CN118272879A - Accelerator for chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte - Google Patents
Accelerator for chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte Download PDFInfo
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- CN118272879A CN118272879A CN202410305104.7A CN202410305104A CN118272879A CN 118272879 A CN118272879 A CN 118272879A CN 202410305104 A CN202410305104 A CN 202410305104A CN 118272879 A CN118272879 A CN 118272879A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 77
- 239000003792 electrolyte Substances 0.000 title claims abstract description 18
- 238000005429 filling process Methods 0.000 title claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 40
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 229960003495 thiamine Drugs 0.000 claims description 14
- 235000019157 thiamine Nutrition 0.000 claims description 14
- 239000011721 thiamine Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001990 thiamine group Chemical group 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 61
- 238000011049 filling Methods 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 7
- 230000008054 signal transmission Effects 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 35
- 238000007747 plating Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000010587 phase diagram Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- -1 polydithio-dipropyl Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- OBDVFOBWBHMJDG-UHFFFAOYSA-M 3-sulfanylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-M 0.000 description 2
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to the technical field of chip packaging, and discloses an accelerator for a chip packaging electrodeposited copper filling process and an electrodeposited copper electrolyte. Compared with the traditional accelerator, the accelerator disclosed by the invention does not contain sodium ions, so that the influence of a subsequent sealing and measuring process on electric signal transmission is avoided, and the electroplating solution prepared by the accelerator disclosed by the invention can meet the filling of through holes with the depth-to-width ratio exceeding 1, meets the requirement of advanced packaging and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of chip packaging, relates to a novel electroplated copper additive and application thereof, and in particular relates to an accelerator for a chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte.
Background
Integrated Circuits (ICs) have evolved in the 60 s of the 20 th century from small scale integrated circuits (SSI), medium scale integrated circuits (MSI), large scale integrated circuits (LSI) to ultra large scale integrated circuits (ULSI) as transistor sizes continue to shrink. Whether a single transistor or an integrated circuit, must function through the package. Encapsulation is the basis for system integration.
In the industry of manufacturing electronic circuits and electronic components, electroplated copper plays a key role in modern electronic industry applications due to its high reliability and productivity and low cost while meeting the electrical and thermal transfer characteristics. Therefore, gap filling with electroplated copper has become an indispensable technology, and is widely used for metallization of high-density interconnects in integrated circuits and filling of micro-vias in printed circuit boards and through-silicon vias in chip packages. Additives are an important component of the plating solution and play an irreplaceable role in the plating process. The additive can effectively improve the current distribution in the electroplating process, improve the uniform plating capacity of the plating solution, influence the transportation of copper ions from a solution body to a reaction interface and the electric crystallization process, and further change the electrochemical deposition rate of microscopic recesses and microscopic protrusions of the plate surface.
Copper electroplating additives generally include accelerators, suppressors and levelers. According to the convection-dependent adsorption (CDA) mechanism, the most widely used accelerators are sodium polydithio-dipropyl sulfonate (SPS) and 3-mercapto-1-propane sulfonate (MPS), which can enhance the copper deposition rate at the bottom of the pores. Inhibitors are mainly macromolecules with polyethers, such as polyethylene glycol (PEG), polypropylene glycol (PPG) or triblock copolymers of PEG and PPG. Inhibitors can generally inhibit copper deposition at the orifice in the presence of chloride ions. Leveling agents in copper electrodeposition are typically small molecule nitrogen-containing heterocyclic compounds, quaternary ammonium salts, or polymers, most commonly Janus Green B (JGB).
At present, the chip copper interconnection is selected by an acid sulfate copper plating system, and the key of the acid sulfate copper plating is the selection and the use of additives. The existing accelerator is mainly sodium salt containing sulfonic acid groups, and researches show that a thiol (-SH) group at the front end of SPS molecules and a sulfonate ion (SO 3 -) at the tail end are two key functional groups for accelerating in the presence of chloride ions (Cl -), and the interaction between the sulfonate ion and the chloride ions can accelerate the reduction of copper ions. However, the above accelerators still have disadvantages: firstly, the accelerating effect is not obvious, and the adding amount of the accelerator is large; secondly, the existing accelerator contains sodium ions, so that the sodium ions have strong penetrating power in the chip processing process, are extremely easy to penetrate into the chip, influence the electric signal transmission of the chip, and cause poor chip performance.
