• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.100-101
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• 2012

The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

• Journal of the Korean Vacuum Society
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• v.18 no.3
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• pp.213-220
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• 2009

The optimal condition of low temperature deposition of transparent conductive Al-doped zinc oxide (AZO) films is studied by RF magnetron sputtering method. To achieve enhanced-electrical property and good crystallites quality, we tried to deposit on glass using a two-step growth process. This process was to deposit AZO buffer layer with optimal growth condition on glass in-situ state. The AZO film grown at rf 120 W on buffer layer prepared at RF $50{\sim}60\;W$ shows the electrical resistivity $3.9{\times}10^{-4}{\Omega}cm$, Carrier concentration $1.22{\times}10^{21}/cm^3$, and mobility $9.9\;cm^2/Vs$ in these results, The crystallinity of AZO film on buffer layer was similar to that of AZO film on glass with no buffer later but the electrical properties of the AZO film were 30% improved than that of the AZO film with no buffer layer. Therefore, the cause of enhanced electrical properties was explained to be dependent on degree of crystallization and on buffer layer's compressive stress by variation of $Ar^+$ ion impinging energy.

• Journal of Ocean Engineering and Technology
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• v.25 no.1
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• pp.39-43
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• 2011

This study has lowered the specific resistance by coating a thin film layer of Ag, playing the role of the electron donor on the ZnO that is used usefully for the transparent conductive oxides. Presently, this study has examined the transmittance and electric characteristics according to the thickness of the Ag thin film layer. Also, this study has observed the transmittance and electric characteristics according to the uppermost ZnO thin film layer of ZnO/Ag/ZnO symmetric film and has conducted the theoretical investigation. In order to observe the transmittance and electric characteristics according to the thickness of the Ag thin film layer and the uppermost ZnO thin film layer, this study conducted the film deposition at room temperature while making use of the DC magnetron sputtering system. In order to see the changes in the thickness of the Ag thin film layer, this study coated a thin film while increasing by 4nm; and, in order to see the changes in the thickness of uppermost ZnO thin film layer, it performed the thin film coating by increasing by 5nm. From the experimental result, the researchers observed that the best transmittance could be obtained when the thickness of the Ag thin film layer was 8nm, but the resistance and mobility increased as the thickness got larger. On the other hand, when the thickness of the uppermost ZnO thin film layer was 20nm, the experiment yielded the best transmittance with excellent electric characteristics. Also, when compared the ZnO/Ag asymmetric film with the ZnO/Ag/ZnO symmetric film, the ZnO/Ag asymmetric film showed better transmittance and electric characteristics.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.410-418
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• 2016

In this study, we prepared electrically conducting composites using epoxy resin of diglycidyl ether of bisphenol A (DGEBA) as a matrix, triethylenetetramine (TETA) as a hardener and nickel powder or multi-walled carbon nanotubes (MWCNTs) grafted with $-NH_2$ groups (MWCNT-$NH_2$) as electrically conducting fillers. Electrical conductivity of composite films were measured by coating on the slide glass with a doctor blade. We measured modification reactions of MWCNT and reaction of MWCNT-$NH_2$ with DGEBA epoxy resin by fourier transform infrared spectrometer (FTIR), thermogravimetric analyzer (TGA) and elemental analyzer (EA). Morphology of composites was investigated by scanning electron microscope (SEM) and sheet resistances of composites were measured by 4-point probe. We found $(9.87{\pm}1.09){\times}10^4{\Omega}/sq$ of sheet resistance for epoxy composite containing both 40 wt% nickel powder and 0.5 wt% of MWCNT-$NH_2$ as fillers, equivalent to epoxy composite containing 53.3 wt% nickel powder only as a filler.

• Journal of the Korean Electrochemical Society
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• v.23 no.3
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• pp.57-65
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• 2020

It is crucial to investigate the thermal degradation of lithium-ion batteries (LIBs) to understand the possible malfunction at high temperature. Herein, we investigated the effects of surface film formation on the thermal degradation of lithium cobalt oxide (LiCoO₂, LCO) cathode that is one of representative cathode materials. Cycling test at 60℃ exhibited poorer cycleability compared with the cycling at 25℃. Cathodes after the initial 5 cycles at 60℃ (60-LCO) exhibited higher impedance compared to the cathode after initial 5 cycles at 25℃ (25-LCO), resulting in the lower rate capability upon subsequent cycling at 25℃, although the capacity values were similar at the lowest C-rate of 0.1C. In order to understand degradation of the LCO cathode at the high temperature, we analyzed the cathodes surface using X-ray photoelectron spectroscopy (XPS). Among various peaks, intensity of lithium hydroxide (LiOH) increased substantially after the operation at 60℃, and the C-C signal that represents the conductive agent was distinctly lower on 60-LCO compared to 25-LCO. These results pointed to an excessive formation of cathode-electrolyte interphase including LiOH at 60℃, leading to the increase in the resistance and the resultant degradation in the electrochemical performances.

