CN109576766A - Preparation of nano TiO by electrophoresis-electrodeposition2Method for enhancing Sn-based micro-bumps - Google Patents
Preparation of nano TiO by electrophoresis-electrodeposition2Method for enhancing Sn-based micro-bumps Download PDFInfo
- Publication number
- CN109576766A CN109576766A CN201811606892.4A CN201811606892A CN109576766A CN 109576766 A CN109576766 A CN 109576766A CN 201811606892 A CN201811606892 A CN 201811606892A CN 109576766 A CN109576766 A CN 109576766A
- Authority
- CN
- China
- Prior art keywords
- tio
- nano
- electrophoresis
- cathode
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims description 20
- 230000002708 enhancing effect Effects 0.000 title claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000001962 electrophoresis Methods 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 108010010803 Gelatin Proteins 0.000 claims abstract description 8
- 229920000159 gelatin Polymers 0.000 claims abstract description 8
- 239000008273 gelatin Substances 0.000 claims abstract description 8
- 235000019322 gelatine Nutrition 0.000 claims abstract description 8
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 238000011161 development Methods 0.000 claims description 7
- 239000005028 tinplate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 210000001367 artery Anatomy 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 210000003462 vein Anatomy 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000009182 swimming Effects 0.000 claims 1
- 238000004100 electronic packaging Methods 0.000 abstract description 6
- 238000003466 welding Methods 0.000 abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 238000005219 brazing Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018471 Cu6Sn5 Inorganic materials 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000013587 production medium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- 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
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A method for preparing nano TiO2 enhanced Sn-based micro-convex points by electrophoresis-electrodeposition belongs to the technical field of electronic packaging. The invention firstly adopts the solution of the following components to carry out electrophoresis on nano TiO2Film formation: 0.3-0.6 g/L, CTAB 0.1.1-0.5 g/L magnesium chloride, nano TiO25-50 g/L of particles; and then carrying out electrodeposition on the micro-convex points by adopting a solution with the following components: 10-60 g/L stannous sulfate, 0.5-2 mol/L concentrated sulfuric acid, 2-10 g/L gelatin, 0.1-0.7 mol/L phenol and nano TiO25-50 g/L, CTAB 0.1.1-0.5 g/L of the particles. Nano TiO in the micro salient point (the size of the salient point is between 20 and 200 mu m) prepared by the invention2Uniform particle distribution, smooth surface of salient point, compact microstructure, and nano TiO2The addition of (2) inhibits Intermetallic compound (IMC) Cu in micro-welding points in electronic packaging6Sn5The growth of (2) has very important significance for improving the reliability of the micro welding spots.
Description
Technical field
The invention belongs to Electronic Packaging fields, and in particular to a kind of electrophoresis-electrodeposited nanocrystalline TiO2It is micro- to enhance Sn base
The method of salient point.
Background technique
Recently as the drive to the basket of constantly bringing forth new ideas for microelectric technique, especially integrated circuit technique, it is greatly facilitated
The development in the fields such as information, communication, the energy.Electronic Packaging has also obtained quickly as the key technology in microelectronic industry
Development.Currently, Electronic Encapsulating Technology realize chip and chip, chip and device, device and device MACHINERY JOINT,
The functions such as electrical connection, signal transmission, heat dissipation and cooling.And in microelectronic packaging technology, welding be most important technology it
One, wherein soldering tech is widely used in Electronic Packaging because welding temperature is relatively low, and solder is molten in brazing process
Change and base material is non-fusible, liquid solder by diffusion with base material realize metallurgical bonding.The most commonly used solder in Electronic Packaging
It is exactly Sn base solder, and pcb board is copper-clad plate mostly, research finds that Sn base solder generates a kind of metal with can react after copper brazing
Between compound (Intermetallic compound, hereinafter referred to as IMC) Cu6Sn5, Cu6Sn5It is a kind of crisp phase, seriously affects
The reliability of solder joint has obtained apparent so researcher starts that nano particle is added into solder joint to inhibit the growth of IMC
Effect.Research finds nano-TiO2Particle can also inhibit the growth of IMC.
