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A bilayer diffusion barrier of atomic layer deposited (ALD)-Ru/ALD-TaCN for direct plating of Cu

  • Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.239-240
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    • 2008
  • As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

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A Mineralogical Study on the Arsenic Behavior in the Tailings of Nakdong Mine (낙동광산의 광미 내 비소 거동에 대한 광물학적 연구)

  • Lee, Woo-Chun;Cho, Hyen-Goo;Kim, Young-Ho;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.4
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    • pp.359-370
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    • 2009
  • Arsenic and heavy metals leached out as a result of oxidation of tailings exposed to the surface pose a serious environmental contamination of mine areas. This study investigated how arsenic behavior is controlled by a variety of processes, such as oxidation of sulfides and formation or alteration of secondary minerals, based on mineralogical methods. The study was carried out using the tailing samples obtained from Nakdong mine located in Jeongseongun, Gangwondo. After separating magnetic and non-magnetic minerals using pretreated tailing samples, each mineral sample was classified according to their colors and metallic lusters observed by the stereoscopic microscope. Subsequently, the mineralogical properties were determined using various instrumental analyses, such as x-ray diffractometer (XRD), energy dispersive spectroscopy (EDS), and electron probe micro analyzer (EPMA). The literature review confirmed that various ore minerals were identified in the Nakdong ore deposits. In this study, however, there were observed a few original ore minerals as well as secondary and/or tertiary minerals newly formed as a result of weathering including oxidation. In particular, we did not recognize pyrrhotite which has been known to originally exist in a large abundance, but peculiarly colloform-type iron (oxy)hydroxides were identified, which indicates most of pyrrhotite has been altered by rapid weathering due to its large reactivity. In addition, a secondary scorodites filling the fissure of weathered primary arsenopyrites were identified, and it is speculated that arsenic is immobilized through such a alteration reaction. Also, we observed tertiary iron (oxy)hydroxides were formed as a result of re-alteration of secondary jarosites, and it suggests that the environment of tailing has been changed to high pH from low pH condition which was initiated and developed by oxidation reactions of diverse primary ore minerals. The environmental change is mainly attributed to interactions between secondary minerals and parental rocks around the mine. As a result, not only was the stability of secondary minerals declined, but tertiary minerals were newly formed. As such a process goes through, arsenic which was immobilized is likely to re-dissolve and disperse into surrounding environments.

Study on Synthesis of Pyrochlore in Gd-Ti-O and Gd-Zr-O Systems (Gd-Ti-O계 및 Gd-Zr-O 계에서의 파이로클로어 합성연구)

  • ;;;S.V. Yudintsev
    • Economic and Environmental Geology
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    • v.37 no.3
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    • pp.303-309
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    • 2004
  • Pyrochlores were known as promising materials for the immobilization of radioactive actinide. Accordingly, we synthesized pyrochlores with Gd$_2$Ti$_2$$O_7$ and Gd$_2$Zr$_2$$O_7$compositions by sintering method, and studied its properties and phase relations in Gd-Ti-O and Gd-Zr-O system. The mixed powders were pressed into pellets under 200-400 kgf/cm$^2$ at room temperature. and then sintered at 1000-1$600^{\circ}C$ for 0.5-40 hours. The synthesized samples were analyzed and were identified with XRD and SEM/EDS analyses. The optimal synthetic conditions of pyrochlores with Gd$_2$Ti$_2$$O_7$composition were at 140$0^{\circ}C$/0.5hrs, 130$0^{\circ}C$/3hrs and 120$0^{\circ}C$/20hrs. Its chemical composition was $Gd_{2.0-2.1}$$Ti_{1.9-2.0}$$O_7$ and similar to the stoichiometric composition without any relationship in temperature and atmosphere. The optimal synthetic conditions of pyrochlores with $Gd_{2}$$Zr_{2}$$O_7$composition were at 155$0^{\circ}C$/40hrs and 1$600^{\circ}C$/30hrs. The compositions of pyrochlore synthesized from these optimal conditions were irregular with $Gd_{1.5-2.4}$$Zr_{1.7-2.4}$$O_7$. Such heterogeneity indicates that the reaction rate of pyrochlore with Gd$_2$Zr$_2$$O_7$composition is very low, and then its equilibrium state could not be attained even for 40 hours which was the longest sintering time in this research.

