Electrodeposición de Cobre para La Fabricación de Metamateriales Tridimensionales

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Article
Electrodeposition of copper for three-dimensional metamaterial fabrication
Shendu Yang, Zachary Thacker, Evan Allison, Megan Bennett, Nicholas Cole, and Patrick Pinhero
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b04721 • Publication Date (Web): 24 Oct 2017
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Page 1 of 30 ACS Applied Materials & Interfaces
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8 Electrodeposition of copper for
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three-dimensional metamaterial fabrication
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16 Shendu Yang, Zachary Thacker, Evan Allison, Megan Bennett, Nicholas Cole, and
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18 Patrick J. Pinhero∗
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21 Department of Chemical Engineering, University of Missouri, Columbia, MO 65211, USA
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24 E-mail: pinherop@missouri.edu
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26 Phone: +1(573)882-7319
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30 Abstract
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32 Metamaterials typically consist of metallic and dielectric repeating structures. Elec-
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34 trodeposition of copper is the preferred approach to fabricating the metallic part of the
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36 metamaterials of interest in this study. The highly-variant topography requires chemical
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38 additives, like chloride ions, 3-mercapto-1-propanesulfonic acid (MPSA), polyethylene
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40 glycol (PEG) and polyvinylpyrrolidone (PVP) to enhance bottom-up superfilling while
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42 maintaining terrace flatness. This study focuses on both experimental and computa-
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44 tional investigations of the degradation potential of the additives and their adsorption
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46 mechanism in a highly-acidic copper electrolyte in order to optimally parameterize the
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48 copper electrodeposition process. Results show Cl-MPSA-PEG-PVP additives perform
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50 well, but substitution of PVP with Janus Green B provides better terrace leveling.
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52 Additionally, NMR data show a quick and complete conversion of MPSA to bis(3-
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sulfopropyl) disulfide (SPS) in the acidic copper bath. Finally, FEM simulations further
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show that the accelerator species may initially accumulate and be transported vertically
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57 until overplating, whereby they are transported laterally.
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Keywords
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7 Electrodeposition, Metamaterial, Additives, Degradation, Copper
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1 Introduction
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14 Metamaterials (MMs), as a class of artificial material, possessing a physical property to
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16 manipulate electromagnetic waves by absorbing, bending, or suppressing waves due to their
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repeating sub-wavelength features. In the past decade, metamaterials have been demon-
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strated in almost every technologically relevant spectral range, from radio, 1 microwave, 2
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mm-Wave, 3 THz, 4 MIR 5 and NIR 6 to the near optical. 7 In the present study, electrodepo-
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25 sition of Cu was utilized to create MMs and investigated for their potential in an energy
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27 harvesting device. This device, seen in Fig. 1, consists of a MM coupled to a rectification
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29 nano-antenna (rectenna). The purpose of the MM is to convert thermal energy into surface
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31 plasmons that are absorbed and rectified by a rectenna. 8 The spatial dimensions of each
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33 functional unit on the device is fabricated relative to the wavelength of EM radiation to be
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35 harvested. The target wavelength of the current device was chosen as a compromise between
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37 energy density and diode operating efficiency. The efficiency of the current diode design de-
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39 creases sharply after 1 THz. 9 Besides, the rectenna efficiency is low at high frequencies while
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41 the thermal radiation intensity is low at low frequencies. 8 So in this work, the geometry of
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43 the device was optimized for operation at 1 THz.
