Investigation of thermal stability of Mo thin-films as the buffer layer and various Cu metallization as interconnection materials for thin film transistor-liquid crystal display applications

Cu/Mo/Si multi-layer structures were fabricated to investigate diffusion behaviors and thermal stability between Cu and Mo. Physical vapor deposition (PVD), chemical vapor deposition, electroplating and electrolessplating were used to grow 100 nm thick Cu films as interconnection materials, and radio-frequency sputtering system was introduced to grow 37.5 nm thick Mo films as a buffer layer. All Cu/Mo/Si multi-layer specimens were annealed at 350 to 700 °C for 30 min. When the annealing temperature was over 600 °C, the Cu diffused through Mo into Si, and the Cu₃Si phase and Mo-Si intermetallic compounds formed at the Mo/Si interface. The diffusion mechanism is the grain boundary diffusion. The results indicate that Cu film deposited by PVD had best crystallinity, lower roughness, large adhesive energy and resistivity. The values of the resistivity, diffusion activity energy and large adhesive energy are 5.47 μΩ-cm, 0.948 eV and 2.46 N/m, respectively.     

Diffusion barrier capability of Zr-Si films for copper metallization with different substrate bias voltage

Efficiency of Zr-Si diffusion barriers in Cu metallization has been investigated. Amorphous Zr-Si diffusion barriers were deposited on the Si substrates by reactive magnetron sputtering with different negative substrate bias. The mass density of Zr-Si films increases with substrate bias voltage up to − 150 V. The deposition rate decreased with the negative substrate bias from 5.4 nm/min to 1.8 nm/min. XRD measurements show that the Zr-Si barriers have amorphous structure in the as-deposited state. The FE-SEM images show that the sizes of spherical granules on the Zr-Si film surface increase with increasing the substrate bias. The Cu/Zr-Si/Si structures were prepared and annealed in Ar ambient at temperatures varying from 500 to 650 °C for an hour. It is shown from the comparison study that the Zr-Si film deposited with − 150 V is better at maintaining good performance in Cu/Zr-Si/Si contact system than that of Zr-Si film deposited with − 50 V.     

Effect of Si target sputtering power on diffusion barrier properties of Ta–Si–N thin films

Abstract

Ta–Si–N thin films and Cu/Ta–Si–N thin films were deposited on p type Si(111) substrates by magnetron reactive sputtering. Then the films were characterised by four point probe sheet resistance measurement, AFM, SEM and XRD respectively. According to the XRD results, the authors found that the crystallisation of Ta nitrides in Ta–Si–N/Si thin films is suppressed effectively when fabricated by a high Si target sputtering power. As the Si target power varies, the failure temperature of Cu/Ta–Si–N/Si is changed. The sample fabricated by the Si target power of 200 W fails after 800°C rapid thermal annealing and it has the highest failure temperature. The investigation of failure mechanism shows that Cu atoms diffuse through grain boundaries or amorphous structure of the Ta–Si–N barrier, and react with Si to form Cu–Si phase. And it causes the failure of the barrier.     

On the structure and surface chemical composition of indium-tin oxide films prepared by long-throw magnetron sputtering

Structures and surface chemical composition of indium tin oxide (ITO) thin films prepared by long-throw radio-frequency magnetron sputtering technique have been investigated. The ITO films were deposited on glass substrates using a 20 cm target-to-substrate distance in a pure argon sputtering environment. X-ray diffraction results showed that an increase in substrate temperature resulted in ITO structure evolution from amorphous to polycrystalline. Field-emission scanning electron microscopy micrographs suggested that the ITO films were free of bombardment of energetic particles since the microstructures of the films exhibited a smaller grain size and no sub-grain boundary could be observed. The surface composition of the ITO films was characterized by X-ray photoelectron spectroscopy (XPS). Oxygen atoms in both amorphous and crystalline ITO structures were observed from O 1 s XPS spectra. However, the peak of the oxygen atoms in amorphous ITO phase could only be found in samples prepared at low substrate temperatures. Its relative peak area decreased drastically when substrate temperatures were larger than 200 °C. In addition, a composition analysis from the XPS results revealed that the films deposited at low substrate temperatures contained high concentration of oxygen at the film surfaces. The oxygen-rich surfaces can be attributed to hydrolysis reactions of indium oxides, especially when large amount of the amorphous ITO were developed near the film surfaces.     

