• Journal of the Microelectronics and Packaging Society
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• v.20 no.4
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• pp.81-85
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• 2013

Wafer stacking technology becomes more important for the next generation IC technology. It requires new process development such as TSV, wafer bonding, and wafer thinning and also needs to resolve wafer warpage, power delivery, and thermo-mechanical reliability for high volume manufacturing. In this study, Cu CMP which is the key process for wafer bonding has been studied using Cu CMP and oxide CMP processes. Wafer samples were fabricated on 8" Si wafer using a damascene process. Cu dishing after Cu CMP and oxide CMP was $180{\AA}$ in average and the total height from wafer surface to bump surface was approximately $2000{\AA}$.

• Tribology and Lubricants
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• v.31 no.3
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• pp.79-85
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• 2015

RC delay is a critical issue for achieving high performance of ULSI devices. In order to minimize the RC delay time, we uses the CMP process to introduce high-conductivity Cu and low-k materials on the damascene. The low-k materials are generally soft and fragile, resulting in structure collapse during the conventional high-pressure CMP process. One troubleshooting method is electrochemical mechanical polishing (ECMP) which has the advantages of high removal rate, and low polishing pressure, resulting in a well-polished surface because of high removal rate, low polishing pressure, and well-polished surface, due to the electrochemical acceleration of the copper dissolution. This study analyzes an electrochemical state (active, passive, transpassive state) on a potentiodynamic curve using a three-electrode cell consisting of a working electrode (WE), counter electrode (CE), and reference electrode (RE) in a potentiostat to verify an electrochemical removal mechanism. This study also tries to find optimum conditions for ECMP through experimentation. Furthermore, during the low-pressure ECMP process, we investigate the effect of current density on surface roughness and removal rate through anodic oxidation, dissolution, and reaction with a chelating agent. In addition, according to the Faraday’s law, as the current density increases, the amount of oxidized and dissolved copper increases. Finally, we confirm that the surface roughness improves with polishing time, and the current decreases in this process.

• Korean Journal of Materials Research
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• v.10 no.6
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• pp.450-455
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• 2000

For further scaling down of the silicon devices, the application of low dielectric constant materials instead of silicon oxide has been considered to reduce power consumption, crosstalk, and interconnection delay. In this paper, the effect of $O_2/SF_6$ plasma chemistry on the etching characteristics of polyimide-one of the promising low-k interlayer dielectrics-has been studied. The etch rate of polyimide decreases with the addition of $SF_6$ gas due to formation of nonvolatile fluorine compounds inhibiting reaction between oxygen and hydrocarbon polymer, while applying substrate bias enhances etching process through physical attack. However, addition of small amount of $SF_6$ is desirable for etching topography. $SiO_2$ hard mask for polyimide etching is effective under $O_2$plasma etching(selectivity~30), while $O_2/SF_6$ chemistry degrades etching selectivity down to 4. Based on the above results, $1-2\mu\textrm{m}$ L&S PI2610 patterns were successfully etched.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

• KOREAN JOURNAL OF CROP SCIENCE
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• v.31 no.4
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• pp.454-464
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• 1986

To find main factors to affect tobacco culture and quality, NC 2326 (Nicotiana tabacum L.) was cultivated in Korea and in the United States under different plant density, fertilization, mulching and curing. Among the chemical characteristics of the both experimental soils, the organic matters were similar concentration in both locations but effective phosphorous contents were higher in Oxford in the United States. Plant height, length and width of the largest leaf, leaf thickness, and midrib ratios were larger in Oxford than in Suwon in Korea. Also they were larger in non mulching system than in mulching system. But the total numbers of the leaves were decreased in non mulching system. The content of nicotine was higher in the plant grown in Suwon than in Oxford. The concentrations of nicotine and sugar tend to increase in mulching system comparing of non mulching system. During the growing, the concentration of non-volatile organic acids was higher in Suwon, while it was lower in cured leaf produced in Suwon. Also the contents of total fatty acids were lower in the harvested leaf grown in Suwon, but not in cured tobacco. Forty three compounds identified among the volatile oils from these experimental samples were quantified. The concentrations of the major components related to the tobacco flavour such as damascone, damascenone, solanone, nor-solanadione, and megastigmatrienones were higher in the cured tobacco produced in Oxford rather than in Suwon.

