The application of very high frequency inductively coupled plasma to high-rate growth of microcrystalline silicon films

High-rate growth of microcrystalline silicon films (μc-Si:H) from inductively coupled plasma (ICP) of H₂ diluted SiH₄ generated with a very high frequency (VHF: 60 MHz) power source has been studied from the viewpoint of efficient gas dissociation. From the VHF power and gas pressure dependences of the film growth rate and optical emission intensities, we have found that the Si and SiH emission intensities and the intensity ratio of H_α to SiH are good indicators for the film growth rate and crystallinity, respectively. The generation rate of film precursors is reflected by the Si and SiH emission intensities while the flux ratio of atomic hydrogen to film precursors, which plays an important role on the structural relaxation for the crystalline network formation, is characterized by the intensity ratio of H_α to SiH. An increase in SiH emission while keeping the intensity ratio of H_α to SiH at a certain level enables us to enhance the film growth rate without significant deterioration in the crystallinity. In this study, a growth rate as high as 10 nm/s was obtained for highly crystallized films.     

Deposition of microcrystalline silicon films at ultrafast rate by using a new microwave induced plasma source

Synthesis of microcrystalline silicon (μc-Si) film at an ultrafast deposition rate over 100 nm/s is achieved from SiH₄ + He by using a high density microwave plasma source even without employing H₂ dilution and substrate heating techniques. Systematic deposition studies show that high SiH₄ flow rate and working pressure increase film deposition rate while high He flow rate decreases the rate. On the other hand, crystallinity of deposited Si film decreases with increasing SiH₄ or He flow rate and working pressure. Enhancements of gas phase and surface reactions during film deposition process are responsible for the achievement of high deposition rate and high film crystallinity.     

Ionic amorphous oxide semiconductors: Material design,carrier transport,and device application

Recently we have reported the room temperature fabrication of transparent and flexible thin film transistors on a polyethylene terephthalate (PET) film substrate using an ionic amorphous oxide semiconductor (IAOS) in an In₂O₃–ZnO–Ga₂O₃ system. These transistors exhibit a field effect mobility of ∼10 cm² (V s)⁻¹, which is higher by an order of magnitude than those of hydrogenated amorphous Si and pentacene transistors. This article describes a chemical design concept of IAOS, and its unique electron transport properties, and electronic structure, by comparing them with those of conventional amorphous semiconductors. High potential of IAOS for flexible electronics is addressed.     

Correlation between micro-roughness,surface chemistry,and performance of crystalline Si/amorphous Si:H:Cl hetero-junction solar cells

The correlation between micro-roughness, surface chemistry, and performance of crystalline Si/amorphous Si:H:Cl hetero-junction solar cells is discussed through a deposition study of amorphous Si:H:Cl (a-Si:H:Cl) films by rf plasma-enhanced chemical vapor deposition using a SiH₂Cl₂–H₂ mixture. The degree of H- and Cl-termination on the growing surface determined the degree of micro-roughness at the p-type a-Si:H:Cl/intrinsic a-Si:H:Cl interface and solar cell performance. A higher degree of Cl-termination compared to H-termination was effective to suppress the micro-roughness at the growing surface and oxygen incorporation into the film, as well as chemical reduction of the intrinsic a-Si:H:Cl layer during the underneath p-layer formation. The study showed that a-Si:H:Cl deposited from SiH₂Cl₂ is a potential material for c-Si hetero-junction solar cells with an intrinsic a-Si:H:Cl thin layer.     

Effect of Al addition on the crystallization of a-AlxSi1−x (0.025 x 0.100) by electron-beam irradiation

Si crystals and nano-rods were formed in Al-added amorphous Si films (a-Al_xSi_1−x; 0.025 x 0.100) by the irradiation of a focused electron-beam; the films were in situ heated to be kept at 400 °C and the current density of the electron-beam was 15.7 pA/cm². The size, shape, and concentration of the Si crystallites were varied sensitively with the Al content as well as the irradiation time. Under the electron-beam irradiation, crystallization occurred to produce polycrystalline phases in the a-Al_0.025Si_0.975 film, while rod-shaped Si nanostructures were formed in the a-Al_0.050Si_0.950 and a-Al_0.100Si_0.900 film. It is evident that the removal of Al and as a result the atomic rearrangements and/or local restructuring in the Al/a-Si film are critically affected by the electron-beam irradiation, which lead to the local crystallization and growth of Si nanocrystallites.     

Remote plasma deposition of microcrystalline silicon thin-films: Film structure and the role of atomic hydrogen

Microcrystalline silicon films grown in an expanding thermal plasma, i.e. in the absence of ion bombardment, are found to be porous and rich in nano-sized voids. By carrying out an extensive investigation on the material quality of films deposited in the amorphous-to-microcrystalline transition regime, on the microcrystalline silicon growth development, and on the influence of the substrate temperature, it is concluded that the inferior material quality is related to the lack of a sufficient amount of amorphous silicon tissue. As possible cause for the insufficient amount of amorphous silicon tissue, the interaction of atomic hydrogen with amorphous silicon films has been studied in order to highlight a possible competition between film growth and H-induced etching of amorphous silicon, and between film growth and H-induced surface/film modification. The etch rates obtained are too low to compete with film growth. Furthermore, atomic H cannot be considered responsible for the poor quality of amorphous tissue present in the microcrystalline silicon films, as the H up-take mainly takes place in divacancies. These results suggest that ion bombardment may be a necessary condition to provide good quality microcrystalline silicon films.     

Effect of laser fluence on c‐axis orientation of LiNbO3 piezoelectric films on nanocrystalline diamond by pulsed laser deposition

Completely c‐axis oriented LiNbO₃ piezoelectric films have been deposited on nanocrystalline diamond (NCD)/Si substrates with SiO₂ buffer layer by pulsed laser deposition. The amorphous SiO₂ buffer layer was formed on NCD/Si substrates by sol‐gel method. The c‐axis orientation and crystallinity of LiNbO₃ films are strongly dependent on the laser fluence, and the laser fluence 3.6 J/cm² is found to be the optimal value for the growth of oriented LiNbO₃ film, which has a smooth surface with composed of a large mount of uniform grains. The average surface roughness of LiNbO₃ films is about 6.7 nm.     

Relative importance of hydrogen atom flux and ion bombardment to the growth of μc-Si:H thin films

An investigation of the relative importance of H atoms and ions to the transition from amorphous to microcrystalline silicon growth was performed by applying in situ plasma diagnostics and a 2D simulator of SiH₄/H₂ discharges. The growth transition was achieved by reducing the % SiH₄ in the SiH₄/H₂ discharges while keeping all the other plasma parameters constant. The distribution of the main species in the discharge space, as well as the flux of H atoms and ions per monolayer and the energy transferred by each to the growing film surface, was estimated from the simulation results. H atoms flux was found to be much higher compared to ions but the total amount of energy transferred from both H atoms and ions was found to be much lower than the activation energy required for crystallization of stable a-Si:H films with low H-content. These results support the theory that in the present conditions the formation of microcrystals proceeds via the initial growth of an unstable a-Si:H with high H content, which reduces significantly the energy barrier for crystallization.     

Photoluminescence in silicon/silicon oxide films produced by the Pulsed Electron Beam Ablation technique

In this work we report studies of the photoluminescence emission in samples based on Si/SiO_x films deposited by the Pulsed Electron Beam Ablation (PEBA) technique. The samples were prepared at room temperature using targets with different Si/SiO₂ concentrations. The samples were characterized using X-ray Absorption Edge Spectroscopy (XANES) at the Si―K edge, Raman spectroscopy, Photoluminescence (PL) and X-ray Photoelectron Spectroscopy (XPS). The concentration of a-Si and nc-Si in the film was dependent on the silicon concentration in the target. It was also observed that the PL is strongly dependent on the structural amorphous/crystalline arrangement.     

Structure and optical properties of light-emitting Si films fabricated by neutral cluster deposition and subsequent high-temperature annealing

As a new development of our previous study on the production of light-emitting amorphous Si (a-Si) films by the neutral cluster deposition (NCD) method, we have fabricated light-emitting Si films with improved emission intensity by the combined methods of NCD and subsequent high-temperature annealing. The structure of these films is best characterized by Si nanocrystals, surrounded by an interfacial a-SiO_x (x < 2) layer, embedded in an a-SiO₂ film. These improved Si films were observed by atomic force microscopy and high-resolution transmission electron microscopy, and analyzed by means of X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence (PL) and Fourier transform infrared-attenuated total reflection measurements. The PL curves of the annealed samples exhibit peaks around 600 nm, at almost the same position as the unannealed samples. Their PL intensities, however, have increased to approximately five times those of the unannealed samples. The source of the luminescence is most likely due to electron-hole recombination in the a-SiO₂/Si interfacial a-SiO_x layer.     

Microstructure and dielectric properties of La2O3 films prepared by ion beam assistant electron-beam evaporation

Ultrathin La₂O₃ gate dielectric films were prepared on Si substrate by ion assistant electron-beam evaporation. The growth processing, interfacial structure and electrical properties were investigated by various techniques. From XRD results, we found that the La₂O₃ films maintained the amorphous state up to a high annealing temperature of 900 °C for 5 min. From XPS results, we also discovered that the La atoms of the La₂O₃ films did not react with silicon substrate to form any La-compound at the interfacial layer. However, a SiO₂ interfacial layer was formed by the diffusion of O atoms of the La₂O₃ films to the silicon substrate. From the atomic force microscopy image, we disclosed that the surface of the amorphous La₂O₃ film was very flat. Moreover, the La₂O₃ film showed a dielectric constant of 15.5 at 1 MHz, and the leakage current density of the La₂O₃ film was 7.56 × 10⁻⁶ A/cm² at a gate bias voltage of 1 V.     

Effect of ex-situ hydrogen passivation on the structural properties of e-beam evaporated amorphous silicon thin film for solar cell applications

Thin-film photovoltaics greatly reduce the semiconductor material content in the finished product, using 150–200 times less material as compared with conventional Si wafer based cells. Electron beam evaporation (e-beam), a non-ultra-high vacuum technique has the potential for being inexpensive, and simpler process for a-Si deposition. It offers specific advantages such as high Si deposition rate (up to 1 μm/min), excellent Si source material usage, avoidance of toxic gases, and simple sample preparation conditions. In this work, we report the growth of a-Si films using e-beam at a growth rate exceeding 30 Å/s (1–5 Å/s for conventional PECVD process). We report the effect of hydrogen passivation on amorphous silicon network and on silicon-bonded hydrogen configuration under ex-situ hydrogenation in hydrogen plasma. The hydrogen concentration and silicon-hydrogen bonding configuration was evaluated using nuclear reaction analysis (NRA) and Fourier transform infrared spectroscopy (FTIR). Hydrogen plasma treatment shows an increase in the monohydride bond concentration with substrate temperature, and is corroborated by our FTIR investigation, in addition to reducing clustered monohydride bonds or polyhydride bonds in a-Si:H film. Raman analysis indicates reduction in silicon bond angle as well as the bond distance, both leading to significant structural improvement in short-range and medium range order in the amorphous phase. Thus, ex-situ hydrogenation clearly demonstrates the possibility of comparable hydrogen passivation in e‐beam evaporated a-Si films with high growth rate. One can easily extrapolate this result to microcrystalline film growth, assuming the structural improvement of the silicon network preceding the microcrystalline nucleation, where ex-situ passivation is most effective. Thus ex-situ hydrogenation opens up new possibilities in minutely tailoring the a:Si film properties especially for solar cell applications.     

An electron diffraction study of amorphous silicon oxide films

Amorphous silicon oxide films have been examined by high energy electron diffraction using the sector-microphotometer method of data collection common to gas phase electron diffraction. This data was analyzed with a least-squares procedure that is designed to minimize extraneous detail in the radial distribution function obtained by the Fourier sine transform of the interference function. The results of this analysis for thin film SiO₂ show that the overall bonding topology of the thin film agress well with that of bulk (vitreous) SiO₂ examined by X-ray diffraction. The experimental short distance parameters for the films whose composition was determined to be ～SiO_1.3, SiO, and SiO_0.8 are found to be consistent with those expected for a mixture of tetrahedrally bonded amorphous Si and SiO₂ phases in which the scale of the Si-like and SiO₂-like regions is of the order of a few basic tetrahedral units. This result is in agreement with previous examinations of SiO powder by X-rays and a previous examination of thin silicon oxide films by electron diffraction.     

Trap-limited diffusion of hydrogen in precursor derived amorphous Si–B–C–N-ceramics

The tracer diffusion of hydrogen is studied in precursor derived amorphous Si–C–N and Si–B–C–N ceramics using deuterium as a tracer and secondary ion mass spectrometry (SIMS). Since the amorphous ceramics are separated in carbon rich phases (amorphous carbon and amorphous C(BN)_x, respectively) and silicon rich phases (amorphous Si₃N₄ and amorphous Si_3+(1/4)xC_xN_4−x, respectively) we additionally measured the diffusivities of hydrogen in amorphous carbon, in amorphous SiC and in amorphous C–B–N films. The silicon rich phases are identified as diffusion paths for hydrogen in the precursor derived ceramics. Diffusion of hydrogen in these materials is explained with a trap limited diffusion mechanism with a single trap level. We found activation enthalpies of about 2 eV for the precursor derived ceramics, where the activation enthalpy is the sum of a migration enthalpy and a binding enthalpy. The low values for the pre-exponential factors of less than 10⁻⁷ m²/s can be explained with an appropriate expression for the entropy factor.     

Microcrystalline germanium thin films prepared by the reactive RF sputtering method

We focus on thin film microcrystalline germanium (μc-Ge) as narrow gap semiconductor materials for high infrared sensitivity and consider applying it to thermo-photo-voltaic (TPV). The μc-Ge films were prepared on glass substrates by the reactive RF sputtering method with Ar and H₂ gas mixtures. We could successfully produce photosensitive μc-Ge films. Higher crystallinity structures do not always result in better carrier properties. Probably, the amorphous portions between crystalline grains have important roles to suppress the grain boundary defects. We applied the μc-Ge to i-layers of pin structure devices, and observed the photovoltaic effect for the first time.     

Microstructure and optical properties of (Pb,Ca)TiO3 films grown on Si(1 0 0) substrates by a simple sol-gel process

Amorphous and polycrystalline (Pb_0.76Ca_0.24)TiO₃ (PCT) thin films deposited on an Si(1 0 0) substrate have been prepared by a simple sol-gel process. The microstructure and surface morphologies of the thin films have been studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The polycrystalline PCT film on the Si(1 0 0) substrate has a tetragonal perovskite structure with grain size from 60 to 110 nm. AFM reveals smooth surfaces and root mean square (rms) roughness of 0.17 and 4.4 nm for amorphous and polycrystalline films, respectively. The refractive index n and extinction coefficient k of the amorphous and polycrystalline thin films was obtained by spectroscopic ellipsometry as a function of the photon energy in the range from 2.0 to 5.4 eV. The maximum n and direct bandgap energies of amorphous and polycrystalline thin films were 2.66 and 4.11 eV, 2.64 and 3.84 eV, respectively.     

XPS characterization of corrosion films formed on the crystalline, amorphous and nanocrystalline states of the alloy Ti60Ni40

X-ray photoelectron spectroscopy investigations were carried out on the crystalline, amorphous and nanocrystalline states of the alloy Ti₆₀Ni₄₀ after corrosion test in 1 M HNO₃ aqueous medium using potentiodynamic polarization method. Polarization plots revealed that the nanocrystalline state is more corrosion resistant than the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀. The XPS characterization of the oxide film formed after corrosion tests revealed that a multiple phase oxide film is formed on the crystalline and amorphous specimens of the alloy Ti₆₀Ni₄₀ consisting of Ti²⁺, Ti³⁺ and Ti⁴⁺ species along with some unoxidized Ti in metallic form (Ti⁰) in the case of crystalline specimen whereas the oxide film formed on nanocrystalline specimen consists of only Ti²⁺ and Ti⁴⁺ species. The high corrosion resistance of nanocrystalline state is attributed to the presence of fewer oxide species in the oxide film than that of the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀.     

Incipient amorphous-to-crystalline transition in HfO2 as a function of thickness scaling and anneal temperature

A series of 1.4, 1.8, and 4.0 nm thick HfO₂ films deposited on Si(1 0 0) substrates have been measured by extended X-ray absorption fine-structure prior to anneal processing, following a standard post deposition anneal of 700 °C for 60 s in NH₃ ambient, and following an additional rapid thermal anneal cycle of 1000 °C for 10 s in N₂ ambient. Analysis of the second coordination shell gives clear evidence of increased ordering with increasing film thickness at each temperature. Similarly, increased ordering with increasing anneal temperature is evident for each film thickness. Although X-ray diffraction and high resolution transmission electron microscopy indicated the 1.4 nm HfO₂ samples to be amorphous, EXAFS has distinguished nanocrystalline from amorphous states for these films.     

The neutron diffraction study of liquid GeTe and As2Te3

The radial distribution analyses for GeTe and As₂Te₃ are made at temperatures above the melting point in the range of momentum transfer between 0.7 and 10.0 Å^?1 by the neutron diffraction technique. Furthermore, the local order in amorphous GeTe is determined by analyzing the intensity data of the electron diffraction of its thin film. The result for the amorphous film indicates that the local distribution of atoms in amorphous GeTe is not characteristic of the structure of its crystalline state. The shape of the peaks of the intensity curve for liquid GeTe differs from that for the amorphous and crystalline states. However, the short bond length and the small coordination number determined from liquid RDF suggest that the covalent-like bonding between nearest-neighbor atoms remains unbroken when melting. The general form of the structure factor for liquid As₂Te₃ is similar to that for the amorphous material reported previously. The position of the first peak of RDF in the liquid state is observed to be shifted to a shorter distance than the average of nearest-neighbor atoms in crystalline As₂Te₃. The structure of GeTe differs considerably between the crystalline, amorphous and liquid states, whereas the local order in the liquid As₂Te₃ is similar to that in the amorphous state but not in the crystalline state.     

Short range antiferromagnetic ordering in vitreous Fe2O3P2O5

An outline is given of the theory of neutron magnetic scattering from amorphous materials, and data are presented for vitreous 0.79 Fe₂O₃ · P₂O₅. The magnetic correlation function shows that at low temperatures the glass exhibits short-range antiferromagnetic ordering with Fe³⁺?Fe³⁺ interionic distances similar to those found in crystalline FePO₄. The neutron data are not consistent with a previous suggestion that the material is microcrystalline.