Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si₃N₄ (Si⁴⁺) but also in the intermediate nitridation states with one (Si¹⁺) or three (Si³⁺) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si¹⁺, Si³⁺, and Si⁴⁺ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si⁴⁺ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si₃N₄ by molecular beam epitaxy (MBE).     

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.     

Effects of substrate bias and nitrogen flow ratio on the surface morphology and binding state of reactively sputtered ZrNx films before and after annealing

ZrN_x films were sputtered in an Ar + N₂ atmosphere, with different substrate biases (0 to −200 V) at various nitrogen flow ratios (%N₂ = 0.5-24%). The surface morphology, resistivity, crystllinity, and bonding configuration of ZrN_x films, before and after vacuum annealing, were investigated. As compared with ZrN_x films grown without substrate bias, before and after annealing, the resistivity of 1% and 2% N₂ films decreases with increasing substrate biases. Simultaneously, if the applied bias is too high, the crystallinity of ZrN_x film will decrease. The surfaces of 1% and 2% N₂ flow films deposited without bias have small nodules, whereas the surface morphology of films deposited at −100 V of substrate bias exhibits large nodules and rugged surface. Once a −200 V of substrate bias is applied to the substrate, the surface morphology of ZrN_x films, grown at 1% and 2% nitrogen flow ratios, is smooth. Furthermore, there are two deconvoluted peaks in XPS spectra (i.e., Zr-O and Zr-N) of ZrN_x films deposited at −200 V of substrate bias before and after annealing. On the other hand, the surface morphology changes dramatically from rugged surfaces for film deposited at lower nitrogen flow ratio (%N₂ < 1%) to smoother and denser surfaces for film grown at higher nitrogen flow ratio (%N₂ ≥ 1%). The Zr-N bonding in 2% N₂ films still exist after annealing at 700 °C, while the Zr-N bonding in 0.5% and 16% N₂ flow film vanish at the same temperature. The connection between the resistivity, crystallinity, surface morphology, and bonding configuration of ZrN_x films and how they are influenced by the substrate bias and nitrogen flow ratio are discussed in this paper.     

Study of nitrogen ion implantation and diffusion phenomena on thin chromium layers followed by the atomic force microscopy and secondary ion mass spectroscopy techniques characterization

This research investigates the effect of ion implantation dosage level and further thermal treatment on the physical characteristics of chromium coatings on Si(1 1 1) substrates. Chromium films had been exposed to nitrogen ion fluencies of 1 × 10¹⁷, 3 × 10¹⁷, 6 × 10¹⁷ and 10 × 10¹⁷ N⁺ cm⁻² with a 15 keV energy level. Obtained samples had been heat treated at 450 °C at a pressure of 2 × 10⁻² Torr in an argon atmosphere for 30 h. Atomic force microscopy (AFM) images showed significant increase in surface roughness as a result of nitrogen ion fluence increase. Secondary ion mass spectroscopy (SIMS) studies revealed a clear increased accumulation of Cr₂N phase near the surface as a result of higher N⁺ fluence. XRD patterns showed preferred growth of [0 0 2] and [1 1 1] planes of Cr₂N phase as a result of higher ion implantation fluence. These results had been explained based on the nucleation-growth of Cr₂N phase and nitrogen atoms diffusion history during the thermal treatment process.     

Valence band studies of the formation of ultrathin pure silicon nitride films on Si(1 0 0)

The growth of ultrathin films of Si₃N₄ directly on Si surfaces is studied with valence band photoemission. The information from these studies about the growth mechanism and the changes of the electronic structure is enhanced by the use of various photon energies with synchrotron radiation. The silicon nitride films are grown isothermally on the Si(1 0 0) and Si(1 1 1) surfaces by reactions with atomic N. The atomic nitrogen is produced by using a remote, microwave excited nitrogen plasma. The growth under these conditions was earlier shown to be self limiting. The details in the valence band spectra are identified and resolved with numerical methods, and followed systematically during the growth. Thus the identification of Si surface states, Si-nitride interface states and bulk nitride states becomes possible. The previously obtained separation between amorphous and crystalline growth occurring around 500 °C is further supported in the present studies.     

Laser sintering of Cu paste film printed on polyimide substrate

We here show that highly conductive copper films are obtainable from Cu paste by laser sintering. The Cu paste synthesized using an organo-metallic compound was screen-printed onto polyimide substrate and the printed films were scanned by an ultraviolet laser beam at 355 nm under nitrogen atmosphere. Very compact microstructure was observed throughout the whole thickness and the sintered films were mechanically robust. Although Cu is known susceptible to oxidation, no Cu oxides were incorporated into the film during laser sintering. An electrical resistivity of 1.86 × 10⁻⁵ Ω cm was obtained. This resistivity is several orders of magnitude lower than those reported for the copper nanoparticle paste thermally sintered under N₂ or H₂ atmosphere.     

