Characterization of sputtered tungsten nitride film and its application to Cu electroless plating

In this study, W and tungsten nitride films were fabricated by reactive sputtering in a N₂/Ar atmosphere, the native oxide growth on the surface of the tungsten nitride films was investigated by X-ray photoelectron spectroscopy (XPS). It was found that tungsten nitride films were the mixture of W and W₂N sputtered in atmospheres of 3 mTorr argon and at the N₂ partial pressure from 0.1 to 2.0 mTorr. The ratio of W and W₂N in films was changed with the nitrogen partial pressure in sputtered chamber. Surface oxidations of the W film and tungsten nitride films advanced with time. Electrochemical measurement shows that all reduction-oxidation (redox) potentials of tungsten and tungsten nitrides were lower than that of copper film in electroless copper solution. And so, electroless-plated copper could be deposited on the surface of tungsten nitride films when the substrates were immersed into electroless copper plating solution without any pretreatment. Tungsten nitride films are appropriate for ULSI Cu interconnections using electroless Cu deposition.     

Degradation of RuO2 thin films in hydrogen atmosphere at temperatures between 150 and 250 °C

Ruthenium dioxide films were sputtered on silicon dioxide/silicon in thin-film resistors and MOS capacitors structures. Such structures with RuO₂ were exposed to H₂/N₂ ambient with 1% hydrogen content in the temperature range from 150 to 250 °C. Severe morphological degradation of RuO₂ films was observed by scanning electron microscope. By X-ray diffraction analysis it was proved that RuO₂ tends to reduce to Ru in the presence of hydrogen. The pattern of degradation is strongly influenced by the preparation condition: films deposited at room temperature show irregular degradation shape, and films deposited at 300 °C exhibit star-like shape. The shift in capacitance–voltage curves of MOS capacitors with RuO₂ gate electrode after degradation also proves the presence of Ru in the electrode. The failure of the above structures when exposed to hydrogen ambient suggests the need of introduction of hydrogen barrier layers to exploit the good properties of RuO₂.     

Hafnium oxide thin films deposited by high pressure reactive sputtering in atmosphere formed with different Ar/O2 ratios

The physical and electrical properties of hafnium oxide (HfO₂) thin films deposited by high pressure reactive sputtering (HPRS) have been studied as a function of the Ar/O₂ ratio in the sputtering gas mixture. Transmission electron microscopy shows that the HfO₂ films are polycrystalline, except the films deposited in pure Ar, which are amorphous. According to heavy ion elastic recoil detection analysis, the films deposited without using O₂ are stoichiometric, which means that the composition of the HfO₂ target is conserved in the deposition films. The use of O₂ for reactive sputtering results in slightly oxygen-rich films. Metal-Oxide-Semiconductor (MOS) devices were fabricated to determine the deposited HfO₂ dielectric constant and the trap density at the HfO₂/Si interface (D_it) using the high–low frequency capacitance method. Poor capacitance–voltage (CV) characteristics and high values of D_it are observed in the polycrystalline HfO₂ films. However, a great improvement of the electrical properties was observed in the amorphous HfO₂ films, showing dielectric constant values close to 17 and a minimum D_it of 2×10¹¹ eV⁻¹ cm⁻².     

The electrical properties and stability of the hafnium silicate/Si<Subscript>0.8</Subscript>Ge<Subscript>0.2</Subscript>(100) interface

The effect of post-oxidation N₂ annealing and post-metallization forming-gas annealing on the electrical properties of Pt/Hf-silicate (3 nm)/Si_0.8Ge_0.2(100)/n-type Si(100) metal-oxide semiconductor (MOS) capacitors is reported. Capacitance-voltage (C-V) and current density-voltage (J-V) measurements of asgrown, 3-nm-thick, hafnium-silicate films containing ∼12at.%Hf indicate a large number of bulk and interface traps with a current density of ∼10⁻² A/cm² at V_FB+1 V. Post-ultraviolet (UV)/O₃ oxidation annealing in N₂ at 350°C for 30 min leads to a significant improvement in the electrical characteristics of the film. A post-metallization anneal (PMA) at 450°C for 30 min in forming gas (90% N₂:10% H₂), however, degraded the electrical properties of the films. X-ray photoelectron spectroscopy (XPS) analyses of the forming-gas-annealed films indicate that a possible cause for the degradation in electrical properties is the hydrogen-induced reduction of GeO₂ in the interfacial Si_xGe_1−xO₂ oxide layer to elemental germanium. Implications for the introduction of hafnium silicate as a viable gate dielectric for SiGe-based devices are discussed.     

