• 한국재료학회지
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• 제34권6호
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• pp.283-290
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• 2024

The aggressive scaling of dynamic random-access memory capacitors has increased the need to maintain high capacitance despite the limited physical thickness of electrodes and dielectrics. This makes it essential to use high-k dielectric materials. TiO₂ has a large dielectric constant, ranging from 30~75 in the anatase phase to 90~170 in rutile phase. However, it has significant leakage current due to low energy barriers for electron conduction, which is a critical drawback. Suppressing the leakage current while scaling to achieve an equivalent oxide thickness (EOT) below 0.5 nm is necessary to control the influence of interlayers on capacitor performance. For this, Pt and Ru, with their high work function, can be used instead of a conventional TiN substrate to increase the Schottky barrier height. Additionally, forming rutile-TiO₂ on RuO₂ with excellent lattice compatibility by epitaxial growth can minimize leakage current. Furthermore, plasma-enhanced atomic layer deposition (PEALD) can be used to deposit a uniform thin film with high density and low defects at low temperatures, to reduce the impact of interfacial reactions on electrical properties at high temperatures. In this study, TiO₂ was deposited using PEALD, using substrates of Pt and Ru treated with rapid thermal annealing at 500 and 600 ℃, to compare structural, chemical, and electrical characteristics with reference to a TiN substrate. As a result, leakage current was suppressed to around 10^-6 A/cm² at 1 V, and an EOT at the 0.5 nm level was achieved.

• JSTS:Journal of Semiconductor Technology and Science
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• 제3권2호
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• pp.76-82
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• 2003

The robust stack storage node and sufficient cell capacitance for high performance is indispensable for 90 nm DRAM capacitor. For the first time, we successfully demonstrated MIS capacitor process integration for 90 nm DRAM technology. Novel cell layout and integration technology of 90 nm DRAM capacitor is proposed and developed, and it can be extended to the next generation DRAM. Diamond-shaped OCS with 1.8 um stack height is newly developed for large capacitor area with better stability. Furthermore, the novel $Al_2O_3/HfO_2$ dielectric material with equivalent oxide thickness (EOT) of 25 ${\AA}$ is adopted for obtaining sufficient cell capacitance. The reliable cell capacitance and leakage current of MIS capacitor is obtained with ~26 fF/cell and < 1 fA/ceil by $Al_2O_3/HfO_2$ dielectric material, respectively.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.463-463
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• 2012

ITRS (international technology roadmap for semiconductors)에 따르면 MOS(metal-oxide-semiconductor)의 CD (critical dimension)가 45 nm node이하로 줄어들면서 poly-Si/$SiO_2$를 대체할 수 있는 poly-Si/metal gate/high-k dielectric이 대두된다고 보고하고 있다. 일반적으로 high-k dielectric를 식각시 anisotropic 한 식각 형상을 형성시키기 위해서 plasma를 이용한 RIE (reactive ion etching)를 사용하고 있지만 PIDs (plasma induced damages)의 하나인 PIED (plasma induced edge damage)의 발생이 문제가 되고 있다. PIED의 원인으로 plasma의 direct interaction을 발생시켜 gate oxide의 edge에 trap을 형성시키므로 그 결과 소자 특성 저하가 보고되고 있다. 그러므로 본 연구에서는 이에 차세대 MOS의 high-k dielectric의 식각공정에 HDP (high density plasma)의 ICP (inductively coupled plasma) source를 이용한 원자층 식각 장비를 사용하여 PIED를 줄일 수 있는 새로운 식각 공정에 대한 연구를 하였다. One-monolayer 식각을 위한 1 cycle의 원자층 식각은 총 4 steps으로 구성 되어 있다. 첫 번째 step은 Langmuir isotherm에 의하여 표면에 highly reactant atoms이나 molecules을 chemically adsorption을 시킨다. 두 번째 step은 purge 시킨다. 세 번째 step은 ion source를 이용하여 발생시킨 Ar low energetic beam으로 표면에 chemically adsorbed compounds를 desorption 시킨다. 네 번째 step은 purge 시킨다. 결과적으로 self limited 한 식각이 이루어짐을 볼 수 있었다. 실제 공정을 MOS의 high-k dielectric에 적용시켜 metal gate/high-k dielectric CMOSFETs의 NCSU (North Carolina State University) CVC model로 구한 EOT (equivalent oxide thickness)는 변화가 없으면서 mos parameter인 Ion/Ioff ratio의 증가를 볼 수 있었다. 그 원인으로 XPS (X-ray photoelectron spectroscopy)로 gate oxide의 atomic percentage의 분석 결과 식각 중 발생하는 gate oxide의 edge에 trap의 감소로 기인함을 확인할 수 있었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2007년도 추계학술대회 논문집
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• pp.171-172
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• 2007

