CN114959810A - Novel electro-coppering additive and application thereof - Google Patents
Novel electro-coppering additive and application thereof Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 53
- 230000000996 additive effect Effects 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 claims abstract description 75
- 239000010949 copper Substances 0.000 claims abstract description 75
- 238000009713 electroplating Methods 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 43
- 229960001950 benzethonium chloride Drugs 0.000 claims abstract description 25
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical group [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008118 PEG 6000 Substances 0.000 claims abstract description 18
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims abstract description 18
- 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 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 abstract description 14
- 238000001465 metallisation Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VJDDAARZIFHSQY-UHFFFAOYSA-N basic black 2 Chemical compound [Cl-].C=1C2=[N+](C=3C=CC=CC=3)C3=CC(N(CC)CC)=CC=C3N=C2C=CC=1NN=C1C=CC(=O)C=C1 VJDDAARZIFHSQY-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a novel electro-coppering additive and application thereof. The novel electro-coppering additive is benzethonium chloride, which is used as a leveler in electro-coppering processes. The copper electroplating process comprises the following steps: preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and benzethonium chloride to obtain electroplating solution; pretreating a test board containing blind holes by using ethanol and dilute sulfuric acid solution in sequence to obtain a pretreated test board; the test board is used as cathode and the copper plate containing phosphorus is used as anode to complete electroplating in electroplating solution. The novel copper electroplating additive provided by the invention is low in price, easy to obtain, low in pollution, stable in electroplating solution and not easy to decompose. The novel electro-coppering additive provided by the invention is applied to the electro-coppering process, can obtain seamless and hollow blind hole electro-coppering filling, has bright and flat plating surface, can be widely applied to metallization of high-density interconnection of integrated circuits and micropore filling of printed circuit boards, and has excellent stability and reliability.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to a novel copper electroplating additive and application thereof.
Background
In recent years, small and lightweight electronic devices have become the mainstream consumer electronics, and the production and interconnection of miniaturized multifunctional microelectronic devices is realized by relying on High Density Interconnect (HDI) technology of Printed Circuit Boards (PCBs), while copper electroplating is an important technology for manufacturing multilayer printed circuit boards, and is widely applied to metallization of high density interconnections of integrated circuits and micro via filling of printed circuit boards. For better stability and reliability, the micro-porous electroplated copper filling requires no gaps or voids. However, when the hole is filled by the direct current electroplating, the current density and convection strength of the hole opening are far higher than those of the hole, and the deposition rate of copper in the hole opening is far higher than that of the hole during the electroplating, so that the hole sealing phenomenon can be caused. It is therefore necessary to add various additives to the base plating solution to reduce the current density at the orifice so that copper is preferentially deposited inside the hole to complete the hole fill.
The technique of filling the pores with electroplated copper is carried out using a specific electroplating formulation, wherein accelerators, suppressors and levelers are important additives in the electroplating process, and the interaction between the additives in the formulation plays a very important role in "super-equal thickness" filling and "bottom-up" pore filling. The leveling agent is introduced on the basis of the combination of the accelerator and the inhibitor, the leveling agent is adsorbed on the copper surface near the micro-pore opening, and when the accelerator replaces the inhibitor, the leveling agent and the accelerator compete for adsorption at the micro-pore opening, so that the deposition of pore opening copper is inhibited.
Levelers are susceptible to current distribution and convection intensities, adsorb at high current areas such as where electrodes protrude and reduce the rate of copper deposition. It is reported that the suppression of electrodeposited copper by levelers is due to adsorption forming a barrier layer on the cathode surface, thereby limiting the entry of copper ions into the copper electrode. During electroplating, leveler molecules are strongly adsorbed at the orifice edges and surface irregularities, thereby causing the greatest polarization and plating suppression effects at these locations, and generally achieving excellent hole-filling effects. Leveling agents are important for achieving defect-free cell filling and can be divided into the dye type and the non-dye type, mostly quaternary ammonium salts or nitrogen-containing heterocyclic compounds. The most commonly used dye-type leveling agents are the nitrogen-containing organic heterocyclic compound Janazure (JGB), which has been studied in a large number of and in detail, and such leveling agents are also Diazine Black (DB), Alcian Blue (ABPV), etc., which are easily decomposed at high temperature, not only increasing the complexity and cost of controlling the plating process, but also the decomposition products are mixed with the copper plating layer, causing quality problems. Non-dye leveling agents are various in types, such as small-molecule tetrazole derivatives and 2-mercaptopyridine, large-molecule VIBDGE (copolymer of 1-vinylimidazole and 1, 4-butanediol glycidyl ether) and FAQAS (fatty acid quaternary ammonium salt surfactant synthesized based on renewable fatty acid), and the like, most of the leveling agents are synthesized organic matters or mixtures of a plurality of organic matters, so that the cost is high, the synthesis process is complex, the yield is low, and the toxicity and the pollution are high.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a novel electro-coppering additive and application thereof. .
