• Title/Summary/Keyword: Interfacial reaction layer

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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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Chemical Vapor Deposition of Ga2O3 Thin Films on Si Substrates

  • Kim, Doo-Hyun;Yoo, Seung-Ho;Chung, Taek-Mo;An, Ki-Seok;Yoo, Hee-Soo;Kim, Yun-Soo
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.225-228
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    • 2002
  • Amorphous $Ga_2O_3$ films have been grown on Si(100) substrates by metal organic chemical vapor deposition (MOCVD) using gallium isopropoxide, $Ga(O^iPr)_3$, as single precursor. Deposition was carried out in the substrate temperature range 400-800 $^{\circ}C$. X-ray photoelectron spectroscopy (XPS) analysis revealed deposition of stoichiometric $Ga_2O_3$ thin films at 500-600 $^{\circ}C$. XPS depth profiling by $Ar^+$ ion sputtering indicated that carbon contamination exists mostly in the surface region with less than 3.5% content in the film. Microscopic images of the films by scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed formation of grains of approximately 20-40 nm in size on the film surfaces. The root-mean-square surface roughness from an AFM image was ${\sim}10{\AA}$. The interfacial layer of the $Ga_2O_3$/Si was measured to be ${\sim}35{\AA}$ thick by cross-sectional transmission electron microscopy (TEM). From the analysis of gaseous products of the CVD reaction by gas chromatography-mass spectrometry (GC-MS), an effort was made to explain the CVD mechanism.

Effect of Reflow Number on Mechanical and Electrical Properties of Ball Grid Array (BGA) Solder Joints (BGA 솔더 접합부의 기계적.전기적 특성에 미치는 리플로우 횟수의 효과)

  • Koo, Ja-Myeong;Lee, Chang-Yong;Jung, Seung-Boo
    • Journal of the Microelectronics and Packaging Society
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    • v.14 no.4
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    • pp.71-77
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    • 2007
  • In this study, the mechanical and electrical properties of three different ball grid array (BGA) solder joints, consisting of Sn-37Pb, Sn-3.5Ag and Sn-3.5Ag-0.75Cu (all wt.%), with organic solderability preservative (OSP)-finished Cu pads were investigated as a function of reflow number. Based on scanning electron microscopy (SEM) analysis results, a continuous $Cu_6Sn5$, intermetallic compound (IMC) layer was formed at the solder/substrate interface, which grew with increasing reflow number. The ball shear testing results showed that the shear force peaked after 3 reflows (in case of Sn-Ag solder, 4 reflows), and then decreased with increasing reflow number. The electrical property of the joint gradually decreased with increasing reflow number.

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Preparation of $Ba_{0.5}Sr_{0.5}TiO_3$ Thin Films by Off-Axis RF Magnetron Sputtering (Off-Axis RF Magnetron Sputtering 방법에 의한 $Ba_{0.5}Sr_{0.5}TiO_3$ 박막의 제조)

  • Shin, Jin;Hahn, Taek-Sang;Kim, Young-Hwan;Lee, Jae-Jun;Park, Soon-Ja;Oh, Myung-Hwan;Choi, Sang-Sam
    • Journal of the Korean Ceramic Society
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    • v.31 no.12
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    • pp.1429-1436
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    • 1994
  • We have prepared Ba0.5Sr0.5TiO3 thin films on Si substrate without buffer layer. Deposition was carried out by off-axis rf magnetron sputtering method using Ba0.5Sr0.5TiO3 stoichiometric target. The substrate temperature was changed from 40$0^{\circ}C$ to $700^{\circ}C$ during deposition. As the substrate temperature increased, relative intensity of (110) peak increased up to $600^{\circ}C$, however preferred orientation changed from (110) to (h00) beyond $650^{\circ}C$ of substrate temperature. Deposited films showed microstructures with fine grains whose diameters are less than 100 nm, and columnar structure was observed in the cross-sectional SEM micrograph. AES depth profile showed no significant diffusion at the interfacial reaction area. The effective dielectric constant of films showed maximum value at $600^{\circ}C$, and the leakage current increased with increasing substrate temperature, which may be ascribed to the crystallization of amorphous phases at grain boundary.

