CN103668356B - Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method - Google Patents
Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method Download PDFInfo
- Publication number
- CN103668356B CN103668356B CN201310697666.2A CN201310697666A CN103668356B CN 103668356 B CN103668356 B CN 103668356B CN 201310697666 A CN201310697666 A CN 201310697666A CN 103668356 B CN103668356 B CN 103668356B
- Authority
- CN
- China
- Prior art keywords
- copper
- mixing
- electro
- additive
- plating method
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention relates to one and add Fe in copper-connection copper sulfate bath
2+and Fe
3+electro-plating method, comprise the following steps: the silicon chip with TSV through hole is placed in pretreatment liquid and carries out ultrasonic wave pre-treatment; Described silicon chip is immersed in containing Cu
2+, Cl
-with in the acid copper sulfate baths of sulfuric acid; By additive PEG, SPS, JGB and Fe
2+/ Fe
3+redox couple carries out pre-mixing, leave standstill, obtain the additive solution of pre-mixing, the additive solution of described pre-mixing is injected described acid copper sulfate baths, after being uniformly mixed, electroplate under constant operation electric current, in electroplating process, make electroplate liquid pass through to be equipped with the electrolyzer of high purity copper particle simultaneously.The present invention adds Fe in the plating solution
2+/ Fe
3+redox couple and PEG and SPS combine, thus accelerate the sedimentation rate of through hole internal copper and effectively can suppress the deposition of surface copper, and then realize zero defect and fill and the thickness reducing copper coating, facilitate subsequent processes.
Description
Technical field
The invention belongs to technical field of electronic encapsulation, be specifically related to one and add Fe in copper-connection copper sulfate bath
2+and Fe
3+electro-plating method.
Background technology
TSV 3-D stacks encapsulation based on silicon through hole is the inexorable trend of encapsulation technology development.The research emphasis that current TSV through hole is filled has been filled from imporosity and has been forwarded at a high speed, and high quality, low cost fills.In electroplating process, be faced with the oxidation consumption of additive, be mingled with the series of problems brought with copper anode.Fe
2+/ Fe
3+redox couple can control electrode current potential, prevents additive oxide inclusion, makes the application of noble electrode become possibility, reduces the phosphorus content in plating solution, reduces impurity; And pass through Fe
3+concentration controls, and utilizes the difference of current efficiency inside and outside through hole can improve the superfilling capabilities of plating solution, reduces the use of additive.But the impact of redox couple on other organic additives in TSV through hole plating, also urgently furthers investigate the impact of filling through hole effect and quality of coating.By research Fe in process of the present invention
2+/ Fe
3+on the impact of kinetics of electrode process, Additive and coating performance particularly stress, specify that the relation between coating stress and impurity, improve the superfilling capabilities of plating solution, improve coating reliability, reduce costs.
Summary of the invention
For the problems referred to above that existing copper facing filling technique exists, the invention provides one and add Fe in copper-connection copper sulfate bath
2+and Fe
3+electro-plating method, the present invention adds Fe in the plating solution
2+/ Fe
3+redox couple and PEG and SPS combine, thus accelerate the sedimentation rate of through hole internal copper and effectively can suppress the deposition of surface copper, and then realize zero defect and to fill and the thickness reducing copper coating facilitates subsequent processes.
The present invention is achieved by the following technical solutions, and one adds Fe in copper-connection copper sulfate bath
2+and Fe
3+electro-plating method, it is characterized in that, comprise the following steps:
Silicon chip with TSV through hole is placed in pretreatment liquid by step (1) carries out ultrasonic wave pre-treatment;
The described silicon chip through pre-treatment is immersed in containing Cu by step (2)
2+, Cl
-with in the acid copper sulfate baths of sulfuric acid, the pH value of described acid copper sulfate baths is 0 ~ 4;
Step (3) is by additive PEG, SPS, JGB and Fe
2+/ Fe
3+redox couple carries out pre-mixing, leave standstill, obtain the additive solution of pre-mixing, the additive solution of described pre-mixing is injected described acid copper sulfate baths, after being uniformly mixed, electroplate under constant operation electric current, in electroplating process, make electroplate liquid pass through to be equipped with the electrolyzer of high purity copper particle simultaneously.
Preferably, in step (1), the time of described ultrasonic wave pre-treatment is 2min.