Pulsed laser deposition and characterization of nitrogen-substituted SrTiO3 thin films

Nitrogen-substituted cubic perovskite-type SrTiO₃ thin films were deposited in a one-step process using pulsed reactive crossed beam laser ablation (PRCLA) and RF-plasma assisted pulsed laser deposition (RF-PLD). Both techniques yield preferentially oriented films on SrTiO₃(0 0 1), LaAlO₃(0 0 1) and MgO(0 0 1) substrates with the unit cell parameters within 0.390(5) < a < 0.394(9) nm. The nitrogen content is higher in films deposited by PRCLA (0.84-2.40 at.%) as compared to films deposited by RF-PLD with nitrogen plasma (0.10-0.66 at.%). PRCLA with an ammonia gas pulse leads to a higher nitrogen content compared to the films grown with a nitrogen gas pulse, while films deposited by RF-PLD with ammonia plasma reveal only minor nitrogen contents (<0.10 at.%). The amount of the incorporated nitrogen can be tuned by adjusting the deposition parameters. Films deposited by PRCLA have a lower roughness of 1-3 nm compared to 12-18 nm for the films grown by RF-PLD. PRCLA yields partially reduced films, which exhibit electronic conductivity, while films deposited by RF-PLD are insulating. There is also a pronounced influence of the substrate material on the resistivity of the films deposited by PRCLA: films grown on SrTiO₃ substrates exhibit a metallic-like behaviour, while the corresponding films grown on MgO and LaAlO₃ substrates reveal a metal-to-semiconductor/insulator transition. Nitrogen incorporation into the SrTiO₃ films results in an increased optical absorption at 370-500 nm which is associated with N(2p) localized states with the energy about 0.7 eV higher than the valence band energy in strontium titanate. The optical band gap energies in the studied N-substituted SrTiO₃ films are 3.35-3.40 eV.     

Structural, optical and electrical properties of Cd-doped SnO2 thin films grown by RF reactive magnetron co-sputtering

Transparent conducting SnO₂:Cd thin films were prepared by RF reactive magnetron co-sputtering on glass slides at a substrate temperature of 500 °C using CdO as cadmium source. The films were deposited under a mixed argon/oxygen atmosphere. The structural, optical and electrical properties were analyzed as a function of the Cd amount in the target. The X-ray diffraction shows that polycrystalline films were grown with both the tetragonal and orthorhombic phases of SnO₂. The obtained films have high transmittance and conductivity. The figure of merit of SnO₂:Cd films are in the order of 10⁻³ Ω⁻¹, which suggests that these films can be considered as candidates for transparent electrodes.     

Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

Molecular materials derived from MPc (M=Fe, Pb, Co) and 1,8-dihydroxiantraquinone thin films: Formation, electrical and optical properties

Semiconductor-like thin films were grown using metallic phthalocyanines (MPc) (M=Fe, Pb, Co) and 1,8 dihydroxiantraquinone as initial compounds. The morphology of the deposited films was studied by using scanning electron microscopy and atomic force microscopy. The powder and thin-film samples of the synthesized materials, deposited by vacuum thermal evaporation, showed the same intra-molecular bonds as in IR spectroscopy studies, which suggests that the evaporation process does not alter these bonds. The optical band gap values of C₆₀H₂₈N₈O₈Fe, C₆₀H₂₈N₈O₈Pb and C₆₀H₂₈N₈O₈Co calculated from the absorption coefficient were found to be 1.60, 1.89 and 1.75 eV, respectively, arising from non-direct transitions. The effect of temperature on conductivity was also measured in these samples. It was found that the temperature-dependent electric current in all cases showed a semiconductor behavior with conductivities in the order of 10⁻⁶ Ω⁻¹ cm⁻¹ where the highest value corresponded to the cobalt material. The linear dependence observed in the films implies only one type of conduction mechanism in all cases, with mean activation energies of the order of 1.55, 1.77 and 1.50 eV for iron, lead and cobalt-based thin films, respectively.     

