Low-Temperature Synthesis of High-Adhesion Cu(Mg) Alloy Films on Glass Substrates

Cu(0.5 at.%Mg) alloy films were deposited on glass substrates, and annealed at 200–400 °C in vacuum. The resistivity of the Cu(Mg) films was reduced to about 3.0 μΩcm after annealing at 200 °C for 30 min, and the tensile strength of adhesion of the Cu(Mg) films to the glass substrates was increased to 30–40 and 35–55 MPa after annealing at 250 and 300 °C, respectively. The reduction in resistivity can be explained as reduced impurity scattering and grain-boundary scattering, since Mg segregation to the film surface and Cu(Mg)/glass interface, and consequent Cu grain growth, were observed. Increased adhesion of the Cu(Mg) films to glass substrates after annealing was also explained by the strong segregation of Mg atoms, and the formation of a reaction layer at the interface. Mg atoms were observed to have reacted with the glass substrates and formed a thin crystalline MgO layer at the interface in the samples annealed at 300 °C, while Mg atoms were highly concentrated above the Cu(Mg)/glass interface without oxide formation at the interface in the samples annealed at 250 °C. Thus, the process temperature and time to obtain low-resistivity and high-adhesion Cu alloy films on glass substrates could be reduced to 250 °C and 30 min using Cu(Mg) films.     

Investigation of Ti/Al and TiN/Al thin films as the stable ohmic contact for p-type 4H-SiC

Interfacial reactions, surface morphology, and current-voltage (I-V) characteristics of Ti/Al/4H-SiC and TiN/Al/4H-SiC were studied before and after high-temperature annealing. It was observed that surface smoothness of the samples was not significantly affected by the heat treatment at up to 900°C, in contrast to the case of Al/SiC. Transmission electron microscopy (TEM) observation of the Ti(TiN)/Al/SiC interface showed that Al layer reacted with the SiC substrate at 900°C and formed an Al-Si-(Ti)-C compound at the metal/SiC interface, which is similar to the case of the Al/SiC interface. The I-V measurement showed reasonable ohmic properties for the Ti/Al films, indicating that the films can be used to stabilize the Al/SiC contact by protecting the Al layer from the potential oxidation and evaporation problem, while maintaining proper contact properties.     

Thermal stability of Cu(W) and Cu(Mo) films for advanced barrierless Cu metallization: Effects of annealing time

The current study investigates the effects of insoluble substances (W and Mo) in pure Cu films on the thermal stability, microstructure, and electrical properties of the films. The results can be used to assess the feasibility of the barrierless Cu film in the metallization process. The films investigated were deposited using magnetron sputtering onto the barrierless Si (100) substrate and then annealed between 400°C and 450°C in vacuum for long periods of time. After annealing, the film properties were examined by x-ray diffraction (XRD), the four-point probe method, leakage current measurements, and focused ion beam (FIB) analysis. The results indicate that no detectable copper silicide is formed after 48-h annealing of Cu(W) films at 400°C. In contrast, for the Cu(Mo) film, copper silicide is formed after 18-h annealing at the same temperature and hence electrical properties are poor. This evidence suggests that the Cu(W) film has better thermal stability during long periods of annealing and is suitable for an advanced barrierless metallization process.     

Effect of annealing on the surface microstructural evolution and the electromigration reliability of electroplated Cu films

This paper presents the effects of annealing, performed over a temperature range from 200°C to 400°C, on the surface microstructural evolution and the electromigration reliability of electroplated Cu films. After annealing, a substantial increase in surface roughness was observed, while variations in mean grain size and nanoindentation hardness were minor. Given the annealing temperature, the surface roughness was larger for the films annealed in forming gas, due to the existence of hydrogen. In particular, the films annealed at 400°C in forming gas demonstrated severe grain-boundary grooving and surface voiding. The defective nature of the annealed surface can be alleviated by chemical-mechanical polishing (CMP), when annealing is conducted prior to the CMP. However, it appears that a sequential thermal excursion at relatively high temperatures re-aggravates the integrity of the Cu surface. This argument may be supported by the electromigration-test results on dual-damascene interconnects fabricated using two different thermal profiles. The electromigration lifetimes were longer by more than a factor of two for the interconnects that skipped a post-passivation anneal at 400°C. The experimental evidence presented in this work suggests that controlling the integrity and quality of the Cu surface is an important step in ensuring good electromigration reliability.     

