• Journal of the Korean Vacuum Society
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• v.10 no.2
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• pp.267-274
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• 2001

Removal of Cr, Ni and Cu impurities on Si surfaces using remote plasma-excited hydrogen was investigated. Si surfaces were contaminated intentionally by acetone with low purity. To determine the optimum process condition, remote plasma-excited hydrogen cleaning was conducted for various rf-powers and plasma exposure times. After remote plasma-excited hydrogen cleaning, Si surfaces were analyzed by Total X-ray Reflection Fluorescence(TXRF), Surface Photovoltage(SPV) and Atomic Forece Microscope(AFM). The concentrations of Cr, Ni and Cu impurities were reduced and the minority carrier lifetime increased after remote plasma-excited hydrogen. Also RMS roughness decreased by more than 30% after remote plasma-excited hydrogen cleaning. AFM analysis results also show that remote plasma-excited hydrogen cleaning causes no damage to the Si surface. TXRF analysis results show that remote plasma-excited hydrogen cleaning is effective in eliminating metallic impurities from Si surface only if it is performed under an optimum process conditions. The removal mechanism of the Cr, Ni and Cu impurities using remote plasma-excited hydrogen treatments is proposed to be the lift-off during removal of underlying chemical oxides.

• Korean Journal of Materials Research
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• v.6 no.7
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• pp.661-670
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• 1996

리모트 수소 플라즈마를 이용하여 실리콘 웨이퍼 표면 위에 있는 금속불순물의 제거 및 제거기구에 관하여 조사하였다. 실리콘의 표면과 내부분석을 위하여 TXRF(total reflection x-ray fluorescence)와 SPV(surface photovoltage), AFM(atomic force microscope)을 사용하였다. TXRF 분석결과 리모트 수소 플라즈마가 금속오염물질 제거에 상당한 효과가 있는 것으로 나타났다. TXRF분석결과 리모트 수소 플라즈마가 금속오염물질 제거에 상당한 효과가 있는 것으로 나타났다. 리모트 수소플라트마 처리 후 금속오염은 금속원소의 종류에 따라 1010atoms/$\textrm{cm}^2$-1011atoms/$\textrm{cm}^2$수준이었다. SPV분석결과를 보면 수소 플라즈마 처리에 의해 minority carrier 수명이 전반적으로 증가하였다. AFM 분석을 통하여 수소 플라즈마 처리가 표면 손상을 일으키지 않으며 표면의 거칠기에 나쁜 영향을 미치지 않음을 알 수 있었다. 또한 본 실험에서 나타난 결과들을 종합해 볼 때 금속오염물의 제거기구는 자연산화막 혹은 수소로 passivate된 실리콘 웨이퍼 표면을 수소 플라즈마에서 발생된 수소원자가 실리콘표면을 약하게 에칭할 때 떨어져 나가는 'lift-off'가 유력한 것으로 판단된다.

• Analytical Science and Technology
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• v.29 no.6
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• pp.261-268
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• 2016

TXRF is a powerful technique for the soil sample analysis due to its ability to conduct quantitative analysis of powder sample without complicated pre-treatment processes. The conventional internal standard method used for this technique suffers from relatively low accuracy because of varying matrix effects of soil. In order to improve the accuracy, external standard method was applied to analyze two types of soil samples; acid-dissolutionized soil solution and detergent-suspended soil powder. Individual ICP-AES/MS grade standards were mixed, diluted and measured to create standard curves, but applying these curves for analyzing the soil solution sample did not make any improvement in comparison with the internal standard method. On the other hand, standard curves were created with using standard soil powders for the analysis of soil powder samples, and we found that this method increased the accuracy significantly relative to the internal standard method. Especially, Al, Fe, K, Ca, Ti, Ba, Mn, Sr, Rb, Cu was measured with relatively high accuracy (relative error = ${\pm}20%$).

• Korean Journal of Materials Research
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• v.6 no.8
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• pp.817-824
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• 1996

Removal of Cu impurities on Si substrates using remote H-plasma was investigated. Si substrates were intentionally contaminated by 1ppm ${CuCI}_{2}$, standard chemical solution. To determine the optimal process condition, remote H-plasma cleaning was conducted varying the parameters of rf power, cleaning time and remoteness(the distance between the center of plasma and the surface of Si substrate). After remote H-plasma cleaning was conducted, Si surfaces were analysed by TXRF(total x-ray reflection fluorescence) and AFM(atomic force microscope). The concentration of Cu impurity was reduced by more than a factor of 10 and its RMS roughness was improved by more than 30% after remote H-plasma cleaning. TXRF analysis results show that remote H-plasma cleaning is effective in eliminating Cu impurity on Si surface when it is performed under the optimal process condition. AFM analysis results also verifies that remote H-plasma cleaning makes no damage to the Si surface. The deposition mechanism of Cu impurity may be explained by the redox potential(oxidation-reduction reaction potential) theory. Based on the XPS analysis results we could draw a conclusion that Cu impurities on the Si substrate are removed together with the oxide by a "lift-off" mechanism when the chemical oxide( which forms when Cu ions are adsorbed on the Si surface) is etched off by reactive hydrogen atoms.gen atoms.

• Korean Journal of Materials Research
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• v.9 no.5
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• pp.491-495
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• 1999

In this study, we focus on Ca contaminant which affects on the roughness Si substrate after thermal process. The initial Si substrates were contaminated intentionally by using a standard Ca solution. The contamination levels of Ca impurity were measured by TXRF and the chemical composition of that was analyzed by AES. Then we gre the thermal oxide to investigate the effect of Ca contaminants. The microroughness of the Si surface, the thermal oxide surface, and the surface after removing the thermal oxide were measured to examine the electrical characteristics. The initial substrates that were contaminated with the standard solution of Ca exhibited the contamination levels of 10\ulcorner~10\ulcorneratoms/$\textrm{cm}^2$ which was measured by TXRF. The Ca contaminants were detected by AES and exhibited the peaks of Ca, SI, C and O.After intentional contamination, the surface microroughness of this initial substrate was increased from $1.5\AA$ to 4$\AA$ as contamination levels became higher. The microroughness of the thermal oxide surfaces of both contaminated and bare Si substrates exhibits similar values. But the microroughness of the contaminated$ Si/SiO_2$ interface was increased as contamination increased. The thermal oxide of contaminated substrate exhibited the small minority carrier diffusion length, low breakdown voltage, and slightly high leakage current.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.13 no.2
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• pp.131-136
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• 2000

We have investigated the slurry induced metallic contaminations of undoped and doped silicate oxides surface on CMP cleaning process. The metallic contaminations by CMP slurry were evaluated in four different oxide films, such as plasma enhanced tetra-ethyl-orthyo-silicate glass(PE-TEOS), O3 boro-phos-pho-silicate glass(O3-BPSG), PE-BPSG, and phospho-silicate glass(PSG). All films were polished with KOH-based slurry prior to entering the post-CMP cleaner. The Total X-Ray fluorescence(TXRF) measurements showed that all oxide surfaces are heavily contaminated by potassium and calcium during polishing which is due to a CMP slurry. The polished O3-BPSG films presented higher potassium and calcium contaminations compared to PE-TEOS because of a mobile ions gettering ability of phosphorus. For PSG oxides, the slurry induced mobile ion contamination increased with an increase of phosphorus contents. In addition, the polishing removal rate of PSG oxides had a linear relationship as a function of phosphorus contents.