Electronic Encapsulating Technology starts to encapsulate to 3D and develop, and flip-chip packaging techniques (Flip Chip Bonding, referred to as
FCB) and through silicon via technology (Through Silicon Via, hereinafter referred to as TSV) is current predominant package method.Chip-scale
3D encapsulation it is general through hole is first formed under wafer state, chip and chip are then subjected to stacked package again.Various TSV tri-
The bonding techniques of dimension chip package include sticking together bonding, metal/solder micro convex point bonding, the bonding of direct oxidation object, anode linkage
It is bonded with glass medium.Compared with other bonding techniques, metal/solder micro convex point bonding is good with the heat-conductive characteristic of bonding line,
It can accelerate to radiate, bump bonding both may be implemented to be mechanically connected or the electrical connection of chip chamber may be implemented and be easily achieved height
The advantages such as reliability and be widely used.Industrial salient point is prepared by the method for electro-deposition, and the ingredient of salient point is usually
Sn base solder, but nano-TiO is prepared by electrophoresis-electro-deposition method2The method of enhancing Sn composite soldering has not been reported, and
And electrodeposition technology is simple, and it is at low cost, it can in high volume be produced.In the industrial production, with the reduction of package dimension, Cu
Solder between column salient point and pad is prepared by electro-deposition mostly, therefore, develops one kind on metallic matrix with electro-deposition system
Standby nano-TiO2The method for enhancing Sn base micro convex point all has important meaning for the development of Electronic Encapsulating Technology and lead-free brazing
Justice.
Summary of the invention
The purpose of the present invention is to provide a kind of electrophoresis-electrodeposited nanocrystalline TiO2Enhance the method for Sn base micro convex point,
Nano-TiO in prepared salient point2It relatively uniform can be distributed in Sn layers, nano-TiO2It can combine closely with matrix Sn, institute
Obtain salient point even compact.
The technical solution adopted by the present invention is that: a kind of electrophoresis-electrodeposited nanocrystalline TiO2Enhance the side of Sn base micro convex point
Method, comprising the following steps:
Step (1) carries out pre-processing to fine copper plate to be plated, successively carries out deionization after carrying out mechanical polishing processing to fine copper plate
Then water ultrasonic cleaning, acetone oil removing, alcohol washes are dried stand-by；
Step (2) prepares electrophoresis liquid, by magnesium chloride (MgCl2·6H2O), cetyl trimethylammonium bromide (CTAB), nanometer
TiO2Particle is added in dehydrated alcohol is added nano-TiO into solution again after mixing evenly2Particle carries out ultrasonic disperse simultaneously
It is sufficiently stirred；
Step (3) carries out treatment before plating to fine copper plate to be plated: the HCl/water for being 5% to the fine copper plate volume fraction in step (1)
Solution pickling is dried after being then cleaned by ultrasonic with deionized water, and the method for PI(Polyimide) glue rotary coating is applied
On fine copper plate, successively toasted, exposure development and etching；PI glue is commercially available, high temperature resistant；
Step (4) TiO2The preparation of film: using fine copper plate obtained in step (3) as cathode, with graphite plate as anode, cathode
With anode forward direction area ratio be 1:1, interpolar away from be 3 ~ 5 cm, cathode and anode are put into electrolytic cell, progress electrophoresis；
Step (5) electrophoresis powers off after a certain period of time, and cathode is taken out from plating solution, is dried after being cleaned with deionized water
Processing, obtains nano-TiO2Film；
Step (6) prepares electric depositing solution: by stannous sulfate, the concentrated sulfuric acid, gelatin, phenol, being add to deionized water stirring
Nano-TiO is added after even into solution again2Particle carries out ultrasonic disperse and is sufficiently stirred；
Electroplate liquid is placed in electrolytic cell by step (7), using fine copper plate obtained in step (4) as cathode, with pure tin plate as
Anode, cathode and anode forward direction area ratio are 1:1, and interpolar is put cathode and anode in electrolytic cell into, away from for 3 ~ 5 cm using arteries and veins
Rush the method preparation micro convex point of electro-deposition；
Step (8) electro-deposition powers off after a certain period of time, and cathode is taken out from plating solution, is done after being rinsed with deionized water
Dry processing obtains nano-TiO after then removing photoresist2Enhance Sn base micro convex point.
