• Title/Summary/Keyword: ICP Etching

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Surface reaction of $HfO_2$ etched in inductively coupled $BCl_3$ plasma ($BCl_3$ 유도결합 플라즈마를 이용하여 식각된 $HfO_2$ 박막의 표면 반응 연구)

  • Kim, Dong-Pyo;Um, Doo-Seunng;Kim, Chang-Il
    • 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).

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The surface kinetic properties between $BCl_3/Cl_2$/Ar plasma and $Al_2O_3$ thin film

  • Yang, Xue;Kim, Dong-Pyo;Um, Doo-Seung;Kim, Chang-Il
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.169-169
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    • 2008
  • To keep pace with scaling trends of CMOS technologies, high-k metal oxides are to be introduced. Due to their high permittivity, high-k materials can achieve the required capacitance with stacks of higher physical thickness to reduce the leakage current through the scaled gate oxide, which make it become much more promising materials to instead of $SiO_2$. As further studying on high-k, an understanding of the relation between the etch characteristics of high-k dielectric materials and plasma properties is required for the low damaged removal process to match standard processing procedure. There are some reports on the dry etching of different high-k materials in ICP and ECR plasma with various plasma parameters, such as different gas combinations ($Cl_2$, $Cl_2/BCl_3$, $Cl_2$/Ar, $SF_6$/Ar, and $CH_4/H_2$/Ar etc). Understanding of the complex behavior of particles at surfaces requires detailed knowledge of both macroscopic and microscopic processes that take place; also certain processes depend critically on temperature and gas pressure. The choice of $BCl_3$ as the chemically active gas results from the fact that it is widely used for the etching o the materials covered by the native oxides due to the effective extraction of oxygen in the form of $BCl_xO_y$ compounds. In this study, the surface reactions and the etch rate of $Al_2O_3$ films in $BCl_3/Cl_2$/Ar plasma were investigated in an inductively coupled plasma(ICP) reactor in terms of the gas mixing ratio, RF power, DC bias and chamber pressure. The variations of relative volume densities for the particles were measured with optical emission spectroscopy (OES). The surface imagination was measured by AFM and SEM. The chemical states of film was investigated using X-ray photoelectron spectroscopy (XPS), which confirmed the existence of nonvolatile etch byproducts.

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A Study on the Leaching and Recovery of Lithium by Reaction between Ferric Chloride Etching Solution and Waste Lithium Iron Phosphate Cathode Powder (폐리튬인산철 양극재 분말과 염화철 에칭액과의 반응에 의한 리튬의 침출 및 회수에 대한 연구)

  • Hee-Seon Kim;Dae-Weon Kim;Byung-Man Chae;Sang-Woo Lee
    • Resources Recycling
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    • v.32 no.3
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    • pp.9-17
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    • 2023
  • Efforts are currently underway to develop a method for efficiently recovering lithium from the cathode material of waste lithium iron phosphate batteries (LFP). The successful application of lithium battery recycling can address the regional ubiquity and price volatility of lithium resources, while also mitigating the environmental impact associated with both waste battery material and lithium production processes. The isomorphic substitution leaching process was used to recover lithium from spent lithium iron phosphate batteries. Lithium was leached by the isomorphic substitution of Fe2+ in LFP using a relatively inexpensive ferric chloride etching solution as a leaching agent. In the study, the leaching rate of lithium was compared using the ferric chloride etching solution at various multiples of the LFP molar ratio: 0.7, 1.0, 1.3, and 1.6 times. The highest lithium leaching rate was shown at about 98% when using 1.3 times the LFP molar ratio. Subsequently, to eliminate Fe, the leachate was treated with NaOH. The Fe-free solution was then used to synthesize lithium carbonate, and the harvested powder was characterized and validated. The surface shape and crystal phase were analyzed using SEM and XRD analysis, and impurities and purity were confirmed using ICP analysis.

