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피로인산구리용액으로부터 전기도금 된 Cu 필름의 특성에 미치는 도금조건의 영향
신동율,심철용,구본급,박덕용,Shin, Dong-Yul,Sim, Chulyong,Koo, Bon-Keup,Park, Deok-Yong 한국전기화학회 2013 한국전기화학회지 Vol.16 No.1
Effects of current density, electrodeposition temperature and solution pH on properties of Cu thin films electrodeposited from pyrophosphate bath were investigated. Current efficiency was decreased with increasing current density and increased with increasing temperature. But solution pH slightly influenced on current efficiency and current efficiency was measured to be above 90% at both room temperature and $55^{\circ}C$. Residual stress of Cu thin film electrodeposited at room temperature was decreased with increasing current density, while current density reaches to 60 $mA/cm^2$ or more, stress became close to zero. Cu thin films electrodeposited at $55^{\circ}C$ exhibited the residual stress range of 0~40 MPa. At room temperature, dendritic surface morphology was observed above the current density of 30 $mA/cm^2$ and at $55^{\circ}C$, above the current density of 100 $mA/cm^2$. Cu thin films electrodeposited from bath solution with room temperature and $55^{\circ}C$ mainly consisted of (111) peaks. Specially, Cu thin film electrodeposited at 30 $mA/cm^2$ and $55^{\circ}C$ exhibited strong preferred orientation of (111) peaks. 피로인산구리용액에서 전기도금공정을 이용하여 상온과 $55^{\circ}C$에서 각각 제조된 Cu박막의 특성에 미치는 전류밀도, 도금용액 온도, pH의 영향에 대한 연구를 수행하였다. 전류효율은 전류밀도가 증가함에 따라 감소하였으나, 도금용액의 온도가 증가함에 따라 증가하는 경향을 나타내었다. 그러나 pH 는 전류효율에 거의 영향을 미치지는 않았으며, 상온과 $55^{\circ}C$에서 모두 90% 이상으로 측정되었다. 상온에서 전기도금 된 Cu 박막의 잔류응력은 전류밀도의 증가에 따라 감소하며, 60 $mA/cm^2$ 이상에서는 거의 0에 근접하였다. $55^{\circ}C$에서 전기도금 된 Cu 박막은 0~40 MPa의 잔류응력을 나타내었다. 상온에서 도금하는 경우 수지상 표면 형상이 30 $mA/cm^2$ 이상의 전류밀도로부터 관찰되었고, $55^{\circ}C$에서는 100 $mA/cm^2$ 이상의 전류밀도부터 관찰되었다. 상온과 $55^{\circ}C$의 도금용액으로부터 전기도금 된 Cu 박막은 거의 (111) 피크들로 구성되어 있다. 특히 $55^{\circ}C$, 30 $mA/cm^2$에서 전기도금 된 Cu 박막의 경우 (111) 피크의 강한 우선방향을 나타내었다.
전기도금 된 Cu 필름 특성에 미치는 피로인산구리용액의 화학성분의 영향
신동율,구본급,박덕용,Shin, Dong-Yul,Koo, Bon-Keup,Park, Deok-Yong 한국전기화학회 2015 한국전기화학회지 Vol.18 No.1
전기도금공정을 이용하여 상온에서 제조된 Cu박막의 특성에 미치는 피로인산구리용액의 화학성분($Cu^{2+}$ 농도, $K_4P_2O_7$ 농도, 첨가제 농도)의 영향에 대한 연구를 수행하였다. 전류효율은 도금용액의 $Cu^{2+}$ 농도가 0.3 M까지 높아짐에 따라 거의 100%까지 증가하는 경향을 나타내었다. $K_4P_2O_7$ 농도는 1.5~1.8 M 농도에서 전류효율의 감소를 나타내었으나, 0.9~1.3 M과 2.1~2.4 M에서는 거의 100%의 전류효율을 나타내었다. 첨가제의 농도 변화는 전류효율에는 거의 영향을 미치지 않았다. 전기도금 된 Cu 박막의 잔류응력은 도금용액의 $Cu^{2+}$ 농도가 0.15 M 이하에서는 약 20 MPa로 측정되었으나, $Cu^{2+}$ 농도가 증가함에 따라 증가하다가 0.25 M 에서 약 120 MPa의 최대치를 나타내었다. 한편 도금용액의 $K_4P_2O_7$ 농도가 0.9 M로부터 2.4M로 증가할수록 잔류 응력은 80MPa로부터 0 MPa까지 감소하는 경향을 나타내었으며, 첨가제의 농도는 잔류응력에 영향을 미치지 않은 것으로 관찰되었다. 표면형상의 경우 $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도는 상당한 영향을 미쳤으나, 첨가제는 약간의 영향만을 나타내었다. XRD 분석 결과 $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도는 Cu 박막의 미세조직에 상당한 영향을 미쳤으나, 첨가제는 거의 영향을 미치지 않는 것으로 나타났다. $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도가 증가할수록 (111) 피크의 강한 우선방향성이 나타내었다. Effects of chemical composition ($Cu^{2+}$, $K_4P_2O_7$ and additive concentrations) of baths on properties of Cu thin films electrodeposited from pyrophosphate copper bath were investigated. Current efficiency was increased to be near 100% with increasing $Cu^{2+}$ concentrations from 0.02 to 0.3M. Decrease of current efficiency was observed in the range of 1.5~1.8M $K_4P_2O_7$ concentration, but current efficiency of about 100% was measured in the ranges of both 0.9~1.3M and 2.1~2.4M. The change of additive concentration did not influenced current efficiency. Residual stress of electrodeposited Cu thin films was measured to be about 20 MPa below 0.15 M $Cu^{2+}$ concentration and increased with the increase of it to 0.25 M. Maximum residual stress of 120MPa was observed at 0.25M $Cu^{2+}$ concentration. On the other hand, residual stress decreased from 80 to near 0 MPa as $K_4P_2O_7$ concentration varied from 0.9 to 2.4M and but The change of additive concentration did not affected on residual stress. $Cu^{2+}$ and $K_4P_2O_7$ concentrations significantly affect on surface morphology of electrodeposited Cu thin films, but additive concentration slightly affected. From XRD analysis, the microstructures of electrodeposited Cu thin film was affected from the changes of $Cu^{2+}$ and $K_4P_2O_7$ concentrations, but not from that of additive concentration. Strong preferred orientation of (111) peak was observed with increasing $Cu^{2+}$ and $K_4P_2O_7$ concentrations.
황산염용액으로부터 전기도금 된 FCCL용 Cu 필름의 특성에 미치는 Cu 이온농도 및 첨가제의 영향
신동율(Dong-Yul Shin),박덕용(Doek-Yong Park),구본급(Bon-Keup Koo) 한국표면공학회 2009 한국표면공학회지 Vol.42 No.5
Nanocrystalline Cu thin films were electrodeposited from sulfate baths and investigated systematically the influences of Cu<SUP>2+</SUP> concentration and additives on current efficiency, residual stress, surface morphology, and XRD patterns of electrodeposited Cu film. Current efficiency was nearly 100% at from 0.2M to 1.0 M Cu<SUP>2+</SUP> concentration. but it was linearly increased with Cu<SUP>2+</SUP> concentration at less than 0.2M . The residual stress was observed in range of 7.9 to 18.4 ㎫ and tensile stress mode. Dendritic and powdered form was obtained at below 0.1 M. As increased with Cu<SUP>2+</SUP> concentration in solution, the main peak in the XRD pattern shifted (111) and (220) from (200). In the other hand, all about 100% current efficiency observed in all additive concentration systems, and residual stress observed in range of 20.4 to 26.3 MPa tensile stress. The condition 5(Ultra make-up - 10 ml/l, Ulta A - 0.5ml/l, Ultr B - 0.5 ml/l) was good surface morphology, and fcc(111) peak in XRD patterns increased with increasing additive concentration.
Sulfate 용액을 이용하여 전기도금 한 FCCL용 Cu 필름의 특성에 미치는 전류밀도와 pH의 영향
신동율(Dong-Yul Shin),박덕용(Doek-Yong Park),구본급(Bon-Keup Koo) 한국표면공학회 2009 한국표면공학회지 Vol.42 No.4
Nanocrystalline Cu thin films for FCCL were electrodeposited from sulfate baths to investigate systematically the influences of current density, solution pH on current efficiency, residual stress, surface morphology, and microstructure of thin Cu films. Current efficiencies were measured to be approximately 100%, irrespective of the applied current density and solution pH. But these influenced residual stress, surface morphology, XRD pattern, and grain size of electrodeposited Cu thin film. The residual stress decreased with decreasing the surface roughness, but increased with increasing the fcc(111) peak strength of XRD patterns.