• Korean Journal of Materials Research
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• v.28 no.4
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• pp.214-220
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• 2018

We report on the fabrication and photoelectrochemical(PEC) properties of a $Cu_2O$ thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in $Cu_2O$ thin film as an efficient photoelectrode for solar-driven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/ZnO$ p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/ZnO$ photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., $0.77mA/cm^2$ at 0.5 V vs $Hg/HgCl_2$ in a $1mM\;Na_2SO_4$ electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs $Hg/HgCl_2$, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.177-177
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• 2007

ZnO는 3.36eV의 넓은 밴드캡을 가지는 II-IV족 반도체로써 태양전지, LED와 같은 광학적 소자로 이용이 기대가 되는 물질이다. 더욱이, 상온에서의 60meV에 해당하는 큰 엑시톤 에너지와 밴드캡 에지니어링이 가능하다는 장점 때문에 광학적 소자로 널리 이용되고 있는 GaN을 대체할 수 있는 물질로 주목을 받고 있다. 하지만, p-type ZnO는 형성이 어렵고 낮은 이동도와 케리어 농도의 특성을 보이고, 대기 중에 장시간 노출할 경우 n-type ZnO의 특성으로 돌아가는 불안정성을 보이고 있다. 최근에 몇몇의 연구자들에 의해 V족의 원소인 P(phosphorous), N(nitrogen), As(arsenic))를 도핑하여 p-type ZnO의 형성에 대한 논문이 발표되고 있다. 또한, V족 원소 중에 P는 p-type ZnO 형성에 효과적인 도핑 물질로 보고되 고 있다. 본 연구는 마그네트론 스퍼터링을 이용하여 다양한 온도에서 성장된 P도핑 ZnO 박막의 특성에 대해 연구하였다. P도핑된 ZnO 박막은 사파이어 기판에 buffer층을 사용한 Insulator 특성의 ZnO박막위에 400, 500, 600, $700^{\circ}C$에서 성장되 었다. 박막의 특성 분석에는 325nm의 파장을 가지는 He-Cd의 레이져 광원을 사용하여 10K의 저온 PL과 0.5T의 자기장을 사용한 van der Pauw configuration에 의한 Hall effect측정, 그리고 결정성 분석에는 XRD와 TEM을 이용하였다. 상온 Hall-effect 측정 결과, $400{\sim}600^{\circ}C$ 에서 성장된 박막은 n-type의 특성을 보였고, $700^{\circ}C$에서 성장된 Phosphorous 도핑 ZnO박막은 $1.19{\times}10^{17}$의 캐리어 농도를 가지는 p-type의 특성을 보였다. 그리고 XRD분석과 TEM분석을 통하여 박막의 성장온도가 증가 할수록 P도핑된 ZnO박막의 결정성이 향상되는 것을 알 수 있었다. 또한 10K의 저온 PL분석을 통해 p도핑에 의한 액셉터에 관련된 피크들을 관찰할 수 있었다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.18 no.11
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• pp.1043-1047
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• 2005

To investigate the electrical properties of the ZnO films which are interested in the next generation of short wavelength LEDs and Lasers, our ZnO thin films were deposited by RF sputtering system. At sputtering process of ZnO thin films, substrate temperature, work pressure respectively is $300^{\circ}C$ and 5.2 mTorr, and the purity of target is ZnO 5N. The thickness of ZnO thin films was about $2.1\;{\mu}m$ at SEM analysis after sputtering process. Phosphorus (P) and arsenic (As) were diffused into the undoped ZnO thin films sputtered by RF magnetron sputtering system in ampoule tube which was below $5\times10^{-7}$ Torr. The dopant sources of phosphorus and arsenic were $Zn_3P_2$ and $ZnAs_2$. Those diffusion was perform at 500, 600, and $700^{\circ}C$ during 3 hr. We found the diffusion condition of the conductive ZnO films which had n- and p-type properties. Our ZnO thin film has not only very high carrier concentration of above $10^{17}/cm^3$ but also low resistivity of below $2.0\times10^{-2}\;{\Omega}cm$.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.96-96
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• 2011