The effects of process conditions and substrate on copper MOCVD using liquid injection of (hfac)Cu(vtmos)

Copper MOCVD (metalorganic chemical vapor deposition) using liquid injection for effective delivery of the (hfac)Cu(vtmos) [1,1,1,5,5,5-hexafluoro-2,4-pentadionato(vinyltrimethoxysilane) copper(I)] precursor has been performed to clarify growth behavior of copper films onto TiN, <100> Si, and Si₃N₄ substrates. Especially, we have studied the influences of process conditions and the substrate on growth rates, impurities, microstructures, and electrical characteristics of copper films. As the reactor pressure was increased, the growth rate was governed by a pick-up rate of (hfac)Cu(vtmos) in the vaporizer. The apparent activation energy for copper growth over the surface-reaction controlled regime from 155°C to 225°C was in the range 12.7–32.5 kcal/mol depending upon the substrate type. It revealed that H₂ addition at 225°C substrate temperature brought about a maximum increase of about 25% in the growth rate compared to pure Ar as the carrier gas. At moderate deposition temperatures, the degree of a <111> preferred orientation for the deposit was higher on the sequence of <Cu/Si<Cu/TiN<Cu/Si₃N₄. The relative impurity content within the deposit was in the range 1.1 to 1.8 at.%. The electrical resistivity for the Cu films on TiN illustrated three regions of the variation according to the substrate temperature, so the deposit at 165°C had the optimum resistivity value. However, the coarsened microstructures of Cu on TiN prepared above 275°C gave rise to higher electrical resistivities compared to those on Si and Si₃N₄ substrates.     

Morphology evolution in TiN/Al-0.5Cu/Ti interconnection during chamber long stay and post-deposition annealing correlated to defect formation in metallization processing

TiN/Al-0.5Cu/Ti film stacks deposited on SiO₂ substrate were studied by X-ray diffraction and electron microscopy to clarify the effects of the chamber long stay and post-deposition annealing on the morphology evolution. Experimental results indicated that the chamber idleness at 270 °C resulted in significant Al₂Cu precipitation and hillock growth for the Al-Cu films, which enhanced the occurrence rate of the microcorrosion-induced bridging defects and caused yield degradation on production line while post-deposition annealing at 400 °C for 30 min was proven to effectively regain good yield for the chamber-idled wafers. The yield recovery could be attributed to the fast Al₂Cu dissolution and hillock mitigation at the annealing temperature. The electrical sheet resistance of the Al-Cu films would somewhat increase due to the formation of the Al₃Ti phase during annealing, but the Al₂Cu precipitates and surface hillocks formed during chamber idleness would scarcely change the electrical property of the films. This study suggests that the evolutions of second phase and surface hillocks can be controlled by the processing duration and post-deposition treatment rather than the deposition temperature or Cu addition amount of Al-Cu alloy.     

Characterization of TiN/TiSi2 bilayer for application to ULSI

The properties of TiN/TiSi₂ bilayer formed by rapid thermal annealing (RTA) in an NH₃ ambient after the titanium film is deposited on the silicon substrate is investigated. It is found that the formation of TiN/TiSi₂ bilayer depends on the RTA temperature and a competitive reaction for the TiN/TiSi₂ bilayer occurs at 600°C. Both the TiN and TiSi₂ layers represent titanium-rich films at 600°C anneal. The TiN layer has a stable structure at 700°C anneal while the TiSi₂ layer has C₄₉ and C₅₄ phase. Both the TiN and TiSi₂ layers have stable structures and stoichiometries at 800°C anneal. When the TiN/TiSi₂ bilayer is formed, the redistribution of boron atoms within the TiSi₂ layer gets active as the anneal temperature is increased. According to secondary ion mass spectroscopy analysis, boron atoms pile up within the TiN layer and at the TiSi₂−Si interface. The electrical properties for n⁺ and p⁺ contacts are investigated. The n⁺ contact resistance increases slightly with increasing annealing temperature but the p⁺ contact resistance decreases. The leakage current indicates degradation of the contact at high annealing temperature for both n⁺ and p⁺ junctions.     