As the present invention to the further preferred of above scheme, the plating metal plate in step (1) is fine copper plate, purity >=
99.99%。
As the present invention to the further preferred of above scheme, the content of electrophoresis liquid each component in step (2) are as follows: magnesium chloride
(MgCl2·6H2O) 0.3 ~ 0.6 0.1 ~ 0.5 g/L of g/L, CTAB, nano-TiO25 ~ 50 g/L of particle, solvent are ethyl alcohol.
As the present invention to the further preferred of above scheme, the anode metal plate in step (4) is graphite plate.
As the present invention to the further preferred of above scheme, the content of electric depositing solution each component in step (6) are as follows: sulphur
Sour 10 ~ 60 g/L of stannous, 0.5 ~ 2 mol/L of the concentrated sulfuric acid, 2 ~ 10 g/L of gelatin, 0.1 ~ 0.7 mol/L of phenol, nano-TiO2Particle
5~50 g/L、CTAB 0.1~0.5 g/L。
As the present invention to the further preferred of above scheme, the plating metal plate in step (7) is pure tin plate, purity >=
99.99%。
As the present invention to the further preferred of above scheme, anode and cathode area ratio is 1:1, and interpolar is away from for 3 ~ 5 cm.
As the present invention to the further preferred of above scheme, step (2) and the middle nano-TiO being added of step (6)2Particle
Partial size be 5 ~ 100 nm, be anatase titanium dioxide.
As the present invention to the further preferred of above scheme, the ultrasonic disperse time is 3 ~ 5 h, ultrasonic function in step (2)
Rate is 150 W, and supersonic frequency is 20 ~ 150 kHz, and the magnetic agitation time is 1 ~ 3 h, and speed of agitator is 500 ~ 2000 r/min,
Temperature is 25 DEG C.
As the present invention to the further preferred of above scheme, the ultrasonic disperse time is 3 ~ 5 h, ultrasonic function in step (6)
Rate is 150 W, and supersonic frequency is 20 ~ 150 kHz, and the magnetic agitation time is 1 ~ 3 h, and speed of agitator is 500 ~ 2000 r/min,
Temperature is 25 DEG C.
As the present invention to the further preferred of above scheme, the electric depositing solution pH value configured is 1 ~ 3.
As the present invention to the further preferred of above scheme, the voltage of electrophoresis is 30 ~ 100 V, bath temperature 25
DEG C, magnetic agitation speed is 200 ~ 300 r/min, and the time is 1 ~ 5 min.
As the present invention to the further preferred of above scheme, the current density of electro-deposition is 1.0 ~ 3.0 A/dm2, duty
Than being 10% ~ 100%, pulse frequency is 5 ~ 1000 Hz；Bath temperature is 20 ~ 50 DEG C, and magnetic agitation speed is 200 ~ 300 r/
min。
The present invention first uses the solution of following components to carry out electrophoretic nano TiO2Film: magnesium chloride 0.3 ~ 0.6 g/L, CTAB
0.1 ~ 0.5 g/L, nano-TiO25 ~ 50 g/L of particle；Then electro-deposition micro convex point: sulfuric acid is carried out using the solution of following components
10 ~ 60 g/L of stannous, 0.5 ~ 2 mol/L of the concentrated sulfuric acid, 2 ~ 10 g/L of gelatin, 0.1 ~ 0.7 mol/L of phenol, nano-TiO2Particle 5 ~
50 g/L,CTAB 0.1~0.5 g/L.Using the dimpling spot size of this method preparation at 20-200 μm.Beneficial effects of the present invention
It is:
(1) method of electrophoresis-electro-deposition of the invention is by nano-TiO2Particle is added in Sn base salient point, the micro convex point table of preparation
Face is smooth, be speckless, burn, peeling, dross, fall off, crack, dendroid deposition phenomena such as, nano-TiO2It is evenly distributed on
In salient point, the stability of salient point is good, is well combined with matrix.