Structural and interfacial properties of high-k HfOxNy gate dielectric films

The thermal stability and interfacial characteristics for hafnium oxynitride (HfO_xN_y) gate dielectrics formed on Si (1 0 0) by plasma oxidation of sputtered HfN films have been investigated. X-ray diffraction results show that the crystallization temperature of nitrogen-incorporated HfO₂ films increases compared to HfO₂ films. Analyses by X-ray photoelectron spectroscopy confirm the nitrogen incorporation in the as-deposited sample and nitrogen substitution by oxygen in the annealed species. Results of FTIR characterization indicate that the growth of the interfacial SiO₂ layer is suppressed in HfO_xN_y films compared to HfO₂ films annealed in N₂ ambient. The growth mechanism of the interfacial layer is discussed in detail.     

Optical and electrical characterization of hafnium oxide deposited by liquid injection atomic layer deposition

Optical and electrical properties of a set of high-k dielectric HfO₂ films, deposited by liquid injection atomic layer deposition (LI-ALD) and post deposition annealed (PDA) in nitrogen (N₂) ambient at various temperatures (400–600 °C), were investigated. The films were prepared using the cyclopentadienyl of hafnium precursor [Cp₂Hf(CH₃)₂] with water deposited at 340 °C. The spectroscopic ellipsometric (SE) results show that the characteristics of the dielectric functions of these films are strongly affected by annealing temperatures. I–V results show that N₂-based PDA enhances the average energy depth of the shallow trapping defects from Poole–Frenkel conduction fitting. This also correlated with the measured increase in MOS capacitance–voltage hysteresis.     

Preparation of conductive HfN by post rapid thermal annealing-assisted MOCVD and its application to metal gate electrode

Conductive hafnium nitride (HfN) with negligible carbon impurity (<0.1 at.%) was chemically synthesized for the first time by post-rapid thermal annealing (PRTA)-assisted metal organic chemical vapor deposition (MOCVD) method. The thermodynamic instability of N-rich hafnium nitride (Hf₃N₄) phase, which is considered to be the dominant phase in CVD deposition of hafnium nitride, was utilized for pure and metallic HfN synthesis. By integrating the PRTA-HfN film into MOS capacitor, the electrical properties of the PRTA-HfN film as metal gate electrode were studied. Well behaved electrical characteristics such as about 4.9 eV of effective work function, low leakage current and large reduction in SiO₂ equivalent oxide thickness (EOT), which was attributed to the combination of physical thinning of SiO₂ and formation of high-κ interfacial layer, suggest the potential capability of PRTA-assisted MOCVD in chemically synthesizing HfN metal gate electrode for pMOS devices application.     

MOS device fabrication using sputter-deposited gate oxide and polycrystalline silicon layers

For applications in the MOS device fabrication the interface properties of sputtered SiO₂ and SiO₂-polycrystalline silicon layers on silicon substrates were investigated and improved to a quality which is equivalent to those of thermally grown SiO₂ with pyrolytical polycrystalline silicon (polySi). For testing these layers as gate oxide and Si electrodes of MOS transistors the well known Si gate process was varied to include sputter deposition and the optimal deposition, annealing and diffusion parameters were integrated.MOS transistors with sputtered SiO₂ and Si gate material layers and for comparison Al gate devices with sputtered SiO₂ have been fabricated and their threshold voltage behavior was tested.     