多靶磁控共溅射纳米Ta-Al-N薄膜的阻挡性能研究

采用磁控反应共溅射方法制备了纳米Ta-Al-N薄膜,并原位制备了Cu/Ta-Al-N薄膜,对薄膜进行了热处理。用四探针测试仪、X射线衍射仪(XRD)、扫描电镜(SEM)、原子力显微镜(AFM)以及台阶仪等研究了退火对薄膜结构及阻挡性能的影响。结果表明,Ta-Al-N薄膜具有优良的热稳定性,保持非晶态且能对Cu有效阻挡的温度可达800°C;同时发现在900°C退火5 min后,薄膜开始晶化,在Cu/Ta-Al-N/Si界面处生成了Cu3Si等相,表明此时Ta-Al-N薄膜阻挡层开始失效。     

The Application of Barrierless Metallization in Making Copper Alloy,Cu(RuHfN), Films for Fine Interconnects

In this study, films of a copper (Cu) alloy, Cu(RuHfN _x ), were deposited on silicon (Si) substrates with high thermal stability by co-sputtering copper and minute amounts of Hf or Hf/Ru in an Ar/N₂ gas mixture. The Cu(RuHfN _x ) films were thermally stable up to 720°C; after annealing at 720°C for 1 h, the thermal stability was great enough to avoid undesired reaction between the copper and the silicon. No copper silicide was formed at the Cu–Si interface for the films after annealing at 720°C for 1 h. The Cu(RuHfN _x ) films appear to be good candidate interconnect materials.     

Sputtered copper films with insoluble Mo for Cu metallization: A thermal annealing study

The thermal annealing behavior of Cu films containing insoluble 2.0 at. % Mo magnetron co-sputtered on Si substrates is discussed in the present study. The Cu-Mo films were vacuum annealed at temperatures ranging from 200°C to 800°C. X-ray diffraction (XRD) and scanning electron microscopy (SEM) observations have shown that Cu₄Si was formed at 530°C, whereas pure Cu film exhibited Cu₄Si growth at 400°C. Twins are observed in focused ion beam (FIB) images of as-deposited and 400°C annealed, pure Cu film, and these twins result from the intrinsically low stacking-fault energy. Twins appearing in pure Cu film may offer an extra diffusion channel during annealing for copper silicide formation. In Cu-Mo films, the shallow diffusion profiles for Cu into Si were observed through secondary ion mass spectroscopy (SIMS) analysis. Higher activation energy obtained through differential scanning calorimetry (DSC) analysis for the formation of copper silicide further confirms the beneficial effect of Mo on the thermal stability of Cu film.     

Novel Cu/Cr/Ge/Pd Ohmic Contacts on Highly Doped n-GaAs

The thermal stability of the Cu/Cr/Ge/Pd/n⁺-GaAs contact structure was evaluated. In this structure, a thin 40 nm layer of chromium was deposited as a diffusion barrier to block copper diffusion into GaAs. After thermal annealing at 350°C, the specific contact resistance of the copper-based ohmic contact Cu/Cr/Ge/Pd was measured to be (5.1 ± 0.6) × 10⁻⁷ Ω cm². Diffusion behaviors of these films at different annealing temperatures were characterized by metal sheet resistance, X-ray diffraction data, Auger electron spectroscopy, and transmission electron microscopy. The Cu/Cr/Ge/Pd contact structure was very stable after 350°C annealing. However, after 400°C annealing, the reaction of copper with the underlying layers started to occur and formed Cu₃Ga, Cu₃As, Cu₉Ga₄, and Ge₃Cu phases due to interfacial instability and copper diffusion.     