(2) present invention prepares nano-TiO2The method for enhancing Sn base micro convex point is simple, and instrument and equipment is easy to operate, Ke Yi
Industrial production medium quantity batch processing, and toxic substance is free of in salient point, it will not all cause damages to human body and environment.
(3) present invention prepares nano-TiO2It is fine to enhance Sn base micro convex point wetability in brazing process, can be formed good
Solder joint, nano-TiO2Addition can inhibit welding point interface intermetallic compound growth, improve welding spot reliability.
The micro convex point surfacing of this method preparation, nano-TiO2It is evenly distributed, microstructure compactness height, nano-TiO2
Uniform particle is distributed in salient point, and TiO2- Sn micro convex point has good weldability, nano-TiO2Addition can inhibit copper
Compound Cu between tin interface metal6Sn5Growth.
Detailed description of the invention
Below with reference to embodiment and attached drawing, the present invention will be described in detail.
Fig. 1 is electrophoresis-electro-deposition preparation nano-TiO2Enhance Sn base micro convex point surface microhardness average value.
Fig. 2 is electrophoresis-electro-deposition preparation nano-TiO2Enhance Sn base micro convex point pattern SEM figure.
Fig. 3 is electrophoresis-electro-deposition preparation nano-TiO2Enhance Sn base micro convex point surface SEM figure.
Fig. 4 is electrophoresis-electro-deposition preparation nano-TiO2Enhance Sn base micro convex point section SEM figure.
Fig. 5 is electrophoresis-electro-deposition preparation nano-TiO2Enhance Sn base micro convex point section Ti element EPMA figure.
Fig. 6 is the nano-TiO of electro-deposition preparation2Enhance Sn base micro convex point surface SEM figure.
Fig. 7 is the nano-TiO of electro-deposition preparation2Enhance Sn base micro convex point section SEM figure.
Fig. 8 is the nano-TiO of electro-deposition preparation2Enhance Sn base micro convex point section Ti element EPMA figure.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, life is not specified in agents useful for same or instrument
Manufacturer person is produced, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
(1) fine copper plate is chosen as plating metal substrate, purity >=99.99%.
(2) pre-processing of fine copper plate to be plated: the fine copper plate in step (1) is subjected to mechanical polishing processing, then successively
Deionized water ultrasonic cleaning, acetone oil removing, alcohol washes are carried out, is then dried stand-by.
(3) electrophoresis liquid is prepared: by 0.048 g magnesium chloride (MgCl2·6H2O), 0.02 gCTAB, 0.8 g partial size are 20 nm
TiO2Particle is successively put into the ethyl alcohol of 100 mL.
(4) by the electrophoresis solution ultrasonic disperse 3h in step (3), ultrasonic power is 150 W, and supersonic frequency is 20 ~ 150
KHz, then 1 h of magnetic agitation, revolving speed are 1000 r/min again.
(5) graphite plate is successively subjected to acetone oil removing, alcohol washes, deionized water ultrasonic cleaning, be then dried to
With.
(6) to the electrophoresis pre-treatment of fine copper plate: the HCL aqueous solution for being 5% by the fine copper plate volume fraction in step (2)
Pickling is carried out, is dried after being then cleaned by ultrasonic with deionized water, the method for PI(Polyimide) glue rotary coating is applied
On fine copper plate, successively toasted, exposure development and etching.
(7) by the fine copper plate in step (6) as cathode, graphite plate in step (5) as anode, cathode and anode it
Between distance be 3 cm.
(8) cathode and anode are put into the electrolytic cell equipped with electrophoresis liquid, carries out electrophoresis and prepares TiO2Film, electrophoretic voltage are
50V, bath temperature are 25 DEG C, and magnetic agitation speed is 230 r/min.
(9) it is powered off after 5 min of electrophoresis, cathode is taken out from solution, place is dried after being rinsed with deionized water
Reason, obtains nano-TiO2Film.
(10) electric depositing solution is prepared: by the 0.7 mol concentrated sulfuric acid, 2 g stannous sulfates, 0.01 g gelatin, 0.5 mol benzene
Phenol, 0.02 gCTAB, the TiO that 1 g partial size is 20 nm2Particle is successively put into the deionized water of 100 mL.