ZnO는 실온에서 3.37 eV의 큰 밴드갭 에너지와 60 meV의 높은 exciton binding energy를 가지고 있어 광소자를 만드는데 큰 관심을 얻고 있다. 또한 최근에는 ZnO를 기반으로 한 동종접합 전광소자를 만드는데 성공하였다. 그러나 소자의 성능을 높이기 위해 여러 가지 개선할 사항이 있다. 그 중에 하나는 캐리어를 잘 주입 시키기 위한 금속-반도체 접합을 구현하는 것이다. 이러한 문제를 개선하기 위해서는 ZnO 기반으로 한 낮은 비저항을 가진 소자가 필요하다. 일반적으로 n-type ZnO Ohmic 접합에서 쓰이는 금속은 Ti/Au, Ta/Au, Al/Au 등이 있다. 실험방법은 c-plane 사파이어 기판 위에 펄스 레이저 증착 방법으로 3시간 동안 $500^{\circ}C$ 환경에서 ZnO 박막을 성장하고, 표면을 고르게 하기 위해 $1000^{\circ}C$에서 1분 동안 열처리를 진행하였다. 샘플 위에 photo-resist 코팅을 한 다음 transfer length method(TLM)를 이용하기 위해 포토리소그래피 장비를 통하여 샘플을 노광하였다. 그 위에 Ti/Au (30 nm/80 nm)를 E-beam/thermal evaporation으로 증착 하였다. 이는 일반적인 반도체 공정과 Lift-off방식을 이용하여 패터닝 하였다. 샘플을 열처리하는 것은 금속과 반도체의 접촉 접착과 전기적인 성질을 개선하고 응력과 계면 결함을 감소시키기 때문에 샘플을 100, 200, 300, 400, $500^{\circ}C$에서 각각 열처리하였다. 저항을 구하기 위해 각각 열처리된 샘플과 as-deposited의 전류, 전압 특성을 측정하고, 이러한 실험 방법으로 n-type ZnO의 Ohmic 접합을 구현하는 것이 목표이다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.209-209
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• 2009

Fabrication of p-type ZnO has already proven difficult and usually inconsistent despite numerous worldwide efforts. Many research groups studied electrical and optical properties P, Li, As, N single doped ZnO thin film. In P-doped ZnO thin film, the reproducibility of p-type conduction with $P_2O_5$ as a dopant source was shown to be relatively poor. In this study, we made P single doped and Li & P co-doped ZnO target. To investigate electrical and optical properties of P single doped and Li & P co-doped ZnO thin film using $P_2O_5$ and $Li_3PO_4$ dopant source respectively was deposited by PLD. The growth temperature was changed 500, $700^{\circ}C$ and various oxygen partial pressure and post-annealing conditions was changed temperature, different gas ambient($O_2,N_2$). We investigate that how to change electrical and optical properties as function of growth temperature, oxygen partial pressure and post-annealing(RTA).

• Proceedings of the Korean Vacuum Society Conference
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• 2009.02a
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• pp.139.2-139.2
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• 2009

• Transactions on Electrical and Electronic Materials
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• v.9 no.2
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• pp.67-72
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• 2008

Al-doped p-type ZnO thin films were fabricated by RF magnetron sputtering on n-Si (100) and homo-buffer layers in pure oxygen ambient. ZnO ceramic mixed with 2 wt% $Al_2O_3$ was selected as a sputtering target. XRD spectra show that the Al-doped ZnO thin films have ZnO crystal structure. Hall Effect experiments with Van der Pauw configuration show that p-type carrier concentrations are arranged from $1.66{\times}10^{16}$ to $4.04{\times}10^{18}\;cm^{-2}$, mobilities from 0.194 to $198\;cm^2V{-1}s^{-1}$ and resistivities from 0.0963 to $18.4\;{\Omega}cm$. FESEM cross section images of different parts of a p-type ZnO:Al thin film annealed at $800^{\circ}C$ show a compact structure. Measurement for same sample shows that density is $5.40\;cm^{-3}$ which is smaller than theoretically calculated value of $5.67\;cm^{-3}$. Photoluminescence (PL) spectra at 10 K show a shoulder peak of p-type ZnO film at about 3.117 eV which is ascribed to electron transition from donor level to acceptor level (DAP).

• Korean Journal of Materials Research
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• v.13 no.8
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• pp.519-523
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• 2003

We report the synthesis of cubic spinel $ZnCo_2$$O_4$thin films and the tunability of the conduction type by control of the oxygen partial pressure ratio. Zinc cobalt oxide films were grown on$ SiO_2$(200 nm)/Si substrates by reactive magnetron sputtering method using Zn and Co metal targets in a mixed Ar/$O_2$atmosphere. We found from X-ray diffraction measurements that the crystal structure of the zinc cobalt oxide films grown under an oxygen-rich condition (the $O_2$/Ar partial pressure ratio of 9/1) changes from wurtzite-type $Zn_{1-x}$ $Co_{X}$O to spinel-type $ZnCo_2$$O_4$with the increase of the Co/Zn sputtering ratio,$ D_{co}$ $D_{zn}$ . We noted that the above structural change accompanied by the variation of the majority electrical conduction type from n-type (electrons) to p-type (holes). For a fixed $D_{co}$ $D_{zn}$ / of 2.0 yielding homogeneous spinel-type $_2$O$ZnCo_4$films, the type of the majority carriers also varied, depending on the$ O_2$/Ar partial pressure ratio: p-type for an $O_2$-rich and n-type for an Ar-rich atmosphere. The maximum electron and hole concentrations for the Zn $Co_2$ $O_4$films were found to be 1.37${\times}$10$^{20}$ c $m^{-3}$ and 2.41${\times}$10$^{20}$ c $m^{-3}$ , respectively, with a mobility of about 0.2 $\textrm{cm}^2$/Vs and a high conductivity of about 1.8 Ω/$cm^{-1}$ /.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.303-304
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• 2008

Al, N-codoped ZnO(ZnO:N,Al) thin films were deposited on n-type Si(100) substrate at $450^{\circ}C$ with various conditions of ambient gas$(N_2:O_2)$ by DC magnetron sputtering method using ZnO:$Al_2O_3$(2wt%) as a target, and then were annealed at 500, 700, $800^{\circ}C$ in $N_2$ gas for one hour. XRD patterns showed that all of the ZnO:N,Al thin films annealed at $80^{\circ}C$ grew with two peaks, which means poor crystallinity of the thin films deposited. Hall effects in Van der Pauw configuration proved that after annealing the films deposited showed low resistivity and high carrier concentration. While the films annealed at $800^{\circ}C$ showed low resistivity of $\sim10^{-2}\Omega$ cm and high carrier concentration of $\sim10^{19}cm^{-3}$.

• Journal of the Korean Ceramic Society
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• v.43 no.11 s.294
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• pp.738-742
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• 2006

We report on the effects of co-doping with fluorine on properties of ZnO thin films grown by pulsed-laser deposition. The transport characteristics of Ag-F and Li-F codoped ZnO films were determined by Hall-effect measurements at room temperature. Ag-F codoped ZnO films showed n-type semiconducting behaviors. An ambiguous carrier type was observed in Li-F codoped ZnO films grown at a temperature of 500$^{\circ}C$ with the oxygen pressures of 20 and 200 mTorr. The qualities of the codoped ZnO films were studied by X-ray diffraction, atomic force microscopy, X-ray photoemission spectroscopy, and photoluminescence.