• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.84-84
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• 2012

소자가 고집적화 됨에 따라, 비저항이 낮고 electro migration (EM), Stress Migration (SM) 특성이 우수한 구리(Cu)를 배선재료로서 사용하고 있다. 그러나, 구리는 Si과 $SiO_2$의 내부로 확산이 빠르게 일어나, Si 소자 내부에 deep donor level을 형성하고, 누설 전류를 증가시키는 등 소자의 성능을 저하시킬 수 있는 문제점을 가지고 있다. 그러나, electroplating 을 이용하여 증착한 Cu 박막은 일반적으로 확산 방지막으로 쓰이는 TiN, TaN, 등의 물질과의 접착 (adhesion) 특성이 나쁘다. 따라서, Cu CMP 에서 증착된 Cu 박막의 벗겨지거나(peeling), EM or SM 저항성 저하 등의 배선에서의 reliability 문제를 야기하게된다. 따라서 Cu 와 접착 특성이 좋은 새로운 확산방지막 또는 adhesion layer의 필요성이 대두되고 있다. 본 연구에서는 이러한 Cu 배선에서의 접착성 문제를 해결하고자 Metal organic chemical vapor deposition (MOCVD)을 이용하여 제조한 코발트(Co) 박막을 $Cu/TaN_x$ 사이의 접착력 개선을 위한 adhesion layer로 적용하려는 시도를 하였다. Co는 비저항이 낮고, Cu 와 adhesion이 좋으며, Cu direct electroplating 이 가능하다는 장점을 가지고 있다. 하지만, 수소 분위기에서 $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) 전구체에 의한 MOCVD Co 박막의 경우 탄소, 산소와 같은 불순물이 다량 함유되어 있어, 비저항, surface roughness 가 높아지게 된다. 따라서 구리 전착 초기에 구리의 핵 생성(nucleation)을 저해하고 핵 생성 후에도 응집(agglomeration)이 발생하여 연속적이고 얇은 구리막 형성을 방해한다. 이를 해결하기 위해, MOCVD Co 박막 증착 시 수소 반응 가스에 암모니아를 추가로 주입하여, 수소/암모니아의 분압을 1:1, 1:6, 1:10으로 변화시켜 $Co/TaN_x$ 박막의 특성을 비교 분석하였다. 각각의 수소/암모니아 분압에 따른 $Co/TaN_x$ 박막을 TEM (Transmission electron microscopy), XRD (X-ray diffraction), AES (Auger electron spectroscopy)를 통해 물성 및 조성을 분석하였고, AFM (Atomic force microscopy)를 이용하여, surface roughness를 측정하였다. 실험 결과, $Co/TaN_x$ 박막은 수소/암모니아 분압 1:6에서 90 ${\mu}{\Omega}-cm$의 낮은 비저항과 0.97 nm 의 낮은 surface roughness 를 가졌다. 뿐만 아니라, MOCVD 에 의해 증착된 Co 박막이4-6 % concentration 의 탄소 및 산소 함량을 가지는 것으로 나타났고, 24nm 크기의 trench 기판 위에 약 6nm의 $Co/TaN_x$ 박막이 매우 균일하게 형성된 것을 확인 할 수 있었다. 이러한 결과들은, 향후 $Co/TaN_x$ 박막이 Cu direct electroplating 공정이 가능한 diffusion barrier로서 성공적으로 사용될 수 있음을 보여준다.

• Korean Journal of Materials Research
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• v.11 no.3
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• pp.184-184
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• 2001

The effect of neutral ligand(L) on the precursor characteristics of (hfac)Cu(I)-L and on Cu MOCVD Process was studied. The neutral ligands of (hac)Cu(I)-L$_{x}$, such as ATMS(allytrimethylsilane), VTMS(vinyltrimethylsilane), VCH(vinylcyclohexane), MP(4-methyl-1-pentene), ACP(allylcyclopentane), and DMB(3,3-dimethyl-1-butene) were investigated. When the dissociation temperature of Cu(I)-L bond is low, low temperature deposition below $100^{\circ}C$ is possible and the resistivity of the film is low. But thermal stability of the precursor is low in this case. The resistivity is almost the same regardless of L at the deposition temperature range of $125~175^{\circ}C$. The resistivity is increased as the molecular weight of L becomes higher above $225^{\circ}C$ The vapor pressure of the precursor was closely related to the boiling point of L, the lower the boiling point of L, the higher the vapor pressurere.

