Influence of Aromatic Functionality on Quaternary Ammonium Levelers for Cu Plating

Hatch, Jeremy J.; Willey, Mark J.; Gewirth, Andrew A.

doi:10.1149/1.3575636

Cited by 29 publications

(33 citation statements)

References 65 publications

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“…21 The decreased E value of compound 1b is probably caused by the rigid phenyl ring moiety which may also hinder the approach of the quaternary nitrogen to the electrode surface to weaken the additive-substrate interaction. 12 Though CTAB possesses a longer alkyl chain (C 16 ), it exhibits a much lower suppressing capability compared to the four compounds. The main difference between the compounds and CTAB is that the compounds have a functional group (a urea-containing group) in their molecular structure whereas CTAB does not.…”

Section: Resultsmentioning

confidence: 98%

“…Hatch and co-workers showed the influence of aromatic functionality on quaternary ammonium levelers for copper plating. 12 Dow and co-workers determined the property of microvia filling by copper electroplating using different levelers and demonstrated the influence of molecular structure. 18 Takeuchi et al reported the relationship of additive function and basicity of amino group at side chain in diallyamine-type copolymer.…”

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confidence: 99%

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Influence of the Hydrophobic Groups on Quaternary Ammonium Additives for Copper Electrodeposition

Wang

Hua

Yin

et al. 2014

J. Electrochem. Soc.

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A series of quaternary ammonium compounds with different hydrophobic groups as spacers were synthesized. The influence of the hydrophobic groups on the additives for copper electrodeposition was investigated using a galvanostatic measurement on a RDE electrode. The increase of the length of the alkyl chain within the compounds enhances the suppressing capability. The introduction of a hydroxyl group or a phenyl ring into the hydrophobic groups in the molecular structures reduces the suppressing capacity. The results obtained from SEM measurements indicate that the presence of the quaternary ammonium compounds in the electrolytes may produce regular and relative leveling morphologies of copper deposits. The via-filling experiments without SPS exhibit that an almost complete filling was achieved for compound 1d (C 6 alkyl chain as a hydrophobic group), whereas a bad filling was obtained for compound 1a (C 3 -OH chain as a hydrophobic group). With SPS, the vias were perfectly filled both for compound 1a and 1d. However, the initial increment of growth was still conformal for the compound 1a. These results indicate the influence of the hydrophobic groups of the quaternary ammonium compounds on the filling behaviors and they are in agreement with the galvanostatic measurements at different electrode rotation speeds.Copper electrodeposition from acidic electrolytes has been widely used in electronic industry for both printed circuit board (PCB) and integrated circuit (IC) applications. The composition of the acidic electrolyte mainly contains cupric ion, acid and additives. Sulfuric acid or methanesulfonic acid (MSA) 1,2 is usually used as a supporting electrolyte. The presence of the additives in the electrolytes results in the improvement of the deposit properties, such as morphology, brightness, and grain refinement. Typically, the additives can be three (accelerator, suppressor, leveler) components for the filling of trenches and vias. 3,4 However, both suppressor and leveler can be taken as inhibiting additives due to their suppressing effect for copper deposition rate. 5 Because of the presence of convection-dependent adsorption (CDA), 5,6 the filling performance for via metallization can be improved by a leveler and the copper via-filling can be performed with a single organic additive. [7][8][9] Levelers are positively charged molecules 10 that produce the deposits topographical homogeneities in electrodeposition. The commonly used levelers in copper electrodeposition are nitrogencontaining or quaternary ammonium compounds including highmolecular weight molecules (e.g., JGB), 11 quaternary ammonium surfactants 12,13 and polymers. 14,15 Recently, a number of new quaternary ammonium compounds have been used as levelers such as Nbutyl-methyl piperidinium bromide, 16 diallylamine-type copolymer 7,8 and branched quaternary ammonium surfactant. 17 Quaternary ammonium compounds contain the quaternary nitrogen atoms in their backbones as the charged species and they also possess the attached hydrophilic or hydrophobic ...