Annealing effects of Al/n-type 6H SiC rectifying contacts

The annealing effects of Al/n-type 6H SiC rectifying contacts have been studied on different surface polarities of Si- and C-faces by V-I, C-V, and AES measurements. Good rectification characteristics with low reverse leakage current were obtained by annealing above 660°C for 3 min in argon. By annealing at 900°C, the electrodes without deep interface levels were fabricated on both Si- and C-faces, and the built-in voltages Obtained were 1.7 V. The preliminary reliabilities of the electrodes were examined at 300 K in dry air for 1000 h, which showed promising results. At annealing temperatures lower than 900°C, Si-faced samples showed smaller degradation of capacitance characteristics than C-faced samples. From the AES measurements at the Al-SiC interfaces, as the effects of heat treatment at 900°C, the isolation of adsorbed oxygen from the intermixed region of Al, Si, and C was clearly observed. The results also suggested the formation of Al4C3. These two mechanisms are considered to contribute to forming stable contacts. Larger amounts of oxygen adsorption were also observed on C-faced samples. This oxygen was considered as the key factor for the electrical degradation that occurred on the C-faced samples.     

Calculation of the concentration profile of copper in the TiN/CoSi<Subscript>2</Subscript>/Si system during thermal heating

The results of the calculation of concentration profiles of copper in the system Cu/TiN/CoSi@2/Si-substrate under thermal heating to 600°C are presented. Possible diffusion mechanisms of Cu in the TiN and CoSi₂ films and bulk Si are considered.     

Investigation of optical and electronic properties in Al–Sn co-doped ZnO thin films

Al-Sn co-doped ZnO thin films were deposited onto quartz substrates by sol-gel processing. The surface morphology and electrical and optical properties were investigated at different annealing temperatures. The surface morphology showed a closely packed arrangement of crystallites in all the doped films. As prepared co-doped films show a preferred orientation along an (0 0 2) plane. This preferred orientation was enhanced by increasing the annealing temperature to between 400 °C and 500 °C, but there was a shift to the (1 0 1) plane when the annealing temperature rose above 500 °C. These samples show, on average, 91.2% optical transmittance in the visible range. In this study, the optical band gap of all the doped films was broadened compared with pure ZnO, regardless of the different annealing temperature. The carrier concentration and carrier mobility of the thin films were also investigated.     

Ti-Rich Barrier Layers Self-Formed on Porous Low-k Layers Using Cu(1?at.%?Ti) Alloy Films

To investigate the applicability of the technique of barrier self-formation using Cu(Ti) alloy films on porous low-k dielectric layers, Cu(1 at.% Ti) alloy films were deposited on porous SiOCH (low-k) dielectric layers in samples with and without ~6.5-nm-thick SiCN pore seals. Ti-rich barrier layers successfully self-formed on the porous low-k layer of both sample types after annealing in Ar for 2 h at 400°C to 600°C. The Ti-rich barrier layers consisted of amorphous Ti oxides and polycrystalline TiC for the samples without pore sealing, and amorphous TiN, TiC, and Ti oxides for the pore-sealed samples. The amorphous TiN originated from reaction of Ti atoms with the pore seal, and formed beneath the Cu alloy films. This may explain two peaks of Ti segregation at the interface that appeared in Rutherford backscattering spectroscopy (RBS) profiles, and suggests that the Ti-rich barrier layers self-formed by the reaction of Ti atoms with the pore seal and porous low-k layers separately. The total molar amount of Ti atoms segregated at the interface in the pore-sealed samples was larger than that in the samples without pore sealing, resulting in lower resistivity. On the other hand, resistivity of the Cu alloy films annealed on the porous low-k layers was lower than that annealed on the nonporous low-k layers. Coarser Cu columnar grains were observed in the Cu alloy films annealed on the porous low-k layers, although the molar amount of Ti atoms segregated at the interface was similar in both sample types after annealing. The cause could be faster reaction of the Ti atoms with the porous dielectric layers.     