Structural Characterization of RF‐Sputtered a‐C:N Thin Films by Raman,IR, and X‐ray Reflectometry Spectroscopies

Abstract

Amorphous carbon nitride thin films (a‐C:N) were deposited from a carbon target, at room temperature onto silicon substrates, by reactive RF sputtering in a gas mixture of argon and nitrogen. The structural properties of these films have been studied by Raman, infrared (IR), and X‐ray reflectometry spectroscopies. Both the IR and Raman spectra of the a‐C:N films reveal the presence of C–C, C?C, C?N, and C≡N bonding types. The Raman spectra analysis shows, an increase of the C≡N triple bonds content when the concentration of nitrogen C(N₂) in the gas mixture is increased. The Raman intensities ratio between the disorder (D) and graphitic (G) bands increases with C(N₂) suggesting an increased disorder with the incorporation of nitrogen in the carbon matrix. The effect of C(N₂) on the density of a‐C:N films was also investigated by X‐ray reflectometry measurement. The increase of the nitrogen concentration C(N₂) was found to have a significant effect on the density of the films: as C(N₂) increases from 0 to 100%, the density of the a‐C:N films decreases slightly from 1.81 to 1.62 g/cm³. The low values of density of the a‐C:N films were related (i) to the absence of C–N single bonds, (ii) to the increase of disorder introduced by the incorporation of nitrogen in the carbon matrix, and (iii) to the presence of the bands around 2350 cm^?1 and 3400 cm^?1 associated with the C–O bond stretching modes and the O–H vibration, respectively, suggesting a high atmospheric contamination by oxygen and water. The presence of these bands suggests the porous character of the studied samples.     

Langmuir probe and spectroscopic studies of RF generated helium-nitrogen mixture plasma

This paper reports the effect of helium percentage variation in a capacitive RF helium-nitrogen mixture plasma on various plasma parameters and concentration of nitrogen active species (N₂(C³Π _u) and N₂ ⁺(B²Σ _u ⁺)). Langmuir probe is used for determination of electron energy distribution functions, effective electron temperature, plasma potential and electron density. Optical emission spectroscopy is used for determination of electron temperature from Boltzmann's plot of He–I lines and the relative changes in the concentration of active species by measuring the emission intensities of nitrogen (0-0) bands of the second positive and the first negative systems. The results demonstrate that electron temperature, electron density and concentration of active species increase significantly with increase in helium percentage in the mixture and RF power.     

Studies on the structural and electrical properties of F-doped SnO2 film prepared by APCVD

Fluorine-doped tin oxide films (SnO₂:F, FTO) were deposited by atmosphere pressure chemical vapor deposition (APCVD) on Na-Ca-Si glass coated with a diffusion barrier layer of SiO_xC_y. The effects of post-heating time at 700 °C on the structural and electrical properties of SnO₂:F films were investigated. The results showed that SnO₂:F films were polycrystalline with tetragonal SnO₂ structure, SnO phase was present in SnO₂ film, and abnormal grain growth was observed. The element distribution in the film depth was measured with X-ray photoelectron spectroscopy (XPS) and revealed that when the heating time increased from 202 s to 262 s, the oxygen content in the surface increased from 78.63% to 83.38%. The resistivity increased from 3.13 × 10⁻⁴ for as-deposited films to 4.73 × 10⁻⁴ Ω cm when post-heated for 262 s. Hall mobility is limited by the ionized impurity scattering rather than the grain boundary scattering.     

Raman spectroscopy of a-C:H:N films deposited using ECR-CVD with mixed gas

Ultraviolet (UV) and visible Raman spectroscopy were used to study a-C:H:N films deposited using ECR-CVD with a mixed gas of CH₄ and N₂. Small percentage of nitrogen from 0 to 15% is selected. Raman spectra show that CN bonds can be directly observed at 2220 cm⁻¹ from the spectra of visible and UV Raman. UV Raman enhances the sp¹ CN peak than visible Raman. In addition, the UV Raman spectra can reveal the presence of the sp³ sites. For a direct correlation of the Raman parameter with the N content, we introduced the G peak dispersion by combining the visible and UV Raman. The G peak dispersion is directly relative to the disorder of the sp² sites. It shows the a-C:H:N films with higher N content will induce more ordered sp² sites. In addition, upper shift of T position at 244 nm excitation with the high N content shows the increment of sp² fraction of films. That means the films with high N content will become soft and contain less internal stress. Hardness test of films also confirmed that more N content is with less hardness.     