• Korean Journal of Materials Research
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• v.11 no.3
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• pp.185-190
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• 2001

The effect of neutral ligand(L) on the precursor characteristics of (hfac)Cu(I)-L and on Cu MOCVD Process was studied. The neutral ligands of (hac)Cu(I)-L$_{x}$, such as ATMS(allytrimethylsilane), VTMS(vinyltrimethylsilane), VCH(vinylcyclohexane), MP(4-methyl-1-pentene), ACP(allylcyclopentane), and DMB(3,3-dimethyl-1-butene) were investigated. When the dissociation temperature of Cu(I)-L bond is low, low temperature deposition below $100^{\circ}C$ is possible and the resistivity of the film is low. But thermal stability of the precursor is low in this case. The resistivity is almost the same regardless of L at the deposition temperature range of $125~175^{\circ}C$. The resistivity is increased as the molecular weight of L becomes higher above $225^{\circ}C$ The vapor pressure of the precursor was closely related to the boiling point of L, the lower the boiling point of L, the higher the vapor pressurere.

• Journal of the Korean Vacuum Society
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• v.4 no.S1
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• pp.113-117
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• 1995

MOCVD of Cu films were carried out on gold-TiN(1000$\AA$)/Ti/Si wafers from hexafluoroacetylacetonate-Cu(l) vinyltrimethylsilane, Cu(l)(hafac)(vtms), in a small cold-wall type reactor. Effects of the substrate and bubbler temperatures on the film growth rate were studied, and a film with $\rho$=1.8$\pm$0.1$\mu$$\Omega$.cm could be deposited 150nm/min at Ts=200 and Tb=$30^{\circ}C$, respectively. The initial stage of the film formation was also investigated by in-situ laser reflectivity monitoring combined with SEM observations, based on which variations in the film properties depending on the growth conditions were discussed in terms of the nucleation rate and grain size.

• Proceedings of the Korea Institute of Applied Superconductivity and Cryogenics Conference
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• 2003.10a
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• pp.83-86
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• 2003

YBa$_2$Cu$_3$$O_{7-x}$ thin films for coated conductor application were deposited on a MgO single crystalline substrate by a metal organic chemical vapor deposition (MOCVD) system of a vertical type using a single liquid source. The film uniformity was enhanced by controlling the gas shower head structure, the distance between the shower head and substrate, and the rotation of the substrate. The source mole ratio of Y(thd)$_3$: Ba(thd)$_2$: Cu(thd)$_2$ was changed for obtaining stoichiometric film. The phase formation, crystal orientation, surface morphology and film composition were investigated with different source mole ratios, and the critical temperature (T$_{c}$) was measured.red.

• Journal of the Microelectronics and Packaging Society
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• v.5 no.1
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• pp.111-118
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• 1998

본 연구에서는 차세대 집적회로 device의 배선재료로서 사용될 가능성이 높은 Cu 금속을 무전해 도금으로 증착시킨 후 집적회로 공정에 필요한 열적 안정성에 대하여 고찰하 였다. MOCVD방법으로 Si 기판위에 TaN 박막을 확산 방지막으로 증착시킨 다음 무전해도 금으로 Cu막을 증착시켜 Cu/TaN/Si 구조의 다층박막을 제조하여 H2 환원 분위기에서 열처 리시킴으로서 열처리 온도에 따른 Cu 박막의 특성과 확산방지막 TaN와의 계면반응 특성에 대하여 고찰하였다. 활성화 처리와 도금용액의 조절을 적절히 행함으로서 MOCVD TaN 박 막위에 적당한 접착력을 지닌 Cu 박막층을 무전해 도금법을 사용하여 성공적으로 증착시킬 수 있었다. XRD, SEM 분석결과에 의하면 H2 환원분위기에서 열처리시켰을겨우 35$0^{\circ}C$~ $600^{\circ}C$ 범위에서 결정립 성장이 일어나 Cu 박막의 미세구조 특성이 개선됨을 알수 있었다. 또한 XRD, AES 분석에 의하여 열처리 온도에 따른 계면반응 상태를 조사해본 결과 $650^{\circ}C$ 온도에서는 Cu 원자가 TaN 확산방지막을 통과하여 Si 기판내로 확산함으로서 계면에서 Cu-Si 중간화합물을 형성하였다.

