• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.286-287
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• 2012

Reset-first resistive switching mechanism based on reduction reaction in HfO2-x with oxygen drift-diffusion was studied. we first report that the indirect evidence of local filamentary conductive path formation in bulk HfO2 film with local TiOx region at Ti top electrode formed during forming process and presence of anion-migration at interface between electrode and HfO2 during resistive switching through high resolution transmission electron microscopy (HRTEM), electron disperse x-ray (EDX), and electron energy loss spectroscopy (EELS) mapping. Based on forming process mechanism, we expected that redox reaction from Ti/HfO2 to TiOx/HfO2-x was responsible for an increase of initial current with increasing the post-annealing process. First-reset resistive switching in above $350^{\circ}C$ annealed Ti/HfO2 film was exhibited and the redox phenomenon from Ti/HfO2 to TiOx/HfO2-x was observed with high angle annular dark field (HAADF) - scanning transmission electron microscopy (STEM), EDX and x-ray photoelectron spectroscopy. Therefore, we demonstrated that the migration of oxygen ions at interface region under external electrical bias contributed to bipolar resistive switching behavior.

• Korean Journal of Materials Research
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• v.18 no.12
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• pp.673-677
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• 2008

Calcia (CaO) stabilized cubic-$HfO_2$ is studied by density functional theory (DFT) with generalized gradient approximation (GGA). When a Ca atom is substituted for a Hf atom, an oxygen vacancy is produced to satisfy the charge neutrality. The lattice parameter of a $2{\times}2{\times}2$ cubic $HfO_2$ supercell then increases by $0.02\;{\AA}$. The oxygen atoms closest to the oxygen vacancy are attracted to the vacancy as the vacancy is positive compared to the oxygen ion. When the oxygen vacancy is located at the site closest to the Ca atom, the total energy of $HfO_2$ reaches its minimum. The energy barriers for the migration of the oxygen vacancy were calculated. The energy barriers between the first and the second nearest sites, the second and the third nearest sites, and the third and fourth nearest sites are 0.2, 0.5, and 0.24 eV, respectively. The oxygen vacancies at the third and fourth nearest sites relative to the Ca atom represent the oxygen vacancies in undoped $HfO_2$. Therefore, the energy barrier for oxygen migration in the $HfO_2$ gate dielectric is 0.24 eV, which can explain the origin of gate dielectric leakage.

• Proceedings of the International Microelectronics And Packaging Society Conference
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• 2003.11a
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• pp.185-190
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• 2003

고유전물질인 $HfO_2$ 극박막에 사용될 TaN metal 전극에 대한 특성에 대한 연구를 하였다. 고유전물질인 $HfO_2$는 4" p-type wafer를 SCI cleaning후 ALD(atomic layer deposition)을 통해 $50\AA$를 증착하였다. Ff source는 TEMAH를 이용하였으며 Oxygen source는 $H_2O$를 이용하였다. 이렇게 증착한 $HfO_2$ 극박막에 Ta target을 이용하여 질소 가스를 Ar가스에 첨가하여 reactive sputtering을 통해서 TaN 전극을 증착하였다. TaN 박막의 증착두께는 a--step과 TEM을 통해서 확인하였으며 면저항은 four point probe를 이용하여 측정하였다. 이렇게 증착된 $HfO_2/TaN$구조에 대한 전기적 특성을 측정하였다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.07a
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• pp.832-835
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• 2001

We report the structural and electrical properties of hafnium oxide (HfO$_2$) films with tungsten silicide (WSi$_2$) metal gate. In this study, HfO$_2$thin films were fabricated by oxidation of sputtered Hf metal films on Si, and WSi$_2$was deposited directly on HfO$_2$by LPCVD. The hysteresis windows in C-V curves of the WSi$_2$HfO$_2$/Si MOS capacitors were negligible (<20 mV), and had no dependence on frequency from 10 kHz to 1 MHz and bias ramp rate from 10 mV to 1 V. In addition, leakage current was very low in the range of 10$^{-9}$ ~10$^{-10}$ A to ~ 1 V, which was due to the formation of interfacial hafnium silicate layer between HfO$_2$and Si. After PMA (post metallization annealing) of the WSi$_2$/HfO$_2$/Si MOS capacitors at 500 $^{\circ}C$ EOT (equivalent oxide thickness) was reduced from 26 to 22 $\AA$ and the leakage current was reduced by approximately one order as compared to that measured before annealing. These results indicate that the effect of fluorine diffusion is negligible and annealing minimizes the etching damage.

• Journal of the Korean Vacuum Society
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• v.21 no.5
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• pp.273-278
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• 2012

Over the last decade, the hafnium-based gate dielectric materials have been studied for many application fields. Because these materials had excellent behaviors for suppressing the quantum-mechanical tunneling through the thinner dielectric layer with higher dielectric constant (high-K) than $SiO_2$ gate oxides. Although high-K materials compensated the deterioration of electrical properties for decreasing the thickness of dielectric layer in MOSFET structure, their nano-mechanical properties of $HfO_2$ thin film features were hardly known. Thus, we examined nano-mechanical properties of the Hafnium oxide ($HfO_2$) thin film in order to optimize the gate dielectric layer. The $HfO_2$ thin films were deposited by rf magnetron sputter using hafnium (99.99%) target according to various oxygen gas flows. After deposition, the $HfO_2$ thin films were annealed after annealing at $400^{\circ}C$, $600^{\circ}C$ and $800^{\circ}C$ for 20 min in nitrogen ambient. From the results, the current density of $HfO_2$ thin film for 8 sccm oxygen gas flow became better performance with increasing annealing temperature. The nano-indenter and Weibull distribution were measured by a quantitative calculation of the thin film stress. The $HfO_2$ thin film after annealing at $400^{\circ}C$ had tensile stress. However, the $HfO_2$ thin film with increasing the annealing temperature up to $800^{\circ}C$ had changed compressive stress. This could be due to the nanocrystal of the $HfO_2$ thin film. In particular, the $HfO_2$ thin film after annealing at $400^{\circ}C$ had lower tensile stress, such as 5.35 GPa for the oxygen gas flow of 4 sccm and 5.54 GPa for the oxygen gas flow of 8 sccm. While the $HfO_2$ thin film after annealing at $800^{\circ}C$ had increased the stress value, such as 9.09 GPa for the oxygen gas flow of 4 sccm and 8.17 GPa for the oxygen gas flow of 8 sccm. From these results, the temperature dependence of stress state of $HfO_2$ thin films were understood.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.19 no.6
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• pp.311-317
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• 2009

3Y-TZP block doped with $HfO_2$ and $CeO_2$ for dental ceramic block to the proliferation of CAD/CAM systems was prepared by heating at $800{\sim}1100^{\circ}C$ and then sintering at $1450^{\circ}C$. The influences of heating temperature and addition of $HfO_2$ and $CeO_2$ on the mechanical and chemical properties of 3Y-TZP block were investigated. Using the EDS mapping images, $HfO_2$ and $CeO_2$ was well dispersed in the 3Y-TZP matrix. 3 wt% $HfO_2$ doped block showed the optimum biaxial strength (1 GPa), while 3 wt% $CeO_2$ doped block enhanced the stability of $t-ZrO_2$ under hydrothermal atmosphere.

• Journal of the Korean Magnetics Society
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• v.15 no.5
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• pp.287-291
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• 2005

We have investigated and tried to improve the characteristics of the thin $HfO_2$ layer deposited by ALD for fabricating a MOSFET device where the $HfO_2$ film worked as the gate dielectric. The substrate of MOSFET device is p-type (100) silicon wafer over which the $HfO_2$ dielectric layer with thickness of $5\~6\;nm$ has been deposited. Then the $HfO_2$ film was annealed with $1\~20\;atm\;H_2$ gas and subsequently aluminum electrodes was made so that the active area was $5{\times}10^{-5}\;cm^2$. We have found out that the drain current and transconductance increased by $5\~10\%$ when the $H_2$ gas pressure was 20 atm, which significantly contributed to the reliable operation of the high-density MOSFET devices.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07a
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• pp.362-365
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• 2002

Hf thin films were deposited on bottom metal using a RF magnetron sputtering method followed by oxidation and annealing in O$_2$ and N$_2$ ambient, respectively. Various top metal electrodes (i.e., Al, Au, and Cu) were deposited by evaporation, and their roles on physical and electrical properties were investigated. Using the XRD, SEM and AFM techniques, we confirmed that the grain size of HfO$_2$ thin films enlarges as a function of oxidation temperature, increasing dielectric constant. However, other electrical properties (e.g., tan) deteriorateas a consequence. The dielectric constant and tan of HfO$_2$ thin films oxidized at 500 $^{\circ}C$ were 17-25 and 3${\times}$10-3 - 2x10-2, respectively, in the frequency range of 1 Hz to 1 MHz. The leakage current density was less than 1${\times}$10-8A/cm2 up to 0.7 MV/cm. In addition, electrical properties of HfO$_2$ thin films (e.g., the dielectric constant, leakage current and tan $\delta$) depend on top metal electrode. We showed that Al top metal electrode results in the best result.

• Journal of IKEEE
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• v.25 no.3
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• pp.501-505
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• 2021

In this study, we fabricated amorphous indium-tin-gallium-zinc-oxide thin-film transistors (a-ITGZO TFTs) with gate dielectrics of HfO₂ and the mixed layers of HfO₂ and Al₂O₃, and investigated the effect of gate dielectric on electrical characteristics of a-ITGZO TFTs. When only HfO₂ was used as the gate dielectric, the mobility and subthreshold swing (SS) were 32.3 cm²/Vs and 206 mV/dec. For the a-ITGZO TFTs with gate dielectric made of HfO₂ and Al₂O (2:1, 1:1), the mobilities and SS were 26.4 cm²/Vs (2:1), 16.8 cm²/Vs(1:1), 160 mV/dec (2:1) and 173 mV/dec (1:1). On the other hand, the hysteresis window shown in transfer curves of the a-ITGZO TFTs was lessened from 0.60 to 0.09 V by the increase of Al₂O₃ ratio in gate dielectric, indicating that the interface trap density between the gate dielectric and channel layer decreases due to Al₂O₃.

• Proceedings of the KIEE Conference
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• 2002.11a
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• pp.145-146
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• 2002

Metal-Oxide-Semiconductor Field Effect Transistor(MOSFET)의 게이트 유전체로서 실리콘 산화막($SiO_2$)은 두께가 1.5nm 이하로 낮아질 경우 터널링 전류가 증가하여 누설 전류가 증가하게 된다. 이로 인해 사용 전력이 증가하게 되고, 소자의 성능을 떨어뜨리게 된다. 본 논문은 높은 유전상수와 넓은 에너지 밴드 갭을 갖는 $HfO_2$를 RF Magnetron Sputter를 이용하여 증착한 다음 RTA 열처리를 통하여 HfSixOy를 생성하여 전기적 특성을 측정하였다. 실험결과, 열처리 시간이 증가함에 따라 HfSixOy의 분포가 균일해지는 반면 두께가 얇아져서 누설 전류가 증가 하는 것으로 관찰되었다. $HfO_2$를 게이트 유전막으로 증착하였을 경우 $HfO_2/HfSixOy/Si$의 이중 박막 구조가 생겨 유전상수를 떨어뜨리는 반면, 실리콘 기판과 우수한 계면 특성을 갖는 HfSixOy만을 증착할 경우 양질의 단층 게이트 유전막으로 활용가능 할 것으로 사료된다.