• Korean Journal of Materials Research
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• v.31 no.10
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• pp.569-575
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• 2021

The reactivity evaluation of copper is performed using ethylenediamine, aminoethanol, and piperidine to apply organic chelators to copper etching. It is revealed that piperidine, which is a ring-type chelator, has the lowest reactivity on copper and copper oxide and ethylenediamine, which is a chain-type chelator, has the highest reactivity via inductively coupled plasma-mass spectroscopy (ICP-MS). Furthermore, it is confirmed that the stable complex of copper-ethylenediamine can be formed during the reaction between copper and ethylenediamine using nuclear magnetic resonance (NMR) and radio-thin layer chromatography. As a final evaluation, the copper reactivity is evaluated by wet etching using each solution. Scanning electron micrographs reveal that the degree of copper reaction in ethylenediamine is stronger than that in any other chelator. This result is in good agreement with the evaluation results obtained by ICP-MS and NMR. It is concluded that ethylenediamine is a prospective etch gas for the dry etching of the copper.

• Journal of the Semiconductor & Display Technology
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• v.22 no.4
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• pp.72-75
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• 2023

Carbon neutrality has been emerged as important mission for all the manufacturing industry to reduce energy usage and carbon emission equivalent. Korean semiconductor and display manufacturing industries are also in huge interest by minimize the energy usage as well as to find a less global warming product gases in both etch and cleaning. In addition, Korean government is also investing long term research and development plan for the safe environment in various ways. In this paper, we revisit previous research activities on carbon emission equivalent and current research activities performed in semiconductor process diagnosis research center at Myongji University with respect to the reduction of NF3 usage for the PECVD chamber cleaning, and we present the analytical result of the exhaust gas with residual gas analysis in both 6 inches and 12 inches PECVD equipment. The presented result can be a reference study of the development of new substitution gas in near future to compare the cleaning rate of the silicon oxide deposition chamber.

• The Journal of Korean Academy of Prosthodontics
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• v.28 no.2
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• pp.53-76
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• 1990

The purpose of this study was to evaluate the tensile bond strength of adhesive resins to successively recast Rexillium III and Degudent-U. Recasting was done 4times successively. Specimen $A_1$, were cast by new metal, and $A_2$ by surpus of $A_1$, $A_3$ by surplus of, $A_2$ $A_4$ by surplus of $A_3$, $A_5$ by surplus of $A_4$ plus 50% new metal. The types of surface treatment for resinbonded restoration in this experiment were electrolytic etching by OXY-ETCH(Oxy dental products, Inc., Hillside, New Jersey, U.S,A.), aluminum oxide blasting, anodic oxidation by EZ-OXISOR( Towagiken Co., Kyoto, Japan), electrotinplating by Kura Ace(Kuralay Co., Kyoto, Japan). Three kinds of cementing resin used in this study were Comspan(K.P. Cauil Co, Milford Delaware, U.S.A.), Super Bond C&B(Sun-Medical Co. Ltd., Kyoto,Japan), Panavia EX(Kuralay Co., Ltd., Osaka, Japan). Tensile bond strength was measured by Instron Universal testing machineModel 1125) and all the specimen were observed with SEM(JEOL, JSM-T2000) and mode of bond failure were recorded. The obtained results were as follows : 1. In electrolytic etched group, tensile bond strength was decreassed when recast alloy was used, and tensile bond strength of Compan and panavia EX were not significantly different(P>0.05). 2. In remaining group treated by aluminum oxide blasting, EZ-OXIOR, Kura Ace, tensile bond strength were not changed when recast alloy were used, and tensile bond strength of SuperBond(C&B and Panavia EX were not significantly different(P>0.05). 3. IN SEM evaluation, electrolytic etched group and electrotinplated group exhibited different image when recast alloy was used, and remaining groups treated by aluminum oxide blasting, EZ-OXISOR exhibited the same. 4. IN observation of bond failure, electrolytic etched group exhibited adhesive failure and remaing groups treated by aluminium oxid blasting, EZ-OXISOR, Kura Ace exhibited adhesive and cohesive failure.