Control of the Ti diffusion in Pt/Ti bottom electrodes for the fabrication of PZT thin film transducers

For the achievement of microactuators based on piezoelectric thin films, a Pt/Ti/Si bottom electrode is widely used. This study presents the experimental results for Ti out-diffusion in Pt and Si for both sputtered Pt/Ti and Pt/TiO_x electrodes. These results have been compared before and after a rapid thermal annealing (RTA). The diffusion has been characterized by secondary ion mass spectroscopy (SIMS) analysis using Cs⁺ as a primary ion source. The Pt orientation has been observed by XRD measurements. Ti thin films (20 nm) have been sputtered in pure Ar whereas TiO_x films have been obtained by reactive sputtering in a mixture of Ar/O₂ (90/10). Finally, the Pt (100 nm) has been sputtered without vacuum breaking. After RTA (400°C, 30 s, in N₂), the Pt film exhibited a (1 1 1) orientation for both Ti and TiO_x adhesion films. The roughness of the Pt film measured by AFM with TiO_x underlayer was 80% less than that of the Pt/Ti bi-layer. The TiO_x film, as shown by SIMS analysis, has drastically reduced the diffusion of Ti in both Pt and Si. This phenomenon is accompanied by a very low Pt roughness. These results are analyzed in terms of diffusion and regrowth mechanisms inside the Pt film.     

Single band electronic conduction in hafnium oxide prepared by atomic layer deposition

Current–voltage and capacitance–voltage measurements on MOS structures with hafnium gate oxide (HfO₂) prepared by atomic layer deposition were conducted to determine the dominant current conduction in the Al/HfO₂/Si structure. In n-type substrate MOS structures, electron injection from Al into HfO₂ is observed when the Al electrode is negatively biased. Whereas in p-type MOS capacitors at negative biasing, no hole injection can be detected and the current in the insulator is again due to the electron injection from Al. These results unambiguously indicate that in both p- and n-type substrates and at both biasing polarities only electronic current conduction in the Si/HfO₂/Al is significant.     

Synthesis and Characterization of Magnesium-Alloyed Hematite Thin Films

We have synthesized pure and Mg-alloyed hematite thin films on F-doped, SnO₂-coated glass substrates by radiofrequency magnetron cosputtering of iron oxide with and without MgO sources in mixed Ar/O₂ and mixed N₂/O₂ ambient. We found that hematite films deposited in N₂/O₂ ambient exhibited much poorer crystallinity than those deposited in Ar/O₂ ambient. We determined that Mg alloying led to increased crystallinity and bandgap. Furthermore, we found that Mg alloying inverted the type of conductivity of the thin films: pure hematite thin films exhibited n-type conductivity, whereas Mg-alloyed hematite thin films exhibited p-type conductivity.     

Influences of bottom electrode TaN on electrical characteristics for metal–HfO2–metal capacitors

For TaN–HfO₂–TaN_x capacitors, the effects of bottom electrode TaN_x with different nitrogen contents on electrical characteristics are exhibited. An obvious oxygen deficiency can be found in HfO₂ film by AES analysis for the sample with bottom electrode TaN_x sputtered at a N₂/(N₂ + Ar) flow ratio of 10%. The bottom electrode TaN_x films with different nitrogen contents apparently affect HfO₂/TaN_x interfacial property and electrical characteristic of follow-up deposited HfO₂ film. Experimental results reveal that the more defective TaN_x structure can induce more oxygen vacancies in subsequently deposited HfO₂ film and result in a higher leakage current density and a worse breakdown electric field. Two factors affect these electrical characteristics including interfacial stress and oxygen vacancy. It indicates that interfacial stress due to various stochiometric TaN_x structure dominates the voltage linearity property of capacitance, but more leak paths and local field breakdown defects can be induced by interfacial stress and oxygen vacancy. Better electrical characteristics can be attained for the sample with bottom electrode TaN_x sputtered at a N₂/(N₂ + Ar) flow ratio of 20%.     

Characterization of rare earth oxides based MOSFET gate stacks prepared by metal-organic chemical vapour deposition

We have prepared rare earth oxides based MOSFET gate stacks using metal-organic chemical vapour deposition, MOCVD. Gd₂O₃, La₂O₃, Nd₂O₃ and Pr₆O₁₁ films with thickness 3–20 nm were deposited on silicon substrate at 500 °C. The films were characterized by X-ray diffraction, X-ray reflectivity, transmission electron microscopy and X-ray photoelectron spectroscopy. As a next step, Ru films were grown on the dielectric films at 300 °C as a gate electrode. Electrical characterization of the MOS structures was performed by capacitance–voltage measurements. The structures annealed at 430 °C in forming gas (90% N₂+10% H₂) exhibited dielectric constant ranging from 12 to 14. Typically, the films showed high values of fixed oxide charge density, . Fixed oxide charges can be decreased by post-deposition annealing in forming gas and in oxygen.     

