• Journal of the Institute of Electronics Engineers of Korea SD
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• v.38 no.5
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• pp.375-381
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• 2001

As the device geometry continuously shrink down less than sub-quarter micrometer, DRAM makers are going to replace conventional tungsten-polycide bit-line with tungsten bit-line structure in order to reduce the chip size and use it as a local interconnection. In this paper we showed low resistance tungsten bit-line fabrication process with various RTP(Rapid Thermal Process) temperature and additional ion implantation. As a result we obtained that major parameters impact on tungsten bit-line process are RTP Anneal temperature and BF$_2$ ion implantation dopant. These tungsten bit-line process are promising to fabricate high density chip technology.

• Proceedings of the Korean Vacuum Society Conference
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• 2000.02a
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• pp.123-123
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• 2000

선폭이 초미세화됨에 따라 게이트 전극에서의 공핍 현상 및 불순물 확산의 물제를 갖는 poly-Si 게이트를 대체할 전극 물질로 텅스텐(W)이 많이 연구되어 왔다. 반도체 소자의 배선물질로 일찍부터 사용되어온 텅스텐은 내화성 금속의 일종으로 용융점이 높고, 저항이 낮다. 그러나, 일반적으로 사용되고 있는 CVD에 의한 텅스텐의 증착은 반응가스(WF6)로부터 오는 불소(F)의 게이트 산화막내로의 확산으로 인해 MOS 소자가 크게 열화될수 있다. 본 연구에서는 W/TiN 이중 게이트 전극 구조를 갖는 MOS 캐패시터를 제작하여 전기적 특성을 살펴보았다. P-Type (100) Si위에 RTP를 이용, 85$0^{\circ}C$에서 110 의 열산화막을 성장 및 POA를 수행한 후, 반응성 스퍼터링법에 의해 상온, 6mTorr, N2/Ar=1/6 sccm, 100W 조건에서 TiN 박막을 150, 300, 500 의 3그룹으로 증착하였다. 그 위에 LPCVD 방법으로 35$0^{\circ}C$, 0.7Torr, WF6/SiH4/H2=5/5~10/500sccm 조건에서 2000~3000 의 텅스텐을 증착하였다. Photolithography 공정 및 습식 에칭을 통해 200$\mu\textrm{m}$$\times$200$\mu\textrm{m}$ 크기의 W/TiN 복층 게이트 MOSC를 제작하였다. W/TiN 복측 게이트 소자와 비교분석하기 위해 같은 조건의 산화막을 이용한 알루미늄(Al) 게이트, 텅스텐 게이트 MOSC를 제작하였다. 35$0^{\circ}C$에서 증착된 텅스텐 박막은 10~11$\Omega$/ 의 면저항을 가졌고 미소한 W(110) peak값을 나타내는 것으로 보아 비정질 상태에 가까웠다. TiN 박막의 경우 120~130$\Omega$/ 의 면저항을 가졌고 TiN (200)의 peak 값이 크게 나타난 반면, TiN(111) peak가 미소하게 나타났다. TiN 박막의 두께와 WF/SiH4의 가스비를 변화시켜가며 제작된 MOS 캐패시터를 HF 및 QS C-V, I-V 그리고 FNT를 통한 전자주입 방법을 이용하여 TiN 박막의 불소에 대한 확산 방지막 역할을 살펴 보았다. W/TiN 게이트 MOS 소자는 모두 순수 텅스텐 게이트보다 우수하였고, Al 게이트와 유사한 전기적 특성을 보여주었다. W/TiN 게이트 MOS 소자는 모두 순수 텅스텐 게이트보다 우수하였고, Al 게이트와 유사한 전기적 특성을 보여주었다. TiN 박막이 300 , 500 이고 WF6/SiH4의 가스비가 5:10인 경우 소자 특성이 우수하였으나, 5:5의 경우에는 FNT 전자주입 특성이 열화되기 시작하였다. 그리고, TiN박막의 두께가 150 으로 얇아질 경우에는 WF6/SiH4의 가스비가 5:10인 경우에서도 소자 특성이 열화되기 시작하였다. W/TiN 복층 게이트 MOS 캐패시터를 제작하여 전기적인 특성 분석결과, 순수 텅스텐 게이트 소자의 큰 저전계 누설 전류 특성을 해결할 수 있었으며, 불소확산에 영향을 주는 조건이 WF6/SiH4의 가스비에 크게 의존됨을 알 수 있었다. TiN 박막의 증착 공정이 최적화 될 경우, 0.1$\mu\textrm{m}$이하의 초미세소자용 게이트 전극으로서 텅스텐의 사용이 가능할 것으로 보여진다.