• Korean Journal of Materials Research
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• v.11 no.6
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• pp.527-532
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• 2001

Dry etching of copper film using $O_2$ plasma and H(hfac) has been investigated. A one-step process consisting of copper film oxidation with an $O_2$ plasma and the removal of surface copper oxide by the reaction with H(hfac) to form volatile Cu(hfac)$_2$ and $H_2O$ was carried but. The etching rate of Cu in the range from 50 to 700 /min was obtained depending on the substrate temperature, the H(hfac)/O$_2$ flow rate ratio, and the plasma power. The copper film etch rate increased with increasing RF power at the temperatures higher than 215$^{\circ}C$. The optimum H(hfac)/O$_2$ flow rate ratio was 1:1, suggesting that the oxidation process and the reaction with H(hfac) should be in balance. Cu patterning using a Ti mask was performed at a flow rate ratio of 1:1 on 25$0^{\circ}C$\ulcorner and an isotropic etching profile with a taper slope of 30$^{\circ}$was obtained. Cu dry patterning with a tapered angle which is necessary for the advanced high resolution large area thin film transistor liquid-crystal displays was thus successfully obtained from one step process by manipulating the substrate temperature, RF power, and flow rate ratio.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.38 no.12
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• pp.8-13
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• 2001

Cerium oxide ($CeO_2$) thin film has been proposed as a buffer layer between the ferroelectric thin film and the Si substrate in Metal-Ferroelectric-Insulator-Silicon (MFIS) structures for ferroelectric random access memory (FRAM) applications. In this study, $CeO_2$ thin films were etched with $Cl_2$/Ar gas mixture in an inductively coupled plasma (ICP). Etch properties were measured for different gas mixing ratio of $Cl_2$($Cl_2$+Ar) while the other process conditions were fixed at RF power (600 W), dc bias voltage (-200 V), and chamber pressure (15 mTorr). The highest etch rate of $CeO_2$ thin film was 230 ${\AA}$/min and the selectivity of $CeO_2$ to $YMnO_3$ was 1.83 at $Cl_2$($Cl_2$+Ar gas mixing ratio of 0.2. The surface reaction of the etched $CeO_2$ thin films was investigated using x-ray photoelectron spectroscopy (XPS) analysis. There is a Ce-Cl bonding by chemical reaction between Ce and Cl. The results of secondary ion mass spectrometer (SIMS) analysis were compared with the results of XPS analysis and the Ce-Cl bonding was monitored at 176.15 (a.m.u). These results confirm that Ce atoms of $CeO_2$ thin films react with chlorine and a compound such as CeCl remains on the surface of etched $CeO_2$ thin films. These products can be removed by Ar ion bombardment.

• Korean Journal of Materials Research
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• v.8 no.7
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• pp.634-640
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• 1998

A well- shaped trench was investigated in view of the defect distribution along trench sidewall and bottom using high resolution transmission electron microscopy. The trench was formed by HBr plasma and additive gases in magnetically enhanced reactive ion etching system. Adding $0_2$ and other additive gases into HBr plasma makes it possible to eliminate sidewall undercut and lower surface roughness by forming the passivation layer of lateral etching, resulted in the well filled trench with oxide and polysilicon by subsequent deposition. The passivation layer of lateral etching was mainly composed of $SiO_xF_y$ $SiO_xBr_y$ confirmed by chemical analysis. It also affects the generation and distribution of lattice defects. Most of etch induced defects were found in the edge region of the trench bottom within the depth of 10$\AA$. They are generally decreased with the thickness of residue layer and almost disappeared below the uni¬formly thick residue layer. While the formation of crystalline defects in silicon substrate mainly depends on the incident angle and energy of etch species, the region of surface defects on the thickness of residue layer formed during trench etching.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.145-145
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• 2008

