Atomic layer deposition of tantalum nitride based thin films from cyclopentadienyl type precursor

Tantalum nitride based thin films have been deposited on p-Si (100) and SiO₂/Si by thermal Atomic Layer Deposition (ALD) using either the Ta(= N^tBu)(NEt₂)₃ or a derivative, in which one dialkylamido ligand is substituted by a η⁵-cyclopentadienyl (η⁵-Cp), as metal organic precursors with ammonia as reducing agent. TaN_xC_y self-limiting temperature dependent ALD growth was achieved for the TaCp(= N^tBu)(NEt₂)₂/NH₃ process with a growth rate of 0.51-0.91 Å cycle⁻¹ in the 400-425 °C temperature range while between 240 and 280 °C, the growth of TaN based films from the Ta(= N^tBu)(NEt₂)₃ was accompanied by a partial decomposition of the precursor. The η⁵-cyclopentadienyl type compound allows lower nitrogen content in the precursor and thereafter in the deposited film. Although N/Ta ratio is close to one at temperatures of 390 and 400 °C, as analyzed by Rutherford Back Scattering and Nuclear Reaction Analysis, films were amorphous independently of the deposition temperature. Since Ta-C bonds are present in the Cp derivative, the TaCp(= N^tBu)(NEt₂)₂ tends more likely to form tantalum carbide compared to Ta(= N^tBu)(NEt₂)₃, which leads to lower thin film resistivity. For both precursors, employed in their respective ALD window, films were smooth with a root-mean-square roughness close to 1 nm.     

Spectroscopic ellipsometry characterization of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride thin films

Carbon nitride (CN_x) and amorphous carbon (a-C) thin films are deposited by reactive magnetron sputtering onto silicon (001) wafers under controlled conditions to achieve amorphous, graphitic and fullerene-like microstructures. As-deposited films are analyzed by Spectroscopic Ellipsometry in the UV-VIS-NIR and IR spectral ranges in order to get further insight into the bonding structure of the material. Additional characterization is performed by High Resolution Transmission Electron Microscopy, X-ray Photoelectron Spectroscopy, and Atomic Force Microscopy. Between eight and eleven resonances are observed and modeled in the ellipsometrically determined optical spectra of the films. The largest or the second largest resonance for all films is a feature associated with C-N or C-C modes. This feature is generally associated with sp³ C-N or sp³ C-C bonds, which for the nitrogen-containing films instead should be identified as a three-fold or two-fold sp² hybridization of N, either substituted in a graphite site or in a pyridine-like configuration, respectively. The π→π? electronic transition associated with sp² C bonds in carbon films and with sp² N bonds (as N bonded in pyridine-like manner) in CN_x films is also present, but not as strong. Another feature present in all CN_x films is a resonance associated with nitrile often observed in carbon nitrides. Additional resonances are identified and discussed and moreover, several new, unidentified resonances are observed in the ellipsometric spectra.     

Synthesis and optical characterization of amorphous carbon nitride thin films by hot filament assisted RF plasma CVD

Carbon nitride thin films were synthesized by hot filament assisted radio frequency plasma chemical vapour deposition using methane and nitrogen gas mixture on silicon and glass substrates. The films were deposited at different substrate bias and at different substrate temperatures. At higher substrate bias (>−120 V) there was no deposition on the substrate, but complete etching of the deposited layer was observed. X-ray diffraction studies indicated the films were amorphous. The Fourier transform infrared spectra showed that the films produced exhibited high transmittance with the presence of the C-N stretching band at 1260 cm⁻¹. For the films deposited at a lower substrate temperature C=N peaks were also present. Raman spectroscopic study indicated the presence of D and G peaks whose relative height varied with substrate temperature. The transmittance versus wavelength measurement in the UV-VIS-NIR region showed the high transmittance in the NIR region. The optical band gap of the films was calculated to be 2.0 eV and the refractive index varied within 1.6-1.7 for the wavelength range 800-1800 nm.     