A diffusion study in the barrier of metallized amorphous binary alloys withnumerical approach

An amorphous Ta-Zr alloy film was studied as a diffusion barrier in the Cu metallization. On the experimental part, a Cu/Ta₅₀Zr₅₀/Si stack with thickness of 50 nm amorphous film was first prepared by sputtering and found effectively to suppress the penetration of Cu atoms into the substrate under rapid thermal annealing up to 650 °C. However, by examining the thermal stability of the barrier it revealed that these amorphous Ta₅₀Zr₅₀ films crystallized at 800 °C, much higher than its failure temperature. Moreover, three metal silicides, TaSi₂, ZrSi₂ and Cu₃Si were found almost simultaneously when samples annealed at 650 °C. This result indicates that the existence of Cu layer not only promotes the diffusion of Ta and Zr to form metal silicides but also the diffusion of itself to pass through the barrier film to react with Si. A failure mechanism of the diffusion barrier is therefore proposed and verified quantitatively based on the relation between the thermal stress and the activation energy of diffusion.     

Diffusion barrier performance of amorphous W-Ti-N films in Cu metallization

W-Ti-N films were prepared on a Si wafer by reactive sputter-deposition, followed by a deposition of a Cu thin film by DC magnetron sputtering. The Cu/W-Ti-N/Si samples prepared were annealed at different temperatures under vacuum and then characterized using X-ray diffraction, scanning electron microscopy and auger electron microscopy. The sheet resistivity was determined by four point probe analysis. The results show that the amorphous W-Ti-N film is mainly composed of TiN and W and the crystallization temperature is above 800 °C. W-Ti-N thin films prepared have good thermal stability at 700 °C, but the Cu film tends to agglomerate when the temperature is above 700 °C. A failure mechanism of the diffusion barrier is proposed based on the thermal stress and interface reaction.     

Effect of substrate temperature on the thermal stability of Cu/Zr-N/Si contact system

The effect of substrate temperature on the thermal stability of Cu/Zr-N/Si contact systems was investigated. Zr-N films were deposited on the Si substrates by RF reactive magnetron sputtering under various substrate temperatures. Cu films were in-situ sputtered onto the Zr-N films subsequently. The contact systems were characterized using four-point probe sheet resistance measurements (Rs), X-ray diffraction (XRD), and scanning electron microscopy (SEM) respectively. It was found that the sheet resistances of Cu/Zr-N (350 °C)/Si contact system were lower than those of Cu/Zr-N (150 °C)/Si specimens after annealing at 650 °C. Cu/Zr-N (350 °C)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected. It is indicated from the comparison analysis results that the Zr-N film showed better diffusion barrier performance deposited under higher substrate temperature.     

Ta基纳米薄膜扩散阻挡特性的比较研究

采用直流磁控溅射方法在p型(100)Si衬底上制备了Cu/Ta、Cu/Ta-N和Cu/Ta-Al-N复合膜,并对薄膜样品进行了卤钨灯快速热退火.用四探针电阻测试仪(FPP)、AFM、SEM、Alpha-step IQ台阶仪和XRD等分析测试方法对样品的形貌结构与特性进行了分析表征,并对N和Al的掺杂机理进行了讨论.实验结果表明,Ta、Ta-N和Ta-Al-N膜层的Cu扩散阻挡特性逐渐增强,Ta/Si界面上的反应和Cu通过多晶Ta膜扩散到Si底并形成Cu3Si共同导致了Ta阻挡层的失效,而Cu通过Ta-N和Ta-Al-N结晶后产生的晶界扩散到Si底并形成Cu3Si是两者失效的唯一机制.N的掺入促进了非晶薄膜的形成且有利于消除界面反应,而Al的掺入将进一步提高薄膜的结晶温度和热稳定性.     

