Nanostructural and optical features of amorphous AlxSi0.45−xO0.55 (0 ⩽ x ⩽ 0.05) thin films prepared by RF-magnetron sputter techniques

The nanostructural, chemical, and optical features of Al_xSi_0.45−xO_0.55 (0 ⩽ x ⩽ 0.05) thin films were investigated in terms of Al concentration and post-deposition annealing conditions; the films were prepared by co-sputtering a Si main target and Al-chips, and the annealing was carried out at temperatures of 400–1100 °C. The a-Si_0.45O_0.55 films prepared without Al-chips and annealed at 800 °C contain ∼3.5 nm-sized Si nanocrystallites. The photoluminescence (PL) intensity as well as the volume fraction of Si nanocrystallites increased with increasing the concentration of Al to a certain level. In particular, the intensity of the PL spectra of the Al_0.025Si_0.425O_0.550 films which were annealed at 800 °C increased significantly at wavelengths of ∼580 nm. It is highly likely that the observed increase in the PL intensity is caused by the raise in the total volume of the ∼3.5 nm-sized nanocrystallites in the films. The addition of Al as well as the post-deposition annealing allow adjustment and control of the nanostructural and light-emission features of the a-SiO_x films.     

Photoluminescence of Si nanocrystallites in different types of matrices

This paper presents the comparative investigation of photoluminescence (PL) and its temperature dependence for rf-magnetron co-sputtered Si-enriched SiO_x systems and amorphous Si films prepared by hot-wire CVD method with Si nanocrystallites of different sizes. It is shown that PL spectra of Si–SiO_x films consist of the five PL bands peaked at 1.30, 1.50, 1.76, 2.05 and 2.32 eV. Amorphous Si films with Si nanocrystallites are characterized by three PL bands only peaked at 1.35, 1.50 and 1.76 eV. The peak position of the 1.50 eV PL band shifts with the change of Si quantum dot sizes and it is attributed to exciton recombination inside of Si quantum dots. The nature of four other PL bands is discussed as well.     

Photoluminescence of Si or Ge nanocrystallites embedded in silicon oxide

This paper presents the results of photoluminescence, its temperature dependence and Raman scattering investigations on magnetron co-sputtered silicon oxide films with (or without) embedded Si (or Ge) nanocrystallites. It is shown the oxide related defect origin of the visible PL centers peaked at 1.7, 2.06 and 2.30 eV. The infrared PL band centered at 1.44–1.58 eV in Si–SiO_x, system has been analyzed within a quantum confinement PL model. Comparative PL investigation of Ge–SiO_x system has confirmed that high energy visible PL bands (1.60–1.70 and 2.30 eV) are connected with oxide related defects in SiO_x. The PL band in the spectral range of 0.75–0.85 eV in Ge–SiO_x system is attributed to exciton recombination inside of Ge NCs.     

Pyrolytic conversion studies of blended polycarbosilane and polyaluminasilazane

Multinuclear solid-state NMR spectroscopy, FTIR and Raman experiments are employed to investigate the pyrolytic conversion of blended polycarbosilane and polyaluminasilazane (denoted CA) up to 800 °C, with the aim of studying structural evolutions and interactions between polycarbosilane and polyaluminasilazane during the pyrolysis process. Vinyl and SiCH₃ units can react with Si–H, SiCH₃ and Si–CH₂–Si groups below 400 °C. These crosslinking reactions can increase the ceramic yield of the blended precursors. At 500 °C aromatic carbon is formed, and N–H and Si–H groups vanish at 600 °C and 700 °C, respectively. At 600 °C, SiCH₃ and Si–H units can further react with SiCN₃, SiC₂N₂, N–H and C–H units. An amount of amorphous carbon and CSi₄ and CSi₃H groups are detectable at 800 °C. Even at this temperature there are still many aromatic protons. In addition, there are also SiC₄, SiC₃N, SiCN₃ and SiN₄ units. Silicon forms SiN₄ more readily than SiC₄. Many AlN₅ groups transform into AlN₆ groups. The D and G bands of graphite are observed in CA pyrolyzed at 1400 °C. According to the XRD patterns, the reflection of crystalline β-Si₃N₄ vanishes at 1700 °C, and the residue pyrolyzed at 1800 °C mainly contains a large number of 2H-SiC/AlN solid solution crystals and a few β-SiC crystals.     

MOCVD and characterization of Hf-silicate thin films using HTB and TEMAS

Hafnium silicate (HfSi_xO_y) films were deposited by metal-organic chemical vapor deposition (MOCVD) using a combination of precursors: hafnium tetra-tert-butoxide [Hf(OC(CH₃)₃)₄, HTB] and tetrakis-ethylmethylamino silane [Si(N(C₂H₅)(CH₃))₄, TEMAS]. The activation energy was independent on the ratio of precursor amounts in the surface reaction regime. The grown films showed Hf-rich characteristics and the impurity concentrations were less than 1 at.% (below detection limits). Hafnium silicate films were amorphous up to 700 °C annealing. Hf/(Hf + Si) composition ratio and dielectric constant (k) of the Hf-silicate films decreased by increasing the growth temperature above 270 °C.     

Influence of amorphous buffer layers on the crystallinity of sputter-deposited undoped ZnO films

Undoped ZnO films were deposited by radio frequency (RF) magnetron sputtering on amorphous buffer layers such as SiO_x, SiO_xN_y, and SiN_x prepared by plasma enhanced chemical vapor deposition (PECVD) for dielectric layer in thin film transistor (TFT) application. ZnO was also deposited directly on glass and quartz substrate for comparison. It was found that continuous films were formed in the thickness up to 10 nm on all buffer layers. The crystallinity of ZnO films was improved in the order on quartz>SiO_x >SiO_xN_y>glass>SiN_x according to the investigated intensities of (0 0 2) XRD peaks. The crystallite sizes of ZnO were in the order of SiO_x～glass >SiN_x. Stable XRD parameters of ZnO thin films were obtained to the thickness from 40 to 100 nm grown on SiO_x insulator for TFT application. Investigation of the ZnO thin films by atomic force microscope (AFM) revealed that grain size and roughness obtained on SiN_x were larger than those on SiO_x and glass. Hence, both nucleation and crystallinity of sputtered ZnO thin films remarkably depended on amorphous buffer layers.     

Dielectric low-k composite films based on PMMA,PVC and methylsiloxane-silica: Synthesis,characterization and electrical properties

This report describes the preparation of low-k inorganic–organic hybrid dielectric films, based on a polymethylmethacrylate–polyvinylchloride (PMMA–PVC) blend and a silica powder functionalized on the surface with methylsiloxane groups (m-SiO₂). By dispersing m-SiO₂ into a [(PMMA)_x(PVC)_y] 50/50 (x/y) wt% polymer blend, six [(PMMA)_x(PVC)_y]/(m-SiO₂)_z hybrid inorganic–organic materials were obtained, with z ranging from 0 to 38.3 wt% and x = y = (100 − z)/2. The transparent, homogeneous, crack-free films were obtained by a solvent casting process from a THF solution. The morphology, thermal stability and transitions of hybrid materials were studied by environmental scanning electron microscopy (ESEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). ESEM revealed that hybrid dielectric films are very homogeneous materials. The electrical response of the dielectric films was studied by detailed broadband dielectric spectroscopy (BDS). BDS measurements were performed at frequencies of 40 Hz to 10 MHz and a temperature range of 0–130°C. In these temperature and frequency ranges the proposed materials have a dielectric constant of <3.5 and a tan δ of <0.05. BDS also revealed molecular relaxation events in [(PMMA)_x(PVC)_y]/(m-SiO₂)_z materials as a function of temperature and sample composition. Results showed that these films with z in the range 25–35 wt% are very promising low-k dielectrics for applications in organic thin film transistor (OTFT) devices.     

Crystallization of polymer-derived SiC/BN/C composites investigated by TEM

The crystallization behavior of two polymer-derived Si/B/C/N ceramics with similar compositions lying close to the three-phase field BN + SiC + C was investigated by (high-resolution) transmission electron microscopy. The materials were high-temperature mass stable up to T = 2000 °C. During thermolysis at 1050 °C a homogeneous amorphous solid formed. SiC crystallization started at about 1400 °C. Further annealing to higher temperatures up to 2000 °C led to formation of microstructures composed of SiC crystals embedded into a structured BNC_x matrix phase. With increasing temperature, both the size of the crystallites and the ordering of the matrix phase increased.     

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.     

High-yield synthesis of semiconductive type-II Si clathrates with low Na content

To develop an efficient synthesis of type-II Si clathrates with low Na content (Na_xSi₁₃₆: x = 0–24), various conditions for annealing the Zintl phase NaSi were examined. The addition of a pre-annealing process under vacuum at 250 °C following the preparation of NaSi resulted in a decrease in the Na content of type-II Si clathrates from 4 to 2 when the pre-annealing duration ranged from 0 to 60 h, while the volume fraction of type-II Si clathrate crystals in the synthesized specimens (type-II/(type-I + type-II + d-Si)) deduced by powder X-ray diffraction and Rietveld analysis was maintained at approximately 85%. These preparation techniques that enable the high-yield synthesis of semiconductive type-II Si clathrates open opportunities for the application of these substances to semiconductor devices.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Morphological control of MgxZn1−xO layers grown on Ga:ZnO/glass substrates for photovoltaics