(11) pure tin metal plate is successively subjected to acetone oil removing, alcohol washes, deionized water ultrasonic cleaning, then at drying
Reason is stand-by.
(12) electroplate liquid is placed in electrolytic cell, using fine copper plate obtained in step (9) as cathode, with pure tin plate as
Anode, cathode and anode forward direction area ratio are 1:1, and interpolar is put cathode and anode in electrolytic cell into, away from for 3 ~ 5 cm using arteries and veins
Rush the method preparation micro convex point of electro-deposition.
(13) it is powered off after electro-deposition 30min, cathode is taken out from plating solution, is dried after being rinsed with deionized water
Processing, obtains nano-TiO after then removing photoresist2Enhance Sn base micro convex point, as shown in Fig. 2,3 and 4.
Embodiment 2
Nano-TiO is prepared according to method described in embodiment 12Enhance Sn base micro convex point, the difference from embodiment 1 is that, plating
Nano-TiO when liquid configures2Additive amount be 20 g/L.
Embodiment 3
Nano-TiO is prepared according to method described in embodiment 12Enhance Sn base micro convex point, the difference from embodiment 1 is that, plating
Nano-TiO when liquid configures2Additive amount be 30 g/L.
Embodiment 4
Nano-TiO is prepared according to method described in embodiment 12Enhance Sn base micro convex point, the difference from embodiment 1 is that, plating
Nano-TiO when liquid configures2Additive amount be 50 g/L.
Comparative example 1
(1) fine copper plate is chosen as plating metal substrate, purity >=99.99%.
(2) pre-processing of fine copper plate to be plated: the fine copper plate in step (1) is mechanically polished, until fine copper plate table
Face is bright, then successively carries out acetone oil removing, alcohol washes, then deionized water ultrasonic cleaning is dried stand-by.
(3) electroplate liquid is prepared: by the 0.7 mL concentrated sulfuric acid, 2 g stannous sulfates, 0.01 g gelatin, 0.5 mol phenol, 1 g
Diameter is the TiO of 20 nm2Particle is successively put into the deionized water of 100 mL.
(4) by the solution ultrasonic disperse 3h in step (3), ultrasonic power is 150 W, and supersonic frequency is 20 ~ 150 kHz,
Then 1 h of magnetic agitation, revolving speed are 1000 r/min again.
(5) pure tin metal plate is successively subjected to acetone oil removing, alcohol washes, deionized water ultrasonic cleaning, then at drying
Reason is stand-by.
(6) to the treatment before plating of fine copper plate: by the fine copper plate volume fraction in step (2) be 5% HCL aqueous solution into
Row pickling is dried after being then cleaned by ultrasonic with deionized water, and the method for PI(Polyimide) glue rotary coating is coated in
It on fine copper plate, is successively toasted, exposure development and etching.
(7) by the fine copper plate in step (6) as cathode, pure tin plate in step (5) as anode, cathode and anode it
Between distance be 3 cm.
(8) cathode and anode are put into the electrolytic cell equipped with plating solution, carries out electro-deposition, the current density of electro-deposition is
2.0 A/dm2, duty ratio 50%, pulse frequency is 50 Hz；Bath temperature is 25 DEG C, and magnetic agitation speed is 230 r/
min。
(9) it is powered off after 30 min of electro-deposition, cathode is taken out from plating solution, is dried after being rinsed with deionized water
Processing, obtains nano-TiO after then removing photoresist2Enhance Sn base micro convex point, as shown in Figure 5 and Figure 6.
Interpretation of result:
The micro convex point for preparing in embodiment 1-4 carries out micro-hardness testing, and each sample successively surveys 5 points, using removing maximum
The average value taken after value and minimum value represents the microhardness of each sample, and measurement result is as shown in the following table 1 and Fig. 1.From Fig. 1
It can be seen that with nano-TiO2Particle additive amount increases, and the hardness number of micro convex point shows the trend being gradually increased, and shows
Nano-TiO2The addition of particle improves the performance of salient point.