The specific technical scheme of the invention is as follows:
the invention provides application of a novel electro-coppering additive in an electro-coppering process, which is characterized in that the electro-coppering process comprises the following steps: step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel electro-coppering additive to obtain an electro-coppering solution; step S2, pretreating a test board with blind holes by using ethanol to obtain an ethanol pretreatment test board; step S3, pretreating the ethanol pretreatment test board with a dilute sulfuric acid solution to obtain a pretreatment test board; and step S4, taking the pretreated test board as a cathode and the phosphorus-containing copper plate as an anode, and finishing electroplating in electroplating solution, wherein the novel electroplating copper additive is benzethonium chloride.
The present invention provides a novel additive for electrolytic copper plating, which is useful in an electrolytic copper plating process, and has a technical feature in that the novel additive for electrolytic copper plating is used as a leveler in the electrolytic copper plating process.
The application of the novel electro-coppering additive in the electro-coppering process is also characterized in that the concentration of copper sulfate pentahydrate in the electroplating solution in the step S1 is 100-300g/L, the concentration of sulfuric acid is 40-70g/L, the concentration of chloride ions is 30-80mg/L, the concentration of SPS is 1-10ppm, the concentration of PEG-6000 is 100-300ppm, and the concentration of the novel electro-coppering additive is 1-15 ppm.
The application of the novel electro-coppering additive in the electro-coppering process also has the technical characteristics that the aperture of the blind hole of the test board in the step S2 is 100-150 μm, and the depth of the blind hole is 50-100 μm.
The application of the novel copper electroplating additive in the copper electroplating process is also characterized in that the mass fraction of phosphorus in the phosphorus-containing copper plate in the step S4 is 0.04-0.065%.
Action and Effect of the invention
The invention uses benzethonium chloride as a novel copper electroplating additive (leveling agent) in the copper electroplating process, and specifically comprises the following steps: preparing a copper sulfate pentahydrate aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel electroplating copper additive benzethonium chloride to obtain an electroplating solution; pretreating a test board containing blind holes by using ethanol and dilute sulfuric acid solution in sequence to obtain a pretreated test board; the test board is used as cathode and the copper plate containing phosphorus is used as anode to complete electroplating in electroplating solution.
The novel copper electroplating additive provided by the invention is low in price, easy to obtain, low in pollution, stable in electroplating solution and not easy to decompose. The novel electro-coppering additive provided by the invention is applied to the electro-coppering process, blind hole electro-coppering filling without gaps and holes can be obtained, and the surface of a plating layer is bright and flat, so that the novel electro-coppering additive can be widely applied to metallization of high-density interconnection of integrated circuits and micropore filling of printed circuit boards, and has excellent stability and reliability.
Drawings
FIG. 1 shows the structural formula of benzethonium chloride, a novel additive for electrolytic copper plating.
FIG. 2 is a diagram of the leading edge molecular trajectory of benzethonium chloride, a novel electro-coppering additive provided by the present invention. Wherein (a) in FIG. 2 is a LUMO diagram; in FIG. 2, (b) is a HOMO diagram.
FIG. 3 is a schematic diagram of a blind hole gold phase plated on a test board according to embodiments 1-3 of the present invention.
FIG. 4 is an FE-SEM topographic map of copper deposition on the surface of the electroplated test boards of examples 1-3 of the present invention.
FIG. 5 is a photograph of a gold phase of blind vias and a FE-SEM topography of surface deposited copper for a comparative electroplated test panel of the present invention.
Detailed Description
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
The reagents used in the following examples are commercially available and the experimental procedures and experimental conditions not specified are those conventional in the art.
In the following examples, benzethonium chloride was used as a novel additive (leveler) for electrolytic copper plating. FIG. 1 shows the structural formula of benzethonium chloride, a novel additive for electrolytic copper plating. The results of the quantum stoichiometry of benzethonium chloride are given in table 1.
