• Journal of the Semiconductor & Display Technology
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• v.8 no.2
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• pp.55-58
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• 2009

Density functional theory was used to investigate the adsorption and reaction of $HfCl_4$ with two hydroxyls on Si (001)-$2{\times}1$ surface in atomic layer deposition (ALD) process. We prepared a reasonable Si substrate which consisted of six inter-dimer dissociated $H_2O$ molecules and two intra-dimer dissociated $H_2O$ molecules. The $HfCl_4$must react with two hydroxyls to be a bulk-like structure. When $HfCl_4$ was adsorbed on a hydroxyl, there was energy benefit of -0.55 eV. Though there was energy loss for $HfCl_4$ to react with H of hydroxyl, thermal energy of ALD chamber would be enough to pass the energy barriers. There were five reaction pathways for $HfCl_4$ to react with two hydroxyls; inter-dimer, intra-dimer, cross-dimer, inter-row, and cross-row. Inter-row, inter-dimer and intra-dimer were relatively favorable among the five reaction pathways based on the energy difference. The electron densities between O and Hf in these three reactions were higher than the others and they had shorter Hf-O and O-O bond lengths than the other two reaction pathways.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.242-246
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• 1999

For the fluorination of $CF_2Cl_2$, the yield of $CF_4$ was found to be increased with the contact time and the reaction temperature. When the mole ratio of HF/$CF_2Cl_2$ is 3 or above, the yield of $CF_4$ was attained to 100% at $370^{\circ}C$ and contact time of 3 seconds. In the case of the fluorination of $CCl_4$ with HF, the yield of $CF_4$ was obtained above 90% at the reaction temperature of $500^{\circ}C$, the contact time of 3 seconds, and the mole ratio of HF/$CCl_4$ of 5.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.109-110
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• 2008

We have performed a density functional theory study to investigate the reaction of the $HfCl_4$ molecule on $H_2O$ terminated Si (001)-$(2\times1)$ surface. The reaction of the $HfCl_4$ molecule is more favorable on OH-terminated site than H-terminated site. The first $HfCl_4$ molecule is adsorbed on a OH-terminated site with 0.21 eV energy benefit. The second $HfCl_4$ molecule is adsorbed on the most adjacent OH-terminated site of the first molecule and the energy benefit is 0.28 eV. The third and forth molecules have same tendency with the first and second ones. The adsorption energies of the fifth and sixth $HfCl_4$ molecules are 0.01 eV, -0.06 eV respectively. Therefore, we find that the saturation Hf coverage is approximately 5/8 of the available hydroxyl site, which is $2.08\times10^{14}/cm^2$. Our model is well matched with an experimental study by reference.

• Transactions on Electrical and Electronic Materials
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• v.15 no.3
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• pp.164-169
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• 2014

We investigated the etching characteristics of $HfAlO_3$ thin films in $O_2/Cl_2/Ar$ and $O_2/BCl_3/Ar$ gas, using a high-density plasma (HDP) system. The etch rates of the $HfAlO_3$ thin film obtained were 30.1 nm/min and 36 nm/min in the $O_2/Cl_2/Ar$ (3:4:16 sccm) and $O_2/BCl_3/Ar$ (3:4:16 sccm) gas mixtures, respectively. At the same time, the etch rate was measured as a function of the etching parameter, namely as the process pressure. The chemical states on the surface of the etched $HfAlO_3$ thin films were investigated by X-ray photoelectron spectroscopy. Auger electron spectroscopy was used for elemental analysis on the surface of the etched $HfAlO_3$ thin films. These surface analyses confirm that the surface of the etched $HfAlO_3$ thin film is formed with nonvolatile by-product. Also, Cl-O can protect the sidewall due to additional $O_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.158-159
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• 2007

반도체 소자의 공정에 있어서 device scaling으로 인한 게이트 산화막 대체 유전체 (high-k)의 공정 개발 확보 방안 필요하다. 본 논문에서는 $Cl_2$/Ar 유도 결합 플라즈마를 이용하여 $HfO_2$ 박막을 식각하였다. $Cl_2$(80 %)/Ar(20 %)의 가스비, 600 W의 RF 전력, -150 V의 직류 바이어스 전압, 20 sccm의 총 가스유랑, 15 mTorr의 압력에서 15.4 nm/min의 최대 식각률을 얻을 수 있었다. 식각 된 $HfO_2$ 박막 표면을 XPS 분석한 결과 Hf와 O는 Cl 라디칼과 반응을 하여 높은 휘발성을 보이지만 Hf-O의 안정된 결합으로 인하여 이온에 의한 스퍼터링 효과에 의해서 식각된다.

• Transactions on Electrical and Electronic Materials
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• v.11 no.4
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• pp.166-169
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• 2010

In this study, we changed the etch parameters (gas mixing ratio, radio frequency [RF] power, direct current [DC]-bias voltage, and process pressure) and then monitored the effect on the $HfAlO_3$ thin film etch rate and the selectivity with $SiO_2$. A maximum etch rate of 108.7 nm/min was obtained in $Cl_2$ (3 sccm)/$BCl_3$ (4 sccm)/Ar (16 sccm) plasma. The etch selectivity of $HfAlO_3$ to $SiO_2$ reached 1.11. As the RF power and the DC-bias voltage increased, the etch rate of the $HfAlO_3$ thin film increased. As the process pressure increased, the etch rate of the $HfAlO_3$ thin films increased. The chemical state of the etched surfaces was investigated with X-ray photoelectron spectroscopy. According to the results, the etching of $HfAlO_3$ thin film follows the ion-assisted chemical etching.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.382-382
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• 2010