Characterization of Cement Solidification for Enhancement of Cesium Leaching Resistance (세슘 침출 저항성 증진 시멘트 고화체의 제조 및 특성 평가)

  • Kim, Gi Yong;Jang, Won-Hyuk;Jang, Sung-Chan;Im, Junhyuck;Hong, Dae Seok;Seo, Chel Gyo;Shon, Jong Sik
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.16 no.2
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    • pp.183-193
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    • 2018
  • Currently, the Korea Atomic Energy Research Institute (KAERI) is planning to build the Ki-Jang Research Reactor (KJRR) in Ki-Jang, Busan. It is important to safely dispose of low-level radioactive waste from the operation of the reactor. The most efficient way to treat radioactive waste is cement solidification. For a radioactive waste disposal facility, cement solidification is performed based on specific waste acceptance criteria such as compressive strength, free-standing water, immersion and leaching tests. Above all, the leaching test is important to final disposal. The leakage of radioactive waste such as $^{137}Cs$ causes not only regional problems but also serious global ones. The cement solidification method is simple, and cheaper than other solidification methods, but has a lower leaching resistance. Thus, this study was focused on the development of cement solidification for an enhancement of cesium leaching resistance. We used Zeolite and Loess to improve the cesium leaching resistance of KJRR cement solidification containing simulated KJRR liquid waste. Based on an SEM-EDS spectrum analysis, we confirmed that Zeolite and Loess successfully isolated KJRR cement solidification. A leaching test was carried out according to the ANS 16.1 test method. The ANS 16.1 test is performed to analyze cesium ion concentration in leachate of KJRR cement for 90 days. Thus, a leaching test was carried out using simulated KJRR liquid waste containing $3000mg{\cdot}L^{-1}$ of cesium for 90 days. KJRR cement solidification with Zeolite and Loess led to cesium leaching resistance values that were 27.90% and 21.08% higher than the control values. In addition, in several tests such as free-standing water, compressive strength, immersion, and leaching tests, all KJRR cement solidification met the waste acceptance or satisfied the waste acceptance criteria for final disposal.

Effect of Physical, Chemical Properties and of Pelleting Solid Materials on the Germination in Pelleted Carrot Seeds (펠렛 피복물질의 물리, 화학적 특성이 당근 펠렛종자의 발아력에 미치는 영향)

  • Kang, Jum-Soon;Son, Beung-Gu;Choi, Young-Whan;Lee, Yong-Jae;Park, Young-Hoon;Choi, In-Soo
    • Journal of Life Science
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    • v.17 no.12
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    • pp.1701-1708
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    • 2007
  • Seed pelleting is generally conducted in order to save the labor for sowing and thinning by enabling the precision mechanical planting. In the present study, the influence of physical and chemical properties of pelleting solid materials was investigated on carrot seed germination. Among the pelleting solid materials evaluated, dialite, kaolin, and talc showed low bulk density and high porosity. Bentonite and dialite carried high water holding capacities of 184% and 173%, respectively, while calcium carbonate, calcium oxide, and fly ash showed relatively low water holding capacity. The pH of kaolin (6.8) and dialite (7.4) were close to neutral, while limestone (12.8), calcium oxide (13.0), and bentonite (10.0) were highly basic. High electro-conductivity was shown in limestone and calcium oxide. EDS analysis revealed that the main elemental compositions of talc were Si (71.0%) and Mg (29.0%), and those of calcium carbonate were Ca (66.6%), Si (22.9%), and Mg (10.5%). High granulation capacity was observed from talc and the mixture of talc and calcium carbonate. Seeds pelleted with bentonite showed the highest hardness. The dissolving type of the pellet layer after imbibition was split type in talc, limestone, zeolite, and fly ash, melt type in calcium carbonate and calcium oxide, and swell type in bentonite and vermiculite. The shortest dissolving time of pellet layer was observed from calcium carbonate and kaolin. The germination speed $(T_{50})$ was delayed as the size of pelleted seeds increased. The optimum size of pelleting was 19 ratio in carrot.

