본 연구는 인쇄회로기판(PCB) 제조 시 에칭공정에서 발생되는 구리이온(Cu+2)을 고농도로 함유한 황산 폐에칭액을 NF 막분리법을 사용하여 에칭액 회수와 구리이온 처리를 효율적으로 수행하기 위한 NF 막여과 공정의 운전 조건을 설정하기 위한 기본 자료를 확보하는데 있다. 이를 위해 미국 Koch사의 SelRO MPS-34 4040 NF 막을 대상으로 구리이온을 고농도(5~25 g/L)로 함유한 모의 황산 폐에칭액의 회분식(dead-end) 나노여과 실험을 수행하여 투과 플럭스와 구리이온의 총괄 배제도를 측정하였다. 이 결과 황산용액에의 막 보관기간이 길수록, 황산용액의 pH가 낮을수록 황산에 의한 NF 막의 손상이 더 크게 발생하여 순수 투과 플러스가 증가하였다. 황산 폐에칭액의 투과 플럭스는 황산용액 내 구리이온의 농도가 증가할수록 막 표면에의 구리이온 농축(농도분극)의 증가에 따라 감소하였으며, 구리이온의 배제도는 구리이온의 농도가 높을수록, pH가 낮을수록, 황산용액 내의 막 보관기간이 길수록 낮아져 초기 37%에서 최소 15% 수준으로까지 감소하였다.

A simple thermal oxidation of Cu thin films deposited on planar substrates established a growth of vertically aligned copper oxide (CuO) nanorods. DC sputter-deposited Cu thin films with various thicknesses were oxidized in environments of various oxygen partial pressures to control the kinetics of oxidation. This is a method to synthesize vertically aligned CuO nanorods in a relatively shorter time and at a lower cost than those of other methods such as the popular hydrothermal synthesis. Also, this is a method that does not require a catalyst to synthesize CuO nanorods. The grown CuO nanorods had diameters of ~100 nm and lengths of 1~25μm. We examined the morphology of the synthesized CuO nanorods as a function of the thickness of the Cu films, the gas environment, the oxidation time, the oxidation temperature, the oxygen gas flow rate, etc. The parameters all influence the kinetics of the oxidation, and consequently, the volume expansion in the films. Patterned growth was also carried out to confirm the hypothesis of the CuO nanorod protrusion and growth mechanism. It was found that the compressive stress built up in the Cu film while oxygen molecules incorporated into the film drove CuO nanorods out of the film.

Recovery of copper powder from copper chloride solution used in leaching process was carried out using a cementation method. Cementation is a simple and economical process, necessitating less energy compared with other recovery methods. Cementation utilizes significant difference in standard reduction potential between copper and iron under standard condition. In the present research, Cementation process variables of temperature, time, and added amount of iron scraps were optimized by using design of experiment method and individual effects on yield and efficiency of copper powder recovery were investigated using bench-scale cementation reaction system. Copper powders thus obtained from cementation process were further characterized using various analytical tools such as XRF, SEM-EDS and laser diffraction and scattering methods. Cementation process necessitated further purification of recovered copper powders and centrifugal separation method was employed, which successfully yielded copper powders of more than 99.65% purity and average in size.

Recently, the demand for the miniaturization of package substrates has been increasing. Technical innovation has occurred to move package substrate manufacturing steps into CMP applications. Electroplated copper filled trenches on the substrate need to be planarized for multi-level wires of less than 10μm. This paper introduces a chemical mechanical planarization (CMP) process as a new package substrate manufacturing step. The purpose of this study is to investigate the effect of surfactant on the dishing and erosion of Cu patterns with the lines and spaces of around 10/10μm used for advanced package substrates. The use of a conventional Cu slurry without surfactant led to problems, including severe erosion of 0.58μm in Cu patterns smaller than 4/6μm and deep dishing of 4.2μm in Cu patterns larger than 14/16μm. However, experimental results showed that the friction force during Cu CMP changed to lower value, and that dishing and erosion became smaller simultaneously as the surfactant concentration became higher. Finally, it was possible to realize more globally planarized Cu patterns with erosion ranges of 0.22μm to 0.35μm and dishing ranges of 0.37μm to 0.69μm by using 3 wt% concentration of surfactant.

Single crystalline Cu nanowires with controlled diameters and aspect ratios have been synthesized using electrochemical deposition within confined nanochannels of a porous anodic aluminium oxide(AAO) template. The diameters of nano-sized cylindrical pores in AAO template were adjusted by controlling the anodization conditions. Cu nanowires with diameters of approximately 38, 99, 274 nm were synthesized by the electrodeposition using the AAO templates. The crystal structure, morphology and microstructure of the Cu nanowires were systematically investigated using XRD, FE-SEM, TEM and SAED. Investigation results revealed that the Cu nanowires had the controlled diameter, high aspect ratio and single crystalline nature.