TABLE 1
The study showed a high E HOMO And low E LUMO Respectively representing the ability of molecules to easily donate and accept electrons, and the adsorption ability of organic substances on the metal surface follows E HOMO Increase and E LUMO Is increased. Therefore, the energy gap (Δ E) can be used for characterizing the adsorption capacity of organic matters, and the smaller the Δ E value, the better the adsorption performance of the additive on the metal surface.
FIG. 2 is a front-edge molecular orbital diagram of benzethonium chloride, a novel electro-coppering additive provided by the present invention. Wherein (a) in FIG. 2 is a LUMO diagram; in FIG. 2, (b) is a HOMO diagram.
As can be seen from (a) in fig. 2, the electron cloud density is mainly distributed on the benzyl group, indicating that the benzyl group is the active site for copper ion attack. As can be seen from (b) in fig. 2, the electron cloud density is mainly concentrated on the oxygen atoms and the alkyl chains, which suggests that benzethonium chloride can strongly adsorb to the copper surface by donating the lone pair of electrons in these heteroatoms to the unoccupied orbital of copper. The calculation result, which is obtained by combining the quantum chemistry calculation result in table 1, i.e., the gap Δ E ═ 1.701, also shows that benzethonium chloride has strong adsorption capacity on the copper surface as a leveling agent, and has a good inhibition effect on copper deposition.
The blind holes of the test boards used in the following examples and comparative examples had a hole diameter of 100-150 μm and a hole depth of 50-100. mu.m.
The phosphorus-containing copper plates used in the following examples and comparative examples each had a phosphorus content of 0.04 to 0.065% by mass.
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings.
< example 1>
This example provides the use of a novel copper electroplating additive (benzethonium chloride, as leveling agent, at a concentration of 9ppm) in a copper electroplating process comprising the steps of:
step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel electro-coppering additive to obtain an electro-coppering solution, wherein the specific process comprises the following steps:
dissolving 220g of blue vitriod in 1L of deionized water, slowly adding 29.9ml of sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel copper electroplating additive benzethonium chloride to ensure that the concentration of the chloride ions is 60ppm, the concentration of the SPS is 1ppm, the concentration of the PEG-6000 is 200ppm and the concentration of the benzethonium chloride is 9ppm to obtain electroplating solution;
step S2, the test board containing blind holes is pretreated by ethanol to obtain the ethanol pretreatment test board, and the specific process is as follows:
soaking the blind hole test board in ethanol for 3-5min to remove pollutants on the surface of the test board, and then washing with deionized water to ensure that the pollutants are washed clean, thereby obtaining an ethanol pretreatment test board;
step S3, pretreating the test board with ethanol by dilute sulfuric acid solution to obtain a pretreated test board, wherein the method comprises the following specific steps:
putting the ethanol pretreatment test board into a 1mol/L dilute sulfuric acid solution, and uniformly shaking for 30-60s to remove oxides on the surface of the copper layer to obtain the pretreatment test board;
step S4, using the pre-treated test board as a cathode and the phosphorus-containing copper board as an anode to finish electroplating in the electroplating solution, the specific process is as follows:
pouring the electroplating solution into 1L electroplating bath, placing the pretreatment test board into an electrolytic bath as a cathode, wrapping a phosphorus-containing copper plate with a filter bag, placing the wrapped phosphorus-containing copper plate into the electrolytic bath as an anode, starting an air pump, introducing continuous bubble flow into the electroplating bath for stable stirring, and introducing Direct Current (DC) to the cathode and the anode, wherein the current density is 1.5A/dm 2 And electrifying for 1h to finish electroplating.
< example 2>
This example provides the use of a novel copper electroplating additive (benzethonium chloride, as leveling agent, at a concentration of 7ppm) in a copper electroplating process comprising the steps of:
step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel electro-coppering additive to obtain an electro-coppering solution, wherein the specific process comprises the following steps:
dissolving 220g of blue vitriod in 1L of deionized water, slowly adding 29.9ml of sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel copper electroplating additive benzethonium chloride to ensure that the concentration of the chloride ions is 60ppm, the concentration of the SPS is 1ppm, the concentration of the PEG-6000 is 200ppm and the concentration of the benzethonium chloride is 7ppm to obtain an electroplating solution;
step S2, the test board containing blind holes is pretreated by ethanol to obtain the ethanol pretreatment test board, and the specific process is as follows:
soaking the blind hole test board in ethanol for 3-5min to remove pollutants on the surface of the test board, and then washing with deionized water to ensure that the pollutants are washed clean, thereby obtaining an ethanol pretreatment test board;
step S3, pretreating the ethanol pretreatment test board with dilute sulfuric acid solution to obtain a pretreatment test board, wherein the specific process is as follows:
putting the ethanol pretreatment test board into a 1mol/L dilute sulfuric acid solution, and uniformly shaking for 30-60s to remove oxides on the surface of the copper layer to obtain the pretreatment test board;
step S4, using the pre-treated test board as a cathode and the phosphorus-containing copper board as an anode to finish electroplating in the electroplating solution, the specific process is as follows:
will be electroplatedPouring the solution into 1L electroplating bath, placing the pretreated test board into an electrolytic bath as cathode, wrapping the phosphorus-containing copper plate with filter bag, placing the wrapped copper plate into the electrolytic bath as anode, starting air pump, introducing continuous air bubble flow into the electroplating bath for stable stirring, and introducing direct current with current density of 1.5A/dm to the cathode and anode 2 And electrifying for 1h to finish electroplating.