• Korean Chemical Engineering Research
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• v.54 no.4
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• pp.548-554
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• 2016

In this study, semi-aqueous solutions containing carboxylic acids such as oxalic acid (OA), lactic acid (LA) and citric acid (CA) were formulated for the removal of copper etching residues produced at the interconnection process, and their characteristics were analyzed. Carboxylic acids in the solutions were apt to form various copper complexes according to the value of pH. Semi-aqueous solution containing 10 wt% CA showed the lowest etching rate of copper in the range from pH2 to pH7 and the highest selectivity in the range of pH 2 to pH 4. However, the cleaning solution containing 10 wt% LA revealed the superior selectivity at the range from pH 5 to pH 7. Appropriate selection of carboxylic acid should be required to improve the performance of cleaning solution. In the case of CA, the etching selectivity of copper oxide complex to copper was increased with the concentration of CA in the solution, when the solutions contain over 5 wt% CA, the copper interconnection layer has a metallic copper surface more than 88% in the area. The result shows that CA contained semi-aqueous solution has a relatively good cleaning ability.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.377-377
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• 2012

Microprocessor technology now relies on copper for most of its electrical interconnections. Because of the high diffusivity of copper, Atomic layer deposition (ALD) $TaN_x$ is used as a diffusion barrier to prevent copper diffusion into the Si or $SiO_2$. Another problem with copper is that it has weak adhesion to most materials. Strong adhesion to copper is an essential characteristic for the new barrier layer because copper films prepared by electroplating peel off easily in the damascene process. Thus adhesion-enhancing layer of cobalt is placed between the $TaN_x$ and the copper. Because, cobalt has strong adhesion to the copper layer and possible seedless electro-plating of copper. Until now, metal film has generally been deposited by physical vapor deposition. However, one draw-back of this method is poor step coverage in applications of ultralarge-scale integration metallization technology. Metal organic chemical vapor deposition (MOCVD) is a good approach to address this problem. In addition, the MOCVD method has several advantages, such as conformal coverage, uniform deposition over large substrate areas and less substrate damage. For this reasons, cobalt films have been studied using MOCVD and various metal-organic precursors. In this study, we used $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) as a cobalt precursor because of its high vapor pressure and volatility, a liquid state and its excellent thermal stability under normal conditions. Furthermore, the cobalt film was also deposited at various $H_2/NH_3$ gas ratio(1, 1:1,2,6,8) producing pure cobalt thin films with excellent conformality. Compared to MOCVD cobalt using $H_2$ gas as a reactant, the cobalt thin film deposited by MOCVD using $H_2$ with $NH_3$ showed a low roughness, a low resistivity, and a low carbon impurity. It was found that Co/$TaN_x$ film can achieve a low resistivity of $90{\mu}{\Omega}-cm$, a low root-mean-square roughness of 0.97 nm at a growth temperature of $150^{\circ}C$ and a low carbon impurity of 4~6% carbon concentration.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.546-546
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• 2008

Copper (Cu) Chemical mechanical polishing (CMP) has been an essential process for Cu wifing of DRAM and NAND flash memory beyond 45nm. Copper has been employed as ideal material for interconnect and metal line due to the low resistivity and high resistant to electro-migration. Damascene process is currently used in conjunction with CMP in the fabrication of multi-level copper interconnects for advanced logic and memory devices. Cu CMP involves removal of material by the combination of chemical and mechanical action. Chemicals in slurry aid in material removal by modifying the surface film while abrasion between the particles, pad, and the modified film facilitates mechanical removal. In our research, we emphasized on the role of chemical effect of slurry on Cu CMP, especially on the effect of amine functional group on removal rate selectivity between Cu and Tantalum-nitride (TaN) film. We investigated the two different kinds of complexing agent both with amine functional group. On the one hand, Polyacrylamide as a polymer affected the stability of abrasive, viscosity of slurry and the corrosion current of copper film especially at high concentration. At higher concentration, the aggregation of abrasive particles was suppressed by the steric effect of PAM, thus showed higher fraction of small particle distribution. It also showed a fluctuation behavior of the viscosity of slurry at high shear rate due to transformation of polymer chain. Also, because of forming thick passivation layer on the surface of Cu film, the diffusion of oxidant to the Cu surface was inhibited; therefore, the corrosion current with 0.7wt% PAM was smaller than that without PAM. the polishing rate of Cu film slightly increased up to 0.3wt%, then decreased with increasing of PAM concentration. On the contrary, the polishing rate of TaN film was strongly suppressed and saturated with increasing of PAM concentration at 0.3wt%. We also studied the electrostatic interaction between abrasive particle and Cu/TaN film with different PAM concentration. On the other hand, amino-methyl-propanol (AMP) as a single molecule does not affect the stability, rheological and corrosion behavior of the slurry as the polymer PAM. The polishing behavior of TaN film and selectivity with AMP appeared the similar trend to the slurry with PAM. The polishing behavior of Cu film with AMP, however, was quite different with that of PAM. We assume this difference was originated from different compactness of surface passivation layer on the Cu film under the same concentration due to the different molecular weight of PAM and AMP.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.375-375
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• 2010