Table 1: embodiment and comparative example salient point salient point micro-hardness testing
Fig. 3 and Fig. 6 is respectively the micro convex point surface microscopic topographic figure of electrophoresis-electro-deposition and electro-deposition preparation, shows dimpling in Fig. 6
Point surfacing, be speckless, burn, peeling, fall off, crack, dendroid deposition phenomena such as.But Sn crystal grain is obvious in Fig. 3
Than tiny in Fig. 6, what is combined between crystal grain is finer and close, micro convex point nano surface TiO2Particle distribution is more evenly.
Fig. 4 is the electron-microscope scanning figure in electrophoresis-electro-deposition preparation micro convex point section, it can be seen that bump structure is fine and close, convex
There is no phenomena such as hole, bubble, layering in point；And it can be seen that the stability of salient point is good, be well combined with matrix, solder and
Substrate junction does not have crackle appearance.Fig. 5 is that the EPMA of electrophoresis-electro-deposition micro convex point section Ti element schemes, and shows this method
TiO in the solder of preparation2Uniform particle is distributed in salient point, and TiO in the micro convex point of conventional electrodeposition preparation2Particle is only distributed
Subsurface (as shown in Figure 7,8).
Claims (1)
1. a kind of electrophoresis-electrodeposited nanocrystalline TiO2 enhancing Sn base micro convex point method, which is characterized in that specifically include following
Step:
(1) pre-processing is carried out to fine copper plate to be plated: fine copper plate is subjected to mechanical polishing processing, it is then successively super with deionized water
Sound cleans, acetone deoils, alcohol washes, is then dried stand-by；
(2) fine copper plate processing to be plated before electrophoresis: the HCL aqueous solution acid for being 5% by fine copper plate volume fraction made from step (1)
Wash, be dried after being cleaned by ultrasonic with deionized water, then the method for PI glue rotary coating is coated on fine copper plate, successively into
Row baking, exposure development and etching；
(3) it prepares electrophoresis solution: magnesium chloride, cetyl trimethylammonium bromide is added in dehydrated alcohol after mixing evenly again
Nano-TiO is added into solution2Particle carries out ultrasonic disperse and is sufficiently stirred, and the content of the electrophoresis liquid each component is respectively as follows:
0.3 ~ 0.6 g/L of magnesium chloride, 0.1 ~ 0.5 g/L of cetyl trimethylammonium bromide, nano-TiO25 ~ 50 g/L of particle；It is described
The ultrasonic disperse time be 3 ~ 5 h, ultrasonic power be 150 W, supersonic frequency be the kHz of 20 kHz ~ 150, the magnetic agitation time be 1 ~
3 h, speed of agitator are 500 ~ 2000 r/min, and temperature is 25 DEG C；
(4) electrophoresis liquid is placed in electrolytic cell, using fine copper plate obtained in step (2) as cathode, with graphite plate as anode,
Cathode and anode forward direction area ratio are 1:1, and interpolar puts cathode and anode in electrolytic cell into away from being 3 ~ 5 cm, progress electrophoresis；Electricity
Swimming voltage be 30 ~ 100V, solution temperature be 25 DEG C, magnetic agitation speed be 200 ~ 300 r/min, electrophoresis time be 1min ~
5min；
(5) it is powered off after electrophoresis, cathode is taken out from electrophoresis liquid, is dried after being cleaned with deionized water,
Obtain nano-TiO2Film；
(6) it prepares electric depositing solution: by stannous sulfate, the concentrated sulfuric acid, gelatin, phenol, being add to deionized water after mixing evenly
Nano-TiO is added into solution again2Particle carries out ultrasonic disperse and is sufficiently stirred, the content of the electric depositing solution each component
It is respectively as follows: 10 ~ 60 g/L of stannous sulfate, 0.5 ~ 2 mol/L of the concentrated sulfuric acid, 2 ~ 10 g/L of gelatin, 0.1 ~ 0.7 mol/L of phenol, receives
