Optical properties and crystallinity of hydrogenated nanocrystalline silicon (nc-Si:H) thin films deposited by rf-PECVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films prepared in a home-built radio-frequency (rf) plasma enhanced chemical vapour deposition (PECVD) system have been studied. The rf powers were fixed in the range of 5 W-80 W. The optical properties and crystallinity of the films were studied by X-ray diffraction (XRD), Micro-Raman scattering spectroscopy, high resolution transmission electron microscope (HRTEM), and optical transmission and reflection spectroscopy. The XRD and Micro-Raman scattering spectra were used to investigate the evidence of crystallinity in order to determine the crystallite sizes and crystalline volume fraction in the films. The HRTEM image of the film was used to correlate with the crystallinity that was determined from XRD and Micro-Raman scattering spectra. Optical constants such as refractive index, optical energy gap, Tauc slope, Urbach energy and ionic constants were obtained from the optical transmission and reflectance spectra. From the results, it was interesting to found that the optical constants showed a good correlation with the crystallinity within the variation of rf power. Also, the ionic constants of the films showed an indication of the degree of crystallinity in the films. The variation of the optical energy gap with the rf power based on structure disorder and the quantum confinement effect is discussed.     

Nanocrystalline silicon films with high conductivity and the application for PIN solar cells

Intrinsic nanocrystalline silicon films (nc-Si:H) were prepared by plasma enhanced chemical vapor deposition (PECVD) method. Films’ microstructures and characteristics were studied with Raman spectroscopy and Atom Force Microscope (AFM). The electronic conductivity of nc-Si:H films was found to be 4.9×10⁰Ω⁻¹ cm⁻¹, which was one order of magnitude higher thanthe reported 10⁻³-10⁻¹ Ω⁻¹ cm⁻¹. And PIN solar cells with nc-Si:H film as intrinsic thin-layer (ITO/n⁺-nc-Si:H/i-nc-Si:H/p-c-Si/Ag) were researched. The cell's performances were measured, the open-circuit voltage V_oc was 534.7 mV, short-circuit current I_sc was 49.24 mA (3 cm²) and fill factor FF was 0.4228.     

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.     

射频功率对RF-PECVD法制备纳米硅薄膜结构特征和光学特性的影响

利用射频等离子体增强型化学气相沉积(RF-PECVD)工艺,以SiH4和H2作为反应气体源,在石英衬底上制备了氢化纳米硅(nc-Si∶H)薄膜。其中衬底温度为250℃,H2稀释比为99%,反应压强为133Pa和射频功率为20～60W。采用α-台阶仪、X射线衍射仪(XRD)、Raman光谱仪、傅立叶变换红外光谱仪(FT-IR)和紫外-可见光分光光度计等对薄膜的结构特征和光学特性进行了测试研究。结果表明,随着射频功率的增大,nc-Si∶H薄膜的沉积速率增加,晶化率提高,晶粒尺寸增大和氢含量减小,同时薄膜的吸收系数增强,光学带隙变窄,结构有序性增强和带尾态宽度减小。     

Phosphorous and boron doping of nc-Si:H thin films deposited on plastic substrates at 150 °C by Hot-Wire Chemical Vapor Deposition

Gas-phase phosphorous and boron doping of hydrogenated nanocrystalline thin films deposited by HWCVD at a substrate temperature of 150 °C on flexible-plastic (polyethylene naphthalate, polyimide) and rigid-glass substrates is reported. The influence of the substrate, hydrogen dilution, dopant concentration and film thickness on the structural and electrical properties of the films was investigated. The dark conductivity of B- and P-doped films (σ_d = 2.8 S/cm and 4.7 S/cm, respectively) deposited on plastic was found to be somewhat higher than that found in similar films deposited on glass. n- and p-type films with thickness below ∼ 50 nm have values of crystalline fraction, activation energy and dark conductivity typical of doped hydrogenated amorphous silicon. This effect is observed both on glass and on plastic substrates.     

Characteristics of hydrogenated silicon thin film deposited by RF-PECVD using He-SiH4 mixture

Nanocrystalline silicon thin films (nc-Si:H) were deposited using He as the dilution gas instead of H₂ and the effect of the operating pressure and rf power on their characteristics was investigated. Especially, operating pressures higher than 4 Torr and a low SiH₄ containing gas mixture, that is, SiH₄(3 sccm)/He(500 sccm) were used to induce high pressure depletion (HPD) conditions. Increasing the operating pressure decreased the deposition rate, however at pressures higher than 6 Torr, crystallized silicon thin films could be obtained at an rf power of 100 W. The deposition of highly crystallized nc-Si:H thin film was related to the HPD conditions, where the damage is decreased through the decrease in the bombardment energy at the high pressure and the crystallization of the deposited silicon thin film is increased through the increased hydrogen content in the plasma caused by the depletion of SiH₄. When the rf power was set at a fixed operating pressure of 6 Torr, HPD conditions were obtained in the rf power range from 80 to 100 W, which was high enough to dissociate SiH₄ fully, but meantime low enough not to damage the surface by ion bombardment. At 6 Torr of operating pressure and 100 W of rf power, the nc-Si:H having the crystallization volume fraction of 67% could be obtained with the deposition rate of 0.28 nm/s.     