< example 3>
This example provides the use of a novel electro-coppering additive (benzethonium chloride, as leveling agent, at a concentration of 3ppm) in an electro-coppering process comprising the steps of:
step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel electro-coppering additive to obtain an electro-coppering solution, wherein the specific process comprises the following steps:
dissolving 220g of blue vitriod in 1L of deionized water, slowly adding 29.9ml of sulfuric acid, and adding chloride ions, SPS, PEG-6000 and a novel copper electroplating additive benzethonium chloride to ensure that the concentration of the chloride ions is 60ppm, the concentration of the SPS is 1ppm, the concentration of the PEG-6000 is 200ppm and the concentration of the benzethonium chloride is 3ppm to obtain electroplating solution;
step S2, the test board containing blind holes is pretreated by ethanol to obtain the ethanol pretreatment test board, and the specific process is as follows:
soaking the blind hole test board in ethanol for 3-5min to remove pollutants on the surface of the test board, and then washing with deionized water to ensure that the pollutants are washed clean, thereby obtaining an ethanol pretreatment test board;
step S3, pretreating the ethanol pretreatment test board with dilute sulfuric acid solution to obtain a pretreatment test board, wherein the specific process is as follows:
putting the ethanol pretreatment test board into a 1mol/L dilute sulfuric acid solution, and uniformly shaking for 30-60s to remove oxides on the surface of the copper layer to obtain the pretreatment test board;
step S4, using the pre-treated test board as a cathode and the phosphorus-containing copper board as an anode to finish electroplating in the electroplating solution, the specific process is as follows:
pouring the electroplating solution into 1L electroplating bath, placing the pretreatment test board into the electroplating bath as cathode, wrapping the phosphorus-containing copper plate with filter bag, and placing into the electroplating bathThe electrolytic bath is used as anode, air pump is started, continuous bubble flow is introduced into the electroplating bath for stable stirring, direct current is introduced into cathode and anode, and current density is 1.5A/dm 2 And electrifying for 1h to finish electroplating.
< comparative example >
The present comparative example provides a copper electroplating process without adding a novel copper electroplating additive (benzethonium chloride), comprising the steps of:
step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS and PEG-6000 to obtain the electroplating solution, wherein the specific process is as follows:
dissolving 220g of blue vitriod in 1L of deionized water, slowly adding 29.9ml of sulfuric acid, and adding chloride ions, SPS and PEG-6000 to ensure that the concentration of the chloride ions is 60ppm, the concentration of the SPS is 1ppm and the concentration of the PEG-6000 is 200ppm to obtain electroplating solution;
step S2, the test board containing blind holes is pretreated by ethanol to obtain the ethanol pretreatment test board, and the specific process is as follows:
soaking the blind hole test board in ethanol for 3-5min to remove pollutants on the surface of the test board, and then washing with deionized water to ensure that the pollutants are washed clean, thereby obtaining an ethanol pretreatment test board;
step S3, pretreating the ethanol pretreatment test board with dilute sulfuric acid solution to obtain a pretreatment test board, wherein the specific process is as follows:
putting the ethanol pretreatment test board into a 1mol/L dilute sulfuric acid solution, and uniformly shaking for 30-60s to remove oxides on the surface of the copper layer to obtain the pretreatment test board;
step S4, using the pre-treated test board as a cathode and the phosphorus-containing copper board as an anode to finish electroplating in the electroplating solution, the specific process is as follows:
pouring the electroplating solution into a 1L electroplating bath, placing the pretreatment test board into an electrolytic bath as a cathode, wrapping a phosphorus-containing copper plate with a filter bag, placing the wrapped phosphorus-containing copper plate into the electrolytic bath as an anode, starting an air pump, introducing continuous bubble flow into the electroplating bath for stable stirring, and introducing direct current to the cathode and the anode, wherein the current density is 1.5A/dm 2 And electrifying for 1h to finish electroplating.
