X-ray photoelectron spectroscopy investigations of Si in non-stoichiometric SiNx LPCVD multilayered coatings

Si nanocrystals were formed in the non-stoichiometric Si-enriched SiN_x low-pressure chemical vapor deposited (LPCVD) coatings on Si wafers treated by various modes. The coating structure as a function of technological conditions was investigated by ellipsometry and X-ray photoelectron spectroscopy (XPS) depth profiling. It was found that nanocomposites on base of SiN_x films enriched by Si have a complex multilayered structure varying in dependence of deposition and annealing parameters. Analysis of the XPS spectra and Si 2s peaks shows the existence and quantity of four chemical structures corresponding to the Si–O, Si–N states, nanocrystalline and amorphous Si. The XPS results show evolution of the chemical structure of silicon nitride and formation of Si nanocrystals. It was found:

• The LPCVD technology of nanocrystals formation allows to get enough high concentration of Si nanocrystals on different depths from the sample surface.

• The volume fraction of nanocrystalline and amorphous Si is changed with depth; this relation depends from SiN_x composition and annealing parameters.

• XPS detects these two phase compositions of Si nanoparticles in SiN_x and SiO₂ layers. The ellipsometry, HR-TEM, and XPS results are in good agreement.

Electrons diffusion study on the nitrogen-doped nanocrystalline diamond film grown by MPECVD method

Nitrogen-doped nanocrystalline diamond (NNCD) films were deposited onto p-type silicon substrates with three different layer structures: (i) directly onto the silicon substrate (NNCD/Si), (ii) silicon with undoped nanocrystalline diamond layer which was deposited in the same way as the above mentioned NNCD by the recipe Ar/CH₄/H₂ with a ratio of 98%/1%/1% (NNCD/NCD/Si), and (iii) silicon wafer with 100 nm thickness SiO₂ layer (NNCD/SiO₂/Si). Atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy were employed to characterize the morphology and microstructure of the as-grown nitrogen-doped diamond films. Silver colloid/silver contacts were made at to measure the current-voltage (I-V) characteristics for the three different structures. Electrons from a CVD reactor hydrogen plasma diffuse toward the p-type silicon substrate during a deposition process under the high temperature (∼800 °C). The study concluded that the SiO₂ layer could effectively prevents the diffusion of electrons.     

Preparation of a Single Layer of Luminescent Nanocrystalline Si Structures by Laser Irradiation Method

KrF excimer laser annealing on ultrathin hydrogenated amorphous Si films with various initial Si thicknesses is carried out to obtain a single layer of nanocrystalline Si structures. It is found that Si nanograins can be obtained with the area density as high as 10^11 cm^-2 under the irradiation with suitable laser fluence. Raman and planar transmission electron microscopy are used to characterize the formation process of Si nanocrystals from amorphous phase. Moreover, a strong photoluminescence is observed at room temperature from well-relaxed nanocrystalline Si structures.     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

The role of microstructure in luminescent properties of Er-doped nanocrystalline Si thin films

In this contribution, we present a structural and photoluminescence (PL) analysis of Er-doped nanocrystalline silicon thin films produced by rf magnetron sputtering method. We show the strong influence of the presence of nanocrystalline fraction in films on their luminescence efficiency at 1.54 μm studied on a series of specially prepared samples with different crystallinity, i.e., percentage and sizes of Si nanocrystals. A strong increase, by about two orders of magnitude, of Er-related PL intensity in these samples with lowering of the Si nanocrystal sizes from 7.9 to about 1.5 nm is observed. The results are discussed in terms of the sensitization effect of Si nanocrystals on Er ions. From Fizika Tverdogo Tela, Vol. 46, No. 1, 2004, pp. 114–118. Original English Text Copyright ? 2004 by Stepikhova, Cerqueira, Losurdo, Giangregorio, Alves, Monteiro, Soares. This article was submitted by the authors in English.     

Reaction between amorphous Si and crystalline Al in Al/Si and Si/Al bilayers: microstructural and thermodynamic analysis of layer exchange

Aluminium-induced crystallization of amorphous silicon (a-Si) in Al/Si and Si/Al bilayers was studied upon annealing at 250 °C by X-ray diffraction and Auger electron spectroscopy. The Al/a-Si bilayers and a-Si/Al bilayers were prepared by sputter deposition on single-crystal silicon wafers with a silicon-oxide film on top. During the isothermal annealing a layer-exchange process occurred in both types of bilayers. A continuous polycrystalline silicon (poly-Si) film was formed within, and thereby gradually replacing, the initial Al metal layer. The sublayer sequence in the original bilayer influenced the speed of the poly-Si formation and the layer-exchange process. After annealing, the Al fiber texture in the as-deposited bilayers had become stronger, the Al crystallites had grown laterally, and the macrostress in the Al layer had been released. The amorphous Si layer had crystallized into an aggregate of nanocrystals with {111} planes parallel to the surface, with a crystallite size of about 15–25 nm. An extensive analysis of the Gibbs energy change due to annealing showed that the layer exchange may be promoted by the release of elastic energy and grain growth for the Al phase. PACS 05.70.Jk; 61.43.Dq; 68.35.Rh; 61.72.Cc; 68.55.Jk     

Electrochemical and hydrothermal deposition of ZnO on silicon: from continuous films to nanocrystals

This article presents the study of the electrochemical deposition of zinc oxide from the non-aqueous solution based on dimethyl sulfoxide and zinc chloride into the porous silicon matrix. The features of the deposition process depending on the thickness of the porous silicon layer are presented. It is shown that after deposition process the porous silicon matrix is filled with zinc oxide nanocrystals with a diameter of 10–50 nm. The electrochemically deposited zinc oxide layers on top of porous silicon are shown to have a crystalline structure. It is also shown that zinc oxide crystals formed by hydrothermal method on the surface of electrochemically deposited zinc oxide film demonstrate ultra-violet luminescence. The effect of the porous silicon layer thickness on the morphology of the zinc oxide is shown. The structures obtained demonstrated two luminescence bands peaking at the 375 and 600 nm wavelengths. Possible applications of ZnO nanostructures, porous and continuous polycrystalline ZnO films such as gas sensors, light-emitting diodes, photovoltaic devices, and nanopiezo energy generators are considered. Aspects of integration with conventional silicon technology are also discussed.     

基于纳米硅结构的氮化硅基发光器件电致发光特性研究

利用等离子体增强化学气相沉积法制备了镶嵌于氮化硅的高密度纳米硅薄膜,并以此作为发光有源层构建基于p-Si/氮化硅基发光层/AZO结构发光二极管,在室温下观察到了电致可见发光.在此基础上,在器件p-Si空穴注入层与氮化硅基发光层之间加入纳米硅薄层作为空穴阻挡层,研究器件电致发光性质,实验结果表明器件的发光强度显著增强,并且发光效率较无纳米硅阻挡层的发光器件提高了80%以上.     

Optical and structural properties of nanocrystalline PbS thin film grown by CBD on Si(1 0 0) substrate

PbS nanocrystalline thin film was prepared by chemical bath deposition on Si(1?0?0) substrate at bath temperatures of 25, 45 and 65 °C. Triethanolamine was added to the aqueous solution, which decreased the grain size and increased the luminescence of the nanocrystalline PbS thin film. PbS nanocrystals were identified using XRD, TEM and AFM. The crystalline size of the PbS film deposited at different bath temperatures was estimated by XRD and TEM to be 7–12 nm. The growth mechanism of the PbS crystallites were described at different bath temperatures. The confinement was reflected in the absorption spectra, photoluminescence excitation and photoluminescence spectra. The luminescence of Si(1?0?0) substrate and PbS nanocrystalline film deposited on Si(1?0?0) were compared, and the results revealed that the PbS nanocrystals altered and notably enhanced the emission features of the Si(1?0?0) substrate. The shifting of the maximum photoluminescence emission wavelength of PbS nanocrystals with a change in bath temperature and the variation in photoluminescent intensity of PbS nanocrystals prepared at 25 °C versus deposition time were investigated. A single-peak fit of a Gaussian function was employed to discern the photoluminescence of PbS on Si(1?0?0) substrate.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

Electrical behavior of size-controlled Si nanocrystals arranged as single layers

A metal–oxide–semiconductor structure containing a single layer of size-controlled silicon nanocrystals embedded into gate oxide was fabricated. Size control for the silicon nanocrystals was realized by using a SiO₂/SiO/SiO₂ layer structure with the embedded SiO layer having the thickness of the desired Si nanocrystals and using a high-temperature annealing for forming the silicon nanocrystals. Current–voltage, capacitance–voltage, and conductance–voltage characteristics were measured for a sample containing 4-nm-sized crystals. From the Fowler–Nordheim plot an effective barrier height of 1.6 eV is estimated for our silicon nanocrystals. Electron trapping, storing, and de-trapping in silicon nanocrystals were observed by capacitance–voltage and conductance–voltage measurements. The charge density was measured to be 1.6×10¹² /cm², which is nearly identical to the silicon-nanocrystal density measured approximately via a transmission electron microscopy image. Conductance measurements reveal a very low interface charge of our structure. PACS 72.80.Sk; 73.63.Bd; 73.40.Qv     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Dependence of Optical Absorption in Silicon Nanostructures on Size of Silicon Nanoparticles

The amorphous silicon nanoparticles (Si NPs) embedded in silicon nitride (SiN_x) films prepared by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique are studied. From Raman scattering investigation, we determine that the deposited film has the structure of silicon nanocrystals embedded in silicon nitride (nc-Si/SiNx) thin film at a certain hydrogen dilution amount. The analysis of optical absorption spectra implies that the Si NPs is affected by quantum size effects and has the nature of an indirect-band-gap semiconductor. Further, considering the effects of the mean Si NP size and their dispersion on oscillator strength, and quantum-confinement, we obtain an analytical expression for the spectral absorbance of ensemble samples. Gaussian as well as lognormal size-distributions of the Si NPs are considered for optical absorption coefficient calculations. The influence of the particlesize-distribution on the optical absorption spectra was systematically studied. We present the fitting of the optical absorption experimental data with our model and discuss the results.     

Structure and electronic properties of nanoscale phases and nanofilms of metal silicides produced by ion implantation in combination with annealing

It is established that ion implantation in combination with annealing makes it possible to produce regularly arranged nanocrystalline phases and continuous films of metal silicides in the surface region of Si. It is shown that silicide nanocrystals and nanofilms crystallize in the cubic lattice. A model of a Si surface with silicide nanocrystals is developed.     

Optical properties of nanocrystalline silicon thin films produced by size-selected cluster beam deposition

Molecular beams of size-selected silicon clusters were used to grow nanocrystalline thin films. This technique allows the control of both average size and size dispersion of Si nanocrystals, and is then very useful to provide model materials for the study of the luminescence in silicon. We report results obtained by high-resolution electron microscopy, Raman spectrometry and photoluminescence spectroscopy.     

纳米晶硅薄膜中氢含量及键合模式的红外分析

采用传统射频等离子体化学气相沉积技术在100—350℃的衬底温度下高速沉积氢化硅薄膜. 傅里叶变换红外光谱和Raman谱的研究表明,纳米晶硅薄膜中的氢含量和硅氢键合模式与薄膜的晶化特性有密切关系,当薄膜从非晶相向晶相转变时,氢的含量减少了一半以上,硅氢键合模式以SiH₂为主. 随着衬底温度的升高和晶化率的增加,纳米晶硅薄膜中氢的含量以及其结构因子逐渐减少. 关键词： 氢化纳米晶硅薄膜 红外透射谱 氢含量 硅氢键合模式     

Features of atomic and electronic structure of oxides on porous silicon surface according to XANES data

Based on synchrotron research of the fine structure main parameters of SiL _{2, 3} X-ray absorption edges (X-ray absorption near edge structure (XANES)) in porous silicon on boron-doped Si(100) wafers, the thickness of the surface oxide layer and the degree of distortions of the silicon-oxygen tetrahedron in this layer were estimated. The thickness of the oxide layer formed on the amorphous layer coating nanocrystals of porous silicon exceeds the thickness of the native oxide on the surface of Si(100) : P and Si(100) : B single-crystal (100) silicon wafers by several times. Distortion of the silicon-oxygen tetrahedron, i.e., the basic unit of silicon oxide, is accompanied by Si-O bond stretching and an increase in the angle between Si-O-Si bonds.     

Laser type of spectral narrowing in electroluminescent Si/SiO2superlattices prepared by low-pressure chemical vapour deposition

Si/ SiO₂superlattices were fabricated by low-pressure chemical vapour deposition. Superlattices of 75–150 nm layer pair thicknesses and having 1–8 layer pairs were investigated in order to evaluate their surface structure and electroluminescent properties. Atomic force microscopy (AFM) studies were performed in order to investigate the surface morphology of a thin SiO₂layer and to evaluate the sizes of polysilicon nanocrystals grown onto the top of it. The current–voltage characteristics and the electroluminescence spectra are also shown. We have observed a blueshift of over 200 nm in the electroluminescence peak wavelength by increasing the driving current. The change in the direction of the driving current through a sample changes the peak wavelength from the yellow to red region. In some samples, we could detect an exponential increase in light intensity in current densities near 100 mA per square millimeter. The increase in intensity is combined with a very prominent spectral narrowing of the electroluminescence spectra. The half width of this spectral peak was less than 5 nm. It is possible that we have observed for the first time a laser type of mechanism in semiconductor structures made solely of silicon and silicon dioxide.     

Growth and optical properties of filamentary GaN nanocrystals grown on a hybrid SiC/Si(111) substrate by molecular beam epitaxy

The potential to grow filamentary GaN nanocrystals by molecular beam epitaxy on a silicon substrate with a nanosized buffer layer of silicon carbide has been demonstrated. Morphological and optical properties of the obtained system have been studied. It has been shown that the intensity of the photoluminescence spectrum peak of such structures is higher than that of the best filamentary GaN nanocrystals without the buffer silicon carbide layer by a factor of more than two.