Coating of carbon nanotubes with amorphous carbon nitride thin films and characterization of long-term emission stability

The effects of amorphous carbon nitride (CN) thin films that were coated on carbon nanotubes (CNTs) and their thermal treatment were investigated, in terms of the chemical bonding and morphologies of the CNTs and their field emission properties. CNTs were directly grown on conical tip-type tungsten substrates via the inductively coupled plasma-chemical vapor deposition (ICP-CVD) system, and the CNTs were coated with CN films using the RF magnetron sputtering system. The CN-coated CNTs were thermally treated using the rapid thermal annealing (RTA) system by varying the temperature (300-700 °C). The morphologies, microstructures, and chemical compositions of the CN-coated CNTs were analyzed as a function of the thickness of the CN layers and the RTA temperatures. The field emission properties of the CN/CNT hetero-structured emitters, and the fluctuation and long-term stability of the emission currents were measured and compared with those of the conventional non-coated CNT-emitter. The results showed that the electron emission capability of CNT was noticeably improved by coating a thin CN layer on the surface of the CNT. This was attributed to the low work function and negative electron affinity nature of the CN film. The CN-coated CNT-emitter had a more stable emission characteristic than that of the non-coated one. In addition, the long-term emission stability of the CN-coated emitter was further enhanced by thermal treatment, which was verified by x-ray photoelectron spectroscopy (XPS) analysis.     

Nanostructured tantalum nitride films as buffer-layer for carbon nanotube growth

Tantalum nitride (TaN_x) films are usually used as barriers to the diffusion of copper in the substrate for electronic devices. In the present work, the TaN_x coating plays an extra role in the iron catalyzed chemical vapor deposition production of carbon nanotubes (CNT). The CNTs were grown at 850 °C on TaN_x films prepared by radio frequency magnetron sputtering. The correlation between the CNT morphology and growth rate, and the pristine TaN_x film nature, is investigated by comparing the evolution of the nano-composition, roughness and nano-crystallinity of the TaN_x films both after annealing and CVD at 850 °C.     

Electrochemical corrosion behavior of amorphous carbon nitride thin films

The corrosion behavior along with biocompatibility and mechanical properties plays an important role in determining of biomedical implants feasibility. Diamond-like carbon seems to be the promising material in which all these three requirements can be achieved. In this study nitrogen doped amorphous carbon (a-C:N) films were deposited on silicon and medical CoCrMo alloy substrates by vacuum glow discharge sputtering technique using different deposition conditions from graphite target. Potentiodynamic polarization tests were employed to assess the corrosion performances of the films at room temperature in 0.89 wt. % NaCl solution. The influence of substrate bias on the electrochemical corrosion behavior was investigated. The highest value off E_corr for CoCrMo substrate was measured on the coating deposited with substrate bias around −0.6 kV. The shift of E_corr to more positive values was about 350 mV.     

Structural characterization of thin amorphous Si films

We present a study of structural changes occurring in thin amorphous silicon (a-Si). The a-Si films were deposited on single-crystalline Si substrates held at room temperature or 200 °C by magnetron sputtering of a Si target in pure Ar atmosphere, and therefore the films were hydrogen-free. All samples were annealed in vacuum and subsequently studied by EPR and GISAXS. A strong decrease in the dangling bonds content at lower annealing temperatures, and then an increase of it at around 550 °C, suggested significant structural changes. In parallel the samples were studied by GISAXS which confirmed changes at the nanometric scale attributed to voids in the material. A nice correlation of the results of the two techniques shows advantages of this approach in the analysis of structural changes in a-Si material.     

Structural and optical properties of amorphous oxygenated iron boron nitride thin films produced by reactive co-sputtering

Amorphous oxygenated iron boron nitride (a-FeBN:O) thin films were prepared by reactive radio-frequency (RF) sputtering, from hexagonal boron nitride chips placed on iron target, under a total pressure of a gas mixture of argon and oxygen maintained at 1 Pa. The films were deposited onto silicon and glass substrates, at room temperature. The power of the generator RF was varied from 150 to 350 W. The chemical and structural analyses were investigated using X-ray photoelectron spectroscopy (XPS), energy dispersive of X-ray and X-ray reflectometry (XRR). The optical properties of the films were obtained from the optical transmittance and reflectance measurements in the ultraviolet-visible-near infrared wavelengths range. XPS reveals the presence of boron, nitrogen, iron and oxygen atoms and also the formation of different chemical bonds such as Fe-O, B-N, B-O and the ternary BNO phase. This latter phase is predominant in the deposited films as observed in the B 1s and N 1s core level spectra. As the RF power increases, the contribution of N-B bonds in the as-deposited films decreases. The XRR results show that the mass density of a-FeBN:O thin films increases from 2.6 to 4.12 g/cm³ with increasing the RF power from 150 to 350 W. This behavior is more important for films deposited at RF power higher than 150 W, and has been associated with the enhancement of iron atoms in the film structure. The optical band gap decreases from 3.74 to 3.12 eV with increasing the RF power from 150 to 350 W.     