FIG. 3 is a schematic view of a blind hole gold phase pattern of a test board plated according to embodiments 1-3 of the present invention. FIG. 4 is an FE-SEM topographic map of copper deposition on the surface of the electroplated test boards of examples 1-3 of the present invention.
As can be seen from FIGS. 3 and 4, the novel electro-coppering additive and the electro-coppering process provided by the invention can be used for obtaining seamless and hollow blind hole electro-coppering filling, and the surface of the coating is bright and smooth, so that the novel electro-coppering additive and the electro-coppering process can be widely applied to the metallization of high-density interconnection of integrated circuits and the micropore filling of printed circuit boards, and have better stability and reliability.
FIG. 5 is a photograph of a gold phase of blind holes and a FE-SEM topography of surface deposited copper for comparative example electroplated test panels of the present invention.
As can be seen from fig. 5, the blind via filling effect of the test board plated in the plating solution without adding the novel copper electroplating additive (benzethonium chloride) was poor, and the surface copper layer had coarse grains.
The foregoing is a detailed description of embodiments that will enable those skilled in the art to make and use the invention. The technical solutions of the present invention, which can be improved or modified only by analysis, analogy or limited enumeration, should be within the scope of protection determined by the claims.
Claims (5)
1. The application of the novel electro-coppering additive in the electro-coppering process is characterized in that the electro-coppering process comprises the following steps:
step S1, preparing a blue copperas aqueous solution, adding sulfuric acid, and adding chloride ions, SPS, PEG-6000 and the novel electro-coppering additive to obtain an electro-coppering solution;
step S2, pretreating a test board with blind holes by using ethanol to obtain an ethanol pretreatment test board;
step S3, pretreating the ethanol pretreatment test board by using a dilute sulfuric acid solution to obtain a pretreatment test board;
step S4, using the pre-treated test board as a cathode and a phosphorus-containing copper board as an anode, completing electroplating in the electroplating solution,
wherein, the novel electro-coppering additive is benzethonium chloride.
2. The use of the novel electro-coppering additive in an electro-coppering process according to claim 1,
wherein the novel electro-coppering additive is used in an electro-coppering process as a leveler.
3. The use of a novel electrolytic copper plating additive according to claim 1 in an electrolytic copper plating process,
wherein the concentration of the copper sulfate pentahydrate in the electroplating solution in the step S1 is 100-300g/L,
the concentration of the sulfuric acid is 40-70g/L,
the concentration of the chloride ions is 30-80mg/L,
the concentration of the SPS is 1-10ppm,
the concentration of the PEG-6000 is 100-300ppm,
the concentration of the novel electro-coppering additive is 1-15 ppm.
4. The use of a novel electrolytic copper plating additive according to claim 1 in an electrolytic copper plating process,
wherein, the aperture of the blind hole of the test board in step S2 is 100-150 μm, and the depth of the blind hole is 50-100 μm.
5. The use of a novel electrolytic copper plating additive according to claim 1 in an electrolytic copper plating process,
wherein the mass fraction of phosphorus in the phosphorus-containing copper plate in step S4 is 0.04-0.065%.
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| CN202210816080.2A CN114959810A (en) | 2022-07-12 | 2022-07-12 | Novel electro-coppering additive and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016040077A1 (en) * | 2014-09-14 | 2016-03-17 | Entergris, Inc. | Cobalt deposition selectivity on copper and dielectrics |
| JP2018021249A (en) * | 2016-07-25 | 2018-02-08 | 住友金属鉱山株式会社 | Plating solution, and method for producing plating film |
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2022
- 2022-07-12 CN CN202210816080.2A patent/CN114959810A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016040077A1 (en) * | 2014-09-14 | 2016-03-17 | Entergris, Inc. | Cobalt deposition selectivity on copper and dielectrics |
| JP2018021249A (en) * | 2016-07-25 | 2018-02-08 | 住友金属鉱山株式会社 | Plating solution, and method for producing plating film |
Non-Patent Citations (1)
| Title |
|---|
| YACHAO MENG ET AL.: "Benzyl-containing quaternary ammonium salt as a new leveler for microvia copper electroplating", 1. ELECTROCHIMICA ACTA, vol. 429, pages 1 - 9 * |
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