The etch characteristics of the $HfAlO_3$ thin films and selectivity of $HfAlO_3$ to $SiO_2$ in $Cl_2/BCl_3$/Ar plasma were investigated in this work. The maximum etch rate was 108.7 nm/min and selectivity of $HfAlO_3$ to $SiO_2$ was 1.11 at $Cl_2$(3sccm)/$BCl_3$(4sccm)/Ar(16sccm), RF power of 500 W, DC-bias voltage of - 100 V, process pressure of 1 Pa and substrate temperature of $40^{\circ}C$. As increasing RF power and DC-bias voltage, etch rates of the $HfAlO_3$ thin films increased. Whereas as decreasing of the process pressure, those of the $HfAlO_3$ thin films were increased. The chemical reaction on the surface of the etched the $HfAlO_3$ thin films was investigated with X-ray photoelectron spectroscopy (XPS).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.477-477
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• 2008

For more than three decades, the gate dielectrics in CMOS devices are $SiO_2$ because of its blocking properties of current in insulated gate FET channels. As the dimensions of feature size have been scaled down (width and the thickness is reduced down to 50 urn and 2 urn or less), gate leakage current is increased and reliability of $SiO_2$ is reduced. Many metal oxides such as $TiO_2$, $Ta_2O_4$, $SrTiO_3$, $Al_2O_3$, $HfO_2$ and $ZrO_2$ have been challenged for memory devices. These materials posses relatively high dielectric constant, but $HfO_2$ and $Al_2O_3$ did not provide sufficient advantages over $SiO_2$ or $Si_3N_4$ because of reaction with Si substrate. Recently, $HfO_2$ have been attracted attention because Hf forms the most stable oxide with the highest heat of formation. In addition, Hf can reduce the native oxide layer by creating $HfO_2$. However, new gate oxide candidates must satisfy a standard CMOS process. In order to fabricate high density memories with small feature size, the plasma etch process should be developed by well understanding and optimizing plasma behaviors. Therefore, it is necessary that the etch behavior of $HfO_2$ and plasma parameters are systematically investigated as functions of process parameters including gas mixing ratio, rf power, pressure and temperature to determine the mechanism of plasma induced damage. However, there is few studies on the the etch mechanism and the surface reactions in $BCl_3$ based plasma to etch $HfO_2$ thin films. In this work, the samples of $HfO_2$ were prepared on Si wafer with using atomic layer deposition. In our previous work, the maximum etch rate of $BCl_3$/Ar were obtained 20% $BCl_3$/ 80% Ar. Over 20% $BCl_3$ addition, the etch rate of $HfO_2$ decreased. The etching rate of $HfO_2$ and selectivity of $HfO_2$ to Si were investigated with using in inductively coupled plasma etching system (ICP) and $BCl_3/Cl_2$/Ar plasma. The change of volume densities of radical and atoms were monitored with using optical emission spectroscopy analysis (OES). The variations of components of etched surfaces for $HfO_2$ was investigated with using x-ray photo electron spectroscopy (XPS). In order to investigate the accumulation of etch by products during etch process, the exposed surface of $HfO_2$ in $BCl_3/Cl_2$/Ar plasma was compared with surface of as-doped $HfO_2$ and all the surfaces of samples were examined with field emission scanning electron microscopy and atomic force microscope (AFM).

• Proceedings of the International Microelectronics And Packaging Society Conference
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• 2002.11a
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• pp.115-121
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• 2002

In this research we have investigated the characteristics of ultra thin $HfO_2 /SiON$stack structure films using several analytical techniques. SiON layer was thermally grown on standard SCI cleaned silicon wafer at $825^{\circ}C$ for 12sec under $N_2$O ambient. $HfO_2 /SiON$$_4$/$H_2O$ as precursors and $N_2$as a carrier/purge gas. Solid HfCl$_4$was volatilized in a canister kept at $200^{\circ}C$ and carried into the reaction chamber with pure $N_2$carrier gas. $H_2O$ canister was kept at $12^{\circ}C$ and carrier gas was not used. The films were grown on 8-inch (100) p-type Silicon wafer at the $300^{\circ}C$ temperature after standard SCI cleaning, Spectroscopic ellipsometer and TEM were used to investigate the initial growth mechanism, microstructure and thickness. The electrical properties of the film were measured and compared with the physical/chemical properties. The effects of heat treatment was discussed.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.12
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• pp.1078-1084
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• 2006

Impurity contamination induced by $CF_4\;and\;HBr/Cl_2/O_2$ plasma etching on Si surface was examined by using surface spectroscopes. XPS(x-ray photoelectron spectroscopy) surface analysis showed that F of 0.4 at % exists in the surface layer in the form of Si-F bonding but Br and Cl are below the detection limit $(0.1{\sim}1.0%)$ of the spectroscope. Static-SIMS(secondary ion mass spectrometry) surface analysis showed that the etched Si surface was contaminated with etching gas elements such as H, F, Cl and Br, and they existed to the depth of about $20{\sim}40nm$. The etched Si surface was treated with three different methods that were HF dip, thermal oxidation followed by HF dip and oxygen-plasma oxidation followed by HF dip. They showed an effect in reducing the impurity contamination and the oxygen-plasma oxidation followed by HF dipping method appears to be a little bit more effective.