Preferably, in step (2), the Cu of described acid copper sulfate baths
2+concentration is 35g/L, Cl
-concentration is 50ppm, sulfuric acid concentration is 0.6mol/L.
Preferably, in step (3), additive PEG, SPS, JGB and Fe
2+/ Fe
3+it is 3 hours that redox couple carries out the time of repose after pre-mixing.
Preferably, in step (3), electroplating process is at 10mA/cm
2constant operation electric current under electroplate, add Fe
2+/ Fe
3+redox couple makes cupric ion deposition current reduce in cathode surface generation reduction reaction thus reduces the sedimentation rate of cupric ion around TSV through hole mouth.
Preferably, in step (3), the insoluble noble electrode that electroplating process adopts size fixing, avoids and uses electrolytic copper anode to introduce impurity.
Preferably, in electroplating process, plating solution is by being equipped with the electrolyzer of high-purity shot copper, supplements the cupric ion and Fe that consume
2+ion, extends the electroplate liquid life-span.
Preferred, the impurity in deposited copper reduces, and coating internal stress is reduced to below 10MPa, thus obtains the more stable TSV interconnection element of performance.
Compared with prior art, beneficial effect of the present invention is as follows: with not containing Fe
2+/ Fe
3+the plating solution of redox couple is compared, because Cu
2+by the electrolyzer Fe containing high purity copper particle by plating solution
3+react with Cu and produce, therefore can use the insoluble anode that size is fixing in the inventive method, so just can prevent because soluble copper anode can be introduced containing phosphorus impurities in dissolution process, while because of Fe
2+/ Fe
3+existence can reduce the use of accelerator, thus ensure that the deposited copper obtained contains less impurity, while adding the stability of performance, also reduce coating stress containing less impurity, ensure that coating stress is at below 10MPa; Due to Fe
3+fe is reduced at cathode surface
2+consume electronics, reduce TSV through hole mouth surrounding silicon surface cupric ion deposition current, thus the copper film that result in through hole circumferential surface place deposition is thinner, and because Fe
3+transmission be mainly subject to diffusion control, therefore the deposition speed of TSV through hole inside is not affected, thus facilitates Cu
2+while facilitate subsequent chemistry polishing process.Fe
2+/ Fe
3+the zero defect that can realize the through hole of larger diameter while the existence of redox couple is thinned surperficial copper film is filled.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to a kind of TSV electro-plating method under fixed electorde condition, comprises the following steps:
Step (1) is with the preparation of the silicon chip of TSV through hole: first adopt deep reaction ion etching (DeepReactiveIonEtch, DRIE) through hole of certain size is made, then utilize plasma enhanced chemical vapor deposition method (PECVD) depositing insulating layer, the deposition material of use is silicon nitride or silicon-dioxide (SiNx or SiO
2), then Metalorganic chemical vapor deposition method (MOCVD) deposited barrier layer (TiN or TaN) is utilized, effect prevents copper to the diffusion of silicon base, finally uses chemical Vapor deposition process (CVD) or physical vaporous deposition (PVD) deposited seed layer (Cu);
Step (2) by the silicon chip with TSV through hole in pretreatment liquid through ultrasonication 2min;
Silicon chip through pre-treatment is immersed in containing Cu by step (3)
2+concentration is 35g/L, Cl
-concentration is 50ppm, sulfuric acid concentration is in the acid copper sulfate baths of 0.6mol/L, and the existence of pH value to effects of ion has vital effect, and when pH value is between 0-4 under positive potential, solution exists with bivalent cupric ion;
Step (4), by following additive pre-mixing process, comprising: 300ppmPEG(polyethyleneglycol), 3ppmSPS(bis-(3-sulfopropyl) disulfide), 20ppmJGB(leveling agent), 50ppmCl
-, 0.5g/LFe
2+and 0.024g/LFe
3+, Fe wherein
2+and Fe
3+pass through FeSO
47H
2o and Fe
2(SO
4)
3add, obtain the additive mixed liquor of pre-mixing; The additive mixed liquor of pre-mixing is joined in electroplate liquid, through being uniformly mixed fully, under fixed electorde condition, at 10mA/cm
2constant operation electric current under adopt size fixing insoluble noble electrode electroplate, electrode potential, for being-150mV, in electroplating process, allows plating solution pass through to be equipped with the electrolyzer of high purity copper particle.