• Resources Recycling
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• v.31 no.6
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• pp.25-35
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• 2022

The adsorption/desorption behavior and separation conditions of vanadium and tungsten ions were investigated using a gel-type anion-exchange resin. In the adsorption experiment with the initial acidity of the solution, the adsorption rate of vanadium was remarkably low in strong acids and bases. Additionally, the adsorption rate of tungsten was low in a strong base. An increase in the reaction temperature increased the adsorption reaction rate and maximum adsorption. The effect of tungsten on the maximum adsorption was minimal. The adsorption isotherms of vanadium and tungsten on the ion-exchange resin were suitable for the Langmuir adsorption isotherms of both the ions. For tungsten, the adsorption isotherms of vanadium and tungsten were polyoxometalate. Both ion-exchange resins were simulated using similar quadratic reaction rate models. Vanadium was desorbed in the aqueous solutions of HCl or NaOH, the desorption characteristics of vanadium and tungsten depended on the desorption solution, and tungsten was desorbed in the aqueous solution of NaOH. It was possible to separate the two ions using the desorption process. The desorption reaction reached equilibrium within 30 min, and more than 90% recovery was possible.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.125-125
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• 2018

반도체 소자의 미새화에 따라 선폭이 10nm 이하로 줄어듦에 따라, 금속 배선의 저항이 급격하게 상승하고 있다. Cu는 낮은 저항과 높은 전도도를 가지고 있어 현재 배선물질로써 가장 많이 사용되고 있지만, 소자가 미세화됨에 따라 Cu를 미래의 배선물질로써 계속 사용하기에는 몇 가지 문제점이 제기되고 있다. Cu는 electron mean free path (EMFP)가 39 nm로 긴 특성을 가지기 때문에, 선폭이 줄어듦에 따라 surface 및 grain boundary scattering이 증가하여 저항이 급격하게 증가한다. 또한, technology node에 따른 소자의 operating temperature와 current density의 증가로 인해 Cu의 reliability가 감소하게 된다. 텅스텐은 EMFP가 19 nm로 짧은 특성을 가지고 있어, 소자의 크기가 줄어듦에 따라 Cu보다 낮은 저항 특성을 가질 수 있으며, 녹는점이 3695K로 1357K인 Cu보다 높으므로 배선물질로써 Cu를 대체할 가능성이 있다. 본 연구에서는 Inductively Coupled Plasma (ICP) assisted magnetron sputtering을 통해 매우 얇은 텅스텐 박막을 증착하여 저항을 낮추고자 하였다. 고밀도 플라즈마의 방전을 위해, internal-type coil antenna를 사용하였으며 텅스텐 박막의 증착을 위해 DC sputter system이 사용되었다. 높은 에너지를 가진 텅스텐 이온을 이용하여 낮은 온도에서 고품위 박막을 증착할 수 있었으며, dense한 구조의 박막 성장이 가능하였다. ICP assisted를 이용하여 증착했을 때와, 그렇지 않을 때를 비교하여 ICP 조건에 따라서 박막의 저항이 감소함을 확인할 수 있었을 뿐만 아니라 최대 약 65% 감소함을 확인할 수 있었다. XRD를 이용하여 ICP power를 인가했을 때, 높은 저항을 갖는 A-15 구조를 가진 ${\beta}$ peak의 감소와 낮은 저항을 갖는 BCC 구조를 가진 ${\alpha}$ peak의 증가를 상온과 673K에서 증착한 박막 모두에서 확인하였으며, 이를 통해 ICP power가 저항 감소에 영향을 미친다는 것을 확인하였다. 또한, 두 온도 조건에서 grain size를 계산하여 ICP power를 인가함에 따라 두 조건 모두 grain size가 증가하였음을 조사하였다. 또한, XPS 분석을 통해 ICP power를 인가하였을 때 박막의 저항에 많은 영향을 끼치는 O peak이 감소하는 것을 통해 ICP assisted의 효과를 확인하였다. 이를 통해, ICP assisted magnetron sputtering을 통해 텅스텐 박막을 증착함으로써 차세대 배선물질로써 텅스텐의 가능성을 확인할 수 있었다.

• Resources Recycling
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• v.30 no.4
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• pp.54-63
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• 2021

Vanadium and tungsten can be obtained by separating/recovering the leaching solution from a spent SCR DeNO_X catalyst using the soda roasting-water leaching process. Therefore, in this study, the adsorption/desorption mechanism of vanadium and tungsten in an ion-exchange column was investigated using Lewatit MonoPlus MP 600, a strong basic anion exchange resin. The operating conditions for the separation of vanadium and tungsten in the ion-exchange column was intended to present. By conducting a continuous adsorption experiment in a pH 8.5 solution, the adsorption capacity of vanadium and tungsten was found to be 44.75 and 64.92 mg/(g of resin), respectively, which showed that the adsorption capacity of tungsten was larger than that of vanadium because of the difference in ion charge. Vanadium has a higher affinity for MP 600 than tungsten. Consequently, as the vanadium-containing solution is eluted through the ion exchange resin onto which tungsten is adsorbed, the adsorbed tungsten is exchanged with vanadium and desorbed. A continuous experiment was performed with a solution of vanadium and tungsten prepared at the same concentration as the spent SCR DeNO_X catalyst leachate. The adsorption capacity of vanadium was found to be 48.72 mg/(g of resin) and 80% of the supplied vanadium was adsorbed; in contrast, almost no tungsten was adsorbed. Therefore, vanadium and tungsten were separated effectively. The ion exchange resin was treated with 2 M HCl at 15 mL/h, and 97.7% of the vanadium(99% purity) could be desorbed. After desorption, NH₄Cl was added to precipitate ammonium polyvanadate at 90℃ and recover 93% of the vanadium.