Synthesis of multiwall boron nitride nanotubes dependent on crystallographic structure of boron

Synthesis and growth of multiwall boron nitride nanotubes (BNNTs) under the B and ZrO₂ seed system in the milling–annealing process were investigated. BNNTs were synthesized by annealing a mechanically activated boron powder under nitrogen environment. We explored the aspects of the mechanical activation energy transferred to milled crystalline boron powder producing structural disorder and borothermal reaction of the ZrO₂ seed particles on the synthesis of BNNTs during annealing. Under these circumstances, the chemical reaction of amorphous boron coated on the seed nanoparticles with nitrogen synthesizing amorphous BN could be enhanced. It was found that amorphous BN was crystallized to the layer structure and then grown to multiwall BNNTs during annealing. Especially, bamboo-type multiwall BNNTs were mostly produced and grown to the tail-side of the nanotube not to the round head-side. Open gaps with ∼0.3 nm of the bamboo side walls of BNNTs were also observed. Based on these understandings, it might be possible to produce bamboo-type multiwall BNNTs by optimization of the structure and shape of boron coat on the seed nanoparticles.     

Surface-complex films of guanidine on tantalum nitride electrochemically characterized for applications in chemical mechanical planarization

Chemical mechanical planarization (CMP) of tantalum nitride is an essential step of material processing in the fabrication of integrated circuits. This CMP step often involves the chemical formation of a structurally weak oxide-complex film on the wafer surface, followed by selective removal of the film with mechanical abrasion under reduced loading. The present work investigates certain chemical aspects of this strategy of TaN-CMP by using guanidine carbonate (GC) as a surface complexing agent, and employing electrochemical experiments. The experiments are designed to study the chemical and electrochemical origins of the CMP-specific surface complex films formed on a TaN wafer in acidic solutions of GC and hydrogen peroxide. Open circuit potential, polarization resistance, and electrochemical impedance measurements are employed to probe the surface effects that facilitate material removal in chemically prevailing CMP of TaN. The results are discussed in view of designing slurry variables to support barrier layer planarization with reduced roles of mechanical abrasion.     

Surface morphology and growth mechanisms for sputtered amorphous silicon nitride thin films

Evolution of surface of sputter-deposited amorphous Si₃N₄ films growth on Si (100) substrates was investigated using atomic force microscopy (AFM). The scaling behaviors of the AFM topographical profiles were analyzed using the one-dimensional power spectral density. The results of root-mean-square surface height variation showed that there is a power law relationship between the surface roughness and deposition time. It is interesting to note that the growth exponent can be divided into one region and two regions, respectively, when Si₃N₄ films are deposited at different working pressures. A very low growth exponent of β = 0.07 ± 0.01 was found when Si₃N₄ films were deposited at a working pressure of 1.6 × 10^− 1 Pa. However, the growth exponent β can be divided into two regions, which is β₁ = 0.09 ± 0.01, β₂ = 0.24 ± 0.03 and β₁ = 0.09 ± 0.01, β₂ = 0.33 ± 0.04, when the films were deposited at a working pressure of 2.1 × 10^− 1 Pa and 2.7 × 10^− 1 Pa, respectively. The mechanisms of anomalous dynamic scaling exponents of Si₃N₄ films deposited at different working pressures were discussed.     

Effects of applied substrate bias during reactive sputter deposition of nanocomposite tantalum carbide/amorphous hydrocarbon thin films

Nanocomposite tantalum carbide/amorphous hydrocarbon (TaC/a-C:H) thin film composition, structure, and mechanical properties depend on the direct current bias voltage (V_b) level applied to the substrate during reactive sputter deposition. A set of TaC/a-C:H films was deposited across the range V_b = 0 to − 300 V with all other deposition parameters held constant except substrate temperature, which was allowed to reach its steady state during the depositions. Effects of V_b on film composition and structure were explored, including TaC crystallite size and dispersion using X-ray diffraction and high resolution transmission electron microscopy. In addition, the dependency of stress and hardness on V_b was studied with an emphasis on relationships to a-C:H phase structure.     

XPS study of carbon nitride films deposited by hot filament chemical vapor deposition using carbon filament

Amorphous carbon nitride, a-CN_x, thin films were deposited by hot filament CVD using a carbon filament with dc negative bias voltage on the substrate. The effects of the negative bias and the filament components on the binding structure of the films are investigated by XPS. The composition ratio of graphite to amorphous carbon in the filaments affects the bonding structure of carbon and nitrogen in the films, although the nitrogen content in the films is almost same as 0.1. The nitrogen content in the films changes from 0.1 to 0.3 as the negative bias changes from 0 to − 300 V.     