In this study, electrolytic copper powders were consolidated by high-pressure torsion process (HPT) which is the most effective process to produce bulk ultrafine grained and nanocrystalline metallic materials among various severe plastic deformation processes. The bulk samples were manufactured by the HPT process at 2.5 GPa and 1/2, 1 and 10 turns. After 10 turns, full densification was achieved by high pressure with shear deformation and ultrafine grained structure (average grain size of 677 nm) was observed by electron backscatter diffraction and a scanning transmission electron microscope.

We investigated cleaning effects using NH4OH solution on the surface of Cu film. A 20 nm Cu film was deposited on Ti / p-Si (100) by sputter deposition and was exposed to air for growth of the native Cu oxide. In order to remove the Cu native oxide, an NH4OH cleaning process with and without TS-40A pre-treatment was carried out. After the NH4OH cleaning without TS-40A pretreatment, the sheet resistance Rs of the Cu film and the surface morphology changed slightly(δRs:~10mΩ/sq.). On the other hand, after NH4OH cleaning with TS-40A pretreatment, the Rs of the Cu film changed abruptly (δRs:till~700mΩ/sq.); in addition, cracks showed on the surface of the Cu film. According to XPS results, Si ingredient was detected on the surface of all Cu films pretreated with TS-40A. This Si ingredient(a kind of silicate) may result from the TS-40A solution, because sodium metasilicate is included in TS-40A as an alkaline degreasing agent. Finally, we found that the NH4OH cleaning process without pretreatment using an alkaline cleanser containing a silicate ingredient is more useful at removing Cu oxides on Cu film. In addition, we found that in the NH4OH cleaning process, an alkaline cleanser like Metex TS-40A, containing sodium metasilicate, can cause cracks on the surface of Cu film.

In an effort to overcome the problems which arise when fabricating high-aspect-ratio TSV(through silicon via), we performed experiments involving the void-free Cu filling of a TSV(10~20 μm in diameter with an aspect ratio of 5~7) by controlling the plating DC current density and the additive SPS concentration. Initially, the copper deposit growth mode in and around the trench and the TSV was estimated by the change in the plating DC current density. According to the variation of the plating current density, the deposition rate during Cu electroplating differed at the top and the bottom of the trench. Specifically, at a current density 2.5 mA/cm2, the deposition rate in the corner of the trench was lower than that at the top and on the bottom sides. From this result, we confirmed that a plating current density 2.5 mA/cm2 is very useful for void-free Cu filling of a TSV. In order to reduce the plating time, we attempted TSV Cu filling by controlling the accelerator SPS concentration at a plating current density of 2.5 mA/cm2. A TSV with a diameter 10 μm and an aspect ratio of 7 was filled completely with Cu plating material in 90 min at a current density 2.5 mA/cm2 with an addition of SPS at 50 mg/L. Finally, we found that TSV can be filled rapidly with plated Cu without voids by controlling the SPS concentration at the optimized plating current density.

In this work, powder metallurgy and severe plastic deformation by high-pressure torsion (HPT) approaches were combined to achieve both full density and grain refinement at the same time. Pure Cu powders were mixed with 5 and 10 vol% diamonds and consolidated into disc-shaped samples at room temperature by HPT at 1.25 GPa and 1 turn, resulting in ultrafine grained metallic matrices embedded with diamonds. Neither heating nor additional sintering was required with the HPT process so that in situ consolidation was successfully achieved at ambient temperature. Significantly refined grain structures of Cu metallic matrices with increasing diamond volume fractions were observed by electron backscatter diffraction (EBSD), which enhanced the microhardness of the Cu-diamond composites.

P/M coppers are subjected to the isothermal compression tests at the strain rate ranging from 0.01 to 10.0 and the temperature from 200 to . The processing map reveals the dynamic recrystallization (DRX) domain in the following temperature and strain rate ranges: and 0.01-10.0 , respectively. In the domain, the region at temperature of and strain rate of shows peak efficiency. From the kinetic analysis, the apparent activation energy in the DRX domain is 190.67 kJ/mol and it suggests that lattice self-diffusion is the rate controlling mechanism.

Ag spot-coated Cu nanopowders were synthesized by a hydrothermal-attachment method (HA) using oleic acid capped Ag hydrosol. Cu nano powders were synthesized by pulsed wire exploding method using 0.4 mm in diameter of Cu wire (purity 99.9%). Synthesized Cu nano powders are seen with comparatively spherical shape having range in 50 nm to 150 nm in diameter. The oleic acid capped Ag hydrosol was synthesized by the precipitation-redispersion method. Oleic acid capped Ag nano particles showed the narrow size distribution and their particle size were less than 20 nm in diameter. In the case of nano Ag-spot coated Cu powders, nanosized Ag particles were adhered in the copper surface by HAA method. The components of C, O and Ag were distributed on the surface of copper powder.

The microstructure and Cu diffusion barrier property of Ta-Si-N films for various Si and N compositions were studied. Ta-Si-N films of a wide range of compositions (Si: 0~30 at.%, N: 0~55 at.%) were deposited by DC magnetron reactive sputtering of Ta and Si targets. Deposition rates of Ta and Si films as a function of DC target current density for various N2/(Ar+N2) flow rate ratios were investigated. The composition of Ta-Si-N films was examined by wavelength dispersive spectroscopy (WDS). The variation of the microstructure of Ta-Si-N films with Si and N composition was examined by X-ray diffraction (XRD). The degree of crystallinity of Ta-Si-N films decreased with increasing Si and N composition. The Cu diffusion barrier property of Ta-Si-N films with more than sixty compositions was investigated. The Cu(100 nm)/Ta-Si-N(30 nm)/Si structure was used to investigate the Cu diffusion barrier property of Ta-Si-N films. The microstructure of all Cu/Ta-Si-N/Si structures after heat treatment for 1 hour at various temperatures was examined by XRD. A contour map that shows the diffusion barrier failure temperature for Cu as a function of Si and N composition was completed. At Si compositions ranging from 0 to 15 at.%, the Cu diffusion barrier property was best when the composition ratio of Ta + Si and N was almost identical.

This study examined the effect of current density on the surface morphology and physical properties of copper plated on a polyimide (PI) film. The morphology, crystal structure, and electric characteristics of the electrodeposited copper foil were examined by scanning electron microscopy, X-ray diffraction, and a four-point probe, respectively. The surface roughness, crystal growth orientation and resistivity was controlled using current density. Large particles were observed on the surface of the copper layer electroplated onto a current density of 25 mA/cm2. However, a uniform surface and lower resistivity were obtained with a current density of 10 mA/cm2. One of the important properties of FCCL is the flexibility of the copper foil. High flexibility of FCCL was obtained at a low current density rather than a high current density. Moreover, a reasonable current density is 20 mA/cm2 considering the productivity and mechanical properties of copper foil.

한국원자력연구원 처분시스템개발과제에서는 처분용기 재료로 개발중인 저온분사코팅 구리에 대한 틈새부식(Crevice Corrosion) 시험을 실시하였다. 본 시험을 통하여 틈새에서의 부식의 발생여부와 발생되는 시점인 재부동태 전위(Repassivation Potential)를 측정하고자 하였다. 틈새부식 시험 방법으로 (1) ASTM G61-86 : Cyclic Potentiodynamic Polarization Measurements, (2) SWRI의 PotentiodynamicPolarization plus intermediate Potentiostatic Hold method, 그리고 (3) ASTM G192-08 (THE method) :Potentiodynamic- Galvanostatic -Potentiostatic Method 등의 3가지 방법을 소개하였다. 실제 저온분사코팅구리의 부식시험에서는 ASTM G61-86에 따라서 틈새부식장치를 설치하고, 저온분사 코팅구리가 KURT 지하수를 모사한 용액에서 어떻게 틈새부식이 일어나는지 살펴보았다. 전기적 부식조건으로는 Cyclic Polarization Test, Potentiostatic Polarization Test, 및 Electrochemical Impedance Spectroscopy등을 사용하였다. 그리고 부식이 된 시편에 대해 Profilometer Measurement를 통해 실제 부식표면의 높낮이를 조사하여 틈새부식 유무를 관찰하였다. 최종적인 결론에서는 저온분사코팅구리는 틈새부식을 나타나지 않는다는 것을 확인할 수 있었다. 그리고 시험에 사용된 세종류의 구리에 대한 상대적인 부식평가를 한 결과, 부식전위를 나타내는 개방회로(Open Cell)에서의 전위는 구리의 제조방식과 상관없이 구리의 순도가 높을수록 높은 값을 보이는 것을 확인할 수 있었다. 결론적으로 KURT 심층지하수 조건에서는 구리는 틈새부식이 발생되지 않는다고 결론지었다.