embodiment 2
The present embodiment relates to a kind of TSV electro-plating method under rotating disk electrode (RDE) condition, comprises the following steps:
Step (1) is with the preparation of the silicon chip of TSV through hole: first adopt deep reaction ion etching (DeepReactiveIonEtch, DRIE) through hole of certain size is made, then utilize plasma enhanced chemical vapor deposition method (PECVD) depositing insulating layer, the deposition material of use is silicon nitride or silicon-dioxide (SiNx or SiO
2), then Metalorganic chemical vapor deposition method (MOCVD) deposited barrier layer (TiN or TaN) is utilized, effect prevents copper to the diffusion of silicon base, finally uses chemical Vapor deposition process (CVD) or physical vaporous deposition (PVD) deposited seed layer (Cu);
Step (2) by the silicon chip with TSV through hole in pretreatment liquid through ultrasonication 2min;
Silicon chip through pre-treatment is immersed in containing Cu by step (3)
2+concentration is 35g/L, Cl
-concentration is 50ppm, sulfuric acid concentration is in the acid copper sulfate baths of 0.6mol/L, and the existence of pH value to effects of ion has vital effect, and when pH value is between 0-4 under positive potential, solution exists with bivalent cupric ion;
Step (4), by following additive pre-mixing process, comprising: 300ppmPEG(polyethyleneglycol), 3ppmSPS(bis-(3-sulfopropyl) disulfide), 20ppmJGB(leveling agent), 50ppmCl
-, 12g/LFe
2+and 0.5g/LFe
3+, wherein Fe
2+and Fe
3+pass through FeSO
47H
2o and Fe
2(SO
4)
3add, obtain the additive mixed liquor of pre-mixing; The additive mixed liquor of described pre-mixing is joined in electroplate liquid, through being uniformly mixed fully, under rotating disk electrode (RDE) condition, at 10mA/cm
2constant operation electric current under adopt size fixing insoluble noble electrode electroplate, wherein the rotating speed of rotating disk electrode be 900rpm(now working current 9% by Fe
3+be converted into Fe
2+reduction reaction consumes), electrode potential is-50mV, in electroplating process, allows electroplate liquid pass through to be equipped with the electrolyzer of high purity copper particle.
implementation result
According to embodiment 1 and embodiment 2, present method is added in electroplate liquid, due to Fe after requiring ratio pre-mixing for some time that additive adds as required again
2+with cupric ion and SPS and Fe
2+between there is following reaction:
2MPS+2Cu
2+→SPS+2H
++2Cu
+(3)
Cu is added by reaction (1)
+concentration thus accelerate the sedimentation rate of copper, because Fe
2+mass transfer velocity by diffusion control, existence maximum value is accelerated in experiment.The MPS produced by reaction (2) is faster than SPS acceleration effect.Reaction (2)-(4) can consume Fe
2+keep the amount of MPS in solution constant, simultaneously Fe
2+fe can be passed through
3+react with high purity copper particle and constantly produce and have part Fe at negative electrode
2+produce, therefore can accelerate the sedimentation rate of the copper of through hole inside.Research shows Fe by experiment
2+/ Fe
3+sPS is not affected substantially in the reaction at deposition surface place, mainly has impact to electrolytic solution composition, namely produce the balance of MPS.
According to embodiment 1 and embodiment 2, under rotating electrode condition, electrode overpotential reduces, and the effect of mass transmitting due to iron ion under rotating electrode condition is accelerated electrode overpotential is reduced, and can better suppress the cupric ion at openings place to deposit.
In the electroplating process of the inventive method, electroplate liquid is allowed to pass through to be equipped with the electrolyzer of high purity copper particle, Fe in this process
3+with copper particle generation redox reaction, generate Fe
2+and Cu
2+, thus achieve iron ion generation and the balance consumed, and the cupric ion generated can supplement the consumption of cupric ion in plating solution, thus the work-ing life of plating solution can be extended.
Due to Fe
2+/ Fe
3+redox couple can slow down the cupric ion deposition at openings place, simultaneously can accelerate through hole internal copper ion deposition speed, so just can reduce the use of additive.