• Korean Chemical Engineering Research
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• v.51 no.3
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• pp.388-393
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• 2013

The study was focused to evaluate the possibility for combination membrane of bacterial cellulose (BC) and graphene with high electrical properties. BC with natural polymer matrix was known to have strong physical strength. For the combination of graphene with BC, the surface of graphene was modified with oxygen plasma by changing strength and time of radio waves in room temperature. Water contact angle of modified graphene grew smaller from $130^{\circ}$ to $12^{\circ}$. XPS analysis showed that oxygen content after treatment increased from 2.99 to 10.98%. Damage degree of graphene was examined from $I_D/I_G$ ratio of Raman analysis. $I_D/I_G$ ratio of non-treated graphene (NTG) was 0.11, and 0.36 to 0.43 in plasma treated graphene (PTG), increasing structural defects of PTG. XRD analysis of PTG membrane with BC was $2{\theta}$ same to BC only, indicating chemically combined membrane. In FT-IR analysis, 1,000 to 1,300 $cm^{-1}$ (C=O) peak indicating oxygen radicals in PTG membrane had formed was larger than NTG membrane. The results suggest that BC as an alternation of plastic material for graphene combination has a possibility in some degree on the part like transparent conductive films.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.229-229
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• 2010

With the scaling down of ultra large integrated circuits (ULSI) to the sub-50 nm technology node, the need for an ultra-thin, continuous and conformal diffusion barrier and Cu seed layer is increasing. However, diffusion barrier and Cu seed layer formation with a physical vapor deposition (PVD) method has become difficult as the technology node is reduced to 30 nm and beyond. Recent work on self-forming barrier processes using PVD Cu alloys have attracted great attention due to the capability of conformal ultra-thin barrier formation using a simple technique. However, as in the case of the conventional barrier and Cu seed layer, PVD of the Cu alloy seed layer will eventually encounter the difficulty in conformal deposition in narrow line trenches and via holes. Atomic layer deposition (ALD) has been known for its good step coverage and precise thickness control, and is a candidate technique for the formation of a thin conformal barrier layer and Cu seed layer. Conformal Cu-Mn seed layers were deposited by plasma enhanced atomic layer deposition (PEALD) at low temperature ($120^{\circ}C$), and the Mn content in the Cu-Mn alloys were controlled form 0 to approximately 10 atomic percent with various Mn precursor feeding times. Resistivity of the Cu-Mn alloy films decreased by annealing due to out-diffusion of Mn atoms. Out-diffused Mn atoms were segregated to the surface of the film and interface between a Cu-Mn alloy and $SiO_2$, resulting in self-formed $MnO_x$ and $MnSi_xO_y$, respectively. No inter-diffusion was observed between Cu and $SiO_2$ after annealing at $500^{\circ}C$ for 12 h, indicating an excellent diffusion barrier property of the $MnSi_xO_y$. The adhesion between Cu and $SiO_2$ was enhanced by the formation of $MnSi_xO_y$. Continuous and conductive Cu-Mn seed layers were deposited with PEALD into 32 nm $SiO_2$ trench, enabling a low temperature process, and the trench was perfectly filled using electrochemical plating (ECD) under conventional conditions. Thus, it is the resultant self-forming barrier process with PEALD Cu-Mn alloy film as a seed layer for plating Cu that has further potential to meet the requirement of the smaller than 30 nm node.

• Applied Chemistry for Engineering
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• v.32 no.2
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• pp.143-148
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• 2021

A thermally conductive 200 ㎛ thick polyimide-based film was made from a polyamic acid (PAA) precursor containing graphene prepared from graphite rod using an electrostatic discharge method in order to improve the thermal conductivity and expand the applicability of polyimide (PI) film. Properties of graphene produced by electrostatic discharge were measured by Raman spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). As a result of Raman spectrum and XPS analyses of as-prepared graphene, the ID/IG ratio was 0.138 and C/O value was 24.91 which are excellent structural and surface chemical properties. Moreover, thermal conductivities of polyimide films increased exponentially according to graphene contents but when the graphene content exceeded 40%, the polyimide film could not maintain its shape. The thermal conductivity of carbonized PI film made from PAA containing 40 wt% of graphene was 51 W/mK which is greatly enhanced from the pristine carbonized PI film (1.9 W/mK). This result could be originated from superior properties of graphene prepared from the electrostatic discharge method.