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levelers 16–21 have been used as additives for the electrodeposition of copper. In this work,
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6 polyethylene glycol 6000 (PEG) is the carrier and wetting agent. 3-mercaptopropanesulfonic
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8 acid (MPSA) is the accelerating agent for acid copper deposition. Among the three additives
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10 used in electrodeposition, MPSA is the most unstable because thiols (S-H) oxidize and form
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12 disulfides (S-S) in the presence of Cu2+ , 22,23 as shown in chemical reaction 1:
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2 MPSA + 2 Cu2+ −−→ SPS + 2 Cu+ + 2 H+ (1)
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19 Levelers are typically molecules having quaternary ammonium cations such as Janus Green B
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21 (JGB) 24 and Diazine Black (DB), 19 or having amine functionality, such as polyvinylpyrroli-
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23 done (PVP). 25 Levelers also act as secondary suppressers that preferentially adsorb on the
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25 peaks of the substrate and inhibit electrodeposition. Some previous work has shown that
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the best leveling effect of PVP can be obtained when the leveler molecular weight is between
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29,000 and 55,000 g/mol. The optimal concentration of PVP is 10 ppm and the leveler
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dose not strongly impact bottom-up fill. 26 On one hand, since a copper atom has two free
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34 electrons at the outermost shell, they can move freely along the lattices when an electric
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36 field is applied. The higher the electric field is, the more empty s bands can be formed.
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38 Therefore, amines can adsorb onto the substrate, especially on the high current density ar-
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40 eas by donating their lone pair electrons to the unoccupied s bands. 27 On the other hand,
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42 as the only non-metallic cation with a permanent positive charge, quaternary ammonium
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44 can also preferentially adsorb onto the high current density area, the convex area, and block
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46 electrodeposition by electrostatic attraction, resulting in a leveling effect on the cathode.
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48 In our study, the surface of the samples to be electroplated have tall structures that
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50 affect the natural distribution of the electric field. Without additives, the electric field is
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52 expected to converge at the top of these structures and diverge at the bottom, as shown in
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54 Fig. 1(c). As the substrate is immersed into the electrolyte, PEG adsorbs at the surface
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56 forming a monolayer to inhibit the fast and disordered electrodeposition of metal. Because
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most of the metal surface is hydrophobic, PEG is able to wet the cathode surface thoroughly
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6 ensuring good contact with the electrolyte. 28,29 The anion of the accelerator additive, MPSA,
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8 preferentially locates at areas with the lowest natural current density. In the current study,
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10 these areas are the sections of the samples with concave shaped features. As an anion, to the
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12 accelerator forms a complex with the copper ion which effectively brings the copper to the
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14 lower sections of the features. After electron exchange, copper can be electrodeposited onto
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16 the bottom first, causing superfilling of copper to these concave areas. However, overplating
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18 above the superfilled area caused by the accumulation of accelerators is commonly observed.
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20 To mitigate this effect, a leveler additive is used. The leveler preferentially adsorb to ar-
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22 eas with highest current density through amine or quaternary ammonium functionalities,
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24 effectively inhibiting deposition and maintaining terrace flatness.
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26 For electrodeposition, the most important driving force comes from the external potential
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28 which can provide large amounts of electrons to the working electrode and maintain the
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30 electrodeposition process. The thickness of deposits can be predicted and calculated by
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32 Faraday’s law:
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34 ε×I m
= (2)
35 n×F MW × t
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37 where ε is the efficiency, I is the observed current, m is the mass of deposits, n is the number
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39 of electrons, F is Faraday’s constant, MW is the molecular weight, and t is the deposition
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41 time.
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46 2 Experimental
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2.1 Materials and experimental setup
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52 Cupric sulfate pentahydrate (CuSO4 · 5H2 O), sulfuric acid (H2 SO4 ), sodium 3-mercapto-1-
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54 propanesulfonate (MPSA, NaSO3 (CH2 )3 SH), and hydrochloric acid (HCl) were purchased
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56 from Fisher Scientific. Polyethylene glycol (PEG, H(OCH2 CH2 )n OH, MW: 6000), polyvinyl-
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pyrrolidone (PVP, (C6 H9 NO)n , average MW: 40,000) and Janus Green B (JGB, C30 H31 CIN6 )
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6 were purchased from Alfa Aesar. All the experiments were completed using DI water (18.2
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8 MΩ). In our study, the basic bath for the electrolyte consists of 0.25 M CuSO4 and 1.8
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10 M H2 SO4 ; the additives used are HCl, MPSA, PEG, PVP and JGB. Two different kinds
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12 of substrates were used as working electrodes for the electrochemical experiment: one is
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14 blanket Si/SiO2 wafers and the other is metamaterial substrates containing SU-8 pillars as
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16 shown in Fig. 1(b). The Ag/AgCl electrode was used as a reference electrode for all of the
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18 measurements. A phosphorous copper anode (purchased from Kocour) was used as counter
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20 electrode.