Mg_xZn_1?xO has been used in various photovoltaic cells because its energy bandgap can be tailored by controlling the Mg composition in this ternary compound. The Mg_xZn_1?xO layers with different surface morphologies including two-dimensional (2-D) films and one-dimensional (1-D) nanostructures are preferred for conventional p–n junction solar cells and polymer–inorganic hybrid solar cells, respectively. The Mg_xZn_1?xO layers are sequentially grown on Ga-doped ZnO (GZO) transparent conductive electrode using metalorganic chemical vapor deposition (MOCVD). The effect of the buffer layers on Mg_xZn_1?xO surface morphology is investigated. It is observed that Mg_xZn_1?xO deposited at ～500 °C on a low-temperature (～250 °C) ZnO buffer layer is in the form of 2-D dense and smooth films, whereas, on a high-temperature (～520 °C) ZnO buffer layer is in the form of 1-D nanostructures. Based on the structure characterization results, a growth mechanism in terms of nucleation and texturing is proposed to explain the buffer layer effect.     

Effect of vacuum annealing on charge transport and trapping in a-Si1 − xCx:H/c-Si heterostructures

The processes of charge transport and trapping in amorphous Si_1 ? xC_x:H films deposited on crystalline p-type Si wafers and annealed in vacuum in the temperature range 300–650 °C have been evaluated. Current–voltage (I–V), capacitance–voltage (C–V) and admittance–temperature (G–T) characteristics were measured in the temperature range 100–350 K. The spectrum of thermal effusion of hydrogen was measured from room temperature up to 1000 °C.C–V characteristics indicate a slight increase of the dielectric constant k and a large hysteresis after annealing at 450 °C. The hysteresis is believed to be associated with mobile hydrogen effusion from the a-SiC:H film, and it is not seen after a 650 °C anneal. From I–V data the maximum rectification ratio is observed after annealing at 450 °C. Variable-range hopping (VRH) conduction at the Fermi level is found to dominate the forward current of the as-deposited structure. After annealing at 450 °C the forward current can be described by space-charge limited (SCL) mechanisms with trapping at shallow levels with energy of about 0.12 eV. After annealing at 650 °C the process of VRH conduction appears again, but the density of hopping sites is much higher than in the as-grown sample. From admittance spectra, the energy position of respective traps in a-SiC:H is at (E_V + 0.45) eV for as-deposited material and it decreases slightly after vacuum annealing. On the basis of these results, an energy band diagram of the a-Si_1 ? xC_x:H/p-Si structure annealed at 450 °C is proposed.     

Role of ballistic transport in photoluminescence excitation of Si nanocrystals

Photoluminescence of Si NCs with the size (10–300 nm) bigger than the exciton Bohr radius in the bulk Si crystals (4.8 nm) has been considered. Photoluminescence in such NC systems is analyzed from the point of view of new concept based on the effect of hot carrier ballistic transport in excitation of suboxide defect-related photoluminescence at the Si/SiO_x interface. The dependence of the 1.70 eV PL band integrated intensity on Si NC sizes was numerically calculated on the base of the hot carrier ballistic PL model. The well correlation between calculated and experimental results has been obtained for Si NCs with the size from the 30–150 nm range.     

Formation and thermal stability of Pd-based bulk metallic glasses

The glass-forming ability and thermal stability of bulk glassy Pd₇₉Cu₆Si₁₀P₅ alloy were studied by substitution of Cu with Ag and with Au + Ag from 0 to 6 at.%. The results indicated that the small addition of Ag strongly affects the thermal stability and glass-forming ability of the Pd₇₉Cu₆Si₁₀P₅ alloy. The alloy doped with 4 at.% Ag (Pd₇₉Cu₂Ag₄Si₁₀P₅) exhibits the largest glass-forming ability among the Pd₇₉Cu_6−xAg_xSi₁₀P₅ (x = 0–6 at.%) alloys. The critical diameter for glass formation of this alloy reaches as large as 7 mm by copper mold casting. On the other hand, the multi-addition of Au + Ag does not increase the glass forming ability though the Ag and Au are similar in atomic size. The largest glass forming ability is obtained at 1 at.% Au + 2 at.% Ag among the Pd₇₉Cu_6−x−yAu_xAg_ySi₁₀P₅ (x = 1–4 at.%, y = 1–3 at.%) alloys. The critical diameter of this alloy is 5 mm by copper mold casting.     