Microstructure of amorphous tantalum nitride thin films

The main purpose of the present microstructural analysis by transmission electron microscopy (TEM) and X-ray diffraction was to investigate whether amorphous TaN films are a potential candidate as diffusion barrier for Cu wiring used in Si devices. The TaN thin films were prepared by a sputter-deposition technique using Ar and N₂ mixed gas, and the film structure was found to be sensitive to the gas flow ratio of N₂ vs. Ar during sputtering. Polycrystalline TaN films were obtained when the N₂/(Ar+N₂) ratio was smaller than 0.10 and amorphous TaN films were obtained when the ratio was larger than 0.15. Cross-sectional TEM observations revealed that the amorphous films had columnar structure with fine grains and that nano-scaled voids segregated at the boundaries. In addition, two-layered structures were observed in the amorphous TaN films and high density of the grain boundaries was formed close to the substrate. The present results suggested that the amorphous TaN films would not have high resistance against interdiffusion between two different materials because the density of grain boundaries with small voids was extremely high.     

High thermal stability of AlCrTaTiZr nitride film as diffusion barrier for copper metallization

To inhibit rapid Cu diffusion in interconnect structures, an effective diffusion barrier layer with high thermal stability, low electrical resistivity and good interface adhesion is strongly demanded. Thus in this study, an amorphous nitride film of equimolar AlCrTaTiZr alloy with an N content of about 41 at.% was deposited by reactive radio-frequency magnetron sputtering. Thermal stability of the AlCrTaTiZr nitride film and its barrier property to Cu diffusion were investigated under thermal annealing at 700-900 °C. The AlCrTaTiZr nitride film remained an amorphous structure after thermal annealing at 700 °C and then crystallized at 800 °C. However, no interdiffusion between Si substrate and Cu metallization through the AlCrTaTiZr nitride film occurred. The electrical resistivity of the film remained at the low level of as-deposited value, indicating its good thermal stability as an effective diffusion barrier layer. With temperature further increasing to 900 °C, severe interdiffusion occurred, along with the formation of silicides and large pores. The electrical resistivity then significantly increased, implying the failure of the AlCrTaTiZr nitride film.     

Diffusion barrier performance of nano-structured and amorphous Ru-Ge diffusion barriers for copper metallization

In the experiment, nano-structured and amorphous ultrathin Ru-Ge interlayers (∼15 nm in thickness) were deposited between Cu(Ru) alloy film and Si substrate via co-sputtering functioning as preventive diffusion barrier layers. After annealing at different temperatures, X-ray diffraction and four-point probe method revealed that the amorphous Ru-Ge layer effectively suppressed the Cu diffusion into Si substrate up to a temperature of at least 873 K; however, it is less than 773 K for the nano-structured Ru-Ge layer. A self-formed amorphous multilayer of Ru(RuO_x)/RuGe_xCu_y could be attained by annealing Cu/Cu(Ru)/Ru-Ge(amorphous)/Si system at a very low temperature (even 473 K). The results proved that the amorphous Ru-Ge system could self-form the multilayer diffusion barrier before the diffusion reaction between Cu and Si and improved the thermal stability of the Cu interconnection significantly.     

Nanomechanical properties of FePtPd ternary alloy thin films

Presented in this study are crystalline structure and mechanical properties of FePt_0.75Pd_0.25 ternary alloy thin films deposited under the various annealing temperatures, obtained by means of transmission electron microscopy (TEM) and nanoindentation techniques. FePtPd ternary alloy thin films are deposited on Si substrates using a multi-target DC magnetron sputtering system. Results indicate that the grain size increase from 40 to 135 nm as the annealing temperature increases from 400 to 600 °C. From nanoindentation measurements, the hardness of FePtPd ternary alloy thin films are 11.6 ± 0.4, 10.4 ± 0.1 and 8.8 ± 0.3 GPa for the annealed temperatures of 400, 500 and 600 °C, respectively. And, the corresponding Young's moduli are 175.4, 152.2 and 142.6 GPa, respectively. Hardness for FePtPd ternary alloy thin films decreased slightly in accordance with the increase of the grain size. By fitting experimental results with the Hall-Petch equation, a probable lattice friction stress of 5.15 ± 0.05 GPa and Hall-Petch constant of 44.25 ± 2.55 GPa nm^1/2 are obtained.     