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22 All the electrochemical experiments were carried out in a conventional three-electrode cell.
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24 In order to make the substrate conductive, all the substrates were thermally evaporated by
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26 20nm Cr as an adhesion layer, followed by a 200 nm copper seed layer. Then, the substrate
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28 was masked with nail polish and only 1 cm2 was exposed as the deposition area. This was
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30 done because the interface of the substrate between the electrolyte and the air is likely to
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32 become corroded, preventing the deposition from continuing. The top conductive area of the
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34 wafer was attached by copper tape in order to connect the alligator clip from pontentiostat.
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36 The electrodeposition was carried out under the mode of controlled potential coulometry or
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38 controlled current mode at room temperature. 400 mL of electrolyte was placed in a beaker
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with a custom-made 3D-printed cover on the top. There were three holes on the cover,
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with 2 cm spacing between each hole in case of a big IR drop, also allowing for consistent
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positioning of the three electrodes for each experiment. No agitation was performed during
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2.2 i-E characterization
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53 Cyclic voltammetry (CV) experiments were carried out using a Gamry (PCI4/300) poten-
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55 tiostat to examine the relationship between current and potential during electrodeposition
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57 and reveals the potential region for reduction and oxidation of different species.
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2.3 Surface topography
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6 An optical microscope (Nicolet 0049-005) was used to characterize the topography of the
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8 samples received from the electrodeposition process in order to analyze the effects and inter-
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10 play of additives. An optical profilometer (Vecco NT 9109) was used to measure the surface
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12 topography, the RMS surface roughness and to acquire 3D images.
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16 2.4 Chemical analysis
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19 H-NMR (300MHz and 600 MHz, Bruker) was used to investigate the chemical structures of
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21 the additives and the changes in their concentrations. The 1 H-NMR samples were prepared
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23 via the following steps: 30 (1) 8M KOH solution was used to neutralize the acid solution; (2)
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25 pure ethanol was added in a solution:ethanol ratio of 2:3 to precipitate the inorganic com-
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27 pounds; (3) the resulting solution was filtered and evaporated to remove the precipitate; (4)
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29 the residue was dissolved in deuterium oxide(D2 O) as the solvent for the NMR measurement.