Prediction of stable high-pressure structures of tantalum nitride TaN2

Structure searches based on a combination of first-principles calculations and a particle swarm optimization technique unravel two new stable high-pressure structures (C2/m and Cmce) for TaN₂. The structural features, mechanical properties, formation enthalpies, electronic structure, and phase diagram of TaN₂ are fully investigated. Being mechanically and dynamically stable, the two phases could be made metastable experimentally at ambient conditions.     

Stress formation and relaxation in amorphous Ta–Cr films

In the present paper, measurements of the intrinsic stress of thin amorphous Ta–Cr alloy films made by magnetron sputtering have been carried out. From the curvature of the substrates and by use of the Stoney formula, the stresses were determined. The bombardment of the growing film with energetic particles is shown to control the magnitude and sign of the intrinsic stress. When changing the deposition parameters, compressive or tensile stresses can be generated in the films in a range from about −2 GPa to +1 GPa. Also the stress relaxation, the change in the stress with time, has been studied for various temperatures. The stress relaxation was measured with a cantilever beam technique using a three-terminal capacitance method to detect the beam (substrate) deflection. The stress-relaxation data have been fitted to a mathematical model for stress relaxation related to inhomogeneous flow in amorphous films. This behaviour is expected to occur in the low-temperature, high-stress regime with deformation taking place along localized shear bands.     

Stress formation in evaporated amorphous Ge-Se and Ge-Se-Ga(Tl, B) thin films

Thin amorphous chalcogenide films from the GeSe_x (x = 1-5), (GeSe₄)_100−yGa_y and (GeSe₅)_100−y Ga(Tl, B)_y (y = 5, 10, 15, 20) systems have been prepared by thermal evaporation and characterized with respect to their internal stress using a cantilever technique. The correlations between the stress, the composition and the structure of the films were investigated. The obtained results were related with some structural and mechanical parameters of the glasses like mean coordination number, number of constrains per atom, density, compactness, microhardness and Young's modulus. For all investigated chalcogenide films a stress relaxation with the time was observed as a result of spontaneous structural rearrangements.     

Hydrogenated amorphous carbon and carbon nitride films deposited at low pressure by plasma enhanced chemical vapor deposition

Hydrogenated amorphous carbon (a-C:H) films were deposited by plasma enhanced chemical vapor deposition from methane, argon diluted methane, and nitrogen diluted methane at 26.7 Pa with a 13.56 MHz RF power supply. In this pressure regime, multiple-scattering of carbon species within the plasma phase is expected during the transport to the substrates placed on both the driven and the earthed electrodes. These films were analyzed using UV-VIS optical transmittance, monochromatic ellipsometry, Raman spectroscopy and current-voltage measurements. From these results, the effect of the plasma conditions and the effective flux of the carbon species controlled by the input power through the negative self bias are found to be important in the deposition process. The growth conditions at the higher pressure regime are important to synthesize a-C:H films from low energetic carbon species, since it reduces the defect density and improves the quality of the films. Furthermore, the effect of nitrogen on the growth conditions of a-C:H:N films is observed.     

Stress reduction for hard amorphous hydrogenated carbon thin films deposited by the self-bias method

Hard amorphous hydrogenated carbon (a-C:H) thin films were deposited by the r.f. (13.56 MHz) self-bias method using 2-methyl-propane as the source gas. To achieve stress reduction, we used the periodic plasma deposition technique: repeated cycles of alternating 5 s of deposition (plasma on) with 180 s of cooling (plasma off). Substrate temperature changes during the plasma deposition were monitored by a fluorescent/ optical thermosensor. We investigated the film deposition rate, density, and internal stress as functions of the deposition temperature.

We found a linear relationship between the internal stress of a-C:H films and the deposition temperature over the range of 0 to 150 °C. The increase in internal film stress from 0.48 to 1.5 GPa, respectively, over this deposition temperature range is the result of the increase in deposition temperature. Within the range of deposition temperature and r.f. power parameters studied, the deposition temperature appeared to play a more significant role in determining the intrinsic film stress than the r.f. power.     

Photoluminescence in amorphous carbon thin films and its relation to the microscopic properties

The photoluminescence properties of amorphous hydrogenated carbon (a-C:H) films grown using a r.f. plasma have been investigated. It is found that the photoluminescence (PL) spectra exhibit a red shift, accompanied by a sharp decrease in PL efficiency and an increase in electron spin density as the applied r.f. power increases. The results can be interpreted by a model in which the a-C:H films consist of two phases with π-bonded clusters embedded in an sp³-bonded amorphous matrix. The excitation and the recombination of electron hole pairs are believed to take place in the π-bonded clusters. As a result of the confinement effect of electron hole pairs in these clusters, the cluster size becomes an important parameter in understanding the PL properties of a-C:H films.