• Korean Journal of Materials Research
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• v.6 no.11
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• pp.1127-1135
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• 1996

반도체 소자가 고집적화 됨에 따라 단위공정의 수가 증가하게 되었고 동시에 실리콘 기판의 오염에 대한 문제가 증가하였다. 실리콘 기판의 주 오염물로는 유기물, 파티클, 금속분순물 등이 있으며 특히, Cu와 Fe과 같은 금속불순물은 이온주입 공정, reactive ion etching, photoresist ashing과 같은 실 공정 중에 1011-1013atoms/㎤정도로 오염이 되고 있다. 그러나 금속불순물 중 Cu와 같은 전기음성도가 실리콘 보다 큰 오염물질은 일반적인 습석세정방법으로는 제거하기 힘들다. 따라서 본 연구에서는 Cu와 Fe과 같은 금속불순물을 제거할 목적을 건식과 습식 세정방법을 혼합한 UV/ozone과 HF세정을 제안하여 실시하였다. CuCI2와 FeCI2 표준용액으로 실리콘 기판을 인위적 오염한 후 split 1(HF-only), split 2 (UV/ozone+HF), split 3 (UV/ozone + HF 2번 반복), split 4(UV/ozone-HF 3번 반복)를 실시하였고 TXRF(Total Reflection X-Ray Fluorescence)와 AFM(Atomic Force Microscope)으로 금속불순물 제거량과 표면거칠기를 각각 측정하였다. 또한 contact angle 측정으로 세정에 따른 표면상태도 측정하였다. TXRF 측정결과 split 4가 가장 적은 양의 금속불순물 잔류량을 보였으며 AFM 분석을 통한 표면거칠기도 가장 작은 RMS 값을 나타내었다. Contact angle 측정 결과 UV/ozone 처리는 친수성 표면을 형성하였고 HF처리는 소수성 표면을 형성하였다.

• Korean Journal of Materials Research
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• v.8 no.9
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• pp.837-842
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• 1998

As the size of the integrated circuit is scaled down the importance of Si cleaning has been emphasized. One of the major concerns is abut the removal of metallic impurities such as Cu and Fe on Si surface. In this study, we intentionally contaminated Cu and Fe on the Si wafers and cleaned the wafer by cleaning splits of the chemical mixture of $\textrm{H}_2\textrm{O}_2$ and HF and the combination of HF treatment with UV/$\textrm{O}_3$ treatment. The contamination level was monitored by TXRF. Surface microroughness of the Si wafers was measured by AFM. The Si wafer surface was examined by SEM. AES analysis was carried out to analyze the chemical composition of Cu impurities. The amount of Cu impurities after intentional contamination was abut the level of $\textrm{10}^{14}$ atoms/$\textrm{cm}^2$. The amount of Cu was decreased down to the level of $\textrm{10}^{10}$ atoms/$\textrm{cm}^2$ by cleaning splits. The repeated treatment exhibited better Cu removal efficiency. The surface roughness caused by contamination and removal of Cu was improved by repeated treatment of the cleaning splits. Cu were adsorbed on Si surface not in a thin film type but in a particle type and its diameter was abut 100-400${\AA}$ and its height was 30-100${\AA}$. Cu was contaminated on Si surface by chemical adsorption. In the case of Fe the contamination level was $\textrm{10}^{13}$ atoms/$\textrm{cm}^2$ and showed similar results of above Cu cleaning. Fe was contaminated on Si surface by physical adsorption and as a particle type.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2000.05b
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• pp.171-174
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• 2000

We have investigated the CMP slurry properties of silicate oxide thin films surface on CMP cleaning process. The metallic contaminations by CMP slurry were evaluated in four different oxide films, such as plasma enhanced tetra-ethyl-ortho-silicate glass(PE-TEOS), $O_3$ boro-phospho silicate giass( $O_3$-BPSG), PE-BPSG, and phospho-silicate glass(PSG). All films were polished with KOH-based slurry prior to entering the post-CMP cleaner. The Total X-Ray Fluorescence(TXRF) measurements showed that all oxide surfaces are heavily contaminated by potassium and calcium during polishing, which is due to a CMP slurry. The polished $O_3$-BPSG films presented higher potassium and calcium contaminations compared to PE-TEOS because of a mobile ions gettering ability of phosphorus. For PSG oxides, the slurry induced mobile ion contamination increased with an increase of phosphorus contents.