CdTe as an absorber material is widely used in thin film solar cells with the heterostructure due to its almost ideal band gap energy of 1.45 eV, high photovoltaic conversion efficiency, low cost and stable performance. The deposition methods and preparation conditions for the fabrication of CdTe are very important for the achievement of high solar cell conversion efficiency. There are some rearranged reports about the deposition methods available for the preparation of CdTe thin films such as close spaced sublimation (CSS), physical vapor deposition (PVD), vacuum evaporation, vapor transport deposition (VTD), closed space vapor transport, electrodeposition, screen printing, spray pyrolysis, metalorganic chemical vapor deposition (MOCVD), and RF sputtering. The RF sputtering method for the preparation of CdTe thin films has important advantages in that the thin films can be prepared at low growth temperatures with large-area deposition suitable for mass-production. The authors reported that the optical and electrical properties of CdTe thin film were closely connected by the thickness-uniformity of the film in the previous study [1], which means that the better optical absorbance and the higher carrier concentration could be obtained in the better condition of thickness-uniformity for CdTe thin film. The thickness-uniformity could be controlled and improved by the some process parameters such as vacuum level and RF power in the sputtering process of CdTe thin films. However, there is a limitation to improve the thickness-uniformity only in the preparation process [1]. So it is necessary to introduce the external or additional method for improving the thickness-uniformity of CdTe thin film because the cell size of thin film solar cell will be enlarged. Therefore, the authors firstly applied the chemical mechanical polishing (CMP) process to improving the thickness-uniformity of CdTe thin films with a G&P POLI-450 CMP polisher [2]. CMP process is the most important process in semiconductor manufacturing processes in order to planarize the surface of the wafer even over 300 mm and to form the copper interconnects with damascene process. Some important CMP characteristics for CdTe were obtained including removal rate (RR), WIWNU%, RMS roughness, and peak-to-valley roughness [2]. With these important results, the CMP process for CdTe thin films was performed to improve the thickness-uniformity of the sputtering-deposited CdTe thin film which had the worst two thickness-uniformities of them. Some optical properties including optical transmittance and absorbance of the CdTe thin films were measured by using a UV-Visible spectrophotometer (Varian Techtron, Cary500scan) in the range of 400 - 800 nm. After CMP process, the thickness-uniformities became better than that of the best condition in the previous sputtering process of CdTe thin films. Consequently, the optical properties were directly affected by the thickness-uniformity of CdTe thin film. The absorbance of CdTe thin films was improved although the thickness of CdTe thin film was not changed.

• Journal of the Microelectronics and Packaging Society
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• v.31 no.2
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• pp.54-62
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• 2024

SICM (Scanning Ion Conductivity Microscopy) is a technique for measuring surface topography in an environment where electrochemical reactions occur, by detecting changes in ion conductivity as a nanopipette tip approaches the sample. This study includes an investigation of the current response curve, known as the approach curve, according to the distance between the tip and the sample. First, a simulation analysis was conducted on the approach curves. Based on the simulation results, then, several measuring experiments were conducted concurrently to analyze the difference between the simulated and measured approach curves. The simulation analysis confirms that the current squeezing effect occurs as the distance between the tip and the sample approaches half the inner radius of the tip. However, through the calculations, the decrease in current density due to the simple reduction in ion channels was found to be much smaller compared to the current squeezing effect measured through actual experiments. This suggests that ion conductivity in nano-scale narrow channels does not simply follow the Nernst-Einstein relationship based on the diffusion coefficients, but also takes into account the fluidic hydrodynamic resistance at the interface created by the tip and the sample. It is expected that SICM can be combined with SECM (Scanning Electrochemical Microscopy) to overcome the limitations of SECM through consecutive measurement of the two techniques, thereby to strengthen the analysis of electrochemical surface reactivity. This could potentially provide groundbreaking help in understanding the local catalytic reactions in electroless plating and the behaviors of organic additives in electroplating for various kinds of patterns used in semiconductor damascene processes and packaging processes.