Therefore, there is a need to develop an accelerator for the chip package electrodeposited copper fill process that does not affect the electrical signal transmission of the chip.
Disclosure of Invention
The invention aims to provide an accelerator for a chip packaging electro-deposition copper filling process and an electro-deposition copper electrolyte, so as to solve the technical problem that the accelerator for the chip packaging electro-deposition copper filling process in the prior art is easy to infiltrate into a chip due to sodium ions, and affects the transmission of electric signals of the chip, so that the chip performance is poor.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides an accelerator for a chip packaging electrodeposited copper filling process, which has the following structural formula:
further, the accelerator is specifically obtained by introducing a benzothiazole structure with a disulfide bond as a center and introducing sulfonic acid groups at two ends of a molecular chain in a space symmetry manner, and the molecular weight of the accelerator is 520.
The principle of the technical proposal is as follows: because the accelerator has the sulfonic group, the disulfide bond and the benzothiazole structure, the N+ and S atoms and the thiazole ring in the accelerator can be used as active sites to enable the accelerator to be adsorbed on the surface of copper while ensuring good water solubility, and the benzene heterocyclic structure can obviously reduce the internal stress effect among coating molecules, so that sulfonic groups at two ends of the accelerator molecules can better cooperate with chloride ions to accelerate the deposition of copper ions, and the copper deposition rate is obviously improved.
The invention also provides an electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process, the electrodeposited copper electrolyte comprising an additive comprising the accelerator of claim 1 or claim 2.
Further, the accelerator is added in an amount of 5 to 50ppm.
Further, the additive also comprises an inhibitor and a leveling agent.
Further, the inhibitor is polyethylene glycol, and the molecular weight of the inhibitor is 5000-10000.
Further, the leveling agent is thiamine or thiourea.
Further, the addition amount of the inhibitor is 50 to 200ppm.
Further, the amount of the leveling agent added is 0.1 to 1ppm.
Further, the electrodeposited copper electrolyte further comprises CuSO 4、H2SO4 and chloride ions; the addition amount of CuSO 4 is 180-240 g/L, the addition amount of H 2SO4 is 45-80 g/L, and the addition amount of chloride ions is 50-70 ppm.
In summary, the invention has the following beneficial effects:
1. The copper deposition accelerator provided by the invention takes a disulfide bond as a center, a benzothiazole structure is introduced in space symmetry, and sulfonic acid groups are introduced at two ends of a molecular chain, so that the copper deposition accelerator has the sulfonic acid groups, the disulfide bond and the benzothiazole structure; the accelerator can ensure good water solubility, and simultaneously N+ and S atoms and thiazole rings in the accelerator can be used as active sites to enable the accelerator to be adsorbed on the surface of copper, and a benzene heterocyclic structure can obviously reduce the internal stress effect among coating molecules, so that sulfonic groups at two ends of the accelerator molecules can better cooperate with chloride ions to accelerate the deposition of copper ions.
2. According to the invention, the experimental result of the test experiment shows that the electroplating solution prepared by the accelerator can meet the filling of the through holes with the depth-to-width ratio exceeding 1 and meet the requirement of advanced packaging; in addition, the electroplating solution prepared by the invention has no sodium ions, so that the problems of poor chip performance and the like caused by the influence of the sodium ions on the transmission of electric signals of the chip due to the penetration of the sodium ions into the chip in the chip processing process can be avoided, and the electroplating solution provided by the invention has a wide application prospect.
Drawings
FIG. 1 is a metallographic microscope image of plated microwells of a wafer in example 1 of the present invention;
FIG. 2 is an FE SEM topography of copper deposited on the micro-porous surface of a wafer in example 1;
FIG. 3 is a metallographic microscope image of plated micro-holes of a wafer in example 2 of the present invention;
FIG. 4 is a metallographic microscope image of plated micro-holes of a wafer in example 3 of the present invention;
FIG. 5 is a metallographic microscope image of plated microwells of a wafer in comparative example 1 of the present invention;
FIG. 6 is a metallographic microscope image of plated microwells of a wafer in comparative example 2 of the present invention.