By using noble electrode and making plating solution by high purity copper particle thus avoid to use anode copper can introduce shortcoming containing phosphorus impurities in the inventive method.Due to Fe
2+/ Fe
3+use can reduce the consumption of additive, the use of additive reduces also can obtain purer copper, can obtain the more stable device of performance, also coating stress can be reduced to below 10MPa containing less impurity.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (6)
1. one kind is added Fe in copper-connection copper sulfate bath
2+and Fe
3+electro-plating method, it is characterized in that, comprise the following steps:
Silicon chip with TSV through hole is placed in pretreatment liquid by step (1) carries out ultrasonic wave pre-treatment;
The described silicon chip through pre-treatment is immersed in containing Cu by step (2)
2+, Cl
-with in the acid copper sulfate baths of sulfuric acid, the pH value of described acid copper sulfate baths is 0 ~ 4;
Step (3) is by additive PEG, SPS, JGB and Fe
2+/ Fe
3+redox couple carries out pre-mixing, leave standstill, obtain the additive solution of pre-mixing, the additive solution of described pre-mixing is injected described acid copper sulfate baths, after being uniformly mixed, electroplate under constant operation electric current, in electroplating process, make electroplate liquid pass through to be equipped with the electrolyzer of high purity copper particle simultaneously;
In the additive solution of described pre-mixing, the concentration of additive is 300ppmPEG, 3ppmSPS, 20ppmJGB, 0.5g/LFe
2+and 0.024g/LFe
3+;
In step (3), additive PEG, SPS, JGB and Fe
2+/ Fe
3+it is 3 hours that redox couple carries out the time of repose after pre-mixing;
In step (3), electroplating process is at 10mA/cm
2constant operation electric current under electroplate, add Fe
2+/ Fe
3+redox couple makes cupric ion deposition current reduce in cathode surface generation reduction reaction thus reduces the sedimentation rate of cupric ion around TSV through hole mouth.
2. electro-plating method according to claim 1, is characterized in that, in step (1), the time of described ultrasonic wave pre-treatment is 2min.
3. electro-plating method according to claim 1, is characterized in that, in step (2), and the Cu of described acid copper sulfate baths
2+concentration is 35g/L, Cl
-concentration is 50ppm, sulfuric acid concentration is 0.6mol/L.
4. electro-plating method according to claim 1, is characterized in that, in step (3), the insoluble noble electrode that electroplating process adopts size fixing, avoids and use electrolytic copper anode to introduce impurity.
5. electro-plating method according to claim 1, is characterized in that, in electroplating process, plating solution is by being equipped with the electrolyzer of high-purity shot copper, supplements the cupric ion and Fe that consume
2+ion, extends the electroplate liquid life-span.
6. electro-plating method according to claim 5, is characterized in that, the impurity in deposited copper reduces, and coating internal stress is reduced to below 10MPa, thus obtains the more stable TSV interconnection element of performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310697666.2A CN103668356B (en) | 2013-12-17 | 2013-12-17 | Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310697666.2A CN103668356B (en) | 2013-12-17 | 2013-12-17 | Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103668356A CN103668356A (en) | 2014-03-26 |
| CN103668356B true CN103668356B (en) | 2016-04-13 |
Family
ID=50307111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310697666.2A Expired - Fee Related CN103668356B (en) | 2013-12-17 | 2013-12-17 | Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103668356B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011822A (en) * | 2019-05-31 | 2020-12-01 | 王美华 | Application of ferric iron copper dissolving system in vertical continuous electroplating line |
| CN113668022A (en) * | 2021-06-21 | 2021-11-19 | 上海天承化学有限公司 | Electroplating solution and electroplating method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674787A (en) * | 1996-01-16 | 1997-10-07 | Sematech, Inc. | Selective electroless copper deposited interconnect plugs for ULSI applications |
| CN1337064A (en) * | 1999-01-21 | 2002-02-20 | 阿托特德国有限公司 | Method for galvanically forming conductor structures of high-purity copper in the production of integrated circuits |
| WO2010094998A1 (en) * | 2009-02-17 | 2010-08-26 | Atotech Deutschland Gmbh | Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) |