Environmental Geochemical Characteristics of the Acid Mine Drainage and Stream Sediments in the Abandoned Honam Coal Mine Area, Korea (호남탄전지역 폐탄광의 산성광산배수와 하상퇴적물의 환경지구화학적 특성)

  • Park, Young-Seog;Kim, Jong-Kyun;Kim, Jin;Jang, Woo-Seog;Lee, Ki-Hyung;Han, Min-Su
    • Economic and Environmental Geology
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    • v.35 no.3
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    • pp.241-255
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    • 2002
  • The purpose of this study is to investigate environmental geochemical characteristics for the acid mine drainage and stream sediments in the abandoned Honam coal mine area. For the chemical analysis, stream winter samples were collected at 54 sites and for the mineralogical and chemical analysis, stream sediments samples were collected at 34 sites. Physical and chemical characteristics of stream water were measured at the site and chemical compositions were analyzed by ICP-AES, ICP-MS and IC. Mineralogical characteristics of stream sediments samples were determined using XRD, SEM and EDS. In physical and chemical properties, stream water shows thats pH 2.85~8.12, Eh -62~215 mV, EC 0.205~146 ms/m, ER 0.234~255 {$\Omega}{\cdot}$m, DO 0.03~1068 mg/L and TDS 10.96~1420mg/L. In chemical compositions, we obtain that K 0.118~3.184 mg/L, Mg 2.1~114.48 mg/L, Ca 2.59~l25.02 mg/L, Al 0.01~44.72 mg/L, Fe 0.108~89.49 mg/L and Na 5.45~125.41 mg/L. Stream sediments are commonly composed of quartz, illite and goethite in the result of x-ray diffraction. After heat treatment at 98$0^{\circ}C$, the hematite peaks are distinctly shown. In consideration of heavy metals (include Fe) for steam sediments, Fe ranges 22575~34713 ppm, Zn 41.66~970.3 ppm, Cd 0.52~52.07 ppm, Cu 1.25~198.5 ppm and Pb 0.43~77.35 ppm.

A longitudinal analysis of high school students' dropping out: Focusing on the change pattern of dropout, changes in school violence and school counseling. (전국 고등학교 학생의 학업중단에 대한 종단적 분석 -학업중단 변화양상에 따른 유형탐색, 학교폭력 및 학교상담의 변화추이를 중심으로-)

  • Kwon, Jae-Ki;Na, Woo-Yeol
    • Journal of the Korean Society of Child Welfare
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    • no.59
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    • pp.209-234
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    • 2017
  • This study viewed schools as a cause of students dropping out and posited that dropping out of high school would vary depending on the characteristics and influencing factors of the school from which students were dropping out. Therefore, focusing on schools, we longitudinally investigated the change patterns of school dropout across high schools in the country, and the types of changes in dropping out of high school. In addition, we predicted the general characteristics of schools according to the type of school students were dropping out from, looked at the changes in the major factors (i.e., school violence and school counseling) affecting school dropout, and reviewed schools' long-term efforts and outcomes in relation to school dropout. For this purpose, KERIS EDSS's "Secondary School Information Disclosure Data" were used. The final model included data collected five years20122016) from high schools across the country. The results were as follows. First, in order to examine the longitudinal change patterns of dropping out of high schools, a latent growth models analysis was conducted, and it revealed that, as time passed, the dropout rate decreased. Second, growth mixture modeling was used to explore types according to the change patterns of the school students were dropping out from. The results showed three types: the "remaining in school" type, the "gradually decreasing school dropout" type, and the "increasing school dropping out". Third, the multinomial logistic regression was conducted to predict the general characteristics of schools by type. The results showed that public schools, vocational schools, and schools with a large number of students who have below the basic levels in Korean, English and mathematics were more likely to belong to the "increasing school dropout" type. Further, the larger the total number of students, the higher the probability of belonging to the "remaining in school" type or the "gradually decreasing school dropout" type. Lastly, growth mixture modeling was used to analyze the trend of school violence and school counseling according to the three types. The focus was on the "gradually decreasing school dropout" type. In the case of the "gradually decreasing school dropout" type, it was found that as time passed, the number of school violence cases and the number of offenders gradually decreased. In addition, in terms of change in school counseling the results revealed that the number of placement of professional counselors in schools increased every year and peer counseling was continuously promoted, which may account for the "gradually decreasing school dropout" type.