Electromagnetic Micro x-y Stage for Probe-Based Data Storage

  • Park, Jae-joon;Park, Hongsik;Kim, Kyu-Yong;Jeon, Jong-Up
    • JSTS:Journal of Semiconductor Technology and Science
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    • v.1 no.1
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    • pp.84-93
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    • 2001
  • An electromagnetic micro x-y stage for probe-based data storage (PDS) has been fabricated. The x-y stage consists of a silicon body inside which planar copper coils are embedded, a glass substrate bonded to the silicon body, and eight permanent magnets. The dimensions of flexures and copper coils were determined to yield $100{\;}\mu\textrm{m}$ in x and y directions under 50 mA of supplied current and to have 440 Hz of natural frequency. For the application to PDS devices, electromagnetic stage should have flat top surface for the prevention of its interference with multi-probe array, and have coils with low resistance for low power consumption. In order to satisfy these design criteria, conducting planar copper coils have been electroplated within silicon trenches which have high aspect ratio ($5{\;}\mu\textrm{m}$in width and $30{\;}\mu\textrm{m}$in depth). Silicon flexures with a height of $250{\;}\mu\textrm{m}$ were fabricated by using inductively coupled plasma reactive ion etching (ICP-RIE). The characteristics of a fabricated electromagnetic stage were measured by using laser doppler vibrometer (LDV) and dynamic signal analyzer (DSA). The DC gain was $0.16{\;}\mu\textrm{m}/mA$ and the maximum displacement was $42{\;}\mu\textrm{m}$ at a current of 180 mA. The measured natural frequency of the lowest mode was 325 Hz. Compared with the designed values, the lower natural frequency and DC gain of the fabricated device are due to the reverse-tapered ICP-RIE process and the incomplete assembly of the upper-sided permanent magnets for LDV measurements.

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Effects of CF4 Plasma Treatment on Characteristics of Enhancement Mode AlGaN/GaN High Electron Mobility Transistors

  • Horng, Ray-Hua;Yeh, Chih-Tung
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.62-62
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    • 2015
  • In this study, we study the effects of CF4 plasma treatment on the characteristics of enhancement mode (E-mode) AlGaN/GaN high electron mobility transistors (HEMTs). The CF4 plasma is generated by inductively coupled plasma reactive ion etching (ICP-RIE) system. The CF4 gas is decomposed into fluorine ions by ICP-RIE and then fluorine ions will effect the AlGaN/GaN interface to inhibit the electron transport of two dimension electron gas (2DEG) and increase channel resistance. The CF4 plasma method neither like the recessed type which have to utilize Cl2/BCl3 to etch semiconductor layer nor ion implantation needed high power to implant ions into semiconductor. Both of techniques will cause semiconductor damage. In the experiment, the CF4 treatment time are 0, 50, 100, 150, 200 and 250 seconds. It was found that the devices treated 100 seconds showed best electric performance. In order to prove fluorine ions existing and CF4 plasma treatment not etch epitaxial layer, the secondary ion mass spectrometer confirmed fluorine ions truly existing in the sample which treatment time 100 seconds. Moreover, transmission electron microscopy showed that the sample treated time 100 seconds did not have etch phenomena. Atomic layer deposition is used to grow Al2O3 with thickness 10, 20, 30 and 40 nm. In electrical measurement, the device that deposited 20-nm-thickness Al2O3 showed excellent current ability, the forward saturation current of 210 mA/mm, transconductance (gm) of 44.1 mS/mm and threshold voltage of 2.28 V, ION/IOFF reach to 108. As IV concerning the breakdown voltage measurement, all kinds of samples can reach to 1450 V.

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유도결합 $Cl_2/CHF_3, Cl_2/CH_4, Cl_2/Ar $플라즈마를 이용한 InGaN 건식 식각 반응 기구 연구