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Deposition of $MgB_2$ Thin Films on Alumina-Buffered Si Substrates by using Hybrid Physical-Chemical Vapor Deposition Method (혼성물리화학기상 증착법에 의한 알루미나 완충층을 가진 실리콘 기판 위의 $MgB_2$ 박막제조에 대한 연구)

  • Lee, T.G.;Park, S.W.;Seong, W.K.;Huh, J.Y.;Jung, S.G.;Lee, B.K.;An, K.S.;Kang, W.N.
    • Progress in Superconductivity
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    • v.9 no.2
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    • pp.177-182
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    • 2008
  • [ $MgB_2$ ] thin films were fabricated using hybrid physical-chemical vapor deposition (HPCVD) method on silicon substrates with buffers of alumina grown by using atomic layer deposition method. The growth war in a range of temperatures $500\;{\sim}\;600^{\circ}C$ and under the reactor pressures of $25\;{\sim}\;50\;Torr$. There are some interfacial reactions in the as-grown films with impurities of mostly $Mg_2Si$, $MgAl_2O_4$, and other phases. The $T_c$'s of $MgB_2$ films were observed to be as high as 39 K, but the transition widths were increased with growth temperatures. The magnetization was measured as a function of temperature down to the temperature of 5 K, but the complete Meissner effect was not observed, which shows that the granular nature of weak links is prevailing. The formation of mostly $Mg_2Si$ impurity in HPCVD process is discussed, considering the diffusion and reaction of Mg vapor with silicon substrates.

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Fabrication of Reverse Osmosis Membrane with Enhanced Boron Rejection Using Surface Modification (표면개질을 이용하여 붕소 제거율이 향상된 역삼투막의 제조)

  • Lee, Deok-Ro;Kim, Jong Hak;Kwon, Sei;Lee, Hye-Jin;Kim, In-Chul
    • Membrane Journal
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    • v.28 no.2
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    • pp.96-104
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    • 2018
  • With the rapid increase in seawater desalination, the importance of boron rejection is rising. This study was conducted to investigate the effect of hydrophilic compounds on surface modification to maximize water flux and increase boron rejection. First, polyamide active layer was fabricated by interfacial polymerization of polysulfone ultrafiltration membrane with M-phenylenediamine (MPD) and trimesoyl chloride (TMC) to obtain Control polyamide membrane. Next, D-gluconic acid (DGCA) and D-gluconic acid sodium salt (DGCA-Na) were synthesized with glutaraldehyde (GA) and hydrochloric acid (HCl) by modifying the surface of Control polyamide membrane. XPS analysis was carried out for the surface analysis of the synthesized membrane, and it was confirmed that the reaction of surface with DGCA and DGCA-Na compounds was performed. Also, FE-SEM and AFM analysis were performed for morphology measurement, and polyamide active layer formation and surface roughness were confirmed. In the case of water flux, the membrane fabricated by the surface modification had a value of 10 GFD or less. However, the boron rejection of the membranes synthesized with DGCA and DGCA-Na compounds were 94.38% and 94.64%, respectively, which were 12.03 %p and 12.29 %p larger than the Control polyamide membrane, respectively.

A study on the improvement of TiN diffusion barrier properties using Cu(Mg) alloy (Cu(Mg) alloy 금속배선에 의한 TiN 확산방지막의 특성개선)

  • 박상기;조범석;조흥렬;양희정;이원희;이재갑
    • Journal of the Korean Vacuum Society
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    • v.10 no.2
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    • pp.234-240
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    • 2001
  • The diffusion barrier properties of TiN by using Cu(Mg) alloy film have been investigated. Cu(Mg) alloy film was deposited on air-exposed TiN film. Upon annealing, interfacial MgO of 100 $\AA$ has been formed due to the reaction of Mg with oxygen existed on the surface of TiN. Combined MgO/TiN structure prevented the interdiffusion of Cu and Si up to $800^{\circ}C$. To improve the adhesion of Cu(Mg) alloy film to the TiN, TiN layer was treated by $O_2$ plasma, followed by vacuum annealing at $300^{\circ}C$. It was found that increased oxygen on the surface of TiN film by plasma treatment enhanced segregation of Mg toward the interface, resulting in the formation of dense MgO layer. Improved adhesion characteristics have been formed through this treatment. However, increased power of $O_2$ plasma led to the formation of TiO$_2$ and decreased the Mg content to be segregated to the interface, resulting in the decrease in adhesion property. In addition, the deposition of 50 ${\AA}$ Si on the TiN enhanced the adhesion of Cu(Mg) alloy to TiN without deteriorating the TiN diffusion barrier characteristics.