AlN thin films prepared by ArF plasma assisted PLD. Role of process conditions on electronic and chemical–morphological properties

Aluminium nitride thin films were deposited on n-Si <100> substrates by RF plasma activated reactive pulsed laser deposition (PLD). An ArF excimer pulsed laser, 10 Hz and 2.5 J/cm² energy fluence, has been used to ablate a pure Al target in a reactive atmosphere of N₂ plasma (generated by a RF source), at varying processing parameters (substrate temperature, time, and N₂ plasma configuration). We studied the dependence and correlation of structural and electronic properties with the experimental conditions. The chemical composition of deposited material has been determined by both Raman and X-ray photoelectron spectroscopy (XPS). Electrical resistivity has been evaluated by the sheet resistance method. Both spectroscopic characterizations (Raman and XPS) show a strong dependence in the formation of AlN on the deposition temperature. At low temperatures, there is little formation of nitride, with a prevalence of aluminium oxide, while at higher temperatures the N uptake increases, with AlN formation. Raman analysis also highlights the formation of nano-structures, for temperatures ≥400^°C. These material characteristics have a fundamental influence on the electronic properties. Indeed, electrical resistivity properties have been found to be strongly dependent on the film structure, nitrogen incorporation, and presence of mixed oxide compounds, closely related to deposition temperature.     

Photomodulated reflectance study on optical property of InN thin films grown by reactive gas-timing rf magnetron sputtering

The photoreflectance (PR) spectroscopy has been applied to investigate the band-gap energy (E_g) of indium nitride (InN) thin films grown by rf magnetron sputtering. A novel reactive gas-timing technique applied for the sputtering process has been successfully employed to grow InN thin films without neither substrate heating nor post annealing. The X-ray diffraction (XRD) patterns exhibit strong peaks in the orientation along (0 0 2) and (1 0 1) planes, corresponding to the polycrystalline hexagonal-InN structure. The band-gap transition energy of InN was determined by fitting the PR spectra to a theoretical line shape. The PR results show the band-gap energy at 1.18 eV for hexagonal-InN thin films deposited at the rf powers of 100 and 200 W. The high rf sputtering powers in combination with the gas-timing technique should lead to a high concentration of highly excited nitrogen ions in the plasma, which enables the formation of InN without substrate heating. Auger electron spectroscopy (AES) measurements further reveal traces of oxygen in these InN films. This should explain the elevated band-gap energy, in reference to the band-gap value of 0.7 eV for pristine InN films.     

Ellipsometric study of a-Be3N2 thin films prepared by radio frequency magnetron sputtering

The ellipsometric characterizations of amorphous beryllium nitride (a-Be₃N₂) thin films deposited on Si (1 0 0) and quartz at temperature <50 °C using reactive RF sputtering deposition were examined in the wavelength range 280-1600 nm. X-ray diffraction of the films showed no structure, suggesting the Be₃N₂ films grown on the substrates are amorphous. The composition and chemical structures of the amorphous thin films were determined by using electron spectroscopy for chemical analysis. The surface morphology of a-Be₃N₂ was characterized by atomic force microscopy. The thicknesses and optical constants of the films were derived from spectroscopic ellipsometry measurements. The variation of the optical constants with thickness of the deposited films has been investigated. From the angle dependence of the polarized reflectivity we deduced a Brewster angle of 64°. At any angle of incidence, the a-Be₃N₂ shown high transmissivity (80-99%) and low reflectivity (<18%) in the visible and near infrared regions. Hence, the a-Be₃N₂ could be a good candidate for antireflection optical coatings under conditions of optimized the type of polarization and the angle of incidence.     

Secondary ion species containing nitrogen atoms from plasma-enhanced chemical vapor deposited silicon oxide films on silicon

Secondary ion species from plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Comparative studies of PECVD SiO₂ films prepared using a mixture of SiH₄/N₂O reaction gas at 400 °C with thermally oxidized SiO₂ films grown at 900 °C were carried out in the mid-range mass spectra from 95 to 165 amu. Small amounts of ion species containing nitrogen atoms, including Si₂O₂N⁺, Si₃O₂N⁺and Si₃O₃N⁺, were detected in the SiO₂ bulk from the PECVD SiO₂ films. Furthermore, large amounts of Si₃O₂N⁺ and Si₂O₃N⁻ were found at the interface between silicon and the SiO₂ films. Depth analysis showed that the intensity peak shapes of these ion species containing nitrogen atoms at the interface were closely coincident with those of Si₃O₃⁺ corrected by subtracting the influence of the SiO₂ matrix. The variation in the spectra of these ion species clearly indicates that two types of structures of oxynitride exist for the PECVD SiO₂ films in the SiO₂ bulk films and at the interface. These are likely produced by the reaction of reactive gas with SiO₂ and silicon surfaces where dangling bonds of silicon may exist in the different form.