  • 이도행;김현수;염근영;이재원;김태일
    • Proceedings of the Korean Vacuum Society Conference
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    • 1999.07a
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    • pp.249-249
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    • 1999
  • GaN과 같은 III-nitride 반도체 관한 식각 기술의 연구는 blue-emitting laser diode(LD)를 위한 경면(mirror facet)의 형성뿐만아니라 새로운 display 용도의 light emitting diodes (LED), 고온에서 작동되는 광전소자 제조 등에도 그 중요성이 증대되고 있다. 최근에는 III-nitride 물질의 높은 식각속도와 미려하고 수직한 식각형상을 이루기 위하여 ECR(Electron Cyclotron Resonance)이나 ICP(Inductively Coupled Plasma)와 같은 고밀도 플라즈마 식각과 CAIBE(Chemically assisted ion beam etching)를 이용한 연구가 진행되고 있다. 현재 제조되어 지고 있는 LED 및 LD와 같은 광소자의 구조의 대부분은 p-GaN/AlGaN/InGaN(Q.W)/AlGaN/n-GaN 와 같은 여러 층의 형태로 이루어져 있다. 이중 InGaN는 광소자나 전자소자의 특성에 영향을 주는 가장 중요한 부분으로써 현재까지 보고된 식각연구는 undoped GaN에 대부분 집중되고 있고 이에 비해 소자 특성에 핵심을 이루는 InGaN의 식각특성에 관한 연구는 미흡한 상황이다. 본 연구에서는 고밀도 플라즈마원인 ICP 장비를 이용하여 InGaN를 식각하였고, 식각에는 Cl2/CH4, Cl2/Ar 플라즈마를 사용하였다. InGaN의 식각특성에 영향을 미치는 플라즈마의 특성을 관찰하기 위하여 quadrupole mass spectrometry(QMS)와 optical emission spectroscopy(PES)를 사용하였다. 기판 온도는 5$0^{\circ}C$, 공정 압력은 5,Torr에서 30mTorr로 변화시켰고 inductive power는 200~800watt, bias voltage는 0~-200voltage로 변화시켰으며 식각마스크로는 SiO2를 patterning 하여 사용하였다. n-GaN, p-GaN 층 이외에 광소자 제조시 필수적인 InGaN 층을 100% Cl2로 식각한 경우에 InGaN의 식각속도가 GaN에 비해 매우 낮은 식각속도를 보였다. Cl2 gas에 소량의 CH4나 Ar gas를 첨가하는 경우와 공정압력을 감소시키는 경우 식각속도는 증가하였고, Cl2/10%Ar 플라즈마에서 공정 압력을 감소시키는 경우 식각속도는 증가하였고, Cl2/10%CHF3 와 Cl2/10%Ar 플라즈마에서 공정압력을 15mTorr로 감소시키는 경우 InGaN과 GaNrks의 선택적인 식각이 가능하였다. InGaN의 식각속도는 Cl2/Ar 플라즈마의 이온에 의한 Cl2/CHF3(CH4) 플라즈마에서의 CHx radical 형성에 의하여 증가하는 것으로 사료되어 진다.

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Dry Etch Characteristic of Ferroelectric $YMnO_3$ Thin Films Using High Density $Ar/Cl_{2}CF_{4}\;PAr/Cl_{2}/CF_{4}$ 고밀도lasma ($Ar/Cl_{2}/CF_{4}$ 고밀도 플라즈마를 이용한 강유전체 $YMnO_3$의 건식식각 특성연구)

  • Park, Jae-Hwa;Kim, Chang-Il;Chang, Eui-Goo;Lee, Cheol-In;Lee, Byeong-Ki
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.11b
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    • pp.213-216
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    • 2001
  • Etching behaviors of ferroelectric $YMnO_3$ thin films were studied by an inductively coupled plasma (ICP). Etch characteristic on ferroelectric $YMnO_3$ thin film have been investigated in terms of etch rate, selectivity and etch profile. The maximum etch rate of $YMnO_3$ thin film is $300{\AA}/min$ at $Ar/Cl_2$ of 2/8, RF power of 800W, dc bias voltage of 200V, chamber pressure of 15mTorr and substrate temperature of $30^{\circ}C$. Addition of $CF_4$ gas decrease the etch rate of $YMnO_3$ thin film. From the results of XPS analysis, YFx compounds were found on the surface of $YMnO_3$ thin film which is etched in $Ar/Cl/CF_{4}$ plasma. The etch profile of $YMnO_3$ film is improved by addition of $CF_4$ gas into the $Ar/Cl_2$ plasma. These results suggest that fluoride yttrium acts as a sidewall passivants which reduce the sticking coefficient of chlorine on $YMnO_3$.

