Nanoindentation on carbon thin films obtained from a C60 ion beam

Raman spectra, atomic force microscope (AFM) images, hardness (H) and Young's modulus (E) measurements were carried out in order to characterize carbon thin films obtained from a C₆₀ ion beam on silicon substrates at different deposition energies (from 100 up to 500 eV). The mechanical properties were studied via the nanoindentation technique. It has been observed by Raman spectroscopy and AFM that the microstructure presents significant changes for films deposited at energies close to 300 eV. However, these remarkable changes have not been noticeable on the mechanical properties: apparently H and E increase with higher deposition energy up to ∼11 and ∼116 GPa, respectively. These values are underestimated if the influence of the film roughness is not taken into account.     

Influence of assisted ion energy on surface roughness and mechanical properties of boron carbon nitride films synthesized by DIBSD

The BCN thin films were produced by dual ion beam sputtering deposition (DIBSD). The influence of assisted ion energy on surface roughness and mechanical properties of BCN films were investigated. The surface roughness was determined by atomic force microscopy (AFM) and the mechanical properties of BCN firms were evaluated by nano-indentation in N₂ gas. The composition, structure and chemical bonding of the BCN thin films were analyzed by using energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), laser Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). These films appeared as amorphous structure. As a result, the BCN films with the smoothest surface (R_a = 0.35 nm and R_p-v = 4.4 nm) and the highest nano-hardness of 30.1 GPa and elastic modulus of 232.6 GPa were obtained at 200 eV and 12 mA with N₂:Ar = 1:1, and the chemical composition of this BCN film was 81 at.% B, 14 at.% C and 5 at.% N. Moreover, several bonding states such as B-N, B-C and C-N were observed in BCN thin films.     

Characterization of Zr-Si-N films deposited by cathodic vacuum arc with different N2/SiH4 flow rates

Zr-Si-N films were deposited on silicon and steel substrates by cathodic vacuum arc with different N₂/SiH₄ flow rates. The N₂/SiH₄ flow rates were adjusted at the range from 0 to 12 sccm. The films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), hardness and wear tests. The structure and the mechanical properties of Zr-Si-N films were compared to those of ZrN films. The results of XRD and XPS showed that Zr-Si-N films consisted of ZrN crystallites and SiN_x amorphous phase. With increasing N₂/SiH₄ flow rates, the orientation of Zr-Si-N films became to a mixture of (1 1 1) and (2 0 0). The column width became smaller, and then appeared to vanish with the increase in N₂/SiH₄ flow rates. The hardness and Young's modulus of Zr-Si-N films increased with the N₂/SiH₄ flow rates, reached a maximum value of 36 GPa and 320 GPa at 9 sccm, and then decreased 32 GPa and 305 GPa at 12 sccm, respectively. A low and stable of friction coefficient was obtained for the Zr-Si-N films. Friction coefficient was about 0.1.     

Intrinsic mechanical properties of ultra-thin amorphous carbon layers

In this work, we extracted the film's hardness (H_F) of ultra-thin diamond-like carbon layers by simultaneously taking into account the tip blunting and the substrate effect. As compared to previous approaches, which did not consider tip blunting, this resulted in marked differences (30-100%) for the H_F value of the thinner carbon coatings. We find that the nature of the substrate influences this intrinsic film parameter and hence the growth mechanisms. Moreover, the H_F values generally increase with film thickness. The 10 nm and 50 nm thick hydrogenated amorphous carbon (a-C:H) films deposited onto Si have H_F values of, respectively, ∼26 GPa and ∼31 GPa whereas the 10 nm and 50 nm thick tetrahedral amorphous carbon (t-aC) films deposited onto Si have H_F values of, respectively, ∼29 GPa and ∼38 GPa. Both the a-C:H and t-aC materials also show higher density and refractive index values for the thicker coatings, as measured, respectively by X-ray reflectometry and optical profilometry analysis. However, the Raman analysis of the a-C:H samples show bonding characteristics which are independent of the film thickness. This indicates that in these ultra-thin hydrogenated carbon films, the arrangement of sp² clusters does not relate directly to the hardness of the film.     

Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.     

Nanomechanical characterizations of InGaN thin films

In_xGa_1−xN thin films with In concentration ranging from 25 to 34 at.% were deposited on sapphire substrate by metal-organic chemical vapor deposition (MOCVD). Crystalline structure and surface morphology of the deposited films were studied by using X-ray diffraction (XRD) and atomic force microscopy (AFM). Hardness, Young's modulus and creep resistance were measured using a nanoindenter. Among the deposited films, In_0.25Ga_0.75N film exhibits a larger grain size and a higher surface roughness. Results indicate that hardness decreases slightly with increasing In concentration in the In_xGa_1−xN films ranged from 16.6 ± 1.1 to 16.1 ± 0.7 GPa and, Young's modulus for the In_0.25Ga_0.75N, In_0.3Ga_0.7N and In_0.34Ga_0.66N films are 375.8 ± 23.1, 322.4 ± 13.5 and 373.9 ± 28.6 GPa, respectively. In addition, the time-dependent nanoindentation creep experiments are presented in this article.     

Nanomechanical characterization of amorphous hydrogenated carbon thin films

Amorphous hydrogenated carbon (a-C:H) thin films deposited on a silicon substrate under various mixtures of methane-hydrogen gas by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD) was investigated. Microstructure, surface morphology and mechanical characterizations of the a-C:H films were analyzed using Raman spectroscopy, atomic force microscopy (AFM) and nanoindentation technique, respectively. The results indicated there was an increase of the hydrogen content, the ratio of the D-peak to the G-peak (I_D/I_G) increased but the surface roughness of the films was reduced. Both hardness and Young's modulus increased as the hydrogen content was increased. In addition, the contact stress-strain analysis is reported. The results confirmed that the mechanical properties of the amorphous hydrogenated carbon thin films improved using a higher H₂ content in the source gas.     

Characterization of the laser ablation plasma used for the deposition of amorphous carbon

The plasma produced by laser ablation of a graphite target was studied by means of optical emission spectroscopy and a Langmuir planar probe. Laser ablation was performed using a Nd:YAG laser with emission at the fundamental line with pulse length of 28 ns. In this work, we report the behavior of the mean kinetic energy of plasma ions and the plasma density, as a function of the laser fluence (J/cm²), and the target to probe (substrate) distance. The characterized regimes were employed to deposit amorphous carbon at different values of kinetic energy of the ions and plasma density. The mean kinetic energy of the ions could be changed from 40 to 300 eV, and the plasma density could be varied from 1 × 10¹² to 7 × 10¹³ cm⁻³. The main emitting species were C⁺ (283.66, 290.6, 299.2 and 426.65 nm) and C⁺⁺ (406.89 and 418.66 nm) with the C⁺ (426.65 nm) being the most intense and that which persisted for the longest times. Different combinations of the plasma parameters yield amorphous carbon with different structures. Low levels (about 40 eV) of ion energy produce graphitic materials, while medium levels (about 200 eV) required the highest plasma densities in order to increase the CC sp³ bonding content and therefore the hardness of the films. The structure of the material was studied by means of Raman spectroscopy, and the hardness and elastic modulus by depth sensitive nanoindentation.     