High-k materials have been paid much more attention for their characteristics with high permittivity to reduce the leakage current through the scaled gate oxide. Among the high-k materials, $ZrO_2$ is one of the most attractive ones combing such favorable properties as a high dielectric constant (k= 20 ~ 25), wide band gap (5 ~ 7 eV) as well as a close thermal expansion coefficient with Si that results in good thermal stability of the $ZrO_2$/Si structure. During the etching process, plasma etching has been widely used to define fine-line patterns, selectively remove materials over topography, planarize surfaces, and trip photoresist. About the high-k materials etching, the relation between the etch characteristics of high-k dielectric materials and plasma properties is required to be studied more to match standard processing procedure with low damaged removal process. Among several etching techniques, we chose the inductively coupled plasma (ICP) for high-density plasma, easy control of ion energy and flux, low ownership and simple structure. And the $BCl_3$ was included in the gas due to the effective extraction of oxygen in the form of $BCl_xO_y$ compounds. During the etching process, the wafer surface temperature is an important parameter, until now, there is less study on temperature parameter. In this study, the etch mechanism of $ZrO_2$ thin film was investigated in function of $Cl_2$ addition to $BCl_3$/Ar gas mixture ratio, RF power and DC-bias power based on substrate temperature increased from $10^{\circ}C$ to $80^{\circ}C$. The variations of relative volume densities for the particles were measured with optical emission spectroscopy (OES). The surface imagination was measured by scanning emission spectroscope (SEM). The chemical state of film was investigated using energy dispersive X-ray (EDX).

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.454-454
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• 2014

Silicon microwire array is one of the promising platforms as a means for developing highly efficient solar cells thanks to the enhanced light trapping efficiency. Among the various fabrication methods of microstructures, deep reactive ion etching (DRIE) process has been extensively used in fabrication of high aspect ratio microwire arrays. In this presentation, we show precisely controlled Si microwire arrays by tuning the DRIE process conditions. A periodic microdisk arrays were patterned on 4-inch Si wafer (p-type, $1{\sim}10{\Omega}cm$) using photolithography. After developing the pattern, 150-nm-thick Al was deposited and lifted-off to leave Al microdisk arrays on the starting Si wafer. Periodic Al microdisk arrays (diameter of $2{\mu}m$ and periodic distance of $2{\mu}m$) were used as an etch mask. A DRIE process (Tegal 200) is used for anisotropic deep silicon etching at room temperature. During the process, $SF_6$ and $C_4F_8$ gases were used for the etching and surface passivation, respectively. The length and shape of microwire arrays were controlled by etching time and $SF_6/C_4F_8$ ratio. By adjusting $SF_6/C_4F_8$ gas ratio, the shape of Si microwire can be controlled, resulting in the formation of tapered or vertical microwires. After DRIE process, the residual polymer and etching damage on the surface of the microwires were removed using piranha solution ($H_2SO_4:H_2O_2=4:1$) followed by thermal oxidation ($900^{\circ}C$, 40 min). The oxide layer formed through the thermal oxidation was etched by diluted hydrofluoric acid (1 wt% HF). The surface morphology of a Si microwire arrays was characterized by field-emission scanning electron microscopy (FE-SEM, Hitachi S-4800). Optical reflection measurements were performed over 300~1100 nm wavelengths using a UV-Vis/NIR spectrophotometer (Cary 5000, Agilent) in which a 60 mm integrating sphere (Labsphere) is equipped to account for total light (diffuse and specular) reflected from the samples. The total reflection by the microwire arrays sample was reduced from 20 % to 10 % of the incident light over the visible region when the length of the microwire was increased from $10{\mu}m$ to $30{\mu}m$.

• 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.

• Clean Technology
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• v.7 no.3
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• pp.203-214
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• 2001

A silicon oxide cleaning characteristic and its mechanism were studied in RF plasma cleaning system with various gases such as $CHF_3$, $CF_4$, Argon, oxygen and mixing gas. The experimental parameters - working pressure (100 mTorr), RF power (300 W, 500 W), electrode distance (5cm, 8cm, 11.5cm), cleaning time (90, 180 seconds), gas flow (50 sccm) were fixed to compare cleaning efficiency by gas types. The results were as follows. First, the argon plasma is retaining only physical sputtering effect and etch rate was low. Second, the oxygen plasma showed good cleaning efficiency in electrode distace of 5cm, 300W, 180secs, but surface roughness increased. Third, $CF_4$ Plasma could get the best cleaning efficiency. Fourth, $CHF_3$ plasma could know that addition gas that can lower the CFx/F ratio need. We could not get good cleaning efficiency in case of added argon to $CHF_3$. But, we could get good cleaning efficiency in case added oxygen.