Effect of different sputtering gas mixtures on the structural,electrical, and optical properties of p-type NiO thin films

We investigated how mixtures of Ar and O₂ or N₂ gases affect the structural, electrical and optical properties of RF-magnetron-sputtered NiO films. It is shown that the addition of O₂ gas to Ar ambient (namely, Ar:O₂=2:1 to 1:2) slightly reduces the (2 0 0) texturing of the NiO films. The introduction of N₂ gas (from 0 to 2 sccm) to Ar:O₂ (2:1) mixture enhances the (2 0 0) texturing, while the addition of N₂ gas (from 0 to 2 sccm) to Ar ambient slightly weakens the (1 1 1) texturing. The deposition rate is reduced from 6.1 to 1.5 nm/min when O₂ gas is added to Ar ambient. The addition of N₂ gas to the Ar:O₂ (2:1) mixture slightly increases the deposition rate from 1.8 to 2.6 nm/min, whereas adding N₂ gas to Ar only ambient somewhat reduces the rate from 6.1 to 4.4 nm/min. The carrier concentration of the films is increased and the mobility is decreased as the O₂ flow rate in the Ar:O₂ mixture is increased. The addition of N₂ gas to the Ar:O₂ (2:1) mixture increases the resistivity of the films, while adding N₂ gas to Ar ambient decreases the resistivity. The transmittance and optical bandgap of the films are reduced (from 58.4 to 45.5% at 550 nm and from 3.5 to 3.3 eV, respectively) with increasing O₂ flow to Ar ambient. When N₂ gas is added to the Ar:O₂ (2:1) mixture, the transmittance in the visible wavelength range increases from 58.4 to 71.3% and the optical bandgap increases from 3.5 to 3.6 eV. However, adding N₂ gas to the Ar only ambient results in decrease in the transmittance in the visible wavelength region (from 69.3 to 56%) and the optical bandgap (from 3.7 to 3.5 eV).     

Carrier trapping centers and interface states induced by r.f. sputtering of molybdenum electrodes in MOS-structure diodes

Electronic properties of interface and oxide layers of Si MOS diodes with an r.f. sputtered molybdenum metal electrodes have been studied. A remarkable density increase of both oxide charge and interface states by the sputtering has been found. IMA data show that the sputtered Mo atoms are implanted into the SiO₂ less than 100 Å from the surface. It is also found from photo I–V data that the charge centroid in the SiO₂ is shifted to a depth of 100 Å below the SiO₂ surface. The energy distribution of the carrier trapping centers having a capture cross section of the order of 10^?13 to 10^?16 cm² has been observed. The interface states density can be reduced about one order of magnitude by an annealing in N₂ 10 min/H₂ 15 min/N₂ 10 min at 450°C. The mechanism of the increase of the carrier trapping centers and the interface states is also studied. Especially it is concluded that the increase of the interface states originates from the ultraviolet-light irradiation emitted from the plasma during the r.f. sputtering.     

Photoelectron spectroscopy (XPS) and photoelectron diffraction (XPD) studies on the system hafnium silicide and hafnium oxide on Si(1 0 0)

Continuous down-scaling of silicon based transistors results in device lengths of less than 100 nm. This requires a reduction of the gate dielectric thickness to less than 15Å which is not possible for SiO₂ due to an increasing leakage current. One of the most promising candidates for a replacement material for the gate dielectric is HfO₂ [Wilk GD, Wallace RM, Anthony JM. J Appl Phys 2001; 89:5243].In this work we applied X-ray photoelectron spectroscopy (XPS) and photoelectron diffraction measurements in order to study the interface of hafnium oxide to Si(1 0 0). The high resolution measurements were performed with synchrotron radiation at beamlines 5 and 11 at DELTA (Dortmund). For the first time, photoelectron diffraction patterns for this system were recorded. The spectral resolution allowed to separate different spectral components.The preparation of hafnium oxide films on Si(1 0 0) was performed by evaporation of hafnium at a partial oxygen background pressure of . Three different spectral components were observed in the hafnium 4f photoemission signal by high resolution XPS. The photoelectron signals with binding energies shift of 3.1 and 1.2 eV with respect to signal of hafnium silicide were assigned to hafnium dioxide and hafnium silicate, respectively. The corresponding high-resolution diffraction patterns result from different local environments for each component. The experimental patterns are compared with simulations for a model structure of hafnium silicide.     