The effects of deposition temperature on the interfacial properties of SiH4 reduced blanket tungsten on TiN glue layer

Low pressure chemical vapor deposition tungsten films were deposited at various temperatures, using a WF₆−SiH₄−H₂ gas mixture. The impurity distribution at the W/TiN interface was investigated by Auger electron spectroscopy depth profiling. Some fluorine accumulation at the interface is observed when the tungsten is deposited below 300°C. However, above 300°C, no accumulation of fluorine could be observed. A result obtained from thermodynamic calculations using SOLGASMIX-PV suggests that this phenomenon is closely associated with the highly oxidized surface layer of TiN at the initial stage of deposition. The reaction of the gas mixture with the TiN surface layer seems to enhance the fluorine accumulation, which lowers the adherence of the interface and increases the contact resistance.     

High conductivity copper-boron alloys obtained by low temperature annealing

The electrical behavior during annealing of copper films with a nominal concentration of 2 at.% boron has been investigated. The evolution of the resistivity of the film was monitored using an in situ technique, in which the film was rampannealed at constant ramp rates. At temperature of 150–200°C, the resistivity of the Cu(B) undergoes a first drop. This is followed by one or two such drops in resistivity, so that after completion of a ramp-anneal from 50°C to 750°C, the room temperature resistivity decreases from the initial value of 13 μΩ cm to 2.1 μΩcm, close to that of bulk copper. Isothermal annealing of the film also leads to substantial decreases in resistivity, from 13 μΩcm to 3 μΩ cm after annealing at 350°C for 8 h and to 2.5 μΩ cm at 400°C for 4 h. These results show that a dramatic reduction in resistivity of Cu(B) alloys takes place at temperatures below 400°C, suggesting possible applications for silicon device interconnections.     

Correlation of microstructure with electrical behavior of Ti/GaN schottky contacts

We correlate structural and electrical characteristics of as-deposited and low-temperature annealed Ti contacts on GaN. Temperature dependent currentvoltage measurements are used to determine the effective barrier heights of the respective contacts, while high-resolution transmission electron microscopy is utilized for structural characterization. As-deposited Ti contacts are slightly rectifying with an effective barrier height of ∼200 meV. After annealing at 230°C, the barrier height increases to values of ∼450 meV. A similar behavior of Schottky contacts with more strongly rectifying diodes upon low-temperature annealing is observed for Zr metal contacts on GaN. As-deposited Ti already forms a thin TiN layer at the GaN interface. After annealing at 230°C, the average thickness and the distribution of TiN grains remain practically unchanged, but the interface with GaN roughens. We correlate the observed barrier height changes with interface roughness and phase formation and we discuss the results in terms of interface damage and the Schottky-Mott theory.     

Optical and microstructural characterization of the effects of rapid thermal annealing of CdTe thin films grown on Si (100) substrates

The effects of rapid thermal annealing (RTA) on CdTe/Si (100) heterostructures have been studied in order to improve the structural quality of CdTe epilayers. Samples of CdTe (111) polycrystalline thin films grown by vapor phase epitaxy (VPE) on Si (100) substrates have been investigated. The strained structures were rapidly thermally annealed at 400°C, 450°C, 500°C, 550°C, and 600°C for 10 sec. The microstructural properties of the CdTe films were characterized by carrying out scanning electron microscopy (SEM), x-ray diffraction (XRD), and atomic force microscopy (AFM). We have shown that the structural quality of the CdTe epilayers improves significantly with increasing annealing temperature. The optimum annealing temperature resulting in the highest film quality has been found to be 500°C. Additionally, we have shown that the surface nucleation characterized by the island size distribution can be correlated with the crystalline quality of the film.     

Study of Ti/W/Cu,Ti/Co/Cu,and Ti/Mo/Cu multilayer structures as schottky metals for GaAs diodes

Schottky structures with copper and refractory metals as diffusion barrier for GaAs Schottky diodes were evaluated. These structures have lower series resistances than the conventionally used Ti/Pt/Au structure. Based on the electrical and material characteristics, the Ti/W/Cu and Ti/Mo/Cu Schottky structures are thermally stable up to 400°C; the Ti/Co/Cu Schottky structure is thermally stable up to 300°C. Overall, the copper-metallized Schottky structures have excellent electrical characteristics and thermal stability, and can be used as the Schottky metals for GaAs devices.