Rice TiO25 ~ 50 g/L of particle, 0.1 ~ 0.5 g/L of cetyl trimethylammonium bromide；The electric depositing solution pH value is 1 ~ 3；
The ultrasonic disperse time is 3 ~ 5 h, and ultrasonic power is 150 W, and supersonic frequency is the kHz of 20 kHz ~ 150, magnetic agitation time
For 1 ~ 3 h, speed of agitator is 500 ~ 2000 r/min, and temperature is 25 DEG C；
(7) electric depositing solution is placed in electrolytic cell, using fine copper plate obtained in step (4) as cathode, with pure tin plate as
Anode, cathode and anode forward direction area ratio are 1:1, and interpolar is put cathode and anode in electrolytic cell into, away from for 3 ~ 5 cm using arteries and veins
The method preparation micro convex point of electro-deposition is rushed, duty ratio is 10% ~ 100%, and pulse frequency is 5 ~ 1000 Hz；The electric current of electro-deposition is close
Degree is 1.5 ~ 2.0 A/dm2, bath temperature be 20 ~ 50 DEG C, magnetic agitation speed be 200 ~ 300 r/min, salient point thickness according to
Electrodeposition time controls；
(8) it is powered off after electro-deposition, cathode is taken out from plating solution, is dried after being rinsed with deionized water,
Then nano-TiO is obtained after photoresist being removed2Enhance Sn base micro convex point;
Purity >=99.99% of the fine copper plate, purity >=99.99% of pure tin plate；Nano-TiO2For anatase titanium dioxide, nano-TiO2Grain
The partial size of son is 5 ~ 100 nm, is anatase titanium dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811606892.4A CN109576766B (en) | 2018-12-27 | 2018-12-27 | A method for preparing nano-TiO2 enhanced Sn-based micro-bumps by electrophoresis-electrodeposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811606892.4A CN109576766B (en) | 2018-12-27 | 2018-12-27 | A method for preparing nano-TiO2 enhanced Sn-based micro-bumps by electrophoresis-electrodeposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109576766A true CN109576766A (en) | 2019-04-05 |
| CN109576766B CN109576766B (en) | 2020-09-25 |
Family
ID=65931952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811606892.4A Active CN109576766B (en) | 2018-12-27 | 2018-12-27 | A method for preparing nano-TiO2 enhanced Sn-based micro-bumps by electrophoresis-electrodeposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109576766B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085429A (en) * | 2019-04-17 | 2019-08-02 | 桂林理工大学 | A kind of method of aluminium electrolutic capacitor mesohigh anode aluminium foil pulsed deposition nanometer tin point |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438069A (en) * | 2003-01-25 | 2003-08-27 | 福州大学 | Electrophoresis preparation method of metal substrate surface photocatalytic film |
| CN103151430A (en) * | 2011-12-06 | 2013-06-12 | 北京大学深圳研究生院 | Preparation method of achieving low-temperature metal interface connection of light-emitting diode (LED) with nanometer metal granules |
| CN103165480A (en) * | 2011-12-15 | 2013-06-19 | 北京大学深圳研究生院 | Preparation method for flip chip salient point |
| CN106384720A (en) * | 2016-10-19 | 2017-02-08 | 北京理工大学 | Method and device for manufacturing solder bumps and electronic component |
| JP2017188488A (en) * | 2016-03-31 | 2017-10-12 | 三菱マテリアル株式会社 | Solder bump manufacturing method and dispersion plating solution |
| CN109594108A (en) * | 2018-12-21 | 2019-04-09 | 上海集成电路研发中心有限公司 | The forming method of tin alloy electric plating bath foam and the preparation method of scolding tin salient point coating |
-
2018
- 2018-12-27 CN CN201811606892.4A patent/CN109576766B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438069A (en) * | 2003-01-25 | 2003-08-27 | 福州大学 | Electrophoresis preparation method of metal substrate surface photocatalytic film |
| CN103151430A (en) * | 2011-12-06 | 2013-06-12 | 北京大学深圳研究生院 | Preparation method of achieving low-temperature metal interface connection of light-emitting diode (LED) with nanometer metal granules |
| CN103165480A (en) * | 2011-12-15 | 2013-06-19 | 北京大学深圳研究生院 | Preparation method for flip chip salient point |
| JP2017188488A (en) * | 2016-03-31 | 2017-10-12 | 三菱マテリアル株式会社 | Solder bump manufacturing method and dispersion plating solution |