Detailed Description
The present invention is further described below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples. Various substitutions and alterations are made according to the ordinary skill and familiar means of the art without departing from the technical spirit of the invention, and all such substitutions and alterations are intended to be included in the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
In the electroplating process described in the following examples, the electrodeposited copper electrolyte was prepared by introducing a benzothiazole structure in a spatially symmetric manner with a disulfide bond as a center and introducing sulfonic acid groups at both ends of the molecular chain, and had a molecular weight of 520, and the chemical structural formula of the accelerator was as follows:
Example 1:
The copper electroplating process of the embodiment comprises the following steps:
step S1, preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions, additives (leveling agent (thiamine), inhibitor PEG (molecular weight is 5000) and accelerator) to obtain electroplating solution;
The specific process is as follows: 220g of copper sulfate pentahydrate is dissolved in 1L of deionized water, 30.5ml of sulfuric acid is slowly added, and chloridion, thiamine and accelerator are added, so that the concentration of chloridion is 55ppm, the concentration of thiamine is 1ppm, the concentration of inhibitor PEG is 100ppm and the concentration of accelerator is 30ppm, and electroplating solution is obtained;
step S2, pretreating a wafer slice (2 x 2 cm) with ethanol to obtain an ethanol pretreatment test board;
The specific process is as follows: soaking the wafer slice in ethanol for 3-5min, removing pollutants of the slice, and then flushing with deionized water to ensure that the pollutants are flushed completely, thus obtaining an ethanol pretreated slice;
And S3, soaking the pretreated wafer slice in the electroplating solution prepared in the step S1 for 10min.
S4, taking the pretreated wafer slice as a cathode, taking a phosphorus-containing copper plate as an anode, and completing electroplating in an electroplating solution;
The specific process is as follows: pouring the electroplating solution prepared in the step S1 into a beaker, putting the pretreated wafer slice in the step S2 into an electrolytic tank AS a cathode, taking a phosphorus-containing copper plate AS an anode, stably stirring in a magnetic stirrer at a rotating speed of 400r/min, electrifying direct current to the cathode and the anode, firstly electroplating for 60S by using 1AS, pre-plating a copper seed layer, then electroplating for 300S by using 5ASD, and finally electroplating for 40min by using 10ASD, wherein the gold phase diagram of the micropore section of the electroplated wafer is shown in FIG. 1, and the FE-SEM morphology diagram of the electroplated wafer surface is shown in FIG. 2.
Example 2:
The copper electroplating process of the embodiment comprises the following steps:
step S1, preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions and additives (leveling agent (thiourea), inhibitor PEG (molecular weight is 10000) and accelerator) to obtain electroplating solution;
The specific process is as follows: 180g of copper sulfate pentahydrate is dissolved in 1L of deionized water, 26ml of sulfuric acid is slowly added, and chloride ions, thiourea and accelerator are added so that the concentration of the chloride ions is 50ppm, the concentration of the thiourea is 0.2ppm, the concentration of the inhibitor PEG is 200ppm and the concentration of the accelerator is 10ppm, thereby obtaining the electroplating solution.
Step S2, pretreating a wafer slice (2 x 2 cm) with ethanol to obtain an ethanol pretreatment test board;
The specific process is as follows: soaking the wafer slice in ethanol for 3-5min, removing pollutants of the slice, and washing with deionized water to ensure that the pollutants are washed cleanly, thus obtaining the ethanol pretreated slice.
And S3, soaking the pretreated wafer slices in the electroplating solution obtained in the step S1 for 10min.
S4, taking the pretreated wafer slice as a cathode, taking a phosphorus-containing copper plate as an anode, and completing electroplating in an electroplating solution;
the specific process is as follows: pouring the electroplating solution into a beaker, placing the pretreated wafer slice into an electrolytic tank as a cathode, taking a phosphorus-containing copper plate as an anode, stirring stably at a magnetic stirring rotating speed of 400r/min, and supplying direct current to the cathode and the anode, firstly 1ASD electroplating for 60s to preplating a copper seed layer, then 5ASD electroplating for 300s, and then 10ASD electroplating for 40min, wherein the gold phase diagram of the micropore section of the electroplated wafer is shown in 3.
