Growth of diamond thin films by chemical vapour deposition

Deposition of diamond thin films on non-diamond substrates at low pressures (<760 torr) and low temperatures (<2000°C) by chemical vapour deposition (CVD) has been the subject of intense research in the last few years. The structural and the electrical properties of CVD diamond films grown on p-type 〈111〉 and high-resistivity (>100 kΩ-cm) 〈100〉 oriented silicon substrates by hot filament chemical vapour deposition technique are described in this review paper.     

Field emission characteristics of high-energy ion-irradiated polycrystalline diamond thin films

Diamond thin films have been synthesized by hot-filament chemical vapor deposition process using a mixture of methane and hydrogen gases. The samples were subjected to very high-energy ion irradiation (100 MeV Au⁷⁺ ions). The field emission characteristics of ion-irradiated samples have been studied. High emission currents and low turn-on and threshold fields were obtained for ion-irradiated samples. The as-deposited and the ion-irradiated samples have been characterized by X-ray Diffraction, Scanning Electron Microscopy and Micro-Raman Spectroscopy techniques and the resulting changes are correlated with field emission results.     

Field emission characteristics of fast grown nanocrystalline diamond/amorphous carbon composite films by microwave plasma-enhanced chemical deposition method

This study synthesized the nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films by the microwave plasma-enhanced chemical vapor deposition (MPCVD) system with Ar/CH₄/N₂ mixtures. A localized rectangular-type jet-electrode with high density plasma was used to enhance the formation of NCD/a-C films, and a maximum growth rate of 105.6 µm/h was achieved. The content variations of sp² and sp³ phases via varying nitrogen gas flow rates were investigated by using Raman spectroscopy. The NCD/a-C film which synthesized with 6% nitrogen concentration and no hydrogen plasma etching treatment possessed a low turn-on electric field of 3.1 V/µm at the emission current of 0.01 µA.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Structure of diamond polycrystalline films deposited on silicon substrates

The article presents results of structural studies of polycrystalline diamond thin films deposited by hot filament CVD on silicon substrates. The films were characterized using Scanning Electron Microscopy (SEM), Raman Spectroscopy (RS), Electron Backscattered Diffraction (EBSD), Energy Dispersive Spectroscopy (EDS) and Secondary Ion Mass Spectroscopy (SIMS). Both the EBSD patterns and Raman spectra confirm that the grains visible in the electron micrographs are diamond micro-crystallites. The residual stress in the films is found to be in the range between −4.29 GPa and −0.56 GPa depending on the sample thickness. No evidence of lonsdalite and graphite has been registered in the polycrystalline material of the investigated samples. Evidence of the existence of silicon carbide at the diamond/silicon interface is presented. It is also suggested that an amorphous carbonaceous film covers the silicon surface in the regions of holes in the thin diamond layers.     

Growth and characteristics of ZnO films on growth side of freestanding diamond substrate dependent on buffer layer thickness

We report the growth and properties of highly c-axis oriented ZnO films, by radio-frequency magnetron sputtering, on the growth side of freestanding chemical vapor deposited diamond film-substrate. Low-temperature ZnO buffer layer is required for the formation of continuous ZnO films. The morphology, structure, and optical properties of the ZnO films deposited are strongly dependent on the thickness of the buffer layer. The optimized thickness of ZnO buffer layer is about 10 nm to realize high-quality ZnO films having small compressive stress and high intensity ultraviolet emission. The ZnO/diamond (growth side) system is available for the applications in numerous fields, especially for high performance surface acoustic wave devices.     

Field emission studies of CVD diamond thin films: effect of acid treatment

Field emission from CVD diamond thin films deposited on silicon substrate has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. Field emission studies of as-deposited and acid-treated films were carried out using ‘diode’ configuration in an all metal UHV chamber. Upon acid treatment, the field emission current is found to decrease by two orders of magnitude with increase in the turn-on voltage by 30%. This has been attributed to the removal of sp² content present in the film due to acid etching. Raman spectra of both the as-deposited and acid-treated films exhibit identical spectral features, a well-defined peak at 1333 cm⁻¹ and a broad hump around 1550 cm⁻¹, signatures of diamond (sp³ phase) and graphite (sp² phase), respectively. However upon acid treatment, the ratio (I_d/I_g) is observed to decrease which supports the speculation of removal of sp² content from the film. The surface roughness was studied using atomic force microscopy (AFM). The AFM images indicate increase in the number of protrusions with slight enhancement in overall surface roughness after acid etching. The degradation of field emission current despite an increase in film surface roughness upon acid treatment implies that the sp² content plays significant role in field emission characteristics of CVD diamond films.     

