• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.326-326
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• 2011

반도체 소자의 집적화/소형화에 따라, 낮은 비저항을 가진 구리(Cu)를 이용한 배선공정에 관한 연구가 활발하게 진행되고 있다. 구리배선 공정에 있어 전기 도금법이 다양하게 적용됨에 따라, 구리도금 박막 형성을 위해 사용되는 Cu seed 층의 상태는 배선으로 형성된 Cu박막 특성에 크게 영향을 미친다 [1-3]. 본 연구에서는 sputter 방식으로 증착된 Cu seed 층(Cu seed / Ti / Si) 위에 형성된 자연산화막을 제거하기 위하여 다양한 세정방법을 도입하여 비교 분석하였다. 계면활성제인 TS-40A를 비롯한 NH4OH 용액과 H2SO4 용액을 사용하여 Cu seed 층 위에 형성된 구리산화막을 제거함으로서 형성된 표면형상 및 표면상태를 조사분석 하였다. FE-SEM (Field Emission Scanning Electron Microscope)을 이용하여 표면 처리된 Cu seed층 표면의 형상 및 roughness 등을 측정하였고, XPS (X-ray Photoelectron Spectroscopy)를 이용하여 표면 처리된 Cu seed 표면의 화학구조 및 불순물 상태를 조사하였다.

• Journal of Electrochemical Science and Technology
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• v.8 no.3
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• pp.215-221
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• 2017

The electroless plating process largely consists of substrate cleaning, seed formation (activator formation), and electroless plating. The most widely used activator in the seed formation step is Pd, and Sn ions are used to facilitate the formation of this Pd seed layer. This is problematic because the Sn ions interfere with the reduction of Cu ions during electroless plating; thus, the Sn ions must be removed by a hydrochloric acid cleaning process. This method is also expensive due to the use of Pd. In this study, Cu electroless plating was performed by forming a seed layer using a silver nanosol instead of Pd and Sn. The effects of the Ag nanosol concentration in the pretreatment solution and the pretreatment time on the thickness and surface morphology of the Cu layer were investigated. The degrees of adhesion to the substrate were similar for the electroless-plated Cu layers formed by conventional Pd activation and those formed by the Ag nanosol.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.189-190
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• 2011

Cu가 기존 배선물질인 Al을 대체함에 따라 resistance-capacitance (RC) delay나 electromigration (EM) 등의 문제들이 어느 정도 해결되었다. 그러나 지속적인 배선 폭의 감소로 배선의 저항 증가, EM 현상 강화 그리고 stability 악화 등의 문제가 지속적으로 야기되고 있다. 이를 해결하기 위한 방법으로 Cu alloy seed layer를 이용한 barrier 자가형성 공정에 대한 연구를 진행하였다. 이 공정은 Cu 합금을 seed layer로 사용하여 도금을 한 후 열처리를 통해 SiO2와의 계면에서 barrier를 자가 형성시키는 공정이다. 이 공정은 매우 균일하고 얇은 barrier를 형성할 수 있고 별도의 barrier와 glue layer를 형성하지 않아 seed layer를 위한 공간을 추가로 확보할 수 있는 장점을 가지고 있다. 또한, via bottom에 barrier가 형성되지 않아 배선 전체 저항을 급격히 낮출 수 있다. 합금 물질로는 초기 Al이나 Mg에 대한 연구가 진행되었으나, 낮은 oxide formation energy로 인해 SiO2에 과도한 손상을 주는 문제점이 제기되었다. 최근 Mn을 합금 물질로 사용한 안정적인 barrier 형성 공정이 보고 되고 있다. 하지만, barrier 형성을 하기 위해 300도 이상의 열처리 온도가 필요하고 열처리 시간 또한 긴 단점이 있다. 본 실험에서는 co-sputtering system을 사용하여 Cu-V 합금을 형성하였고, barrier를 자가 형성을 위해 300도에서 500도까지 열처리 온도를 변화시키며 1시간 동안 열처리를 실시하였다. Cu-V 공정 조건 확립을 위해 AFM, XRD, 4-point probe system을 이용하여 표면 거칠기, 결정성과 비저항을 평가하였다. Cu-V 박막 내 V의 함량은 V target의 plasma power density를 변화시켜 조절 하였으며 XPS를 통해 분석하였다. 열처리 후 시편의 단면을 TEM으로 분석하여 Cu-V 박막과 SiO2 사이에 interlayer가 형성된 것을 확인 하였으며 EDS를 이용한 element mapping을 통해 Cu-V 내 V의 거동과 interlayer의 성분을 확인하였다. PVD Cu-V 박막은 기판 온도에 큰 영향을 받았고, 200 도 이상에서는 Cu의 높은 표면에너지에 의한 agglomeration 현상으로 거친 표면을 가지는 박막이 형성되었다. 7.61 at.%의 V함량을 가지는 Cu-V 박막을 300도에서 1시간 열처리 한 결과 4.5 nm의 V based oxide interlayer가 형성된 것을 확인하였다. 열처리에 의해 Cu-V 박막 내 V은 SiO2와의 계면과 박막 표면으로 확산하며 oxide를 형성했으며 Cu-V 박막 내 V 함량은 줄어들었다. 300, 400, 500도에서 열처리 한 결과 동일 조성과 열처리 온도에서 Cu-Mn에 의해 형성된 interlayer의 두께 보다 두껍게 성장 했다. 이는 V의 oxide formation nergyrk Mn 보다 작으므로 SiO2와의 계면에서 산화막 형성이 쉽기 때문으로 판단된다. 또한, V+5 이온 반경이 Mn+2 이온 반경보다 작아 oxide 내부에서 확산이 용이하며 oxide 박막 내에 여기되는 전기장이 더 큰 산화수를 가지는 V의 경우 더 크기 때문으로 판단된다.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.256-256
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• 2012