We fabricated the metal-ferroelectric-insulator-semiconductor filed-effect transistors (MFIS-FETs) using the $(Bi,La)_4Ti_3O_{12}\;and\;LaZrO_x$ thin films. The $LaZrO_x$ thin film had a equivalent oxide thickness (EOT) value of 8.7 nm. From the capacitance-voltage (C-V) measurements for an Au/$(Bi,La)_4Ti_3O_{12}/LaZrO_x$/Si MFIS capacitor, a hysteric shift with a clockwise direction was observed and the memory window width was about 1.4 V for the bias voltage sweeping of ${\pm}9V$. From drain current-gate voltage $(I_D-V_G)$ characteristics of the fabricated Fe-FETs, the obtained threshold voltage shift (memory window) was about 1 V due to ferroelectric nature of BLT film. The drain current-drain voltage $(I_D-V_D)$ characteristics of the fabricated Fe-FETs showed typical n-channel FETs current-voltage characteristics.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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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.

• JSTS:Journal of Semiconductor Technology and Science
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• 제1권4호
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• pp.202-208
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• 2001

In Recent results suggested that doping $Ta_2O_5$ with a small amount of $TiO_2$ using standard ceramic processing techniques can increase the dielectric constant of $Ta_2O_5$ significantly. In this paper, this concept is studied using RTCVD (Rapid Thermal Chemical Vapor Deposition). Ti-doped $Ta_2O_5$ films are deposited using $TaC_{12}H_{30}O_5N$, $C_8H_{24}N_4Ti$, and $O_2$ on both Si and $NH_3$-nitrided Si substrates. An $NH_3$-based interface layer at the Si surface is used to prevent interfacial oxidation during the CVD process and post deposition annealing is performed in $H_2/O_2$ ambient to improve film quality and reduce leakage current. A sputtered TiN layer is used as a diffusion barrier between the Al gate electrode and the $TaTi_xO_y$ dielectric. XPS analyses confirm the formation of a ($Ta_2O_5)_{1-x}(TiO_2)_x$ composite oxide. A high quality $TaTi_xO_y$ gate stack with EOT (Equivalent Oxide Thickness) of $7{\AA}$ and leakage current $Jg=O.5A/textrm{cm}^2$ @ Vg=-1.0V has been achieved. We have also succeeded in forming a $TaTi_x/O_y$ composite oxide by rapid thermal oxidation of the as-deposited CVD TaTi films. The electrical properties and Jg-EOT characteristics of these composite oxides are remarkably similar to that of RTCVD $Ta_2O_5, suggesting that the dielectric constant of $Ta_2O_5$ is not affected by the addition of $TiO_2$.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2009년도 하계학술대회 논문집
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• pp.104-104
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• 2009

Critical dimensions has rapidly shrunk to increase the degree of integration and to reduce the power consumption. However, it is accompanied with several problems like direct tunneling through the gate insulator layer and the low conductivity characteristic of poly-silicon. To cover these faults, the study of new materials is urgently needed. Recently, high dielectric materials like $Al_2O_3$, $ZrO_2$ and $HfO_2$ are being studied for equivalent oxide thickness (EOT). However, poly-silicon gate is not compatible with high-k materials for gate-insulator. To integrate high-k gate dielectric materials in nano-scale devices, metal gate electrodes are expected to be used in the future. Currently, metal gate electrode materials like TiN, TaN, and WN are being widely studied for next-generation nano-scale devices. The TaN gate electrode for metal/high-k gate stack is compatible with high-k materials. According to this trend, the study about dry etching technology of the TaN film is needed. In this study, we investigated the etch mechanism of the TaN thin film in an inductively coupled plasma (ICP) system with $O_2/BCl_3/Ar$ gas chemistry. The etch rates and selectivities of TaN thin films were investigated in terms of the gas mixing ratio, the RF power, the DC-bias voltage, and the process pressure. The characteristics of the plasma were estimated using optical emission spectroscopy (OES). The surface reactions after etching were investigated using X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES).

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.1
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• pp.54-57
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• 2003

[ $HfO_xN_y$ ] films using a hafnium tertiary-butoxide $(Hf[OC(CH_3)_3]_4)$ in plasma and $N_2$ ambient were prepared to improve the thermal stability of hafnium-based gate dielectrics. A 10% nitrogen incorporation into $HfO_2$ films showed a smooth surface morphology and a crystallization temperature as high as $200^{\circ}C$ compared with pure $HfO_2$ films. The $TaN/HfO_xN_y/Si$ capacitors showed a stable capacitance-voltage characteristics even at post-metal annealing temperature of $1000^{\circ}C$ in $N_2$ ambient and a constant value of 1.6 nm EOT (equivalent oxide thickness) irrespective of an increase of PDA and PMA temperature. Leakage current densities of $HfO_xN_y$ capacitors annealed at PDA temperature of 800 and $900^{\circ}C$, respectively were approximately one order of magnitude lower than that of $HfO_2$ capacitors.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 하계학술대회 논문집 Vol.9
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• pp.168-168
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• 2008