• Proceedings of the Materials Research Society of Korea Conference
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• 1992.05b
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• pp.147-148
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• 1992

• Resources Recycling
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• v.19 no.4
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• pp.41-50
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• 2010

A fundamental study was carried out to develop a process for recycling tungsten and cobalt from WC-Co hardmetal sludge generated in the manufacturing process of hardmetal tools. The complete extraction of cobalt and simultaneous formation of tungstic was achieved by treating the sludge using aqua regia. The effect of aqua regia concentration, reaction temperature and time, pulp density on cobalt leaching and tungstic acid formation was investigated. The complete leaching of cobalt was attained at the optimum conditions: 100 vol.% aqua regia concentration, $100^{\circ}C$ temperature, 60 min. reaction time and 400 g/L pulp density. A complete conversion of tungsten carbide of the sludge to tungstic acid was however, obtained at the pulp densities lower than 150 g/L under the above condition. The progress of reaction during the aqua regia treatment of the sludge was monitored through the XRD phase identification of the residue. The metallic impurities in the tungstic acid so produced could be further removed as insoluble residues by dissolving the tungsten values in ammonia solution. The ammonium paratungstate($(NH_4)_{10}{\cdot}H_2W_{12}O_{42}{\cdot}4H_2O$) of 99.85% purity was prepared from the ammonium polytungstate solution by the evaporation crystallization method.

• Korean Journal of Materials Research
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• v.9 no.11
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• pp.1137-1143
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• 1999

Microstructure and mechanical properties of Mod.9Cr-1Mo and W added 9Cr-0.5Mo2W steels were investigated for liquid metal reactor (LMR) heat exchange tube. The tempering temperatures at which cell structure was formed were $700^{\circ}C$ for Mod.9Cr-1Mo steel and $750^{\circ}C$ for W added 9Cr0.5Mo-2W steel. indicating the recovery of dislocation was delayed by the addition of W. 9Cr-0.5Mo-2W steel had the same kinds of precipitates with Mod.9Cr-1Mo steel, but the W was included in the precipitates in 9Cr-0.5Mo-2W steel. Micro-hardness and ultimate tensile strength of 9Cr-0.5Mo-2W steel were higher than those of Mod.9Cr-1Mo steel. The impact property of Mod.9Cr-1Mo steel was superior to that of 9Cr-0.5Mo-2W steel.

• Resources Recycling
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• v.31 no.4
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• pp.19-25
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• 2022

In this study, tungsten carbide (WC) powder was prepared using a novel recycling process for hard metal sludge that does not use ammonium paratungstate. Instead of ammonia, acid was used to remove the sodium and crystallized tungstate, resulting in the formation of tungstic acid (H₂WO₄). The WC powder was successfully synthesized by the carbothermal reduction of tungstic acid through H₂O decomposition, reduction of WO₃ to W, and formation of WC. The carbon content and holding time at the carbothermal reduction temperature were optimized to remove free carbon from the WC powder. As a result, most of the free carbon in the WC powder prepared from sludge was removed, and the content of free carbon in the synthesized WC powder was lower than that in commercial WC powder. Moreover, the crystallite size of WC prepared from H₂WO₄ was much smaller than that of commercial micron-sized WC powder produced from APT. The small crystallite size of WC induces grain growth during the sintering of the WC-Co composite; thus, a WC-Co composite with large WC grains was fabricated using the WC powder prepared from H₂WO₄. The large WC grains affected the mechanical properties of the WC-Co composite. Further, due to the large grain size, the WC-Co composite fabricated from H₂WO₄ exhibited a higher toughness than that of the WC-Co composite prepared from commercial WC powder.

• Korean Journal of Materials Research
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• v.10 no.1
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• pp.29-33
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• 2000

The amorphous tungsten nitrides, WNx, film could be fabricated by reactive sputtering process. The nitrogen concentration for the amorphization ranges from 10 at% to 40at%. The amorphous $W_{67}N_{33}$ film was crystallized into low resistivity $\alpha$-tungsten phase with equiaxed grains and excess nitrogen after the rapid thermal annealing for 1min at 1273K, which was similar to the resistivity of the sputtered pure tungsten film. The excess nitrogen was depleted from $\alpha$-tungsten crystals and then segregated at $\alpha$-tungsten/poly-Si interface. The segregated nitrogen has favored the formation of the homogeneous diffusion barrier layer comprised of silicon nitride, $Si_3N_4$, nano-crystals, which undertaken the inhibition of the high resistivity tungsten silicide reaction.