Cu가 기존 배선물질인 Al을 대체함에 따라 resistance-capacitance delay와 electromigration (EM) 등의 문제들이 어느 정도 해결되었다. 그러나 지속적인 배선 폭의 감소로 배선의 저항 증가, EM 현상 강화 그리고 stability 악화 등의 문제가 지속적으로 야기되고 있다. 이를 해결하기 위한 방법으로 Cu alloy seed layer를 이용한 barrier 자가형성 공정에 대한 연구를 진행하였다. 이 공정은 Cu 합금을 seed layer로 사용하여 도금을 한 후 열처리를 통해 $SiO_2$와의 계면에서 barrier를 자가 형성시키는 공정이다. 이 공정은 매우 균일하고 얇은 barrier를 형성할 수 있고 별도의 barrier와 glue layer를 형성하지 않아 seed layer를 위한 공간을 추가로 확보할 수 있는 장점을 가지고 있다. 또한, via bottom에 barrier가 형성되지 않아 배선 전체 저항을 급격히 낮출 수 있다. 합금 물질로는 초기 Al이나 Mg에 대한 연구가 진행되었으나, 낮은 oxide formation energy로 인해 SiO2에 과도한 손상을 주는 문제점이 제기되었다. 최근 Mn을 합금 물질로 사용한 안정적인 barrier 형성 공정이 보고 되고 있다. 하지만, barrier 형성을 하기 위해 300도 이상의 열처리 온도가 필요하고 열처리 시간 또한 긴 단점이 있다. 본 실험에서는 co-sputtering system을 사용하여 Cu-V 합금을 형성하였고, barrier를 자가 형성을 위해 300도에서 500도까지 열처리 온도를 변화시키며 1시간 동안 열처리를 실시하였다. Cu-V 공정 조건 확립을 위해 AFM, XRD, 4-point probe system을 이용하여 표면 거칠기, 결정성과 비저항을 평가하였다. Cu-V 박막 내 V의 함량은 V target의 plasma power density를 변화시켜 조절 하였으며 XPS를 통해 분석하였다. 열처리 후 시편의 단면을 TEM으로 분석하여 Cu-V 박막과 $SiO_2$ 사이에 interlayer가 형성된 것을 확인 하였으며 EDS를 이용한 element mapping을 통해 Cu-V 내 V의 거동과 interlayer의 성분을 확인하였다. PVD Cu-V 박막은 기판 온도에 큰 영향을 받았고, 200도 이상에서는 Cu의 높은 표면에너지에 의한 agglomeration 현상으로 거친 표면을 가지는 박막이 형성되었다. 7.61 at.%의 V함량을 가지는 Cu-V 박막을 300도에서 1시간 열처리 한 결과 4.5 nm의 V based oxide interlayer가 형성된 것을 확인하였다. 열처리에 의해 Cu-V 박막 내 V은 $SiO_2$와의 계면과 박막 표면으로 확산하며 oxide를 형성했으며 Cu-V 박막 내 V 함량은 줄어들었다. 300, 400, 500도에서 열처리 한 결과 동일 조성과 열처리 온도에서 Cu-Mn에 의해 형성된 interlayer의 두께 보다 두껍게 성장했다. 이는 V의 oxide formation energy가 Mn 보다 작으므로 SiO2와의 계면에서 산화막 형성이 쉽기 때문으로 판단된다. 또한, $V^{+5}$이온 반경이 $Mn^{+2}$이온 반경보다 작아 oxide 내부에서 확산이 용이하며 oxide 박막 내에 여기되는 전기장이 더 큰 산화수를 가지는 V의 경우 더 크기 때문으로 판단된다.