铜与硅之间W/Mo-N薄膜的扩散阻挡层性能

研究了铜与硅之间W／Mo-N薄膜的扩散阻挡性能。在Si(100)基片上利用反应溅射沉积一层Mo-N薄膜,然后再利用直流溅射在Mo-N上面沉积Cu／W薄膜。样品在真空下退火,并利用四点探针、X射线衍射分析、扫描电镜分析、俄歇电子能谱原子深度剖析等测试方法研究了Cu／W／Mo-N／Si的热稳定性及W／Mo-N薄膜对铜与硅的扩散阻挡性能。实验分析表明,Cu／W／Mo-N／Si结构具有非常好的热稳定性,在600℃退火30min仍未发生相变,并能有效的阻挡铜与硅之间的扩散。     

Oxidation of magnetron sputtered La-Si thin films for solide oxide fuel cell electronlytes

La-Si thin films were deposited on stainless steel substrates by magnetron sputtering from pure La and Si targets. The Si/(Si + La) atomic ratio in the films was varied from 43.2 to 59.3% by adjusting the discharge current on the La target. The films had a homogeneous chemical composition down to the substrate and sharp interfaces. Annealing the films in air at 1173 K promotes the formation of apatite-structure La_9.33Si₆O₂₆ and the diffusion of different species from the film to the substrate and vice-versa, resulting in broadening the interfaces. X-Ray diffraction showed that all the as-deposited films had an amorphous structure. The formation of the LaSi₂ phase at intermediate temperatures was observed for the films deposited with higher Si contents while the films deposited with lower Si contents remained amorphous up to the start of the apatite structure crystallization process. The lanthanum silicate apatite-like phase (La_9.33Si₆O₂₆) was obtained only after annealing at 1173 K, excepted for the film with the lower Si content which is already partially crystallized after annealing at 1073 K. Quite pure La_9.33Si₆O₂₆ was obtained only after annealing the film with the highest Si content (Si/(Si + La) = 59.3%) although the theoretical Si/(Si + La) atomic ratio for apatite structure lanthanum silicate is 39%. For the other films, La₂O₃ was always detected when the lanthanum silicate phase was formed. Both phenomena clearly resulted from the strong diffusion of silicon excess towards the stainless steel substrate.     

Barrier capability of Zr–N films with titanium addition against copper diffusion

Zr–Ti–N film prepared by sputtering deposition has been employed as a potential diffusion barrier for Cu metallization. It is thought that the existing states of Ti and Zr in the films are Ti–N and Zr–N phase in Zr–Ti–N films. Material analysis by XRD, XPS and sheet resistance measurement reveal that the failure of Zr–N film is mainly due to the formation of Cu₃Si precipitates at the Zr–N/Si interface by Cu diffusion through the grain boundaries or local defects of the Zr–N barrier layer into Si substrate. In conjunction with sheet resistance measurement, XRD and XPS analyses, the Cu/Zr–Ti–N/Si contact system has high thermal stability at least up to 700 °C. The incorporation of Ti atoms into Zr–N barrier layer was shown to be beneficial in improving the thermal stability of the Cu/barrier/Si contact system.     

Preparation and characterization of sputtered Cu films containing insoluble Nb

Copper films containing various amounts of insoluble Nb (up to 24.7 at.%) were prepared by r.f. magnetron sputtering. The crystallography and microstructure of the films were investigated for as-deposited and annealed Cu(Nb) thin films. Cu(Nb) thin films are found to consist of non-equilibrium supersaturated solid solution of Nb in Cu with a nanocrystalline microstructure. X-ray diffraction and scanning electron microscope analyses revealed a reduction in the grain sizes of the films with increasing Nb content in the films leading to a grain refinement. The electrical resistivity of as-deposited and annealed Cu(Nb) thin films is found to be low for an Nb content 2.7 at.%. Significant drops in the resistivity were observed for the high Nb contents after annealing at 530 °C which may be due to grain growth and formation of Nb-bearing phase in the film. Microhardness of the films was found to increase with the Nb concentration due to the combined effects of grain refinement and the solute strengthening of Nb.     