Example 3:
The copper electroplating process of the embodiment comprises the following steps:
Step S1, preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions, additives (leveling agent (thiamine), inhibitor PEG (molecular weight is 8000) and accelerator) to obtain electroplating solution;
the specific process is as follows: 240g of copper sulfate pentahydrate was dissolved in 1L of deionized water, 42ml of sulfuric acid was slowly added, and chloride ions, thiamine and accelerator were added so that the concentration of chloride ions was 70ppm, the concentration of thiamine was 0.5ppm, the concentration of inhibitor PEG was 60ppm and the concentration of accelerator was 50ppm, to obtain a plating solution.
Step S2, pretreating a wafer slice (2 x 2 cm) with ethanol to obtain an ethanol pretreatment test board;
The specific process is as follows: soaking the wafer slice in ethanol for 3-5min, removing pollutants of the slice, and washing with deionized water to ensure that the pollutants are washed cleanly, thus obtaining the ethanol pretreated slice.
And S3, soaking the pretreated wafer slices in the electroplating solution obtained in the step S1 for 10min.
S4, taking the pretreated wafer slice as a cathode, taking a phosphorus-containing copper plate as an anode, and completing electroplating in an electroplating solution;
The specific process is as follows: pouring the electroplating solution into a beaker, placing the pretreated wafer slice into an electrolytic tank as a cathode, taking a phosphorus-containing copper plate as an anode, stirring stably at a magnetic stirring rotation speed of 400r/min, and supplying direct current to the cathode and the anode, firstly 1ASD electroplating for 60s to preplating a copper seed layer, then 5ASD electroplating for 300s, and then 10ASD electroplating for 40min, wherein a gold phase diagram of a micropore section of the electroplated wafer is shown in fig. 4.
As can be seen from FIGS. 1 to 4, the accelerator and the copper electroplating process provided by the invention can be used for obtaining seamless and hollow blind hole copper electroplating filling, and the surface of the coating is bright and flat, so that the accelerator and the copper electroplating process can be widely applied to metallization of high-density interconnection of integrated circuits and micropore filling of printed circuit boards, and have better stability and reliability.
Comparative example 1:
the comparative example provides an electrolytic copper plating process with an accelerator PSP, comprising the following steps:
Step S1, preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions, additives (leveling agent (thiamine), inhibitor PEG (molecular weight 5000) and accelerator PSP) to obtain electroplating solution;
the specific process is as follows: 220g of copper sulfate pentahydrate is dissolved in 1L of deionized water, 30.5ml of sulfuric acid is slowly added, and chloride ions, thiamine and accelerator are added so that the concentration of the chloride ions is 55ppm, the concentration of the thiamine is 1ppm, the concentration of the inhibitor PEG is 100ppm and the concentration of the accelerator PSP is 30ppm, thereby obtaining the electroplating liquid.
Step S2, pretreating a wafer slice (2 x 2 cm) with ethanol to obtain an ethanol pretreatment test board;
The specific process is as follows: soaking the wafer slice in ethanol for 3-5min, removing pollutants of the slice, and washing with deionized water to ensure that the pollutants are washed cleanly, thus obtaining the ethanol pretreated slice.
And step S3, immersing the wafer slice pretreated in the step S2 in the electroplating solution prepared in the step S1 for 10min.
S4, taking the wafer slice pretreated in the step S2 as a cathode, taking a phosphorus-containing copper plate as an anode, and finishing electroplating in an electroplating solution;
The specific process is as follows: pouring the electroplating solution prepared in the step S1 into a beaker, putting the wafer slice pretreated in the step S2 into an electrolytic tank to serve as a cathode, taking a phosphorus-containing copper plate as an anode, stirring stably in a magnetic stirrer at a rotating speed of 400r/min, applying direct current to the cathode and the anode, firstly electroplating for 60S by using 1ASD, pre-plating a copper seed layer, then electroplating for 300S by using 5ASD, and finally electroplating for 25min by using 10ASD, wherein the gold phase diagram of the micropore section of the electroplated wafer is shown in FIG. 5, and the growth mode of electroplated copper is super-equal thickness deposition (V-shaped growth) as known from FIG. 5.