• 한국초전도학회:학술대회논문집
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• 2009.07a
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• pp.90-90
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• 2009

• Korean Journal of Materials Research
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• v.11 no.5
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• pp.361-366
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• 2001

It is difficult to obtain high Cu nucleation density and continuous Cu films in Cu-MOCVD without cleaning the TiN substrate prior to Cu deposition. In this study effects of plasma precleaning on the Cu nucleation density were investigated using SEM, XPS, AES, AFM analyses. Direct plasma pretreatment is much more effective than remote plasma pretreatment in enhancing Cu nucleation. Cleaning effects are enhanced with increasing the rf-power and the plasma exposure time in hydrogen plasma pretreatment. The mechanism through which Cu nucleation is enhanced by plasma pretreatment is as follows: Hydrogen ion\ulcorner in the hydrogen plasma react with TiN to form Ti and $NH_3$ Cu nucleation is easier on the Ti substrate than TiN substrate.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.246-246
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• 2010

As the trench width in the interconnect technology decreases down to nano-scale below 50 nm, superconformal gap-filling process of Cu becomes very critical for Cu interconnect. Obtaining superconfomral gap-filling of Cu in the nano-scale trench or via hole using MOCVD is essential to control nucleation and growth of Cu. Therefore, nucleation of Cu must be suppressed near the entrance surface of the trench while Cu layer nucleates and grows at the bottom of the trench. In this study, suppression of Cu nucleation was achieved by treating the Ru barrier metal surface with capacitively coupled hydrogen plasma. Effect of hydrogen plasma pretreatment on Cu nucleation was investigated during MOCVD on atomic-layer deposited (ALD)-Ru barrier surface. It was found that the nucleation and growth of Cu was affected by hydrogen plasma treatment condition. In particular, as the plasma pretreatment time and electrode power increased, Cu nucleation was inhibited. Experimental data suggests that hydrogen atoms from the plasma was implanted onto the Ru surface, which resulted in suppression of Cu nucleation owing to prevention of adsorption of Cu precursor molecules. Due to the hydrogen plasma treatment of the trench on Ru barrier surface, the suppression of Cu nucleation near the entrance of the trenches was achieved and then led to the superconformal gap filling of the nano-scale trenches. In the case for without hydrogen plasma treatments, however, over-grown Cu covered the whole entrance of nano-scale trenches. Detailed mechanism of nucleation suppression and resulting in nano-scale superconformal gap-filling of Cu will be discussed in detail.

• Proceedings of the Korea Institute of Applied Superconductivity and Cryogenics Conference
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• 2003.10a
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• pp.79-82
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• 2003

We prepared YBCO coated conductor by direct deposition of YBCO on Ag substrate by a MOCVD method. The Ag substrate was only prepared by cold rolling. The XRD data of the as-rolled Ag tape showed the formation of dominant (420) oriented grains. Processing variables were the oxygen partial pressure (Po$_2$) and deposition temperature (T$_{d}$). It was found that the a-axis oriented films were grown at lower T$_{d}$ below 80$0^{\circ}C$, while the c-axis oriented films were grown about 80$0^{\circ}C$. The surface of the films consisted of a second inclusion phase dispersed in the YBCO matrix. The Cu-rich phase regions were observed at the YBCO/Ag interface probably due to the inter-diffusion of Ag and Cu. Cu.