• Journal of the Korean institute of surface engineering
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• v.51 no.4
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• pp.243-248
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• 2018

All solid state thin film batteries with two types of cell structure, Pt / $LiCoO_2$ / LiPON / Cu and Pt / $LiCoO_2$ / LiPON / $LiCoO_2$ / Cu, are prepared and their electrochemical performances are investigated to evaluate the effect of $LiCoO_2$ interlayer at the interface of LiPON / Cu. The crystallinity of the deposited $LiCoO_2$ thin films is confirmed by XRD and Raman analysis. The crystalline $LiCoO_2$ cathode thin film is obtained and $LiCoO_2$ as the interlayer appears to be amorphous. The surface morphology of Cu current collector after cycling of the batteries is observed by AFM. The presence of a 10 nm-thick layer of $LiCoO_2$ at the interface of LiPON / Cu enhances the interfacial adhesion and reduces the interfacial resistance. As a result, Li plating / stripping at the interface of LiPON / Cu during charge/discharge reaction takes place more uniformly on Cu current collector, while without the interlayer of $LiCoO_2$ at the interface of LiPON / Cu, the Li plating / stripping is localized on current collector. The thin film batteries with the interlayer of $LiCoO_2$ at the interface of LiPON / Cu exhibits enhanced initial coulombic efficiency, reversible capacity and cycling stability. The thickness of the anode current collector Cu also appears to be crucial for electrochemical performances of all solid state thin film batteries.

• Journal of the Korean Electrochemical Society
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• v.3 no.2
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• pp.115-120
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• 2000

All solid-state thin film micro-batteries consisting of lithium metal anode, an amorphous LiPON electrolyte and cathode of vanadium oxide have been fabricated and characterized, which were fabricated with cell structure of $Li/LiPON/V_2O_5Pt$. The effect of various oxygen partial pressure on the electrochemical properties of vanadium oxide thin films formed by d.c. reactive sputtering deposition were investigated. The vanadium oxide thin film with deposition condition of $20\%\;O_2/Ar$ ratio showed good cycling behavior. In in-siか process, the LiPON electrolyte was deposited on the $V_2O_5$ films without breaking vacuum by r.f. magnetron sputtering at room temperature. After deposition of the amorphous LiPON, the Li metal films were grown by a thermal evaporator in a dry room. The charge-discharge cycle measurements as a function of current density and voltage variation revealed that the $Li/LiPON/V_2O_5$ thin film had excellent rechargeable properly when current density was $7{\mu}A/cm^2$. and cut-off voltage was between 3.6 and 2.7V In practical experiment, a stopwatch ran on this $Li/LiPON/V_2O_5$ thin film micro-battery. This result means that thin film micro-battery fabricated by in-siか process is a promising for power source for electronic devices.

• Journal of the Korean institute of surface engineering
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• v.50 no.4
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• pp.237-243
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• 2017

We demonstrated the thin film deposition of sodium phosphorous oxynitride (NaPON) via RF magnetron sputtering of $Na_3PO_4$, as a solid-state Na-ion conductor similar to lithium phosphorous oxynitride (LiPON), which is a commonly used solid electrolyte. The deposited NaPON thin film was characterized by scanning electron microscopy, X-ray diffractometry, and electrochemical impedance spectroscopy, to investigate the feasibility of the solid-state electrolyte in several different cell configurations. The key properties of a solidstate electrolyte, i.e., ionic conductivity and activation energy, were estimated from the complex non-linear least square fitting of the measured impedance spectra at various temperatures in the range of $27-90^{\circ}C$. The ionic conductivity of the NaPON film was measured to be $8.73{\times}10^{-6}S\;cm^{-1}$ at $27^{\circ}C$, which was comparable to that of the LiPON film. The activation energy was estimated to be 0.164 eV, which was lower than that of the LiPON film (0.672 eV). The obtained values encourage the use of a NaPON thin film in the future as a reasonable solid-state electrolyte.

• Proceedings of the Materials Research Society of Korea Conference
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• 2001.11a
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• pp.176-176
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• 2001

• Korean Journal of Materials Research
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• v.11 no.8
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• pp.671-678
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• 2001

All solid-state thin film micro supercapacitor, which consists of $RuO_2$/LiPON/$RuO_2$ multi layer structure, was fabricated on Pt/Ti/Si substrate using a $RuO_2$ electrode. Bottom $RuO_2$ electrode was grown by dc reactive sputtering system with increasing $O_2/[Ar+O_2]$ ratio at room temperature, and a LiPON electrolyte film was subsequently deposited on the bottom $RuO_2$ electrode at pure nitrogen ambient by rf reactive sputtering system. Room temperature charge-discharge measurements based on a symmetric $RuO_2$/LiPON/$RuO_2$ structure clearly demonstrates the cyclibility dependence on the microstructure of the $RuO_2$ electrode. Using both glancing angle x-ray diffraction (GXRD) and transmission electron microscopy (TEM) analysis, it was found that the microstructure of the $RuO_2$ electrode was dependent on the oxygen flow ratio. In addition, x- ray photoelectron spectroscopy(XPS) examination shows that the Ru-O binding energy is affected by increasing oxygen flow ratio. Furthermore, TEM and AES depth profile analysis after cycling demonstrates that the interface layer formed by interfacial reaction between LiPON and $RuO_2$ act as a main factor in the degradation of the cyclibility of the thin film micro-supercapacitor.