Comparisons on the properties of (Zn1-xCox)2-W type barium hexaferrite thin films prepared on the Si (100) and (111) substrates

The (Zn_1-xCo_x)₂-W type barium hexaferrite thin films have been prepared by a radio frequency magnetron sputtering method on the Si (100) and the Si (111) substrates respectively. With increasing the annealing temperatures (800, 850, 900, 950, and 1000 °C), the Ba(CoZn)₂Fe₁₆O₂₇ phases emerge from the amorphous matrix. The hexaferrite thin films on Si (111) substrates have a larger saturation magnetic field (636.6 kA/m) than those on Si (100) substrates (159.1 kA/m). The magnetic hysteresis measurements show that they exhibit an isotropic behavior for thin films deposited on both substrates. Films on the Si (111) substrates are magnetically harder than those on the Si (100) substrates.     

Preparation of high quality polycrystalline silicon thin films by aluminum-induced crystallization

High quality polycrystalline silicon (poly-Si) thin films without Si islands were prepared by using aluminum-induced crystallization on glass substrates. Al and amorphous silicon films were deposited by vacuum thermal evaporation and radio frequency magnetron sputtering, respectively. The samples were annealed at 500 °C for 7 h and then Al was removed by wet etching. Scanning electron microscopy shows that there are two layers in the thin films. After the upper layer was peeled off, the lower poly-Si thin film was found to be of high crystalline quality. It presented a Raman peak at 521 cm^− 1 with full width at a half maximum of 5.23 cm^− 1, which is similar to c-Si wafer.     

Structural and optical properties of nanocrystalline WO<Subscript>3</Subscript> thin films

The nanocrystalline WO₃ thin films were deposited by r.f. magnetron sputtering on quartz and p- type Si (100) substrates at a constant power of 25 W and at three different sputtering pressures (0.05, 0.01 and 0.5 mbar) and post annealed at different temperatures. The deposited films were characterized by XRD, UV–VIS spectrophotometry, ellipsometry and atomic force microscopy (AFM). The structural studies from XRD spectra reveals that the films deposited at 0.05 mbar and post annealed at 573 and 673 K have the predominant orthorhombic phase, whereas at 0.1 mbar and 573, 673 K triclinic phase is predominant. When sputtering pressure is at 0.5 mbar the predominant phase is monoclinic when annealed at 473 K and triclinic at 673 K. The optical energy gap is influenced significantly by sputtering pressure and post annealing temperatures. The optical energy gap of the films deposited at higher sputtering pressures and post annealed at lower temperatures is high due to smaller crystallite sizes. The thickness of all deposited films at different conditions is around 200 nm.     

Heat treatment effects on the formation of lanthanum-modified lead zirconate titanate thin films

The microstructural and compositional properties of lanthanum-modified lead zirconate titanate (PLZT) thin films deposited on platinum coated Si substrates by RF magnetron sputtering have been studied. The heat treatment processes of substrate heating during deposition and post deposition furnace and rapid thermal annealing were compared as processes for obtaining the desired pervoskite phase. PLZT thin films deposited with in-situ substrate heating showed little evidence of micro-cracking. The XRD data obtained showed the formation of pervoskite phase at 550 °C and indicated the suppression of the pyrochlore phase for increasing temperatures. The RBS analysis revealed a film thickness of 140 nm and composition of (Pb_0.91La_0.09)(Zr_0.6Ti_0.4)O₃. Deposition performed with in-situ substrate heating at 650 °C resulted in highly (110) pervoskite orientated thin films with an average grain size around 160 to 200 nm and an RMS roughness of 3 nm.