Berkovich nanoindentation and deformation mechanisms in GaN thin films

The deformation mechanisms of GaN thin films obtained by metal-organic chemical vapor deposition (MOCVD) method were studied using nanoindentation with a Berkovich diamond indenter, micro-Raman spectroscopy and the cross-sectional transmission electron microscopy (XTEM) techniques. Due to the sharpness of the tip of Berkovich indenter, the nanoindentation-induced deformation behaviors can be investigated at relatively lower load and, hence, may cover wider range of deformation-related phenomena over the same loading range. The load-displacement curves show the multiple “pop-ins” during nanoindentation loading. No evidence of nanoindentation-induced phase transformation and cracking patterns were found up to the maximum load of 300 mN, as revealed from the micro-Raman spectra and the scanning electron microscopy (SEM) observations within the mechanically deformed regions. In addition, XTEM observation performed near the cross-section of the indented area revealed that the primary deformation mechanism in GaN thin film is via propagation of dislocations on both basal and pyramidal planes. The continuous stiffness measurement (CSM) technique was used to determine the hardness and Young's modulus of GaN thin films. In addition, analysis of the load-displacement data reveals that the values of hardness and Young's modulus of GaN thin films are 19 ± 1 and 286 ± 25 GPa, respectively.     

Synthesis and structure of nitrogenated tetrahedral amorphous carbon films prepared by nitrogen ion bombardment

The tetrahedral amorphous carbon (ta-C) films with more than 80% sp³ fraction firstly were deposited by filtered cathode vacuum arc (FCVA) technique. Then the energetic nitrogen (N) ion was used to bombard the ta-C films to fabricate nitrogenated tetrahedral amorphous carbon (ta-C:N) films. The composition and structure of the films were analyzed by visible Raman spectrum and X-ray photoelectron spectroscopy (XPS). The result shows that the bombardment of energetic nitrogen ions can induce the formation of CN bonds, the conversion of C-C bonds to CC bonds, and the increase of size of sp² cluster. The CN bonds are made of CN bonds and C-N bonds. The content of CN bonds increases with the increment of N ion bombardment energy, but the content of C-N bonds is inversely proportional to the increment of nitrogen ion energy. In addition, C≡N bonds are not existed in the films. By the investigation of AFM (atom force microscopy), the RMS (root mean square) of surface roughness of the ta-C film is about 0.21 nm. When the bombarding energy of N ion is 1000 eV, the RMS of surface roughness of the ta-C:N film decreases from 0.21 to 0.18 nm. But along with the increment of the N ion energy ranging from 1400 to 2200 eV again, the RMS of surface roughness of the ta-C:N film increases from 0.19 to 0.33 nm.     

Effect of gas flow ratio on the microstructure and mechanical properties of boron phosphide films prepared by reactive magnetron sputtering

Boron phosphide films were grown on silicon substrate by radio frequency reactive magnetron sputtering using boron target and hydrogen phosphine at different gas flow ratios (PH₃/Ar) at lower temperature. The chemical composition, microstructure and mechanical properties were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectrum, FTIR spectrum, surface profilometer and nano-indenter. The results indicate that the atomic ratio (P/B) rises from 1.06 up to 1.52 with the gas flow ratio increasing from 3/50 to 15/50. Simultaneously, the hardness and Young's modulus decrease from 25.4 GPa to 22.5 GPa, and 250.4 GPa to 238.4 GPa, respectively. Microstructure transforms from microcrystalline state to amorphous state along with the gas flow ratio increasing. Furthermore higher gas flow ratio leads to lower stress. The BP film prepared at the gas flow ratio of 3/50 can be contributed with the best properties.     

Effect of deposition and annealing temperature on mechanical properties of TaN film

Tantalum nitride films (TaN) were synthesized by microwave ECR-DC sputtering. The effects of deposition and annealing temperature on mechanical properties of TaN films were investigated. Cross-section pattern, microstructure and binding energy of the films were investigated by scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. Mechanical properties were evaluated using nano-indentation and scratch tester. The results showed that the maximal hardness value of approximately 40 GPa was deposited in the TaN sample at 573 K. While the preparation temperature decreased, the hardness, modulus and adhesion of TaN film also decreased. Hardness and modulus also decreased with the increase in annealing temperature. Meanwhile the adhesion strength was also sensitive to the annealing temperature, with a maximum adhesion strength of 40 N measured in the TaN film annealed at 448 K. The results demonstrated that a desirable mechanical property of TaN films deposited by DC reactive magnetron sputtering can be obtained by controlling the deposition and annealing temperature.     