Effects of oxygen doping on properties of microcrystalline silicon film grown using rapid thermal chemical vapor deposition

An oxygen doped microcrystalline silicon (μc-Si) deposition process is developed by mixing small amounts of nitrous oxide (N₂O) with silane (SiH₄) in a rapid thermal chemical vapor deposition (RTCVD) reactor. The effects of oxygen doping on the properties of RTCVD μc-Si films are studied. Experimental results show that the RTCVD process provides high deposition rates for μc-Si and polycrystalline silicon (polySi) films at elevated deposition temperatures and pressures. The surface roughness of the RTCVD μc-Si films can be significantly reduced compared to that of conventional LPCVD polySi films. Steep side walls can be realized due to the small grain size of the μc-Si films. The sheet resistance of BF₂ doped μc-Si films is slightly higher than that of BF₂ doped polySi films, whereas sheet resistances of P and As doped μc-Si films are much higher than those of the corresponding P and As doped polySi films. Measurements of the catastrophic breakdown strength of metal-oxide-semiconductor (MOS) capacitors indicate that the quality of gate electrodes fabricated using μc-Si is improved relative to that of MOS capacitors fabricated using polySi gate electrodes.     

Investigation of 4H-SiC MOS capacitors annealed in diluted N2O at different temperatures

Thermally grown oxide on 4H-SiC has been post-annealed in diluted N₂O (10% N₂O in N₂) at different temperatures from 900 to 1100 °C. The quality of the nitrided oxide and the SiO₂/4H-SiC interface was investigated by AC conductance and high frequency C-V measurements based on Al/SiO₂/4H-SiC metal-insulator-semiconductor (MOS) structure. It is found that N₂O annealing at 1000 °C produces the lowest interface state density, though the difference is not so significant when compared to the other samples annealed at 900 and 1100 °C. These results can be explained by the high temperature dynamic decomposition process of N₂O. By fitting the AC conductance data, it is found that higher temperature nitridation increases the capture cross-section of the interface traps.     

Characterization of hafnium oxide grown on silicon by atomic layer deposition: Interface structure

Ultra-thin films of hafnium oxide deposited on Si(1 0 0) substrates by means of atomic layer deposition using tetrakis(diethylamino)hafnium as the hafnium precursor are characterized. These films and interface structures are probed using Fourier transform infrared spectroscopy along with Z-contrast imaging and electron energy loss spectroscopy (EELS) of a scanning transmission electron microscope. The interface structure of HfO₂/Si(1 0 0) is further investigated using angle resolved X-ray photoelectron spectroscopy to probe the core level orbitals (Hf 4f, Si 2p, O 1s) at high resolution. The interfacial differences are also examined by probing the Hf 4f bonding with normal incidence XPS in thin and thick films. The XPS studies show that the binding energies remain unchanged with film depth and that there is no apparent signature of silicate structure in the as-deposited films. EELS spectra taken at the interface and XPS measurements suggest the interface is mainly silicon oxide. Two different cleaning methods used show difference only in the thickness of the silicon oxide interlayer.     

Electrical properties of carbon nitride thin films: Role of morphology and hydrogen content

The influence of hydrogen content and ambient humidity on the electrical properties of carbon nitride (CN_x) films deposited by reactive magnetron sputtering from a graphite target in Ar discharges mixed with N₂ and H₂ at a substrate temperature of 350°C have been investigated. Carbon films deposited in pure Ar exhibit a dark resistivity at room temperature of ∼4 × 10⁻² Ωcm, while the resistivity is one order of magnitude lower for CN_0.25 films deposited in pure N₂, due to their denser morphology. The increasing H₂ fraction in the discharge gas leads to an increased resistivity for all gas mixtures. This is most pronounced for the nitrogen-free films deposited in an Ar/H₂ mixture, where the resistivity increases by over four orders of magnitude. This can be related to a decreased electron mobility as H inhibits the formation of double bonds. After exposure to air, the resistivity increases with time through two different diffusion regimes. The measured electrical properties of the films are related to the apparent film microstructure, bonding nature, and ambient humidity.