• Korean Journal of Materials Research
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• v.11 no.5
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• pp.339-344
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• 2001

An all solid-state thin film supercapacitor (TFSC) with Co$_3$O$_4$/LiPON/Co$_3$O$_4$ structure was fabricated on Pt/Ti/Si substrate using Co$_3$O$_4$ thin film electrode. Each Co$_3$O$_4$ film was grown by reactive dc reactive magnetron sputtering with increasing $O_2$/[Ar+O$_2$] ratio. Amorphous LiPON electrolyte film was deposited on Co$_3$O$_4$/Pt/Ti/Si in pure nitrogen ambient by using reactive rf magnetron sputtering. The electrochemical behavior of the Co$_3$O$_4$/LiPON/Co$_3$O$_4$ multi-layer structures exhibits a behavior of a bulk-type supercapacitor, even though much lower capacity (from 5 to 25 mF/$\textrm{cm}^2$-$\mu\textrm{m}$) than that of the bulk one. It was found that the TFSC showed a fairly constant discharge capacity with a constant current of 50 $\mu\textrm{A}/\textrm{cm}^2$ at the cut-off voltage 0-2V during 400 cycles. It is shown that the electrochemical behavior of the Co$_3$O$_4$/LiPON/Co$_3$O$_4$ TFSC is dependent upon the sputtering gas ratio. The capacity dependency of electrode films on different gas ratios was explained by different structural, electrical, and surfacical properties.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.11a
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• pp.159-162
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• 1999

All solid state thin film micro-batteries consisting of lithium metal anode, an amorphous LiPON electrolyte and cathode of vanadium oxide have been fabricated and characterized, which were fabricated with cell structure of Li/LiPON/V$_2$O$\sub$5/Pt. The vanadium oxide thin films were formed by d.c. reactive sputtering on Pt current collector. After deposition of vanadium oxide films, in-situ growths of lithium phosphorus oxynitride film were conducted by r.f. sputtering of Li$_3$PO$_4$ target in mixture gas of N$_2$ and O$_2$. The pure metal lithium film was deposited by thermal evaporation on thin film LiPON electrolyte. The cell capacity was about 45${\mu}$Ah/$\textrm{cm}^2$ $\mu\textrm{m}$ after 200 cycle. No appreciable degradation of the cell capacity could be observed after 50 cycles .

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.30 no.7
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• pp.447-453
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• 2017

In this study, $Li_2MnSiO_4$ cathode material and LiPON solid electrolyte were manufactured into thin films, and the possibility of their use in thin-film batteries was researched. When the RTP treatment was performed after $Li_2MnSiO_4$ cathode thin-film deposition on the SUS substrate by a sputtering method, a ${\beta}-Li_2MnSiO_4$ cathode thin film was successfully manufactured. The LiPON solid electrolyte was prepared by a reactive sputtering method using a $Li_3PO_4$ target and $N_2$ gas, and a homogeneous and flat thin film was deposited on a $Li_2MnSiO_4$ cathode thin film. In order to evaluate the electrochemical properties of the $Li_2MnSiO_4$ cathode thin films, coin cells using only a liquid electrolyte were prepared and the charge/discharge test was conducted. As a result, the amorphous thin film of RTP treated at $600^{\circ}C$ showed the highest initial discharge capacity of about $60{\mu}Ah/cm^2$. In cases of coin cells using liquid/solid double electrolyte, the discharge capacities of the $Li_2MnSiO_4$ cathode thin films were comparable to those without solid LiPON electrolyte. It was revealed that $Li_2MnSiO_4$ cathode thin films with LiPON solid electrolyte were applicable in thin film batteries.

• 한국전기화학회:학술대회논문집
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• 2005.04a
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• pp.21-21
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• 2005

• Journal of the Korean Ceramic Society
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• v.38 no.3
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• pp.274-279
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• 2001

Pt/Ti/Si 기판 위에 성장시킨 박막 전지용 비정질 산화 바나듐 박막에 고상 전해질 박막 LiPON을 이용하여 전고상형 박막전지를 제작하여 충-방전 시험을 시행하였다. 이렇게 제작된 전고상형 박막전지는 500 사이클 이상까지 평균 15$\mu$Ah의 방전용량을 나타내었으나 초기 사이클 영역부터 방전 용량의 감소가 일어나기 시작했다. 박막 전지의 방전 용량 감소에 따른 비정질 산화 바나듐 박막의 구조적 특성 변화를 관찰하기 위하여 고분해능 현미경 분석을 시행하였다. 충-방전을 하지 않은 초기의 산화 바나듐 박막은 입계를 갖지 않고 다결정 특성을 보이지 않는 완전한 비정질 특성을 보였고 이는 TED 결과와 일치하였다. 그러나 450번의 반복적인 충-방전을 시행한 후의 비정질 산화 바나듐 박막 내에는 microcrystalline 형태의 산화 바나듐의 형성됨을 고분해능 전자 현미경 분석을 통해 발견할 수 있었다. 비정질 산화바나듐 박막의 방전 용량 감소의 원인인 Li의 비가역적 탈-삽입은 비정질 내에 형성된 microcrystalline에 의해 유발된다고 사료된다. 또한 LiPON 전해질 박막과 산화 바나듐 박막사이의 계면에 Li 이온과 산화바나듐과의 반응에 의해 형성된 계면 층에 발견할 수 있었는데 이러한 계면 층 역시 Li 확산과 계면 저항에 영향을 주어 방전 용량 감소에 원인으로 작용한다.