RF-PACVD of water repellent and protective HMDSO coatings on bell metal surfaces: Correlation between discharge parameters and film properties

Hexamethyldisiloxane (HMDSO) films have been deposited on bell metal using radiofrequency plasma assisted chemical vapor deposition (RF-PACVD) technique. The protective performances of the HMDSO films and their water repellency have been investigated as a function of DC self-bias voltage on the substrates during deposition. Plasma potential measurements during film deposition process are carried out by self-compensated emissive probe. Optical emission spectroscopy (OES) analyses of the plasma during deposition reveal no significant change in the plasma composition within the DC self-bias voltage range of −40 V to −160 V that is used. Raman and X-ray photoelectron spectroscopy (XPS) studies are carried out for film chemistry analysis and indicate that the impinging ion energy on the substrates influences the physio-chemical properties of the HMDSO films. At critical ion energy of 113 qV (corresponding to DC self-bias voltage of −100 V), the deposited HMDSO film exhibits least defective Si-O-Si chemical structure and highest inorganic character and this contributes to its best corrosion resistance behavior. The hardness and elastic modulus of the films are found to be bias dependent and are 1.27 GPa and 5.36 GPa for films deposited at −100 V. The critical load for delamination is also bias dependent and is 11 mN for this film. The water repellency of the HMDSO films is observed to be dependent on the variation in surface roughness. The results of the investigations suggest that HMDSO films deposited by RF-PACVD can be used as protective coatings on bell metal surfaces.     

Influence of annealing temperature on the structural, optical and mechanical properties of ALD-derived ZnO thin films

ZnO thin films grown on Si(1 1 1) substrates by using atomic layer deposition (ALD) were annealed at the temperatures ranging from 300 to 500 °C. The X-ray diffraction (XRD) results show that the annealed ZnO thin films are highly (0 0 2)-oriented, indicating a well ordered microstructure. The film surface examined by the atomic force microscopy (AFM), however, indicated that the roughness increases with increasing annealing temperature. The photoluminescence (PL) spectrum showed that the intensity of UV emission was strongest for films annealed at 500 °C. The mechanical properties of the resultant ZnO thin films investigated by nanoindentation reveal that the hardness decreases from 9.2 GPa to 7.2 GPa for films annealed at 300 °C and 500 °C, respectively. On the other hand, the Young's modulus for the former is 168.6 GPa as compared to a value of 139.5 GPa for the latter. Moreover, the relationship between the hardness and film grain size appear to follow closely with the Hall-Petch equation.     

Structure and elastic recovery of Cr-C:H films deposited by a reactive magnetron sputtering technique

Cr-containing hydrogenated amorphous carbon (Cr-C:H) films were deposited on silicon substrates using a DC reactive magnetron sputtering with Cr target in an Ar and C₂H₂ gas mixture. The composition, bond structure, mechanical hardness and elastic recovery of the films were characterized using energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and nano-indentation. The film tribological behavior was also studied by a ball-on-disc tribo-tester. The results showed that the films deposited at low C₂H₂ flow rate (<10 sccm) presented a feature of composite Cr-C:H structure, which consisted of hard brittle chromium carbide phases and amorphous hydrocarbon phase, and thus led to the observed low elastic recovery and poor wear resistance of the films. However, the film deposited at high C₂H₂ flow rate (40 sccm) was found to present a typical feature of polymer-like a-C:H structure containing a large amount of sp³ C-H bonds. As a result, the film revealed a high elastic recovery, and thus exhibited an excellent wear resistance.     