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Effect of RuO$_2$ Thin Film Microstructure on Characteristics of Thin Film Micro-supercapacitor ($RuO_2$박막의 미세 구조가 박막형 마이크로 슈퍼캐패시터의 특성에 미치는 영향)

  • Kim, Han-Ki;Yoon, Young-Soo;Lim, Jae-Hong;Cho, Won-Il;Seong, Tae-Yeon;Shin, Young-Hwa
    • Korean Journal of Materials Research
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    • v.11 no.8
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    • pp.671-678
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    • 2001
  • All solid-state thin film micro supercapacitor, which consists of $RuO_2$/LiPON/$RuO_2$ multi layer structure, was fabricated on Pt/Ti/Si substrate using a $RuO_2$ electrode. Bottom $RuO_2$ electrode was grown by dc reactive sputtering system with increasing $O_2/[Ar+O_2]$ ratio at room temperature, and a LiPON electrolyte film was subsequently deposited on the bottom $RuO_2$ electrode at pure nitrogen ambient by rf reactive sputtering system. Room temperature charge-discharge measurements based on a symmetric $RuO_2$/LiPON/$RuO_2$ structure clearly demonstrates the cyclibility dependence on the microstructure of the $RuO_2$ electrode. Using both glancing angle x-ray diffraction (GXRD) and transmission electron microscopy (TEM) analysis, it was found that the microstructure of the $RuO_2$ electrode was dependent on the oxygen flow ratio. In addition, x- ray photoelectron spectroscopy(XPS) examination shows that the Ru-O binding energy is affected by increasing oxygen flow ratio. Furthermore, TEM and AES depth profile analysis after cycling demonstrates that the interface layer formed by interfacial reaction between LiPON and $RuO_2$ act as a main factor in the degradation of the cyclibility of the thin film micro-supercapacitor.

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Comparative Study of Interfacial Reaction and Drop Reliability of the Sn-3.0Ag-0.5Cu Solder Joints on Electroless Nickel Autocatalytic Gold (ENAG) (Electroless Nickel Autocatalytic Gold (ENAG) 표면처리와 Sn-Ag-Cu솔더 간 접합부의 계면반응 및 취성파괴 신뢰성 비교 연구)

  • Jun, So-Yeon;Kwon, Sang-Hyun;Lee, Tae-Young;Han, Deog-Gon;Kim, Min-Su;Bang, Jung-Hwan;Yoo, Sehoon
    • Journal of the Microelectronics and Packaging Society
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    • v.29 no.3
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    • pp.63-71
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    • 2022
  • In this study, the interfacial reaction and drop impact reliability of Sn-Ag-Cu (SAC) solder and electroless nickel autocatalytic gold (ENAG) were studied. In addition, the solder joint properties with the ENAG surface finish was compared with electroless nickel immersion gold (ENIG) and electroless nickel electroless palladium immersion gold (ENEPIG). The IMC thickness of SAC/ENAG and SAC/ENEPIG were 1.15 and 1.12 ㎛, respectively, which were similar each other. The IMC thickness of the SAC/ENIG was 2.99 ㎛, which was about two times higher than that of SAC/ENAG. Moreover, it was found that the IMC thickness of the solder joint was affected by the metal turnover (MTO) condition of the electroless Ni(P) plating solution, and it was found that the IMC thickness increased when the MTO increased from 0 to 3. The shear strength of SAC/ENEPIG was the highest, followed by SAC/ENAG and SAC/ENIG. It was found that when the MTO increased, the shear strength was lowered. In terms of brittle fracture, SAC/ENEPIG was the lowest among the three joints, followed by SAC/ENAG and SAC/ENIG. Likewise, it was found that as MTO increased, brittle fracture increased. In the drop impact test, it was confirmed that the 0 MTO condition had a higher average number of failures than the 3 MTO condition, and the average number of failures was also higher in the order of SAC/ENEIG, SAC/ENAG, and SAC/ENIG. As a result of observing the fracture surface after the drop impact, it was found that the fracture was between the IMC and the Ni(P) layer.