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Study of dry etching chrateristics of freeoelectric $YMnO_{3}$ thin films (강유전체 $YMno_{3}$ 박막의 건식식각 특성연구)

  • Kim, In-Pyo;Park, Jae-Hwa;Kim, Kyoung-Tae;Kim, Chang-Il;Jang, Eui-Goo;Eom, Joon-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2002.11a
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    • pp.159-162
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    • 2002
  • Ferroelectric $YMnO_{3}$ thin films were etched with $Ar/Cl_{2}$ and $CF_{4}/Cl_{2}$ inductivly coupled plasma (ICP). The maximum etch rate of $YMnO_{3}$ thin film was $300{\AA}/min$ at a $Ar/Cl_{2}$ gas mixing ratio of 2/8, a RF power of 800 W, a dc bias of 200 V, a chamber pressure of 15 mTorr, and a substrate temperature of ${30^{\circ}C}$. From the X-ray photoelectron spectroscopy (XPS) analysis , yttrium not only etched by chemical reactions with Cl radicals, but also assisted by Ar ion bombardments in $Ar/Cl_{2}$ plasma. In $CF_{4}/Cl_{2}$ plasma, yttrium are remained on the etched surface of $YMnO_{3}$ and formed of nonvolatile YFx compounds Manganese etched effectively by chemical reactions with Cl and F radicals. From the X-ray diffraction (XRD) analysis, the (0004) diffraction peak intensity of the $YMnO_{3}$ thin film etched in $Ar/Cl_{2}$ plasma shows lower value than that in $CF_{4}/Cl_{2}$ plasma. It is indicates that the crystallinty of $YMnO_{3}$ thin film is more easily damaged by the Ar ion bombardment than the changes of stoichiometry due to nonvolatile etch by-products.

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Study on Damage Reduction of $(Ba_{0.6}Sr_{0.4})TiO_{3}$ Thin Films in $Ar/CF_{4}$ Plasma ($Ar/CF_{4}$ 유도결합 플라즈마에서 식각된 $(Ba_{0.6}Sr_{0.4})TiO_{3}$ 박막의 손상 감소)

  • Kang, Pil-Seung;Kim, Kyung-Tae;Kim, Dong-Pyo;Kim, Chang-Il;Hwang, Jin-Ho;Kim, Tae-Hyung
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2002.11a
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    • pp.171-174
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    • 2002
  • The barium strontium titannate (BST) thin films were etched in $CF_{4}/Ar$ inductively coupled plasma (ICP). The high etch rate obtained at a $CF_{4}(20%)/Ar(80%)$ and the etch rate in pure argon was twice higher than that in pure $CF_{4}$. This indicated that BST etching is sputter dominant process. It is impossible to avoid plasma-induced damages by the energetic particles in the plasma and the nonvolatile etch products. The plasma damages were evaluated in terms of leakage current density, residues on the etched sample, and the changes of roughness. After the BST thin films exposed in the plasma, the leakage current density and roughness increases. In addition, there are appeared a nonvolatile etch byproductsand from the result of X-ray photoelectron spectroscopy (XPS). After annealing at ${600^{\circ}C}$ for 10 min in $O_{2}$ ambient, the increased leakage current density, roughness and nonvolatile etch byproducts reduced. From the this results, the plasma induced damage recovered by annealing process owing to the relaxation of lattice mismatches by Ar ions and the desorption of metal fluorides in high temperature.

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Nb-carbonitride Analysis Techniques in Nb-steels (강 중 Nb계 탄질화 석출물 정량분석 기술)

  • Lee, J.J.;Jung, S.W.;Yoo, K.S.
    • Analytical Science and Technology
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    • v.7 no.4
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    • pp.493-504
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    • 1994
  • The morphology and structure of precipitates of formed in Nb steels were investigated using SEM, TEM and XRD. The quantitative analysis of the precipitates was performed by ICP-AES. The potentiostatic etching method was employed as an extraction method using 10% AA-methanol and 15% Na-citrate electrolytes. The two selected potentials relative to SCE(Standard Calomel Electrode), -100mV in 10% AA-methanol solution and -250mV in 15% Na-citrate solution were found to be effective for the extraction. XRD analysis showed that composition of Nb carbonitride in Nb-steel(0.01% C-0.7% Nb-0.004N) was $NbC_{0.65}N_{0.2}$.

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