Control of Accumulation of Cu(I) in Copper Sulfate Electroplating Plating Solution

Koga, Toshiaki; Hirakawa, Chieko; Sakata, Yoshitaro; Noma, Hiroaki; Nonaka, Kazuhiro; Terasaki, Nao

doi:10.1149/07535.0015ecst

Cited by 8 publications

(9 citation statements)

References 7 publications

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“…Oxygen, once incorporated into the TE material, is known to deteriorate the materials power factor PF = S 2 σ. [ 39 ] Since the physically dissolved O 2 can be easily integrated into the electrochemically deposited material, [ 40 ] its replacement by N 2 helps to improve the electrical transport properties. [ 41 ] The electrolytes were hence bubbled with N 2 for 20 min so that the physically dissolved O 2 gas within the electrolytes would be replaced by N 2 gas.…”

Section: Resultsmentioning

confidence: 99%

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Dutt

Deng

et al. 2022

Adv Elect Materials

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any moving parts and are thus maintenance free, and also environmentfriendly. [1][2][3][4] They are used for the thermal management of parts of electric circuits [5] or optoelectronic devices, [6] cooling of power electronics, [7] powering devices for the internet-of-things, [8] and body-powered wearable electronics. [9][10][11] With increased reliability and accurate temperature control, they could also be effective replacements for macroscopic thermoelectric devices (TEDs) in medical applications, [12][13][14] for example DNA replication [15] or heating and cooling experiments for treating lowgrade tissue injuries. [16] Early μTEDs were fabricated by J.-P. Fleurial and co-workers. [17] During the past two decades, as the approaches to fabrication have evolved continuously, so has the performance of μTEDs. [1,2,[18][19][20] In 2003, Snyder et al. fabricated a cross plane μTED using electrochemical deposition, which showed a maximum cooling of 2 K at 110 mA. [2] μTEDs based on superlattice materials were later fabricated but were not characterized as coolers. [21] In 2007, Huang et al. fabricated a device using MEMS technology in combination with electroplating and reported a maximum cooling of Micro-thermoelectric devices (μTEDs) are used for bio-medical applications, powering internet-of-things devices, and thermal management. For such applications, μTEDs need to have a robust packaging so that the devices can be brought in direct thermal contact with the target heat sink and source. The packaging technology developed for macroscopic modules needs improvement as it cannot be applied to μTEDs due to a large thermal resistance between the capping material and the device which deteriorates its performance. In this work, μTEDs with high net cooling temperature are fabricated by optimizing the contact resistance and device design combined with a novel packaging technique that is fully compatible with on-chip integration. The simulations and experiments demonstrate that the additional thermal loss caused by the packaging leads to an only marginal decrease in the net cooling temperature. The devices achieve a high net cooling temperature of 10.8 K without packaging and 9.6 K with packaging at room temperature. The packaging only slightly increases the thermal response time of the devices, which also shows an extremely high reliability of over 85 million cooling cycles. This simple packaging technique together with robust device performance is a step toward wide-spread application of μTEDs.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/aelm.202101042.

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Section: Resultsmentioning

confidence: 99%

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Dutt

Deng

et al. 2022

Adv Elect Materials

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“…In the injection method, the plating solution was injected into a buffer solution through a hole in the upper lid during the time-resolved absorbance measurement of the buffer as a baseline. 13 The reaction of BCS with Cu(I) can be divided into three components: (1) the instantaneous component of the time constant, which requires less than 1 s, A0; (2) a fast component, which is completed within a few seconds, AS; and (3) components having large time constants that are slower than a few minutes, AL. Assuming that the reaction of BCS with Cu(I) is a first order reaction with respect to the Cu(I) concentration, we obtained following reaction kinetics of the absorbance, At.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Formation and Accumulation of Cu(I) in Copper Sulfate Electroplating Solution