| CN102124551A (en) * | 2008-08-18 | 2011-07-13 | 诺发系统有限公司 | Process for through silicon via filling |
| CN103258810A (en) * | 2013-05-10 | 2013-08-21 | 江苏物联网研究发展中心 | Method for reducing over electroplating on surface of wafer after through silicon via (TSV) is electroplated with copper |
-
2013
- 2013-12-17 CN CN201310697666.2A patent/CN103668356B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674787A (en) * | 1996-01-16 | 1997-10-07 | Sematech, Inc. | Selective electroless copper deposited interconnect plugs for ULSI applications |
| CN1337064A (en) * | 1999-01-21 | 2002-02-20 | 阿托特德国有限公司 | Method for galvanically forming conductor structures of high-purity copper in the production of integrated circuits |
| CN102124551A (en) * | 2008-08-18 | 2011-07-13 | 诺发系统有限公司 | Process for through silicon via filling |
| WO2010094998A1 (en) * | 2009-02-17 | 2010-08-26 | Atotech Deutschland Gmbh | Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) |
| CN102318041A (en) * | 2009-02-17 | 2012-01-11 | 埃托特克德国有限公司 | Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) |
| CN103258810A (en) * | 2013-05-10 | 2013-08-21 | 江苏物联网研究发展中心 | Method for reducing over electroplating on surface of wafer after through silicon via (TSV) is electroplated with copper |
Non-Patent Citations (3)
| Title |
|---|
| "Effects of Electroplating Parameters on the Defects of Copper Via for 3D SiP;Byeong-Hoon Cho et al;《Solid State Phenomena》;20070615;第124-126卷;第49-52页 * |
| 利用电镀铜填充微米盲孔与通孔之应用;窦维平;《复旦学报(自然科学版)》;20120415;第51卷(第2期);第131-138页 * |
| 半导体芯片铜线工艺中的添加剂作用机理研究进展;孙建军 等;《 2007（第13届）全国电子电镀学术年会暨绿色电子制造技术论坛论文集》;20071124;第112-119页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103668356A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI522499B (en) | A method of modifying the reduced graphene layer on the surface of the substrate | |
| CN113026068B (en) | Cyanide-free electroless gold plating solution applied to advanced wafer packaging field and gold plating process thereof | |
| TW200304966A (en) | ||
| CN108251869B (en) | Tin plating electrolyte and the preparation method and application thereof | |
| CN104651893A (en) | Alkaline pretreatment for electroplating | |
| EP2852696A1 (en) | Copper plating solution and method for preparing the same | |
| CN103668356B (en) | Fe is added in copper-connection copper sulfate bath 2+and Fe 3+electro-plating method | |
| CN104328397B (en) | A kind of chemical plating fluid of low temperature rapid chemical plating ternary alloy three-partalloy nickel-molybdenum-phosphorus | |
| CN103695973B (en) | Copper-connection pyrovinic acid copper electrolyte adds Fe2+And Fe3+Electro-plating method | |
| CN114031769A (en) | Quaternary ammonium salt leveling agent, preparation method thereof, electroplating solution containing quaternary ammonium salt leveling agent and electroplating method | |
| TWI506727B (en) | Semiconductor components High aspect ratio (HAR) hole or trough of the nickel-tungsten alloy filling plating solution and filling process | |
| CN104141120B (en) | Cuprous chemical copper plating solution | |
| CN107675233A (en) | The new method and system of TSV blind holes filling | |
| CN106637159B (en) | A kind of chemical plating fluid, preparation method and a kind of method of Chemical Plating of Non metal Material | |
| CN104480500A (en) | Cyanide-free electroplating solution for silver plating of copper or copper alloy, preparation method and silver plating process | |
| CN103611933B (en) | A kind of sonochemistry efficiently prepares the method for nickel coated copper composite powder | |
| CN103046089B (en) | Functional copper electroplating solution of and method thereof | |
| JP5774488B2 (en) | Plating solution for electroless deposition of ruthenium | |
| CN105603472A (en) | Acidic copper-plated series addition agents | |
| CN111041533A (en) | Electroplating solution for electroplating pure cobalt and application thereof | |
| Koo et al. | Electrochemical process for 3D TSV without CMP and lithographic processes | |
| CN105002529A (en) | Bismuth-plating electroplating liquid and pulse plating method for bismuth thin film | |
| Wu et al. | Dual effects of CTAB on Co-deposition of SiC/Cu in micro via | |
| Le et al. | Void free TSV copper filling using single additive 3-(1-pyridinio)-1-propanesulfonate (PPS) | |
| TWI298751B (en) | Composition for copper electroplating solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20181217 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |