Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

Structural changes studies of a-Si:H films deposited by PECVD under different hydrogen dilutions using various experimental techniques

Plasma enhanced chemical vapour deposition (PECVD) has been used to prepare hydrogenated amorphous silicon (a-Si:H) thin films at different hydrogen dilution of silane source gas. The films were deposited on Corning glass 1737 substrate and on (100) oriented c-Si wafers and characterized by XRD diffraction, micro-Raman and FTIR spectrometry. Experimental data show evolution from amorphous to nanocrystalline silicon and contain the medium-range order (MRO) with varying hydrogen dilution during deposition. From X-ray diffraction and Raman analysis, it is found that the presence of crystalline phase depends on the kind of substrate and on the dilution scale.     

The influence of substrate morphology on the growth of thin silicon films: A GISAXS study

Thin Si films, with thickness between 100 and 300 nm, were deposited by PECVD (Plasma Enhanced Chemical Vapour Deposition) in silane gas (SiH₄) highly diluted by hydrogen. The degree of dilution and the discharge power were varied in order to obtain different crystalline to amorphous fractions in the films. Two types of substrates were used. The first one was amorphous and relatively flat while the second one was polycrystalline with a roughness of a few tens of nanometers. The crystal fraction in the deposited samples, as estimated by Raman spectroscopy, varied between 0 and 40%, and the individual crystal size was between 2 and 8 nm. The larger individual crystals are usually present in those samples with the highest crystal fraction. The sample density, estimated upon the spectral distribution of the dielectric function in the infra red, was 15-25% less than the density of crystalline silicon. The GISAXS pattern of all of the examined samples indicated the presence of not-spherical-like “particles” in the “bulk” of the thin films, with an average “particle” size between 1.5 and 4 nm. These “particles” are most probably voids and their shape indicates columnar growth. By applying the GISAXS technique on samples deposited on different substrates, the borderline deposition conditions between “transport limited growth” and “growth dominantly influenced by plasma surface reactions” was estimated.     

SiNx薄膜中硅纳米粒子的制备及表征

通过等离子增强化学气相沉积(PECVD)法, 以氨气和硅烷为反应气体, P型单晶硅和石英为衬底, 低温下(200℃)制备了含硅纳米粒子的非化学计量比氮化硅(SiN_x)薄膜. 经高温(范围500~950℃)退火处理优化了薄膜结构. 室温下测试了不同温度退火后含硅纳米粒子SiN_x薄膜的拉曼(Raman)光谱、光致发光(PL)光谱及傅立叶变换红外吸收(FTIR)光谱, 对薄膜材料的结构特性、发光特性及其键合特性进行了分析. Raman光谱表明. SiN_x薄膜内的硅纳米粒子为非晶结构. PL光谱显示两条与硅纳米粒子相关的光谱带, 随退火温度的升高此两光谱带峰位移动方向相同. 当退火温度低于800℃时, PL光谱峰位随退火温度的升高而蓝移. 当退火温度高于800℃时, PL光谱峰位随退火温度的升高而红移. 通过SiNx薄膜的三种光谱分析发现薄膜的光致发光源于硅纳米粒子的量子限制效应. 这些结果对硅纳米粒子制备工艺优化和硅纳米粒子光电器件的应用有重要意义.     

High band gap nanocrystallite embedded amorphous silicon prepared by hotwire chemical vapour deposition

Hydrogenated silicon films ranging from pure amorphous to biphasic silicon i.e., nanocrystallites embedded amorphous silicon are prepared in an indigenously fabricated hot wire chemical vapor deposition chamber by varying the substrate temperature (T_s) and process pressure (PP). The deposition rates are found to be about 2.5-14 Å/s, which is very much appreciated for the fabrication of cost effective devices. While the films deposited at low T_s are amorphous in nature, those deposited at T_s ≥ 200 °C contain nanocrystallites embedded in the amorphous network. These mixed phase films show high crystalline fraction of 50-56%. All the films deposited at 250 °C, by varying PP, are nanocrystallite embedded with crystalline fraction 60-75%. The optical band gaps of the films (2.0-2.37 eV) are high compared to the regular films, whereas the hydrogen content remains in the reported range of 2.5-5 at.%. We attribute the high optical band gap to the improved order as well as the presence of low density amorphous tissues surrounding the grain boundary regions. The ease of depositing films with tunable band gap is useful for fabrication of tandem solar cells.     

Suppression of crystalline growth in silicon films deposited from hydrogen diluted silane using a layer-by-layer approach

Si:H films with a thickness of approximately 450 nm have been deposited with rf-PECVD using a plasma of silane diluted with hydrogen. The aim was to grow heterogeneous films without an amorphous to microcrystalline phase transition. A layer-by-layer scheme was applied in which thin interlayers deposited from pure silane are included with the intention to interrupt the crystalline growth that is characteristic to the deposition with hydrogen dilution of silane. Raman spectroscopy and TEM imaging have confirmed that the application of the amorphous interlayers results in a decrease of the crystalline fraction of the layer-by-layer films compared to films grown with continuous hydrogen dilution. Absorption coefficient spectra of the films before and after light soaking have been investigated.     

Microstructure characterization of microcrystalline silicon thin films deposited by very high frequency plasma-enhanced chemical vapor deposition by spectroscopic ellipsometry

We applied ex situ spectroscopic ellipsometry (SE) on silicon thin films across the a-Si:H/μc-Si:H transition deposited using different hydrogen dilutions at a high pressure by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). The optical models were based on effective medium approximation (EMA) and effective to estimate the thickness of the amorphous incubation layer and the volume fractions of amorphous, microcrystalline phase and void in μc-Si:H thin films. We obtained an acceptable data fit and the SE results were consistent with that from Raman spectroscopy and atomic force microscopy (AFM). We found a thick incubation layer in μc-Si:H thin films deposited at a high rate of ~ 5 Å/s and this microstructure strongly affected their conductivity.     

金属镍诱导p型多晶硅薄膜的光电性能研究

利用电子束蒸镀方法及重掺杂p型硅为蒸发源在K8玻璃衬底上沉积非晶硅薄膜,采用镍诱导晶化法在氮气氛围下进行退火处理制备出p型多晶硅薄膜.研究了不同温度热处理条件对p型多晶硅薄膜的光电性能的影响,通过霍尔测量、拉曼光谱、原子力显微镜、紫外-可见光吸收光谱等测试手段对薄膜进行分析.结果表明,随着晶化温度的提高晶化程度先增强后...     

N-type crystalline silicon films free of amorphous silicon deposited on glass by HCl addition using hot wire chemical vapour deposition

Since n-type crystalline silicon films have the electric property much better than those of hydrogenated amorphous and microcrystalline silicon films, they can enhance the performance of advanced electronic devices such as solar cells and thin film transistors (TFTs). Since the formation of amorphous silicon is unavoidable in the low temperature deposition of microcrystalline silicon on a glass substrate at temperatures less than 550 degrees C in the plasma-enhanced chemical vapour deposition and hot wire chemical vapour deposition (HWCVD), crystalline silicon films have not been deposited directly on a glass substrate but fabricated by the post treatment of amorphous silicon films. In this work, by adding the HCl gas, amorphous silicon-free n-type crystalline silicon films could be deposited directly on a glass substrate by HWCVD. The resistivity of the n-type crystalline silicon film for the flow rate ratio of [HCl]/[SiH4] = 7.5 and [PH3]/[SiH4] = 0.042 was 5.31 x 10(-4) ohms cm, which is comparable to the resistivity 1.23 x 10(-3) ohms cm of films prepared by thermal annealing of amorphous silicon films. The absence of amorphous silicon in the film could be confirmed by high resolution transmission electron microscopy.     

氢稀释比与衬底温度对硅基薄膜相变及其光电性能影响的研究

采用热丝辅助微波电子回旋共振化学气相沉积法(HWAMWECR-CVD),通过改变衬底温度及氢稀释比制备了系列硅基薄膜,研究了衬底温度及氢稀释比对薄膜由非晶相转晶相相变及其光电性能的影响。研究结果表明,当采用低温制备硅基薄膜时,衬底温度和氢稀释比的提高都有利于非晶相向晶相的转变,但提高氢稀释比对相变的影响更为显著;晶化比越高并不代表薄膜光电性能越好,95%氢稀释比条件下制备的微晶硅薄膜具有优良的光电性能。     

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cm s⁻¹ on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cm s⁻¹ on n- and p-type silicon.     

Incorporation of amorphous and microcrystalline silicon in n–i–p solar cells

We have investigated the material properties and n–i–p solar cell quality of hot-wire deposited amorphous and microcrystalline silicon. Although it is possible to make high quality amorphous silicon solar cells, occasionally many cells show shunting behavior. Therefore, better control over the variation in cell performance is needed. We prove that this behavior is correlated with the filament age and different methods for improving the reproducibility of the cell performance are presented. Furthermore, the influence of different deposition parameters of microcrystalline silicon layers on the material and solar cell properties was studied. Although some of these microcrystalline layers are porous and oxidize in air, an initial efficiency of 4.8% is obtained for an n–i–p cell on untextured stainless steel.     

Structural characterization of thin amorphous Si films

We present a study of structural changes occurring in thin amorphous silicon (a-Si). The a-Si films were deposited on single-crystalline Si substrates held at room temperature or 200 °C by magnetron sputtering of a Si target in pure Ar atmosphere, and therefore the films were hydrogen-free. All samples were annealed in vacuum and subsequently studied by EPR and GISAXS. A strong decrease in the dangling bonds content at lower annealing temperatures, and then an increase of it at around 550 °C, suggested significant structural changes. In parallel the samples were studied by GISAXS which confirmed changes at the nanometric scale attributed to voids in the material. A nice correlation of the results of the two techniques shows advantages of this approach in the analysis of structural changes in a-Si material.     

Large-grain polycrystalline silicon thin films obtained by low-temperature stepwise annealing of hydrogenated amorphous silicon

Large grained polycrystalline silicon thin films have been prepared by low-temperature solid phase crystallisation of sputter-deposited hydrogenated amorphous silicon (a-Si:H), with relatively short processing times, and a considerably low thermal budget. Various a-Si:H samples, deposited under different conditions and with varying hydrogen concentrations and hydrogen bonding configurations, were simultaneously annealed. Only a particular set of deposition conditions led to crystallisation. The a-Si:H thin film which was successfully crystallised was prepared in an argon-hydrogen mixture, in which the last few minutes of film deposition occurred in a hydrogen-rich atmosphere. For that film, the hydrogen concentration profile resulted in a much higher hydrogen content on the sample surface than in the bulk, and H-Si bonds were predominantly of the weak type. Crystallisation was accomplished by low-temperature stepwise annealing from 200°C to 600°C at 100°C steps, with samples being cooled down to room-temperature between each annealing step. This resulted in large grained (> 10 μm range) polycrystalline silicon after the 600°C annealing step for a 1.1 μm thick sample. Fourier transform infrared (FTIR) spectroscopy, elastic recoil detection analysis (ERDA) and scanning electron microscopy (SEM) techniques were used to analyse samples before and after crystallisation.     

Characterization of amorphous and nanostructured Si films by differential scanning calorimetry

Over the last 5 years, we have successfully applied differential scanning calorimetry (DSC) to study silicon thin films. The aim of this paper is to review our main results to give an overview of the possibilities offered by this technique, which is widely used to characterize solid state transformations. We will address some classical subjects related to the structure of pure and hydrogenated a-Si, such as the strength of the Si–H bond, hydrogen diffusion and the contribution of structural defects and strained bonds to the enthalpy of structural relaxation and crystallization. Special attention will be paid to the crystallization kinetics of films with structures ranging from pure amorphous to highly crystalline. Despite previous expectations, in films deposited at low temperature, the presence of nanocrystals embedded in the amorphous phase does not promote crystallization. In fact, the crystallization temperature is much higher than expected from a simple solid state epitaxy mechanism, which indicates low coupling between the amorphous and crystalline phases.     

Characterization of europium doped zinc aluminate luminescent coatings synthesized by ultrasonic spray pyrolysis process

Europium doped zinc aluminate (ZnAl₂O₄) photoluminescent films have been deposited by ultrasonic spray pyrolysis deposition process. Different substrate temperatures and doping concentrations in the start spraying solution were studied. It is observed that the crystalline structure of this material depends on the substrate temperature during deposition of the films. For low substrate temperatures, the deposited films are amorphous. When the substrate temperature is increased at 500 °C some peaks corresponding to hexagonal phase of ZnO (zincite) appears. At substrate temperatures of 550 °C, the crystalline structure of the ZnAl₂O₄:Eu films presents the close-packed face centered cubic phase. The excitation and emission spectra were obtained; for an excitation wavelength of 260 nm, all the photoluminescence (PL) spectra show peaks located at 589, 615, 652 and 700 nm. Concentration quenching of the PL occurs at activator concentrations greater than 0.85 at.% inside the deposited films. The PL intensity increases as the substrate temperature rises. In addition, the surface morphology features of the films, as a function of the deposition temperature, are shown.     

Electrical, optical and structural characterization of high-k dielectric ZrO2 thin films deposited by the pyrosol technique

High-k dielectric zirconium oxide (ZrO₂) thin films have been deposited on silicon substrates at temperatures from 400 to 600 °C using the spray pyrolysis technique. The films were deposited from two spraying solution concentrations (0.033 and 0.066 M) of zirconium acetylacetonate dissolved in N,N-dimethylformamide. These films were stoichiometric, transparent and with a very low surface roughness (5–40 ). The refractive index of these films was of the order of that obtained for a bulk material (2.12). Films deposited with high molar concentration presented the best electrical characteristic, have a dielectric constant in the range 12.5–17.5, depending on the deposition temperature, and can stand electric fields up to 3 MV cm^–1 without observing destructive dielectric breakdown. Transmission electron microscopy measurements, indicate that the films consist of nano-crystallites of the tetragonal ZrO₂ crystalline phase embedded into an amorphous matrix. Infrared spectroscopy measurements of the films show peaks associated with ZrO₂ and a peak related to silicon dioxide (SiO₂). The analysis of spectroscopic ellipsometry measurements on these films indicates the existence of a layer at the ZrO₂/Si interface composed of SiO₂ as well as ZrO₂ and crystalline silicon.     

Thin film deposition on plastic substrates using silicon nanoparticles and laser nanoforming

Reduced melting temperature of nanoparticles is utilized to deposit thin polycrystalline silicon (c-Si) films on plastic substrates by using a laser beam without damaging the substrate. An aqueous dispersion of 5 nm silicon nanoparticles was used as precursor. A Nd:YAG (1064 nm wavelength) laser operating in continuous wave (CW) mode was used for thin film formation. Polycrystalline Si films were deposited on flexible as well as rigid plastic substrates in both air and argon ambients. The films were analyzed by optical microscopy for film formation, scanning electron microscopy (SEM) for microstructural features, energy dispersive spectroscopy (EDS) for impurities, X-ray photoelectron spectroscopy (XPS) for composition and bond information of the recrystallized film and Raman spectroscopy for estimating shift from amorphous to more crystalline phase. Raman spectroscopy showed a shift from amorphous to more crystalline phases with increasing both the laser power and irradiation time during laser recrystallization step.     

Amorphous silicon carbide thin films (a-SiC:H) deposited by plasma-enhanced chemical vapor deposition as protective coatings for harsh environment applications

We investigated amorphous silicon carbide (a-SiC:H) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) as protective coatings for harsh environment applications. The influence of the deposition parameters on the film properties was studied. Stoichiometric films with a low tensile stress after annealing (< 50 MPa) were obtained with optimized parameters. The stability of a protective coating consisting of a PECVD amorphous silicon oxide layer (a-SiO_x) and of an a-SiC:H layer was investigated through various aging experiments including annealing at high temperatures, autoclave testing and temperature cycling in air/water vapor environment. A platinum-based high-temperature metallization scheme deposited on oxidized Si substrates was used as a test vehicle. The a-SiO_x/a-SiC:H stack showed the best performance when compared to standard passivation materials as amorphous silicon oxide or silicon nitride coatings.