plating process uses air stirring, and current density is controlled in 30-50A/dm2, need in electroplating process to increase bath filter pump, be connected
It is continuous to recycle, it is washed after electroplating processes using ultrapure adverse current.
6. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that in step 3
The stainless steel plate is 304 stainless steel plates of mesh, thickness 0.2-0.6mm.
7. pretreating process is electroplated in a kind of super roughening lead frame according to claim 1, which is characterized in that the super roughening
Pretreating process, which is electroplated, in lead frame can carry out selective setting according to the different of coarsening rate, can be organic with cancellation step 1
Acid roughening and the cleaning of step 2 hydrochloric acid carry out step 3 acid copper-plating technique only to be roughened；Or 3 acid copper-plating work of cancellation step
Skill is roughened using the roughening of step 1 organic acid and the cleaning of step 2 hydrochloric acid.
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Cited By (4)
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| CN111748806A (en) * | 2020-07-21 | 2020-10-09 | 江苏悦锌达新材料有限公司 | Roughening liquid for polyphenylene sulfide and composite material thereof, preparation method and use method thereof |
| CN112331566A (en) * | 2020-11-02 | 2021-02-05 | 昆山一鼎工业科技有限公司 | Manufacturing equipment and manufacturing method for surface roughness of lead frame |
| TWI749886B (en) * | 2020-11-20 | 2021-12-11 | 長華科技股份有限公司 | Method for roughening surface of lead frame and electrochemical device |
| CN114134505A (en) * | 2021-12-02 | 2022-03-04 | 上海贝尼塔实业有限公司 | Alkaline microetching coarsening liquid and circuit board lead coarsening method |
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