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the sequence of the reduction reaction is: Cu+ + e- → Cu(s) (first), Cu2+ + 2e- → Cu (s)
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6 (second), Cu2+ + e- → Cu+ (third). Since the predominant valence state of Cu in the
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8 electrolyte is Cu2+ , the major reduction reaction is Cu2+ + 2e- → Cu(s), whose reduction
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10 peak is at -0.37 V. The standard reduction potential for Cu(II)/Cu(0) couple, E0 , is 0.12 V
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12 vs Ag/AgCl as shown in Table 1. The onset of Cu reduction on the working electrode begins
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Fig. 3(top) shows that the electrodeposition profiles under different controlled potentials
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8 reaching a steady state current density. In Fig. 3, panel (c) shows a fine, smooth and bright
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10 mirror-like copper surface when the applied potential was -0.08 V with a 14 mA/cm2 steady
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12 state current density. However, lower or higher voltages give rise to rough and dull copper
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14 films. As we know, the cyclic voltammogram (Fig. 2) can provide a general potential and
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16 current density range for the electrodeposition of desired species in the electrolyte. The
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18 current density during electrodeposition has a large effect on the surface roughness and
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20 grain structure of the film. In general, the larger the current density the finer the grain
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22 refinement. 31 However, an increase in the current density results in a higher overpotential
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24 that increases the nucleation rate, thus resulting in a higher degree of roughness. Therefore,
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26 there is an optimal current density for a typical electrodeposition of metal. From panel a
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28 to c, the more negative potential, and therefore higher current density, give rise to a finer
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30 surface. As the potential and current density is increased further clusters begin to form due
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As other work stated, in a Cl-MPSA-PEG-PVP additive system, MPSA is the most
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6 unstable component since in the presence of Cu2+ , thiols (S-H) can be easily oxidized result-
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8 ing in the formation of disulfides and this process is reversible. 30,32 In the present studies,
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10 H-NMR was used to characterize the degradation and the concentration change of the ad-
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12 ditives. As shown in the chemical structures in Fig. 7, both MPSA and SPS have three
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14 different kinds of protons with the only difference that SPS is a dimer of MPSA. As shown
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16 in Fig. 7 (a), the spectra of MPSA aged in the NMR solvent D2 O for one hour, two days
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18 and three days are the same as that of fresh MPSA, having three peaks at 2.07 ppm (M1),
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20 2.71 ppm (M2), and 3.07 ppm (M3), which indicates MPSA is stable at ambient condition
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22 in water. Fig. 7(b) is the 1 H-NMR spectra of the powder extracted from fresh and aged
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24 solution consisting of MPSA and acid copper bath. It is apparent that all four spectra
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26 are the same, which means the compound in the solution remains the same in both fresh
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28 and aged solution. Besides, in Fig. 7(b), the chemical shift of the peaks S1 (2.18 ppm), S2
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30 (2.89ppm), and S3 (3.06ppm) agrees with the three characteristic peaks of pure SPS that can
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32 be found in the work of others, 30 indicating that MPSA converts to SPS in acid copper solu-
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34 tion immediately and SPS would not convert back to MPSA during aging. In contrast with
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36 others’ work, the present data shows that this conversion process is not reversible, for which
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38 two potential causes are likely. First, it may be caused by different experimental conditions
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such as low PH and the concentration of copper ions. Second, it should be noted that, the
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extraction process of MPSA in an acid copper bath involves neutralization, extraction and
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evaporation; however, this potential cause was ruled out (shown in Section 2 in Supporting
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47 Information). So the acid copper bath is likely the reason to drive MPSA to SPS and this
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49 process is irreversible in the present experimental conditions.
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the three peaks are 1: 0.63: 0.67 for the fresh electrolyte, and 1: 0.35: 0.36 for the used
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6 electrolyte, indicating that the degradation of the accelerators. It is conceivable that in the
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8 presence of three more additives, more interactions take place between additives, especially
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10 since the accelerators form complexes with copper ions and other additives, which has also
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12 been shown by mass spectrometry conducted by other researchers. 23,33 Additionally, there
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14 is a single peak at 2.4 ppm which aligns with the characteristic peak of H-C-S, indicating
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16 MPSA and SPS would break down into segments during aging and electrodeposition.