Dimension of a transistor has rapidly shrunk to increase the speed of device and to reduce the power consumption. However, it is accompanied with several problems like direct tunneling through the gate dioxide layer and low conductivity characteristic of poly-Si gate in nano-region. To cover these faults, study of new materials is urgently needed. Recently, high dielectric materials like $Al_2O_3$, $ZrO_2$, and $HfO_2$ are being studied for equivalent oxide thickness (EOT). However, poly-Si gate is not compatible with high-k materials for gate-insulator. Poly Si gate with high-k material has some problems such as gate depletion and dopant penetration problems. Therefore, new gate structure or materials that are compatible with high-k materials are also needed. TiN for metal/high-k gate stack is conductive enough to allow a good electrical connection and compatible with high-k materials. According to this trend, the study on dry etching of TiN for metal/high-k gate stack is needed. In this study, the investigations of the TiN etching characteristics were carried out using the inductively coupled $BCl_3$-based plasma system and adding $Cl_2$ gas. Dry etching of the TiN was studied by varying the etching parameters including $BCl_3$/Ar gas mixing ratio, RF power, DC-bias voltage to substrate, and $Cl_2$ gas addition. The plasmas were characterized by optical emission spectroscopy analysis. Scanning electron microscopy was used to investigate the etching profile.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.264-264
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• 2016

최근에 charge trap flash (CTF) 기술은 절연막에 전하를 트랩과 디트랩 시킬 때 인접한 셀 간의 간섭현상을 최소화하여 오동작을 줄일 수 있으며 낸드 플래시 메모리 소자에 적용되고 있다. 낸드 플래시 메모리는 고집적화, 대용량화와 비휘발성 등의 장점으로 인해 핸드폰, USB, MP3와 컴퓨터 등에 이용되고 있다. 기존의 실리콘 기반의 플래시 메모리 소자는 좁은 밴드갭으로 인해 투명하지 않고 고온에서의 공정이 요구되는 문제점이 있다. 따라서, 이러한 문제점을 개선하기 위해 실리콘의 대체 물질로 산화물 반도체 기반의 플래시 메모리 소자들이 연구되고 있다. 산화물 반도체 기반의 플래시 메모리 소자는 넓은 밴드갭으로 인한 투명성을 가지고 있으며 저온에서 공정이 가능하여 투명하고 유연한 기판에 적용이 가능하다. 다양한 산화물 반도체 중에서 비정질 In-Ga-Zn-O (a-IGZO)는 비정질임에도 불구하고 우수한 전기적인 특성과 화학적 안정성을 갖기 때문에 많은 관심을 받고 있다. 플래시 메모리의 고집적화가 요구되면서 절연막에 high-k 물질을 atomic layer deposition (ALD) 방법으로 적용하고 있다. ALD 방법을 이용하면 우수한 계면 흡착력과 균일도를 가지는 박막을 정확한 두께로 형성할 수 있는 장점이 있다. 또한, high-k 물질을 절연막에 적용하면 높은 유전율로 인해 equivalent oxide thickness (EOT)를 줄일 수 있다. 특히, HfOx와 AlOx가 각각 trap layer와 blocking layer로 적용되면 program/erase 동작 속도를 증가시킬 수 있으며 넓은 밴드갭으로 인해 전하손실을 크게 줄일 수 있다. 따라서 본 연구에서는 ALD 방법으로 AlOx와 HfOx를 게이트 절연막으로 적용한 a-IGZO 기반의 thin-film transistor (TFT) 플래시 메모리 소자를 제작하여 메모리 특성을 평가하였다. 제작 방법으로는, p-Si 기판 위에 열성장을 통한 100 nm 두께의 SiO2를 형성한 뒤, 채널 형성을 위해 RF sputter를 이용하여 70 nm 두께의 a-IGZO를 증착하였다. 이후에 소스와 드레인 전극에는 150 nm 두께의 In-Sn-O (ITO)를 RF sputter를 이용하여 증착하였고, ALD 방법을 이용하여 tunnel layer에 AlOx 5 nm, trap layer에 HfOx 20 nm, blocking layer에 AlOx 30 nm를 증착하였다. 최종적으로, 상부 게이트 전극을 형성하기 위해 electron beam evaporator를 이용하여 platinum (Pt) 150 nm를 증착하였고, 계면 결함을 최소화하기 위해 퍼니스에서 질소 가스 분위기, $400^{\circ}C$, 30 분의 조건으로 열처리를 했다. 측정 결과, 103 번의 program/erase를 반복한 endurance와 104 초 동안의 retention 측정으로부터 큰 열화 없이 메모리 특성이 유지되는 것을 확인하였다. 결과적으로, high-k 물질과 산화물 반도체는 고성능과 고집적화가 요구되는 향후 플래시 메모리의 핵심적인 물질이 될 것으로 기대된다.