Plasma-enhanced chemical vapour deposition of thin films from tetraethoxysilane and methanol: optical properties and XPS analyses

The thin films were produced from tetrathoxysilane (TEOS) and TEOS/methanol mixtures by the plasma-enhanced chemical vapour deposition technique in a diode planar reactor capacitatively coupled to r.f. generator at 13.56 MHz. The optical properties of the films deposited on silicon substrates and on glass substrates were studied by means of spectrophotometry in the visible and monochromatic ellipsometry applied at the wavelength of 632.8 nm. The dependences of the deposition rate, the refractive and absorption indices on the deposition parameters were determined for the substrates mentioned. The X-ray photoelectron spectroscopy analyses were performed for the films deposited on the silicon substrates to find film composition dependences on the deposition conditions.     

Optical and mechanical properties of diamond like carbon films deposited by microwave ECR plasma CVD

Diamond like carbon (DLC) films were deposited on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapour deposition (CVD) process using plasma of argon and methane gases. During deposition, a d.c. self-bias was applied to the substrates by application of 13·56 MHz rf power. DLC films deposited at three different bias voltages (−60 V, −100 V and −150 V) were characterized by FTIR, Raman spectroscopy and spectroscopic ellipsometry to study the variation in the bonding and optical properties of the deposited coatings with process parameters. The mechanical properties such as hardness and elastic modulus were measured by load depth sensing indentation technique. The DLC film deposited at −100 V bias exhibit high hardness (∼ 19 GPa), high elastic modulus (∼ 160 GPa) and high refractive index (∼ 2·16–2·26) as compared to films deposited at −60 V and −150 V substrate bias. This study clearly shows the significance of substrate bias in controlling the optical and mechanical properties of DLC films.     

Growth process observation of homoepitaxial ZnO thin films using optical emission spectra during pulsed laser deposition

Homoepitaxial ZnO thin films were prepared on the Zn-polar or O-polar ZnO substrates by pulsed laser deposition method. Optical emission spectroscopy of the plume was carried out to estimate O/Zn flux ratio under the various deposition conditions such as oxygen pressure, laser fluence, and the distance between target and substrate. It is revealed that the O/Zn flux ratio could be controlled by laser fluence, oxygen pressure, and target-substrate distance. Zn-rich O/Zn flux promotes pit formation and O-rich flux yields the three-dimensional growth. The difference of the growth process on Zn-polar or O-polar substrates is also discussed.     

Blue-shifted stimulated emission from ZnO films deposited on SiO2 by atomic layer deposition

ZnO films were prepared by atomic layer deposition upon a SiO₂ layer on a Si substrate and treated by rapid thermal annealing. The optically-pumped random lasing actions with low threshold values were observed in the ZnO films on SiO₂/Si substrates. With the decrease in ZnO film thickness or the increase in post-annealing duration, the stimulated emission shifted toward the shorter wavelength and the lasing threshold increased. The results can be attributed to the inter-diffusion between ZnO and SiO₂, which causes the modification of bandgap renormalization in ZnO.     

Properties of ZnO:Al films deposited on polycarbonate substrate

Transparent conducting aluminum-doped zinc oxide (ZnO:Al) films have been prepared on polycarbonate (PC) substrates by pulsed laser deposition technique at low substrate temperature (room-100 °C); Nd-YAG laser with wavelength of 1064 nm was used as laser source. The experiments were performed at various oxygen pressures (3 pa, 5 pa, and 7 Pa). In order to study the influence of the process parameters on the deposited (ZnO:Al) films, X-ray diffraction and atomic force microscopy were applied to characterize the structure and surface morphology of the deposited (ZnO:Al) films. Polycrystalline ZnO:Al films having a preferred orientation with the c-axis perpendicular to the substrate were deposited with a strong single violet emission centering about 377–379 nm without any accompanying deep level emission. The average transmittances exceed 85% in the visible spectrum for 300 nm thick films deposited on polycarbonate.     

Optical and field emission characteristics of anodic aluminium oxide/ZnO hybrid nanostructure

Arrays of ZnO nanowires (NWs) were fabricated within the well-distributed pores of anodic aluminium oxide (AAO) template by a simple chemical method. The photoluminescence (PL) and field emission (FE) properties of the AAO/ZnO NWs hybrid structure were investigated in detail. The hybrid nanostructure exhibits interesting PL characteristics. ZnO NWs exhibit UV emission at 378 nm and two prominent blue-green emissions at about 462 and 508 nm. Intense blue emission from the AAO template itself was observed at around 430 nm. Herein, for the first time we report the FE characteristics of the ZnO/AAO hybrid structure to show the influence of the AAO template on the FE property of the hybrid structure. It is found that the turn-on electric field of the vertically grown and aligned ZnO NWs within the pores of AAO template is lower than the entangled unaligned ZnO NWs extracted from the template. Although the AAO template exhibits no FE current but it helps to achieve better FE property of the ZnO NWs through better alignment. The turn-on electric field of aligned NWs was found to be 3 V μm⁻¹ at a current of 0.1 μA. Results indicate that the AAO embedded ZnO NW hybrid structure may find useful applications in luminescent and field emission display devices.     

Pulsed laser deposited ZnO:In as transparent conducting oxide

Zinc oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown by pulsed laser deposition technique on corning glass substrate. The effect of indium concentration on the structural, morphological, optical and electrical properties of the film was studied. The films were oriented along c-direction with wurtzite structure and highly transparent with an average transmittance of more than 80% in the visible wavelength region. The energy band gap was found to decrease with increasing indium concentration. High transparency makes the films useful as optical windows while the high band gap values support the idea that the film could be a good candidate for optoelectronic devices. The value of resistivity observed to decrease initially with doping concentration and subsequently increases. IZO with 1% of indium showed the lowest resistivity of 2.41 × 10⁻² Ω cm and large transmittance in the visible wavelength region. Especially 1% IZO thin film was observed to be a suitable transparent conducting oxide material to potentially replace indium tin oxide.     

Characterization of SiNx:H films deposited by rapid thermal chemical vapor deposition

Hydrogenated silicon nitride films were deposited with NH₃, SiH₄ and N₂ gas mixture at 700 °C by rapid thermal chemical vapor deposition (RTCVD) system. The NH₃/N₂ flow ratio and deposition pressure are found to influence the film properties. The stress of SiN_x:H films deposited by RTCVD is tensile, which can reach ~ 1.5 GPa in our study. The stress of SiN_x:H films is dependent on the deposition parameters, which can be associated with chemical configuration of the film. It is suggested that the presence of hydrogen atoms will relax the Si-N network, which results in the decrease of tensile stress of the SiN_x:H film.     

Nucleation and growth study of copper thin films on different substrates and wetting layers by metal-organic chemical vapour deposition

Chemical vapour deposition of copper thin films on different diffusion barrier/adhesion promoter layers have been studied. Copper thin films were grown in low pressure CVD reactor, using Cu(dpm)₂ as precursor and argon as carrier gas. Growth rates, film adhesion to the substrate, and surface morphology were studied in detail. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Ultrathin silicon oxide films deposited by synchrotron irradiation of condensed layers of silanes and water

Silicon oxide and carbide ultrathin films (less than 50 Å thick) were grown at rates of up to 1 Å s⁻¹ using a previously developed technique. To form silicon oxide, a mixture of silane or tetramethylsilane and water was condensed onto a metal surface, which was then exposed to either broad-band or monochromatized synchrotron radiation. Characterization by soft X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure showed that clean, near-stoichiometric films of self-limited thickness were grown. The results also suggested that the reactions leading to film growth were predominantly excited by electrons produced by photon absorption in the substrate.     

Study of plasma enhanced chemical vapor deposition of ZnO films by non-thermal plasma jet at atmospheric pressure

Plasma enhanced chemical vapor deposition using a non-thermal plasma jet was applied to deposition of ZnO films. Using vaporized bis(octane-2,4-dionato)zinc flow crossed by the plasma jet, the deposition rate was as high as several tens of nm/s. From the results of infrared spectra, the films deposited at the substrate temperature T_sub = 100 °C contained a significant amount of carbon residue, while the films prepared at T_sub = 250 °C showed less carbon fraction. The experimental results confirmed that the plasma jet decomposed bis(octane-2,4-dionato)zinc in the gaseous phase and on the substrate, and that there should be the critical T_sub to form high-quality ZnO films in the range from 100 to 250 °C.     

Effect of silver doping on optical property of diamond like carbon films

Optical properties of silver doped diamond like carbon films (Ag:DLC) deposited by the RF reactive sputtering technique were studied in detail. The chemical binding energy and the composition of the films were investigated by using an X-ray photoelectron spectroscopy. Optical transparency and optical band gap decreased with the silver incorporation to the DLC film. Optical band gap calculated from transmittance spectra decreased from 2.55 to 1.95 eV with a variation of Ag concentration from 0 to 12.5 at.%. Urbach parameter determined from the band tail of the transmittance spectra showed to increase with the doping concentration.     

Optimization of field emission properties of carbon nanotubes by Taguchi method

It is the purpose of this study to evaluate the field emission property of carbon nanotubes (CNTs) prepared by microwave plasma-enhanced chemical vapor deposition (MPCVD) method. Nickel layer of 5 nm in thickness on 20-nm thickness titanium nitride film was transformed into discrete islands after hydrogen plasma pretreatment. CNTs were then grown up on Ni-coated areas by MPCVD. Through the practice of Taguchi method, superior CNT films with very low emission onset electric field, about 0.7 V/μm (at J = 10 μA/cm²), are attained without post-deposition treatment. It is found that microwave power has the most important influence on the field emission characteristics of CNT films. The increase of methane flow ratio will downgrade the degree of graphitization of CNT and thus its field emission characteristics. Scanning electron microscope and transmission electron microscopy (TEM) observation and energy dispersive X-ray spectrometer analysis reveal that CNT growth by MPCVD is based on tip-growth mechanism. TEM micrographs validate the hollow, bamboo-like structure of the multi-walled CNTs.