• Journal of the Korean Vacuum Society
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• v.9 no.3
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• pp.267-272
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• 2000

Electroplating Cu was deposited on Si(100) wafer after seed Cu was deposited by sputtering first. TaN was deposited as a diffusion barrier before depositing the seed Cu. Electroplating Cu thin films show highly (111)-oriented microstructure for both before and after annealing at $450^{\circ}C$ for 30min and no copper silicide was detected in the same samples, which indicates that TaN barrier layer blocks well the Cu diffusion into silicon substrate. After annealing the electroplating Cu film up to $450^{\circ}C$, the Cu film became columnar from non-columnar, its grain size became larger about two times, and also defects density of stacking faults, twins and dislocations decreased greatly. Thus the heat treatment will improve significantly electromigration property caused by the grain boundary in the Cu thin films.

• Journal of Surface Science and Engineering
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• v.47 no.2
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• pp.68-74
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• 2014

The seed step-coverage enhancement process (SSEP) using Pd/Cu/PVP colloids was investigated for the filling of through silicon via (TSV) without void. TEM analysis showed that the Pd/Cu nano-particles were well dispersed in aqueous solution with the average diameter of 6.18 nm. This Pd/Cu nano-particles were uniformly deposited on the substrate of Si/$SiO_2$/Ti wafer using electrophoresis with the high frequency Alternating Current (AC). After electroless Cu deposition on the substrate treated with Pd/Cu/PVP colloids, the adhesive property between deposited Cu layer and substrate was evaluated. The Cu deposit obtained by SSEP with Pd/Cu/PVP colloids showed superior adhesion property to that on Pd ion catalyst-treated substrate. Finally, by implementing the SSEP using Pd/Cu/PVP colloids, we achieved 700% improvement of step coverage of Cu seed layer compared to PVD process, resulting in void-free filling in high aspect ratio TSV.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2000.11a
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• pp.328-331
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• 2000

The effect of the constituent elements and their composition of the seed layer on the properties of the evaporated Zn thin films was investigated. It was carried out by the analysis of the preferred orientation and the grain size, and the corrosion characteristics. Seed layers were prepared by evaporation of Al and AlCu respectively, and here the Cu content as additives of the source materials of seed layers were designed 5 a/o to 20 a/o. The values of full width at half maximum (FWHM) of the (002) x-ray diffraction peaks of Zn decreased by increasing the amount of the additives on Al seed layer, as a results, the grain sizes also decreased. In order to characteristics of Zn thin films evaporated on the various seed layers, electrical resistivity changes with a function of time at the temperature of 40$^{\circ}C$ and the relative humidity of 80%, as a result, the relative resistivity changes were increased by decreasing the grain size and the FWHM values of (002) peaks of Zn.

• Proceedings of the International Microelectronics And Packaging Society Conference
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• 2003.11a
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• pp.84-87
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• 2003

Since Pb-free solder alloys have been used extensively in microelectronic packaging industry, the interaction between UBM (Under Bump Metallurgy) and solder is a critical issue because IMC (Intermetallic Compound) at the interface is critical for the adhesion of mechanical and the electrical contact for flip chip bonding. IMC growth must be fast during the reflow process to form stable IMC. Too fast IMC growth, however, is undesirable because it causes the dewetting of UBM and the unstable mechanical stability of thick IMC. UP to now. Ni and Cu are the most popular UBMs because electroplating is lower cost process than thin film deposition in vacuum for Al/Ni(V)/Cu or phased Cr-Cu. The consumption rate and the growth rate of IMC on Ni are lower than those of Cu. In contrast, the wetting of solder bumps on Cu is better than Ni. In addition, the residual stress of Cu is lower than that of Ni. Therefore, the alloy of Cu and Ni could be used as optimum UBM with both advantages of Ni and Cu. In this paper, the interfacial reactions of Sn-3.5Ag-0.7Cu solder on Ni-xCu alloy UBMs were investigated. The UBMs of Ni-Cu alloy were made on Si wafer. Thin Cr film and Cu film were used as adhesion layer and electroplating seed layer, respectively. And then, the solderable layer, Ni-Cu alloy, was deposited on the seed layer by electroplating. The UBM consumption rate and intermetallic growth on Ni-Cu alloy were studied as a function of time and Cu contents. And the IMCs between solder and UBM were analyzed with SEM, EDS, and TEM.

• Journal of Surface Science and Engineering
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• v.51 no.5
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• pp.263-270
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• 2018

Ag-coated Cu dendrites were prepared as a filler for an electromagnetic interference shielding application. Ag layers on the Cu dendrites was coated by two approaches. One is a direct autocatalytic plating with a reducing agent. The other approach was achieved by two-step plating, a galvanic displacement reaction to form Ag seed layers on Cu following by an autocatalytic plating with a reducing agent. The procedure-dependent average particle size and tap density of Ag-coated Cu dendrites were characterized. The electrical resistance and electromagnetic interference shielding effect (EMI SE) were analyzed with the Ag-coated Cu dendrites prepared in the two approaches. Additionally, the content of the Ag coated on Cu dendrites was controlled from 2% to 20%. The electrical resistance and EMI SE were critically determined by Ag contents coated on Cu.