| CN106384720A (en) * | 2016-10-19 | 2017-02-08 | 北京理工大学 | Method and device for manufacturing solder bumps and electronic component |
| CN109594108A (en) * | 2018-12-21 | 2019-04-09 | 上海集成电路研发中心有限公司 | The forming method of tin alloy electric plating bath foam and the preparation method of scolding tin salient point coating |
Non-Patent Citations (4)
| Title |
|---|
| ASHUTOSH SHARMA等: ""Development of lead free pulse electrodeposited tin based composite solder coating reinforced with ex situ cerium oxide nanoparticles"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 初红涛: ""电沉积Sn-SiC纳米复合镀层及其可焊性研究"", 《哈尔滨工业大学博士学位论文》 * |
| 李爱昌等: ""复合电沉积法制备Sn-TiO2纳米薄膜"", 《材料保护》 * |
| 王燕峰: ""电沉积Sn-TiO2复合钎料及钎焊界面反应研究"", 《大连理工大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085429A (en) * | 2019-04-17 | 2019-08-02 | 桂林理工大学 | A kind of method of aluminium electrolutic capacitor mesohigh anode aluminium foil pulsed deposition nanometer tin point |
| CN110085429B (en) * | 2019-04-17 | 2021-07-02 | 桂林理工大学 | A method for pulse deposition of nano-tin dots on medium and high voltage anode aluminum foil for aluminum electrolytic capacitors |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109576766B (en) | 2020-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100461908B1 (en) | Electroplating method using combination of vibrational flow of plating bath and plating current of pulse | |
| JP3827276B2 (en) | Barrel electroplating method for extremely small articles | |
| JP2002527621A (en) | Electrodeposition of metals in small recesses using modulated electric fields | |
| CN103334134B (en) | A kind of method of electroplating in ultrasonic field aluminium alloy | |
| CN113089036B (en) | Preparation method of variable-frequency power ultrasonic electrodeposition nano metal ceramic composite layer | |
| TW202010370A (en) | High-speed electroplating method | |
| JP2007070730A (en) | Metal duplex and method | |
| CN116334702A (en) | Directional-arrangement nano twin crystal copper film material and preparation method and application thereof | |
| CN107313088A (en) | A kind of method based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition | |
| CN110172717A (en) | A kind of copper electroplating method of ceramic substrate | |
| CN109576766A (en) | Preparation of nano TiO by electrophoresis-electrodeposition2Method for enhancing Sn-based micro-bumps | |
| CN115863275A (en) | A kind of ceramic substrate containing heat dissipation copper tube and preparation method thereof | |
| CN109735890B (en) | Nano TiO (titanium dioxide)2Preparation method of (E) -Sn micro bump | |
| JP2023168651A (en) | Copper-zinc alloy electroplating solution, formation method of copper-zinc alloy bump, formation method of nanoporous copper bump, substrate with copper-zinc alloy bump, and substrate with nanoporous copper bump | |
| CN110724983A (en) | Method for preparing nano-copper-coated tungsten carbide core-shell structure powder by pulse electrodeposition | |
| CN1676674A (en) | Preparation method of nickel-phosphorus alloy-based composite coating containing nanoparticles | |
| CN101748453B (en) | Double pulse plating solution for preparing lead-free Sn-Cu alloy solder and plating process | |
| CN115846885A (en) | Method and system for manufacturing graph by laser etching | |
| Roh et al. | Electroplating characteristics of Sn–Bi microbumps for low-temperature soldering | |
| CN116065208A (en) | A preparation method of nano-nickel-based composite layer deposited by frequency-variable power ultrasonic electrodeposition on the surface of magnesium alloy | |
| CN105779979A (en) | Aluminum welding wire coppering process | |
| CN103526246A (en) | Method for preparing composite Al-Ni coating on engine rotor surface | |
| JP3735173B2 (en) | Method of depositing electroplating in a columnar shape in fine holes | |
| Li et al. | Effect of ultrasonic on copper electroplating from the non-cyanide alkaline baths | |
| JPH05243699A (en) | Substrate for module and its manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |