• ETRI Journal
• /
• v.13 no.4
• /
• pp.58-69
• /
• 1991

고집적회로에서 A1 금속공정의 diffusion barrier로 널리 사용되는 titanium nitride의 성질을 조사하였다. 실제 회로 구조의 열적 안정성을 관찰하기 위하여 준비된 TiN/Ti다층 barrier를 $600^{\circ}C$까지 열처리하여 x-ray photoelectron spectroscopy (XPS), cross-sectional transmission electron microscopy(XTEM) 등으로 분석하였다. 열처리 온도가 증가됨에 따라 oxygen은 TiN 층의 표면과 pure-Ti 층에 pile up 된다. TiN 층의 표면에서는 $600^{\circ}C$열처리시 TiN이 분해되어 완전히 $TiO_2$가 형성되며, TiN 층 내에서는 oxygen 함량은 열처리 온도의 증가에 따라 커지고 이때 형성되는 Ti-oxide는 $TiO_2$ 보다 TiO, $Ti_2$$O_3$ 상태로 존재하게 된다. Pure-Ti 층은 열처리시 두개의 층으로 나누어 지는 데, 표면에서 침투하는 oxygen과 pure-Ti이 반응하여 Ti-oxide 층이 생기며 실리콘 기판과의 반응으로 Ti-silicide를 형성한다. $600^{\circ}C$에서 모든 Ti 층이 반응으로 소모되고 열적 stress, Ti-silicide의 grain growth, oxygen의 침입으로 TiN 층에 blistering이 발생한다.

• Journal of the Korean Vacuum Society
• /
• v.10 no.3
• /
• pp.321-327
• /
• 2001

Ti-Si-N films obtained by using RF reactive sputtering of targets with various Ti/Si ratios in a $N_2(Ar+N_2)$ gas mixture have been investigated in terms of films resistivity and diffusion barrier performance. The chemical bonding state of Si in the Ti-Si-N film which contained a higher Si content was in the form of amorphous $Si_3N_4$, producing increased film resistivity with increased $N_2$flow rate. Lowering the Si content in the deposited Ti-Si-N film favored the formation of crystalline TiN even at low $N_2$flow rates, and leads to low film resistivity. In addition increasing the N content led to Ti-Si-N films having a higher density and compressive stress, suggesting that the N content in the films appear to be one of the most important factors affecting the diffusion barrier characteristics. Consequently, we proposed the optimum composition in the range of 29~49 at.% of Ti, 6~20 at.% of Si, and 45~55 at.% of N for the Ti-Si-N films having both low resistivity and excellent diffusion barrier performance.

• Korean Journal of Materials Research
• /
• v.9 no.5
• /
• pp.503-508
• /
• 1999

We have investigated the physical and diffusion barrier property of Ti-Si-N film for Cu metallization. The ternary compound was deposited by using reactive rf magnetron sputtering of a TiSi$_2$target in an Ar/$N_2$gas mixture. Resistivities of the films were in range of 358$\mu$$\Omega$-cm, to 307941$\mu$$\Omega$-cm, and tended to increase with increasing the $N_2$/Ar flow rate ratio. The crystallization of the Ti-Si-N compound started to occur at 100$0^{\circ}C$ with the phases of TiN and Si$_3$N$_4$identified by using XRD(X-ray Diffractometer). The degree of the crystallization was influenced by the $N_2$/Ar flow ratio. The diffusion barrier property of Ti-Si-N film for Cu metallization was determined by AES, XRD and etch pit by secco etching, revealing the failure temperature of 90$0^{\circ}C$ in 43~45at% of nitrogen content. In addition, the very thin compound (10nm) with 43~45at% nitrogen content remained stable up to $700^{\circ}C$. Furthermore, thermal treatment in vacuum at $600^{\circ}C$ improved the barrier property of the Ti-Si-N film deposited at the $N_2$(Ar+$N_2$) ratio of 0.05. The addition of Ti interlayer between Ti-Si-N films caused the drastic decrease of the resistivity with slight degradation of diffusion barrier properties of the compound.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.17 no.2
• /
• pp.150-155
• /
• 2004

This study attempts to form a TiN barrier layer against Cu diffusion by the easier and more convenient method. In this new approach, Ti was sputter-deposited, and nitrided by heat-treating in the NH$_3$ambient. Sheet resistance of as-deposited Ti was 20 Ω/$\square$, but increased to 195 Ω/$\square$ after the heat-treatment at 30$0^{\circ}C$, and lowered to 120 Ω/$\square$ after the heat-treatment at 50$0^{\circ}C$, and $600^{\circ}C$. AES results for these thin films confirmed that the atomic ratio of Ti and N was close to 1:1 at or above 40$0^{\circ}C$ heat-treatment. However, it was also found that excessive oxygen was contained in the TiN layer. To examine the barrier property against Cu diffusion, 100nm Cu was deposited on the TiN layer and then annealed at 40$0^{\circ}C$ for 40 min.. Cu remained at the surface without diffusing into the Si layer.

• Korean Journal of Materials Research
• /
• v.11 no.3
• /
• pp.215-220
• /
• 2001

Amorphous Ti-Si-N films of approximately 200 and 650 thickness were reactively sputtered on Si wafers using a dc magnetron sputtering system at various $N_2$/Ar flow ratios. Their barrier properties between Cu (750 ) and Si were investigated by using sheet resistance measurements, XRD, SEM, RBS, and AES depth profiling focused on the effect of the nitrogen content in Ti-Si-N thin film on the Ti-Si-N barrier properties. As the nitrogen content increases, first the failure temperature tends to increase up to 46 % and then decrease. Barrier failure seems to occur by the diffusion of Cu into the Si substrate to form Cu$_3$Si, since no other X- ray diffraction intensity peak (for example, that for titanium silicide) than Cu and Cu$_3$Si Peaks appears up to 80$0^{\circ}C$. The optimal composition of Ti-Si-N in this study is $Ti_{29}$Si$_{25}$N$_{46}$. The failure temperatures of the $Ti_{29}$Si$_{25}$N$_{465}$ barrier layers 200 and 650 thick are 650 and $700^{\circ}C$, respectively.ely.

• Korean Journal of Materials Research
• /
• v.5 no.1
• /
• pp.87-95
• /
• 1995

The effect of stuffing of TiN on the diffusion barrier property between A1 and Si was investigated. The stuffing of TiN was performed by annealing in a Nz ambient at $450^{\circ}C$ for 30min. By TEM analysis, it is identified that there are solid-free or open spaces of a b u t 10-20$\AA$ between the grains of asdeposited TiN. In the case of stuffed TiN, the width of solid-free or open spaces has been reduced to about 10$\AA$ or below. The combination of RBS and AES analyses showed that the asdeposited TiN had about 7at.% of oxygen, and that the stuffed TiN had about 10-15at.% of oxygen. The diffusion barrier test result shows that after annealing at $650^{\circ}C$ for lhour, the asdeposited TiN fails due to the formation of A1 spikes and Si pits in the Si substrate. However, in the case of stuffed TiN, there is no indication of Al spikes and Si pits at the same annealing condition. Thus, it is concluded that this stuffing of TiN significantly improves the diffusion barrier property of TiN between A1 and Si. It is considered that the stuffing effect results from the reduced diffusion through grain boundaries due to the reduced spacing of grain boundaries.

• Korean Journal of Materials Research
• /
• v.15 no.5
• /
• pp.318-322
• /
• 2005

Ti-capped NiSi contacts were formed on $p^+/n$ junctions to improve the leakage problem and then Cu was deposited without removing the Ti-capping layer in an attempt to utilize as a diffusion barrier. The electrical characteristics of these $p^+/n$ diodes with Cu/Ti/NiSi electrodes were measured as a function of drive-in RTA(rapid-thermal annealing) and silicidation temperature and time. When drive-in annealed at $900^{\circ}C$, 10 sec. and silicided at $500^{\circ}C$, 100 sec., the diodes showed the most excellent I-V characteristics. Especially, the leakage current was $10^{-10}A$, much lower than reported data for diodes with NiSi contacts. However, when the $p^+/n$ diodes with Cu/Ti/NiSi contacts were furnace-annealed at $400^{\circ}C$ for 40 min., the leakage current increased by 4 orders. The FESEM and AES analysis revealed that the Ti-capping layer effectively prohibited the Cu diffusion, but was ineffective against the NiSi dissociation and consequent Ni diffusion.

• Korean Journal of Materials Research
• /
• v.14 no.4
• /
• pp.246-250
• /
• 2004

We have investigated the effects of boron added to Cu film on the Cu-Ti reaction and microstructural evolution of Cu(B) alloy film during annealing of Cu(B)/Ti/$SiO_2$/Si structure. The result were compared with those of Cu(B)/$SiO_2$ structure to identify the effects of Ti glue layers on the Boron behavior and the result grain growth of Cu(B) alloy. The vacuum annealing of Cu(B)/Ti/$SiO_2$ multilayer structure allowed the diffusion of B to the Ti surface and forming $TiB_2$ compounds at the interface. The formed $TiB_2$ can act as a excellent diffusion barrier against Cu-Ti interdiffusion up to $800^{\circ}C$. Also, the resistivity was decreased to $2.3\mu$$\Omega$-cm after annealing at $800^{\circ}C$. In addition, the presence of Ti underlayer promoted the growth Cu(l11)-oriented grains and allowed for normal growth of Cu(B) film. This is in contrast with abnormal growth of randomly oriented Cu grains occurring in Cu(B)/$SiO_2$ upon annealing. The Cu(B)/Ti/$SiO_2$ structure can be implemented as an advanced metallization because it exhibits the low resistivity, high thermal stability and excellent diffusion barrier property.

• Journal of the Korean Vacuum Society
• /
• v.5 no.4
• /
• pp.333-340
• /
• 1996

The properties of TiN as a barrier against Cu diffusion ere studied by sheet resistance measurement, X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and capacitance-voltage(C-V) measurement. The sensitivities of the various methods were compared. Specimens with Cu/TiN/Ti/SiO2/Si structure were prepared by various deposition techniques and annealed at various temperatures ranging from $500^{\circ}C$ to $800^{\circ}C$ in 10%H2/90%Ar ambient for hours. As the effectiveness of the barrier property of TiN against Cu diffusion was vanished, the irregular-shaped sports were observed and outdiffused Si were detected on the surface of the Cu thin film. The C-V characteristics of the MOS capacitors varied drastically with annealing temperatures. In C-V measurement, the inversion capacitance decreased at annealing temperature range from $500^{\circ}C$ to $700^{\circ}C$ and increased remarkably at $800^{\circ}C$. These variations may be due to the Cu diffusion through TiN into $SiO_2$ and Si.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2000.02a
• /
• pp.169-169
• /
• 2000

최근 반도체 소자의 초고집적화 현상에 따라 기존의 Al-base 합금에 대한 한계에 달하면서 그에 대한 대체 물질로 Cu가 관심을 모으게 되었고 그럼으로써 Cu metallization을 위한 많은 연구가 진행되어 왔다. Cu는 Al-base 합금계보다 비저항이 낮고, 녹는점이 높으며, 또한 electromigration 특성이 뛰어난 것으로 알려져 있다. 공학적인 면에서 이미 이들 계에 대한 adhesion 및 전기적 특성에 대한 많은 연구가 있어왔지만, 이들 특성 변화에 대한 물리적 의미를 제공할 만한 기초 자료들이 부족한 상태이다. 본 연구에서는 부도체인 polyimide 박막과 diffusion barrier인 TiN 박막위에서의 Cu 박막성장에 따르는 interface chemical reaction의 변화를 XPS를 이용하여 관찰함으로서 이들 계에 있어서의 adhesion과의 관계를 조사하였다. 그리고 XPS를 이용한 modified surface accumulation method를 적용시켜 TiN diffusion barrier를 통한 Cu의 grain boundary diffusion 상수들을 측정하였다. Cu/TiN system의 경우에는 interface chemical reaction이 일어나지 않았지만 Cu/polymide system에 있어서는 boundary diffusivity는 특히 40$0^{\circ}C$에서 $650^{\circ}C$ 영역에서, Db=60$\times$10-11exp[-0.29/(kBT)]cm2/sec 이었다.