Comparative example 2:
the comparative example provides a copper electroplating process without adding an accelerator, comprising the following steps:
step S1, preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding a chloride ion additive (leveling agent (thiamine) and inhibitor PEG) to obtain electroplating solution;
The specific process is as follows: 220g of copper sulfate pentahydrate was dissolved in 1L of deionized water, 30.5ml of sulfuric acid was slowly added, and chloride ions and thiamine were added so that the concentration of chloride ions was 55ppm, the concentration of thiamine was 1ppm, and the concentration of inhibitor PEG was 100ppm, to obtain a plating solution.
Step S2, pretreating a wafer slice (2 x 2 cm) with ethanol to obtain an ethanol pretreatment test board;
The specific process is as follows: soaking the wafer slice in ethanol for 3-5min, removing pollutants of the slice, and washing with deionized water to ensure that the pollutants are washed cleanly, thus obtaining the ethanol pretreated slice.
And step S3, immersing the wafer slice pretreated in the step S2 in the electroplating solution prepared in the step S1 for 10min.
S4, taking the wafer slice obtained after the pretreatment in the step S2 as a cathode, taking a phosphorus-containing copper plate as an anode, and completing electroplating in an electroplating solution;
The specific process is as follows: pouring the electroplating solution prepared in the step S1 into a beaker, putting the wafer slice pretreated in the step S2 into an electrolytic tank to serve as a cathode, taking a phosphorus-containing copper plate as an anode, stirring stably in a magnetic stirrer at a rotating speed of 400r/min, electrifying direct current to the cathode and the anode, firstly electroplating for 60S by using 1ASD, then electroplating for 300S by using 5ASD, and finally electroplating for 40min by using 10ASD, wherein a blind hole gold phase diagram of the electroplated test plate is shown in fig. 6, and the wafer micropore filling effect of the electroplated test plate in the electroplating solution without the accelerator is poor, and the surface of the electroplated test plate is prominent and has defects as shown in fig. 6.
In conclusion, the electroplating solution prepared by the accelerator provided by the invention is applied to the copper electroplating process, so that seamless and hollow blind hole copper electroplating filling can be obtained, and the surface of a plating layer is bright and flat; the method can be widely applied to metallization of high-density interconnection of integrated circuits and micropore filling of a printed circuit board, and has better stability and reliability compared with the prior art.
The foregoing is merely exemplary embodiments of the present application, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. An accelerator for a chip package electrodeposited copper filling process, characterized by the following structural formula:
2. The accelerator for a chip package electrodeposited copper filling process according to claim 1, wherein the accelerator is obtained by introducing a benzothiazole structure spatially symmetrically with a disulfide bond as a center and introducing sulfonic acid groups at both ends of a molecular chain, and the molecular weight of the accelerator is 520.
3. An electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process, wherein said electrodeposited copper electrolyte comprises an additive comprising the accelerator of claim 1 or claim 2.
4. An electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 3, wherein said accelerator is added in an amount of 5 to 50ppm.
5. An electrodeposited copper electrolyte solution for use in a chip package electrodeposited copper fill process according to claim 4, wherein said additives further comprise inhibitors and leveling agents.
6. The electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 5, wherein said inhibitor is polyethylene glycol and said inhibitor has a molecular weight of 5000-10000.
7. An electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 5, wherein said leveler is thiamine or thiourea.
8. Electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 5 or 6, wherein said inhibitor is added in an amount of 50 to 200ppm.
9. An electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 5,6 or 7, wherein said leveler is added in an amount of 0.1 to 1ppm.
10. An electrodeposited copper electrolyte for use in a chip package electrodeposited copper fill process according to claim 3, 4, 6 or 7, wherein said electrodeposited copper electrolyte further comprises CuSO 4、H2SO4 and chloride ions;
the addition amount of CuSO 4 is 180-240 g/L, the addition amount of H 2SO4 is 45-80 g/L, and the addition amount of chloride ions is 50-70 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410305104.7A CN118272879A (en) | 2024-03-18 | 2024-03-18 | Accelerator for chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410305104.7A CN118272879A (en) | 2024-03-18 | 2024-03-18 | Accelerator for chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN118272879A true CN118272879A (en) | 2024-07-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410305104.7A Withdrawn CN118272879A (en) | 2024-03-18 | 2024-03-18 | Accelerator for chip packaging electrodeposited copper filling process and electrodeposited copper electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118272879A (en) |
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- 2024-03-18 CN CN202410305104.7A patent/CN118272879A/en not_active Withdrawn
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