Research of Diffusion Bonding of Tungsten/Copper and Their Properties under High Heat Flux

  • Li, Jun;Yang, Jianfeng
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.14-14
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    • 2011
  • W (tungsten)-alloys will be the most promising plasma facing armor materials in highly loaded plasma interactive components of the next step fusion reactors due to its high melting point, high sputtering resistance and low deuterium/tritium retention. The bonding technology of tungsten to Cu alloy was one of the key issues. In this paper, W/CuCrZr diffusion bonding has been performed successfully by inserting pure metal interlay. The joint microstructure, interfacial elements migration and phase composition were analyzed by SEM, EDS, XRD, and the joint shear strength and micro-hardness were investigated. The mock-ups were fabricated successfully with diffusion bonding and the cladding technology respectively, and the high heat flux test and thermal fatigue test were carried out under actively cooling condition. When Ni foil was used for the bonding of tungsten to CuCrZr, two reaction layers, Ni4W and Ni(W) layer, appeared between the tungsten and Ni interlayer with the optimized condition. Even though Ni4W is hard and brittle, and the strength of the joint was oppositely increased (217 MPa) due primarily to extremely small thicknesses (2~3 ${\mu}m$). When Ti foil was selected as the interlayer, the Ti foil diffused quickly with Cu and was transformed into liquid phase at $1,000^{\circ}C$. Almost all of the liquid was extruded out of the interface zone under bonding pressure, and an extremely thin residual layer (1~2 ${\mu}m$) of the liquid phase was retained between the tungsten and CuCrZr, which shear strength exceeded 160 MPa. When Ni/Ti/Ni multiple interlayers were used for bonding of tungsten to CuCrZr, a large number of intermetallic compound ($Ni_4W/NiTi_2/NiTi/Ni_3T$) were formed for the interdiffusion among W, Ni and Ti. Therefore, the shear strength of the joint was low and just about 85 MPa. The residual stresses in the clad samples with flat, arc, rectangle and trapezoid interface were estimated by Finite Element Analysis. The simulation results show that the flat clad sample was subjected maximum residual stress at the edge of the interface, which could be cracked at the edge and propagated along the interface. As for the rectangle and trapezoid interface, the residual stresses of the interface were lower than that of the flat interface, and the interface of the arc clad sample have lowest residual stress and all of the residual stress with arc interface were divided into different grooved zones, so the probabilities of cracking and propagation were lower than other interfaces. The residual stresses of the mock-ups under high heat flux of 10 $MW/m^2$ were estimated by Finite Element Analysis. The tungsten of the flat interfaces was subjected to tensile stresses (positive $S_x$), and the CuCrZr was subjected to compressive stresses (negative $S_x$). If the interface have a little microcrack, the tungsten of joint was more liable to propagate than the CuCrZr due to the brittle of the tungsten. However, when the flat interface was substituted by arc interfaces, the periodical residual stresses in the joining region were either released or formed a stress field prohibiting the growth or nucleation of the interfacial cracks. Thermal fatigue tests were performed on the mock-ups of flat and arc interface under the heat flux of 10 $MW/m^2$ with the cooling water velocity of 10 m/s. After thermal cycle experiments, a large number of microcracks appeared at the tungsten substrate due to large radial tensile stress on the flat mock-up. The defects would largely affect the heat transfer capability and the structure reliability of the mock-up. As for the arc mock-up, even though some microcracks were found at the interface of the regions, all microcracks with arc interface were divided into different arc-grooved zones, so the propagation of microcracks is difficult.

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