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Section: Resultsmentioning

confidence: 98%

mentioning

confidence: 99%

Influence of the Hydrophobic Groups on Quaternary Ammonium Additives for Copper Electrodeposition

Wang

Hua

Yin

et al. 2014

J. Electrochem. Soc.

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“…In order to obtain a well surface morphology and crystallization copper layer, a pack of organic additives is an adopted method for the metallization of TH with low cost and easy control . Actually, the time dependent interplaying additives of Cu electrodeposition has been explored for decades, depending on their phenomenological impact usually distinguishing so‐called suppressor, accelerator and leveler …”

Section: Introductionmentioning

confidence: 99%

Fatty Acid Quaternary Ammonium Surfactants Based on Renewable Resources as a Leveler for Copper Electroplating

Zhao

et al. 2019

ChemElectroChem

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A series of fatty acid quaternary ammonium surfactants (FAQAS 1 a–1 f) derived from renewable resource of fatty acid have been rationally designed and investigated as levelers applied in copper electroplating. Surface tension and contact angle indicated the FAQAS's surfactivity and wettability were closely related to the length of hydrophobic chains. FAQAS 1 a–1 f displayed the capability to inhibit the copper deposition in CV tests and their inhibiting abilities agreed with the order of their surfactivity and wettability. Compound 1 e showed the best inhibition capability, and was comprehensively tested by field‐emission scanning electron microscopy (FE‐SEM), X‐ray photoelectron spectroscopy (XPS) and other electrochemical measurements. The strong inhibition ability of compound 1 e on copper electrodeposition could be attributed to its fast and strong absorption of 1 e on the cathode surface. Moreover, galvanostatic measurements (GMs) indicated that compound 1 e not only cause polarization but also has stable synergistic effects with other additives to form a convection dependent competitive adsorption layer. In addition, through‐hole (TH) electroplating experiments verified that uniform TH could be obtained on copper electrodeposition using the bath containing compound 1 e. This work may shed some light on the pratical application of surfactants as effective leveler in acid copper electroplating.

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“…Hence, the cation could reach the cathode surface easily and inhibit the copper electrodeposition under the electric field, particularly the protrusion with high current density during electroplating. 20,21 The quaternary ammonium salts, being proved as effective levelling agent, 20,[22][23][24] have been used extensively in copper electroplating industry. However polyquaternium, a strong cationic polymer, having good water solubility, can be found in particular application such as in conditioners, shampoo and hair mousse, and has been rarely researched as a kind of leveler applied in copper electroplating.…”

Section: Introductionmentioning

confidence: 99%

Polyquaternium-2: A New Levelling Agent for Copper Electroplating from Acidic Sulphate Bath

Chen

Wang

et al. 2016

Electrochemistry

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Poly[bis(2-chloroethyl)ether-alt-1,3-bis [3-(dimethylamino)propyl]urea] (Polyquaternium-2) was employed as a leveler in the through-hole (TH) electroplating experiments from an acidic sulphate bath. The interaction between Polyquaternium-2 and copper surface was investigated using Field Emission Scanning Electronic Microscope (FE-SEM) and X-ray Photoelectron Spectra (XPS). The electrochemical behavior of Polyquaternium-2 and its interaction with other additives, such as a suppressor and an accelerator were characterized using rotating disk electrode. Polyquaternium-2 could absorb on copper surface to form an adsorption layer and inhibit the copper electrodeposition. As shown in the TH electroplating experiments, a copper deposit with uniform thickness was obtained when 0.17 µmol/L Polyquaternium-2 was added. The addition of Polyquaternium-2 could also increase the cathodic polarization, which is attributed to the adsorption of Polyquaternium-2 on the cathode in the process of TH electroplating. The results indicate that Polyquaternium-2 is an effective leveler used for TH electroplating, having a good synergy with SPS, PEG and Cl − .

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Influence of Aromatic Functionality on Quaternary Ammonium Levelers for Cu Plating

Cited by 29 publications

References 65 publications

Influence of the Hydrophobic Groups on Quaternary Ammonium Additives for Copper Electrodeposition

Influence of the Hydrophobic Groups on Quaternary Ammonium Additives for Copper Electrodeposition

Fatty Acid Quaternary Ammonium Surfactants Based on Renewable Resources as a Leveler for Copper Electroplating

Polyquaternium-2: A New Levelling Agent for Copper Electroplating from Acidic Sulphate Bath

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