Dry reforming of Propane to Syngas over Ni-CeO2/γ-Al2O3 Catalysts in a Packed-bed Plasma Reactor (충전층 플라즈마 반응기에서 Ni-CeO2/γ-Al2O3 촉매를 이용한 프로페인-합성 가스 건식 개질)

  • Sultana, Lamia;Rahman, Md. Shahinur;Sudhakaran, M.S.P.;Hossain, Md. Mokter;Mok, Young Sun
    • Clean Technology
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    • v.25 no.1
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    • pp.81-90
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    • 2019
  • A dielectric barrier discharge (DBD) plasma reactor packed with $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was used for the dry ($CO_2$) reforming of propane (DRP) to improve the production of syngas (a mixture of $H_2$ and CO) and the catalyst stability. The plasma-catalytic DRP was carried out with either thermally or plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst at a $C_3H_8/CO_2$ ratio of 1/3 and a total feed gas flow rate of $300mL\;min^{-1}$. The catalytic activities associated with the DRP were evaluated in the range of $500{\sim}600^{\circ}C$. Following the calcination in ambient air, the ${\gamma}-Al_2O_3$ impregnated with the precursor solution ($Ni(NO_3)_2$ and $Ce(NO_3)_2$) was subjected to reduction in an $H_2/Ar$ atmosphere to prepare $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst. The characteristics of the catalysts were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectrometry (EDS), temperature programmed reduction ($H_2-TPR$), temperature programmed desorption ($H_2-TPD$, $CO_2-TPD$), temperature programmed oxidation (TPO), and Raman spectroscopy. The investigation revealed that the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst exhibited superior catalytic activity for the production of syngas, compared to the thermally reduced catalyst. Besides, the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was found to show long-term catalytic stability with respect to coke resistance that is main concern regarding the DRP process.

Study on the Casting Technology and Restoration of "Sangpyong Tongbo" (상평통보 주조와 복원기술연구)

  • Yun, Yong-hyun;Cho, Nam-chul;Jeong, Yeong-sang;Lim, In-ho
    • Korean Journal of Heritage: History & Science
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    • v.47 no.4
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    • pp.224-243
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    • 2014
  • This study examined the materials and casting technology(cast, alloy, etc.) used in the manufacturing of bronze artifacts based on old literature such as Yongjae Chonghwa, Cheongong Geamul, and The Korea Review. In the casting experiment for restoration of Sangpyong Tongbo, a bronze and brass mother coin mold was made using the sand mold casting method described in The Korea Review. The cast was comprised of the original mold plate frame, wooden frame, and molding sand. Depending on the material of the outer frame, which contains the molding sand, the original mold plate frame can be either a wooden frame or steel frame. For the molding sand, light yellow-colored sand of the Jeonbuk Iri region was used. Next, the composition of the mother alloy used in the restoration of Sangpyong Tongbo was studied. In consideration of the evaporation of tin and lead during actual restoration, the composition of Cu 60%, Zn 30%, and Pb 10% for brass as stated in The Korea Review was modified to Cu 60%, Zn 35%, and Pb 15%. For bronze, based on the composition of Cu 80%, Sn 6%, and Pb 14% used for Haedong Tongbo, the composition was set as Cu 80%, Sn 11%, and Pb 19%. The mother coin mold was restored by first creating a wooden father coin, making a cast from the wooden frame and basic steel frame, alloying, casting, and making a mother coin. Component analysis was conducted on the mother alloy of the restored Sangpyong Tongbo, and its primary and secondary casts. The bronze mother alloy saw a 5% increase in copper and 4% reduction in lead. The brass parent alloy had a 5% increase in copper, but a 4% and 12% decrease in lead and tin respectively. Analysis of the primary and secondary mother coin molds using an energy dispersive spectrometer showed that the bronze mother coin mold had a reduced amount of lead, while the brass mother coin mold had less tin. This can be explained by the evaporation of lead and tin in the melting of the primary mother coin mold. In addition, the ${\alpha}$-phase and lead particles were found in the mother alloy of bronze and brass, as well as the microstructure of the primary and secondary coin molds. Impurities such as Al and Si were observed only in the brass mother coin mold.