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20 3.4 Finite element modeling
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Two-dimentional FEM of differing electrodeposition conditions, including variance of the
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25 following: aspect ratio of the features, the size of the electrodes, deposition time, and the
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27 distance between the cathode and anode, have been investigated. The basic settings can be
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is identical across the horizontal direction as shown in Fig. 9 (c). Besides, seen in Fig. 9 (d)
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6 the concentration of the copper ions remains the same as the initial concentration of the bulk
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8 electrolyte except that the concentration on the anode is higher than the bulk concentration
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10 because the consumable copper anode would lose electrons and generate copper ions while
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12 on the cathode the concentration is lower than the bulk due to the reduction of the copper
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14 ions to accomplish electrodeposition. The overall concentration on the cathode is uniform
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16 except at the edges, which is the reason for the non-uniform electrodeposition profile on the
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source of copper ions. Besides, it is better that the cathode and anode are close to each
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6 other to avoid a large IR drop. In order to make the simulation as similar as the real
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8 experiment, the length of the cathode was changed to 1 cm, one-third of the anode, and the
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10 distance between the two electrodes was changed to 1 cm, as shown in Fig. 10. The profile
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12 of three hours electrodeposition of copper dose not show a flat surface and some sharp peaks
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14 appear close to the boundaries ( Fig. 10 (b)), but due to the presence of additives, in real
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16 electrodeposition the copper film is even across the wafer (shown in Fig. S1 in the Supporting
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18 Information). The comparison between the simulation and the experimental results prove
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20 again the importance of the additives. The electrolyte potential of electrodeposition of
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22 10 minutes and three hours is shown in Fig. 10 and it is clear that after three hours
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24 electrodeposition the potential between the cathode and anode is smaller than that of 10
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26 minutes electrodeposition, which means the overpotential increases with the increase of the
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28 electrodeposition time. In addition, the concentration of copper ions in the electrolyte is
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30 the same as the original solution while after three hours electrodeposition, the concentration
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32 gradient appears and the concentration is highest on the anode while lowest on the cathode.
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30 minutes and the color shows the surface concentration of accelerator. No voids are seen
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6 in the trenches indicating the success of superfilling, however, overplating appears above the
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8 superfilled area and bumps were formed, which is a common phenomenon for electrodeposi-
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10 tion with the addition of accelerators. Besides, the lateral diameter of the bumps decreases
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12 as the aspect ratio increases and the concentration of accelerators on the overplated area
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14 is higher than that of the flat area, which is caused by the accumulation of accelerators in
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16 the trenches during the superfilling process. In addition, from the highest to lowest aspect
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18 ratio, the highest concentration area of accelerator that is represented by red color moves
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20 from the top to the shoulder of the bumps, which means after overplating takes place, the
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22 highest accelerating changes from the vertical direction to the lateral direction.
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29 4 Conclusion
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32 A series of experiments was conducted involving the electrodeposition of copper for the
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34 fabrication of metamaterials under different conditions. In our work, Cl-MPSA-PEG-PVP
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36 additives can interplay with each other well and they are effective in both bottom-up su-
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38 perfill and leveling for electrodeposition of copper for metamaterials. Compared to PVP,
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40 another leveler Janus Green B exhibits a better leveling effect. NMR and FTIR data show
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42 that even without current flow the accelerator MPSA converts to SPS in acid copper bath
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44 immediately and this process is not reversible in our experimental conditions. When there
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46 are Cl-MPSA-PEG-PVP four additives in the acid copper solution, accelerators interact with
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48 other additives and form complexes resulting in the breakdown of accelerators and the de-
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50 crease of the concentration; with current flow, this degradation process can be enhanced. We
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52 have also successfully conducted a series of 2D COMSOL simulations of electrodeposition
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54 and investigated the mechanism of basic electrodeposition, the superfilling of features and
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56 adsorption of accelerators. The COMSOL simulation shows that additives are very impor-
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tant to get a uniform and bright deposits and it illustrates that the accelerators accumulate
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6 and move vertically in the trench first, after overplating happens, accelerators move along
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8 the lateral direction.
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13
Acknowledgement
14
15 The authors thank RedWave Energy, Inc. and the US DOE-ARPA-E for funding this work.
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17 We also wish to thank the MU NMR facility and the MU Center of Nano/Micro Systems
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19
and Nanotechnology.
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22
23
24 Supporting Information Available
25
26
27 Discussion of the degradation of additives; surface topography characterization; resistivity
28
29 measurement; chemical analysis (1 H-NMR and FTIR) of additives. This material is avail-
30
31 able free of charge via the Internet at http://pubs.acs.org/.
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33
34
35
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Electrodeposición de Cobre para La Fabricación de Metamateriales Tridimensionales

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