Structural investigations of nitrided Nb2O5 and Nb2O5–SiO2 sol–gel derived films

Sol–gel derived xNb₂O₅–(100 ? x)SiO₂ films (where x = 100, 80, 60, 50, 40, 20, 0 mol%) were nitrided at various temperatures (800 °C, 900 °C, 1000 °C, 1100 °C and 1200 °C). The structural transformations occurring in the films as a result of ammonolysis were studied using X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The XRD results have shown that the temperatures below 1100 °C were too low to obtain a pure NbN phase in the samples. The AFM observations indicate that the formation of the NbN phase and the size of NbN grains are related to the silica content in the layer. NbN grains become more regular and larger as the niobium content increases. The maximum grain size of about 100 nm was observed for x = 100. Preparation of the Nb₂O₅–SiO₂ sol–gel derived layers and the subsequent nitridation is a promising method of inducing crystalline NbN in amorphous matrices. It follows from the XPS results that a small amount of Nb₂O₅ remains in the films after nitridation at 1200 °C and that nitrogen reacted not only with Nb₂O₅ but also with SiO₂.     

Structure–property correlations in lead borate and borosilicate glasses doped with aluminum oxide

Glass samples from four systems: xPbO–(100?x)B₂O₃ (x = 30, 40, 50 and 60 mol%), 50PbO–yAl₂O₃–(50?y)B₂O₃ (y = 2, 4, 6, 8 mol%), 50PbO–ySiO₂–(50?y)B₂O₃ (y = 5, 10, 20, 30 mol%) and 50PbO–5SiO₂–yAl₂O₃–(45?y)B₂O₃ (y = 2, 4, 6, 8 mol%) were prepared by a melt-quench technique. Characterization of these systems was carried out using density measurements, UV–visible spectroscopy, differential scanning calorimetry (DSC), and ¹¹B and ²⁷Al magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR). Our studies reveal an increase in glass density with increasing lead(II) oxide concentration in pure lead borates and also with addition of silica into 50PbO–50B₂O₃ glass. ¹¹B MAS NMR measurements determine that the fraction of tetrahedral borons (N₄) reaches a maximum for the glass containing 50 mol% of PbO in the PbO–B₂O₃ glass series and that N₄ is sharply reduced upon adding small amounts of Al₂O₃ into lead borate and lead borosilicate systems. ²⁷Al MAS NMR experiments performed on glasses doped with aluminum oxide show that the Al³⁺ are tetra-, penta- and hexa-coordinated with oxygen, even without any excess concentration of Al³⁺ over charge-balancing Pb²⁺ cations. ^[5]Al and ^[6]Al concentrations are found to have unusually high values of up to 30%. The results of UV–visible absorption spectroscopy, DSC and density measurements support the conclusions drawn from the NMR studies, providing a consistent picture of structure–property relations in these glass systems.     

Optical band gap and Raman spectra in some (Bi2O3)x(WO3)y(TeO2)100−x−y and (PbO)x(WO3)y(TeO2)100−x−y glasses

The glasses representing (Bi₂O₃)_x(WO₃)_y(TeO₂)_100?x?y and (PbO)_x(WO₃)_y(TeO₂)_100?x?y systems were prepared. The dilatometric glass-transition temperatures of examined glass samples were found in the region 383–434 °C, the coefficient of thermal expansion varied from 12 to 16 ppm/°C and the density ranged from 6.30₂ to 6.80₈ g/cm³. From the optical transmission measurements of thin glassy bulk samples prepared by a glass blowing, the optical gap values were found in the narrow region 3.21–3.36 eV. For the temperature interval 300–480 K, the values of the temperature coefficient of the optical band gap varied from 3.7 × 10^?4 to 5.24 × 10^?4 eV/K. It is suggested that Raman feature observed at around 350 cm^?1 can be assigned to an overlap of Raman bands attributed to WO₆ corner shared octahedra and to the following three atomic linkages: Bi–O–Te, Pb–O–Te and W–O–Te.     

Reduction of bulk and interface defects by network self-organizations in gate dielectrics for silicon thin film and field effect transistors (TFTs and FETs,respectively)

Studies of binary chalcogenide alloys have established that the onset of network rigidity is generally delayed by a network self-organization resulting in an intermediate phase with significant deviations from mean-field chemical bonding. In Ge_xSe_1−x, the onset of local chemical bonding rigidity occurs for a mean-field coordination, r_c = 2.4 at x = 0.2, but percolation of stress resulting in network rigidity is delayed until r_c = 2.52. This paper demonstrates that low levels of electrically active defects in gate dielectrics for (i) thin film transistors (TFTs) in liquid crystal displays (LCDs), and (ii) aggressively-scaled metal- oxide-semiconductor field effect transistors (MOSFETs) are derived from similar network self-organizations that occur for a narrow range of dielectric compositions. The dielectrics of this article are non-crystalline (nc-) Si_xN_yH_z alloys in which a chemical self-organization occurs during deposition at 300 °C, and nc-(SiO₂)_x(Si₃N₄)_y(ZrO₂)_z alloys in which it occurs during post-deposition annealing at ∼900 °C. For each of these alloys, the values of x, y and z, are approximately 0.3, 0.4 and 0.3.     

ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.