Continuous Control of Acetaminophen Poisoning after Implementation of Regulation for Ease Access of Acetaminophen: Cohort Study from Emergency Department Based in-depth Injury Surveillance (아세트아미노펜 사용 편의성 증가 후 중독발생 위험의 지속적 관리 필요성)

  • Jo, Seung Jik;Gang, Hyun Young;Lee, Si Jin;Bae, Gyu Hyun;Lee, Eui Jung;Han, Kap Su;Kim, Su Jin;Lee, Sung Woo
    • Journal of The Korean Society of Clinical Toxicology
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    • v.18 no.2
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    • pp.57-65
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    • 2020
  • Purpose: Since 2012, acetaminophen can be accessed easily not only at pharmacies but also at convenience stores. The relationship between the easy access of acetaminophen and the risk of poisoning has been controversial. Several studies also reported different results regarding the risk of acetaminophen poisoning after access to acetaminophen was relaxed. This study examined the long-term effects on the risk of acetaminophen poisoning after easy access to acetaminophen was implemented. Methods: This was a retrospective analysis of an emergency department (ED)-based in-depth Injury Surveillance Cohort by the Korea Center for Disease Control and prevention from 2011 to 2018. Poisoning cases were selected from the Cohort, and the incidence of acetaminophen poisoning and the characteristics of the cases of acetaminophen poisoning were analyzed. The purchase path and the amount of ingestion in acetaminophen poisoning were sub-analyzed from data of six EDs. Results: Of 57,326 poisoning cases, 4.0% (2,272 cases) were acetaminophen poisoning. Of 2,272 cases of acetaminophen poisoning, 42.8% (974 cases) required in-patient care after ED management. Two hundred and sixty-four of these 964 cases required intensive care. The rates of cases that required in-patient treatment and the rates of cases that required intensive care increased from 29.4% in 2011 to 48.1% in 2018, and from 3.1% in 2011 to 15.2% in 2018, respectively (p<0.001, p<0.001). In the poisoning group with in-depth toxic surveillance (n=15,908), the incidence and proportion of acetaminophen (AAP) poisoning increased from 55 cases per year to 187 cases per year and 4.9% to 6.1%, respectively (p=0.009, p<0.001, respectively). The most common age group of acetaminophen poisoning was teenagers, which is different from the most common age group of other pharmaceutical agents: the middle age group of 40-49 years (p<0.001). Of 15,908 in-depth toxic surveillance patients, 693 patients had AAP poisoning, of whom 377 cases (54.2%) purchased acetaminophen from a non-pharmacy. The proportions of the purchase path from non-pharmacy were 41.4% at 2011-12 and 56.4% (2013-18) (p=0.004). The amount of acetaminophen ingestion was 13.5±14.3 g at 2011-12 and 13.9±15.1 g at 2013-18 (p=0.794). Conclusion: Although the incidence of acetaminophen poisoning did not increase remarkably in the short term after the implementation of the new regulation, the incidence of acetaminophen poisoning has increased slightly during the study period of 2017-18. In addition, the proportion of the purchase path from non-pharmacies has increased since the emergence of new regulations for the easy access of acetaminophen in 2012. The incidence of acetaminophen poisoning might have been affected after the increasing accessibility of acetaminophen in convenience stores. Continuous control of acetaminophen poisoning is required. Furthermore, the prevention of acetaminophen poisoning should be focused on teenagers with specialized school education programs.