Post deposition annealing temperature effect on silicon quantum dots embedded in silicon nitride dielectric multilayer prepared by hot-wire chemical vapor deposition

The preparations of the 20-period of a Si quantum dot (QD)/SiN_x multilayer in a hot-wire chemical vapor deposition (HWCVD) chamber is presented in this paper. The changes in the properties of Si-QDs after the post deposition annealing treatment are studied in detail. Alternate a-Si:H and SiN_x layers are grown in a single SiN_x deposition chamber by cracking SiH₄, and SiH₄ + NH₃, respectively at 250 °C. The as-deposited samples are annealed in the temperature range of 800 °C to 950 °C to grow Si-QDs. All the samples are characterized by confocal micro Raman, transmission electron microscope (TEM), and photoluminescence (PL) to study the changes in the film structures after the annealing treatment. The micro Raman analysis of the samples shows the frequency line shifting from 482 cm^− 1 to 500 cm^− 1 indicating the Si transition from an amorphous to a crystalline phase. The TEM micrograph inspection indicates the formation of Si-QDs of size 3 to 5 nm and a density of 5 × 10¹²/cm². The high resolution TEM micrographs show an agglomeration of Si-QDs with an increase in the annealing temperature. The PL spectra show a peak shifting from 459 nm to 532 nm with increasing the annealing temperature of the film.     

Structured ZnO-based contacts deposited by non-reactive rf magnetron sputtering on ultra-thin SiO2/Si through a stencil mask

In this paper, we study the localized deposition of ZnO micro and nanostructures deposited by non-reactive rf-magnetron sputtering through a stencil mask on ultra-thin (10 nm) SiO₂ layers containing a single plane of silicon nanocrystals (NCs), synthetized by ultra-low energy ion implantation followed by thermal annealing. The localized ZnO-deposited areas are reproducing the exact stencil mask patterns. A resistivity of around 5 × 10^− 3 Ω cm is measured on ZnO layer. The as-deposited ZnO material is 97% transparent above the wavelength at 400 nm. ZnO nanostructures can thus be used as transparent electrodes for Si NCs embedded in the gate-oxide of MOS devices.     

Correlation between surface damage and micro-defects in Si covered with insulating layer by implantation of He and H ions

Cz n-type Si (100) wafers covered with a 220 nm SiO₂ layer or a 170 nm Si₃N₄ layer were singly implanted with 160 keV He ions at a dose of 5 × 10¹⁶/cm² or successively implanted with 160 keV He ions at a dose of 5 × 10¹⁶/cm² and 110 keV H ions at a dose of 1 × 10¹⁶/cm². Surface morphologies together with defect microstructures have been studied by means of several techniques, including optical microscopy, atomic force microscopy, and cross-sectional transmission electron microscopy (XTEM). Only surface blistering has been observed for He and H sequentially implanted SiO₂/Si samples after annealing in temperature range up to 1000 °C. However, as for the He and H implanted Si₃N₄/Si samples, surface features including blistering and the localized exfoliation of both the top Si₃N₄ layer and the implanted Si layer have been well demonstrated during subsequent annealing. XTEM observations reveal quite different defect morphologies in two kinds of materials under the same implantation and annealing conditions. The possible mechanisms of surface damage in two kinds of materials have been discussed and presented based on the XTEM results.     

Growth, structure and luminescence properties of multilayer Si/β-FeSi2NCs/Si/…/Si nanoheterostructures

Multilayer structures (up to 15 layers) with β-FeSi₂ nanocrystallites (NCs) buried in silicon crystalline lattice were grown by successive repetition of reactive deposition epitaxy (RDE) or solid phase epitaxy (SPE) of thin iron film on Si(100) or Si(111) substrates and silicon molecular beam epitaxy (MBE) (100-200 nm). Cross-section high resolution transmission electron microscopy (HR TEM) images and ex situ optical and Raman spectroscopy data prove that NCs formed in silicon matrix have the structure and optical properties of β-FeSi₂. The growth conditions provide no dislocations in silicon lattice were found in the course of TEM analysis. Two types of NCs depth distribution were observed: (i) layered that corresponds to iron RDE and (ii) uniform that occurs in the case of iron SPE. The uniform NCs distribution points out the fact that during a growth process NCs moves up to the surface. In spite of small nanocrystallites size (5-50 nm) and their distribution in silicon cap layers the significant photoluminescence (PL) signal at 0.8 eV was observed for all grown samples.     

Simulations of Si and SiO2 etching in SF6 + O2 plasma

Chemical etching of Si and SiO₂ in SF₆ + O₂ plasma is considered. The concentrations of plasma components are calculated using values extrapolated from experimental data. Resulting calculations of plasma components are used for the calculation of Si and SiO₂ etching rates. It is found that the reaction constants for reactions of F atoms with Si atoms and SiO₂ molecules are equal to (3.5 ± 0.1) × 10⁻² and (3.0 ± 0.1) × 10⁻⁴, respectively. The influence of O₂ addition to SF₆ plasma on the etching rate of Si is quantified.     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Influence of plasma heating of wafer substrates on SiO2 deposition rate in a TEOS/O2 high-density plasma CVD system

The influence of plasma heating of the Si and glass wafer substrates on silicon dioxide (SiO₂) deposition rates by a tetraethylorthosilicate/O₂ supermagnetron (high-density) plasma CVD were investigated. With a fixed RF power of 100 W supplied to both upper and lower electrodes, the SiO₂ deposition rate on the Si wafer substrate decreased with increasing wafer-stage temperature, showing a negative activation energy for the deposition rate. When Si and glass wafers were attached to the electrode using adherent thermal conductors, the film thickness increased almost linearly with regard to the deposition time, and both deposition rates became almost the same (about 310 Å/min). When both wafers were simply laid on the electrode without an adhesive bond and hence with poor thermal contact, the film thickness increased nonlinearly with deposition time, showing a gradual decrease in deposition rate with time, being as low as 80 and 150 Å/min, respectively for Si and glass wafers, for a deposition time of 15 min. The difference between the two deposition rates on Si and glass wafers in the case of poor thermal contact to the lower electrode is thought to be caused by plasma heating and related mainly to differences in optical absorption characteristics of the two wafer substrates. Variations in measured thickness distributions across the substrate surface were attributed to an antisymmetric plasma density distribution in the direction perpendicular to the magnetic field lines caused by E×B electron drift.     

Characterisation of amorphous silica in air-oxidised Ti3SiC2 at 500–1000 °C using secondary-ion mass spectrometry,nuclear magnetic resonance and transmission electron microscopy

In this paper we have described the use of secondary-ion mass spectrometry (SIMS), solid state ²⁹Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) to detect the existence of amorphous silica in Ti₃SiC₂ oxidised at 500–1000 °C. The formation of amorphous SiO₂ and growth of crystalline TiO₂ with temperature was monitored using dynamic SIMS and synchrotron radiation diffraction. A duplex structure with an outer TiO₂-rich layer and an inner mixed layer of SiO₂ and TiO₂ was observed. Results of NMR and TEM verified for the first time the direct evidence of amorphous silica formation during the oxidation of Ti₃SiC₂ at the temperature range 500–1000 °C.     

Electroluminescence of as-sputtered silicon-rich SiOx films

Si-rich oxide films (SiO_x, 0 < x < 2) were synthesized by reactive magnetron sputtering of a single Si target in a gas mixture of argon and oxygen. Intense visible electroluminescence was observed from the as-deposited SiO_x film. The microstructure of the as-sputtered SiO_x films was characterized by Raman and X-ray photoelectron spectroscopy techniques. Nanoscale amorphous Si clusters formed in the as-sputtered films. The electroluminescence was attributed to the oxygen-deficient defect luminescent centres and the formation of the amorphous Si nanoclusters.     

Hot-wire chemical vapor deposition and characterization of p-type nanocrystalline Si films for thin film photovoltaic applications

P-type nanocrystalline Si (p-nc-Si) films were deposited by hot-wire chemical vapor deposition (HWCVD) system using SiH₄, B₂H₆, and H₂ as reactants. The effect of H₂ flow rate on the material properties of p-nc-Si films were investigated using Raman spectroscopy, X-ray diffractormeter, ultraviolet-visible-near infrared spectrophotometer, Fourier transform infrared spectroscopy, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). Moreover, the electrical properties, such as carrier concentration, activation energy, dark conductivity, and Hall mobility, of p-nc-Si films were also measured. It was found that H₂ flow rate played an important role in forming of p-nc-Si, decreasing the deposition rate, and increasing the crystallinity of p-nc-Si films. FESEM and TEM micrographs also showed the enhancement of crystallinity with adding H₂ flow rate. Furthermore, the change of microstructure at various H₂ flow rates was found to affect the electrical properties of p-nc-Si films. Details of the growth mechanism in p-nc-Si films will be discussed also. Moreover, the optimum p-nc-Si film was used as window layer in n-type crystalline Si heterojunction (HJ) solar cell. After the deposition parameters were optimized, the Si HJ solar cell with the open-circuit voltage of 0.58 V, short-circuit current density of 33.46 mA/cm², fill factor of 64.44%, and the conversion efficiency of 12.5% could be obtained.     

Preparation and analysis of amorphous carbon films deposited from (C6H12)/Ar/He chemistry for application as the dry etch hard mask in the semiconductor manufacturing process

Amorphous carbon layers (ACL) were deposited on Si (100) wafers by plasma enhanced chemical vapor deposition (PECVD) by using 1-hexene (C₆H₁₂) as a carbon source for dry etch hard mask of semiconductor devices manufacturing process. The deposition characteristics and film properties were investigated by means of ellipsometry, Raman spectroscopy, X-ray photo electron spectroscopy (XPS) and stress analysis. Hardness, Young's modulus, and surface roughness of ACL deposited at 550 °C were investigated by using nano-indentation and AFM. The deposition rate was decreased from 5050 Å/min to 2160 Å/min, and dry etch rate was decreased from 2090 Å/min to 1770 Å/min, and extinction coefficient was increased from 0.1 to 0.5. Raman analysis revealed a higher shift of the G-peak and a lower shift of the D-peak and the increase of I(D)/I(G) ratio as the deposition temperature was increased from 350 °C to 550 °C. XPS results of ACL deposited at 550 °C revealed a carbon 1s binding energy of 284.4 eV. The compressive film stress was decreased from 2.95 GPa to 1.28 GPa with increasing deposition temperature. The hardness and Young's modulus of ACL deposited at 550 °C were 5.8 GPa and 48.7 GPa respectively. The surface roughness RMS of ACL deposited at 550 °C was 2.24 Å, and that after cleaning in diluted HF solution (H₂O:HF = 200:1), SC1 (NH₄OH:H₂O₂:H₂O = 1:4:20) solution, and sulfuric acid solution (H₂SO₄:H₂O₂ = 6:1) was 2.28 Å, 2.30 Å and 7.34 Å, respectively. The removal amount of ACL deposited at 550 °C in diluted HF solution, SC1 solution and sulfuric acid solution was 6 Å, 36 Å and 110 Å, respectively. These results demonstrated the viability of ACL deposited by PECVD from C₆H₁₂ at 550 °C for application as the dry etch hard mask in fabrication of semiconductor devices.     

Fe3Si nanodots epitaxially grown on Si(111) substrates using ultrathin SiO2 film technique

Ultrahigh density (> 10¹² cm⁻²) Fe₃Si nanodots (NDs) are epitaxially grown on Si(111) substrates by codeposition of Fe and Si on the ultrathin SiO₂ films with ultrahigh density nanovoids. We used two kinds of methods for epitaxial growth: molecular beam epitaxy (MBE) and solid phase epitaxy. For MBE, low temperature (< 300 °C) growth of the Fe₃Si NDs is needed to suppress the interdiffusion between Fe atoms deposited on the surfaces and Si atoms in the substrate. These epitaxial NDs exhibited the ferromagnetism at low temperatures, which were expected in terms of the application to the magnetic memory device materials.     

Reactive magnetron sputtering from a composite target for large area BaPbO3 thin film electrode

Radio frequency reactive magnetron sputtering from a composite target made of PbO pellets uniformly positioned on a metallic Ba disc has been utilized for BaPbO₃ electrode deposition on 150 mm Si wafers. The reactive sputtering process has been analyzed in relation to sputtering parameters for composite targets with different percentage of PbO coverage. The process optimization method for in situ crystallized BaPbO₃ thin film fabrication has been emphasized. The growth of BaPbO₃ films has been discussed from the viewpoint of the BaO-PbO phase diagram and thermodynamics of Ba_n + 1Pb_nO_3n + 1 (n = 1, 2, ∞) phase formation. The microstructure analysis of the deposited films has been performed with atomic force microscopy and wide-angle X-ray diffraction (XRD) techniques. The grazing angle XRD measurements reveal the formation of a Ba₂PbO₄ phase in the film fabricated at 450 °C. The Ba₂PbO₄ phase content decreases with decreasing substrate temperature. The BaPbO₃ film deposited at a substrate temperature of 430 °C on naturally oxidized (001) Si wafers shows an electrical resistivity of 1.13 mΩ·cm. The BaPbO₃ films deposited on SiO₂ (native oxide)/Si wafer do not exhibit a preferred orientation whereas use of (111) Pt/SiO₂/Si substrate results in highly (111)-oriented films.     

GISAXS study of Si nanoclusters in SiO/SiO2 layers

We present a study on amorphous SiO/SiO₂ superlattice using grazing-incidence small-angle X-ray scattering (GISAXS). Such nanostructured material might be of great interest for photovoltaic conversion and optoelectronics. Amorphous SiO/SiO₂ superlattices were prepared by magnetron sputtering of thin SiO and SiO₂ films (20 layers each) on Si (1 0 0) substrate. Rotation of the Si substrate during evaporation ensures homogeneity of the films over the whole substrate. After the evaporation, the samples were annealed at 1100 °C for 1 h in vacuum. The analysis of the 2-D GISAXS pattern has shown that Si nanocrystals are formed in the remaining SiO₂ films in the annealed samples. From the 2-D GISAXS pattern, their shape, size and inter-particle distance are determined.     

Preparation and thermoelectric properties of nc-Si:(Al2O3 + SiO2) composite film

A composite film of nanocrystalline Si (nc-Si) embedded in (Al₂O₃ + SiO₂) has been prepared on a quartz substrate by thermally evaporating a 400 nm thick Al film on a quartz substrate and annealing in air at 580 °C for 1 h. During annealing, the Al reacts with the SiO₂ of the quartz substrate and produces nc-Si, which is embedded in the (Al₂O₃ + SiO₂) film. The average size of nc-Si is ~ 22 nm and the thickness of the nc-Si:(Al₂O₃ + SiO₂) composite film is ~ 810 nm. It is found that the prepared film is thermoelectric with a Seebeck coefficient of − 624 μV/K at 293 K and − 225 μV/K at 413 K.     

Ferroelectricity of ultrathin ferroelectric Langmuir-Blodgett polymer films on conductive LaNiO3 electrodes

LaNiO₃ (LNO) films with a surface roughness rms of 0.384 nm and a sheet resistance of about 200 Ω were prepared on SrTiO₃ and Si/SiO₂ substrates respectively by rf magnetron sputtering technique. The surface of LNO on Si/SiO₂ substrate is smoother than that on SrTiO₃ substrate. A nominal 2-monolayer (ML) poly(vinylidenefluoride-trifluoroethylene) film with a thickness of about 3 nm was deposited on LNO coated Si/SiO₂ substrate by Langmuir-Blodgett (LB) technology. Piezoresponse force microscopy (PFM) measurements show that the LB films demonstrate an obvious feature of polarization switching and good voltage durability. The results suggest that the ultrathin polymer films may be utilized to explore ferroelectric tunnel junctions.     

High-resolution X-ray photoemission spectroscopy study of AlN nano-columns grown by nitridation of Al nano-squares on Si(111) substrates with ammonia

The growth of AlN nano-columns by ammonium nitridation of Al nano-squares embedded in SiO₂ on Si(111) substrates was studied by high-resolution X-ray photoemission spectroscopy from a synchrotron radiation source and scanning electron microscopy (SEM). Selective nitridation of the Al nano-squares on the SiO₂ mask was obtained in the temperature window of 600 °C-700 °C. The well-shaped AlN nano-column arrays with diameters confined by the lateral size of the Al nano-squares (~ 100 nm) were observed in SEM.     

Optimization of silicon nanocrystals growth process by low pressure chemical vapor deposition for non-volatile memory application

The processes of silicon nanocrystals (Si-NCs) growth on both SiO₂ and Si₃N₄ substrates by low pressure chemical vapor deposition have been systematically investigated. A two-step process was adopted for Si-NCs growth: nucleation at a high temperature (580-600 °C) and growth at a low temperature (550 °C). By adjusting the pre-deposition waiting time and deposition time, the density, size and uniformity can be effectively controlled. Compared to the growth of Si-NCs on SiO₂, the coalescence speed of Si-NCs on Si₃N₄ is faster. Uniform Si-NCs with a high density of 1.02 × 10¹² cm^− 2 and 1.14 × 10¹² cm^− 2 have been obtained on SiO₂ and Si₃N₄, respectively. Finally, a Si-NCs-based memory structure with a 2.1 V memory window was demonstrated.     

Vacuum-ultraviolet reflectance difference spectroscopy for characterizing dielectrics-semiconductor interfaces

Reflectance difference spectroscopy (RDS) was applied to the characterization of SiO₂/Si, GeO₂/Ge, and high-k/III-V interface structures. We extended the spectral range of RDS to 8.4 eV in order to explore the optical transitions at the dielectrics-semiconductor interfaces as well as to have a high sensitivity to the interface anisotropy. Si surfaces with (110), (113), (331) and (120) orientations showed oxidation-induced RD changes in the vacuum-ultraviolet (VUV) range which were dependent on the surface orientation, oxidation method (dry or wet), and oxidation temperature. The Ge(110) surface also showed characteristic oxidation-induced changes in the VUV range, whereas Al₂O₃ deposition on GaAs(001) and InP(001) surfaces induced only the RD amplitude changes.     

Microscale meshes of Ti3O5 nano- and microfibers prepared via annealing of C-doped TiO2 thin films

A new technique to produce microscale Ti₃O₅ nano- and microfiber meshes is proposed. When a 3 wt% carbon-doped TiO₂ film on Si(1 0 0) was annealed at 1000 °C in wet nitrogen (0.8%H₂O), the amorphous TiO₂ phase gave rise to crystalline phases of λ-Ti₃O₅ (75%) and rutile + trace of TiO_2−xC_x (25%). From Raman and FTIR Spectroscopy results, it was concluded that rutile is formed at the inner layer located at the interface between the mesh and the Si that was located away from the surface such that the meshes of nano- and microfibers are predominantly composed of Ti₃O₅ grown from the reaction of rutile with Si to form Ti₃O₅ and SiO₂. On the other hand, it was noteworthy that the microscale mesh of nano- and microfibers showed increased photoluminescence compared with amorphous TiO₂. The PL spectrum which had a broad band in the visible spectrum, fitted as three broad Gaussian distributions centered at 571.6 nm (∼2.2 eV), 623.0 nm (∼2.0 eV) and 661.9 nm (∼1.9 eV).