Koga

Nonaka

Sakata

et al. 2018

J. Electrochem. Soc.

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The formation and accumulation of Cu(I) in copper sulfate electroplating solutions are discussed. Using electrolysis, the accumulation of Cu(I) in the plating solutions was also confirmed. The accumulation rate and amount depend on the current density and electrolysis time and the dissolved gases. Cu(I) is present in the aqueous solution as a complex with polyethylene glycol and is gradually consumed by oxidation or disproportionation reactions. In the plating solutions of nanobubbled water, the formation and accumulation rate of Cu(I) was different depending on the dissolved gas species. Our results indicate the possibility of controlling the Cu (I) With the increase in the density of printed circuit boards and the development of through-silicon via (TSV) plating technology, the management of the plating solution during the manufacturing process is crucial to maintain the quality of the product. In copper sulfate electroplating, monovalent copper ions (cuprous ion: Cu(I)) have been identified as one of the main causes of low quality plating such as high roughness and a dull finish on the copper plated surface. On the other hand, it has also been suggested that the formation of stable Cu(I)-complexes is a key process in bottom-up via filling. There have been some studies concerning the behavior and roles of Cu(I) in the plating process; 1-6 however, the analysis of the aqueous solutions used in the plating process has been insufficient. Therefore, accurate measurement of the Cu(I) concentrations in the plating process is required. However, it is challenging to measure and monitor the Cu(I) concentration in the electroplating process because of the instability of Cu(I) in solution and its consequent rapid oxidation. In fact, although there is a large amount of Cu(I) in the plating solution used on electroplating production lines, there is insufficient knowledge concerning the structures of Cu(I)-containing compounds in the plating solutions.The disodium salt of bathocuproinedisulfonic acid (BCS) can be used to quantify the Cu(I) concentration in aqueous solutions. [7][8][9] We have succeeded in optically analyzing the Cu(I) contained in plating solutions by monitoring the absorption of a chelate of Cu(I) with BCS.10-13 Here, we report the formation and accumulation of Cu(I) in copper sulfate electroplating solutions and discuss the relationship of the Cu(I) activity to the electrolysis conditions, such as current density, time, and dissolved gases, based on experiment. These results are important for the control of processing factors such as the concentrations of the Cu(I)-containing compounds in the plating solutions in industrial plating lines. ExperimentalBCS was used for the stable detection of Cu(I) ion in aqueous solution, and its chemical formula is shown in Figure 1. Two molecules of BCS coordinate to one Cu(I) ion to form 1:2 complexes that absorbs visible light at wavelengths between 400 and 550 nm. However, this absorption peak does not appear in the reaction with Cu(II). Therefore, the Cu(I) concent...

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“…30) Cu(I) of about 1 mmol=L is contained in the electrolysis-treated solution, and since it is diluted 100 times for measurement, the sample eventually contains 10 −6 mol=L Cu(I). 21) In the absorption spectrum [Fig. 3(a)], no difference in spectrum can be confirmed between the new solution and the electrolysis solution, and it is regarded as being lower than the detection limit.…”

Section: Resultsmentioning

confidence: 99%

“…Electrolysis was carried out at a current density of 62.5 mA=cm 2 . 21,22) Absorbance was measured with JASCO V-630, and fluorescence measurement was performed with JASCO FR-8200 or Hamamatsu Photonics FLS920S at room temperature.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…[16][17][18] We have succeeded in optically analyzing Cu(I) contained in plating solutions by monitoring the absorption of a chelate of Cu(I) with BCS. [19][20][21][22][23][24][25][26][27][28] On the basis of our method, it was shown that the Cu(I) concentration in a plating solution can be easily determined and that the holding structure of Cu(I) can also be analyzed. This information makes it possible to predict the roughness of the surface structure by electrodeposition.…”

Section: Introductionmentioning

confidence: 99%

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Quenching characteristics of bathocuproinedisulfonic acid, disodium salt in aqueous solution and copper sulfate plating solution

Koga

Hirakawa

Takeshita

et al. 2018

Jpn. J. Appl. Phys.

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Bathocuproinedisulfonic acid, disodium salt (BCS) is generally used to detect Cu(I) through a color reaction. We newly found BCS fluorescence in the visible blue region in an aqueous solution. However, the fluorescence mechanism of BCS is not well known, so we should investigate its fundamental information. We confirmed that the characteristics of fluorescence are highly dependent on the molecular concentration and solvent properties. In particular, owing to the presence of the copper compound, the fluorescence intensity extremely decreases. By fluorescence quenching, we observed that a copper compound concentration of 10 %6 mol/L or less could easily be measured in an aqueous solution. We also observed BCS fluorescence in copper sulfate plating solution and the possibility of detecting monovalent copper by fluorescence reabsorption.

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Control of Accumulation of Cu(I) in Copper Sulfate Electroplating Plating Solution

Cited by 8 publications

References 7 publications

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Electrochemical Formation and Accumulation of Cu(I) in Copper Sulfate Electroplating Solution

Quenching characteristics of bathocuproinedisulfonic acid, disodium salt in aqueous solution and copper sulfate plating solution

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