Improvement in micro-structural and mechanical properties of zinc film by surface treatment with low temperature argon plasma

Nanocrystalline zinc films were deposited on gold coated borosilicate glass substrates by thermal evaporation method using zinc powders as the source material and then treated with argon plasma at various temperatures. From X-ray diffraction study, the as-deposited films are found to be metallic Zn and polycrystalline in nature. The crystalline nature improves with the increase of temperature up to 200 °C and decreases with the further increase of temperature to 300 °C. The binding energy observed for Zn 2p_3/2, and the binding energy separation between Zn 2p_3/2 and Zn 2p_1/2 in the X-ray photoelectron spectrum indicate that the films are metallic zinc films. Transmission electron microscopic study shows hexagonal shaped grains having size ∼58 nm upon treatment with Ar plasma. It is clearly shown the grain growth and distinct grain boundary with the increase in temperature. The average Young's modulus (E) and hardness (H) are measured to be 84 GPa and 4.0 GPa for as-deposited film, whereas 98 GPa and 5.8 GPa for plasma treated film at 200 °C. The enhancement in mechanical properties is attributed to improvement in crystalline nature of the film and better interlinking between grains and boundaries.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Reactive pulsed laser deposition of gold nitride thin films

We report on the growth and characterization of gold nitride thin films on Si 〈1 0 0〉 substrates at room temperature by reactive pulsed laser ablation. A pure (99.95%) Au target was ablated with KrF excimer laser pulses in nitrogen containing atmosphere (N₂ or NH₃). The gas ambient pressure was varied in the range 0.1-100 Pa. The morphology of the films was studied by using optical, scanning electron and atomic force microscopy, evidencing compact films with RMS roughness in the range 3.6-35.1 nm, depending on the deposition pressure. Rutherford backscattering spectrometry and energy dispersion spectroscopy (EDS) were used to detect the nitrogen concentration into the films. The EDS nitrogen peak does not decrease in intensity after 2 h annealing at 250 °C. Film resistivity was measured using a four-point probe and resulted in the (4-20) × 10⁻⁸ Ω m range, depending on the ambient pressure, to be compared with the value 2.6 × 10⁻⁸ Ω m of a pure gold film. Indentation and scratch measurements gave microhardness values of 2-3 GPa and the Young's modulus close to 100 GPa. X-ray photoemission spectra clearly showed the N 1s peak around 400 eV and displaced with respect to N₂ phase. All these measurements point to the formation of the gold nitride phase.     

A study on electrical and mechanical properties of hybrid-polymer thin films by a controlled TEOS bubbling ratio

Organic-inorganic hybrid-polymer thin films were deposited on silicon(1 0 0) substrates at room temperature by PECVD (plasma enhanced chemical vapor deposition). Ethylcyclohexane and TEOS (tetraethoxysilane) were utilized as organic and inorganic precursors with hydrogen gas for the ethylcyclohexane bubbler and argon gas for both the TEOS bubbler and as a carrier gas. To compare the electrical and the mechanical properties of the plasma polymerized thin films, we grew the hybrid-polymer thin films under conditions of various TEOS bubbling ratios. MTS nano-indenter was used to measure the hardness and Young's modulus and showed that these values increased as the TEOS bubbling ratio increased, with the highest hardness at 0.8 GPa in this experiment. An impedance analyzer was utilized for the measurements of I-V curves and capacitance, showing the lowest dielectric constant at approximately 1.83, with a leakage current density of 10⁻⁸ A/cm² at 1 MV/cm, respectively.     

Formation of α-Si1−xCx:H and nc-SiC films grown by HWCVD under different process pressure

In this work, hydrogenated amorphous silicon carbide (α-Si_1−xC_x:H) and nanocrystalline SiC (nc-SiC) thin films were deposited by hot wire CVD (HWCVD) using SiH₄/C₂H₂/H₂ gas mixtures. It was found that the films prepared under low gas pressure were α-Si_1−xC_x:H and those prepared under high gas pressure were nc-3C-SiC. The α-Si_1−xC_x:H films showed enhanced density of C-H_n and Si-C bonds with increasing C₂H₂ fraction, which induced an increase in optical gap from 1.8 to 3.0 eV. For the deposition process of nc-SiC, the E_g opt of the deposited films varied from 1.9 eV to 2.5 eV as the filament temperature increased from 1700 to 2100 °C. The deposition rate decreased rapidly from 5.74 nm/min to 0.8 nm/min with increasing T_F.