Hydrogen plasma treatment of very thin p-type nanocrystalline Si films grown by RF-PECVD in the presence of B(CH3)3

Abstract

We have characterized the structure and electrical properties of p-type nanocrystalline silicon films prepared by radio-frequency plasma-enhanced chemical vapor deposition and explored optimization methods of such layers for potential applications in thin-film solar cells. Particular attention was paid to the characterization of very thin (～20 nm) films. The cross-sectional morphology of the layers was studied by fitting the ellipsometry spectra using a multilayer model. The results suggest that the crystallization process in a high-pressure growth regime is mostly realized through a subsurface mechanism in the absence of the incubation layer at the substrate-film interface. Hydrogen plasma treatment of a 22-nm-thick film improved its electrical properties (conductivity increased more than ten times) owing to hydrogen insertion and Si structure rearrangements throughout the entire thickness of the film.     

Hydrogen plasma treatment of very thin p-type nanocrystalline Si films grown by RF-PECVD in the presence of B(CH3)3

We have characterized the structure and electrical properties of p-type nanocrystalline silicon films prepared by radio-frequency plasma-enhanced chemical vapor deposition and explored optimization methods of such layers for potential applications in thin-film solar cells. Particular attention was paid to the characterization of very thin (∼20 nm) films. The cross-sectional morphology of the layers was studied by fitting the ellipsometry spectra using a multilayer model. The results suggest that the crystallization process in a high-pressure growth regime is mostly realized through a subsurface mechanism in the absence of the incubation layer at the substrate-film interface. Hydrogen plasma treatment of a 22-nm-thick film improved its electrical properties (conductivity increased more than ten times) owing to hydrogen insertion and Si structure rearrangements throughout the entire thickness of the film.     

Properties of nitrogen diluted hydrogenated amorphous carbon (n-type a-C:H) films and their realization in n-type a-C:H/p-type crystalline silicon heterojunction diodes

Nitrogen incorporated hydrogenated amorphous carbon (a-C:N:H) films were grown in an asymmetric rf PECVD system using C₂H₂ and N₂ gaseous mixture. Deposition rate, stress, hardness, optical bandgap, refractive index, and electrical characteristics have been studied as a function of self bias. Microstructures of these films were also studied using LASER Raman technique. Finally nitrogen diluted a-C:H films were realized as n-type semiconductor in n-type a-C:H/p-type crystalline silicon hetrojunction diodes. Current-voltage (I-V) and capacitance-voltage (C-V) characteristics have also been studied as a function of self bias on these heterojunction diodes.     

Nanostructure, electrical and optical properties of p-type hydrogenated nanocrystalline silicon films

In this paper, p-type hydrogenated nanocrystalline (nc-Si:H) films were prepared on corning 7059 glass by plasma-enhanced chemical vapor deposition (PECVD) system. The films were deposited with radio frequency (RF) (13.56 MHz) power and direct current (DC) biases stimulation conditions. Borane (B₂H₆) was a doping agent, and the flow ratio η of B₂H₆ component to silane (SiH₄) was varied in the experimental. Films’ surface morphology was investigated with atomic force microscopy (AFM); Raman spectroscopy, X-ray diffraction (XRD) was performed to study the crystalline volume fraction X_c and crystalline size d in films. The electrical and optical properties were gained by Keithly 617 programmable electrometer and ultraviolet-visible (UV-vis) transmission spectra, respectively. It was found that: there are on the film surface many faulty grains, which formed spike-like clusters; increasing the flow ratio η, crystalline volume fraction X_c decreased from 40.4% to 32.0% and crystalline size d decreased from 4.7 to 2.7 nm; the optical band gap E_g^opt increased from 2.16 to 2.4 eV. The electrical properties of p-type nc-Si:H films are affected by annealing treatment and the reaction pressure.     

Preparation and photoluminescence of nanocrystalline Si-rich silicon oxide films by PECVD

Nanocrystalline Si-rich silicon oxide films were deposited using plasma enhanced chemical vapor deposition technique with the mixture of silane (SiH₄), nitrous oxide (N₂O) and hydrogen (H₂) as gas source on quartz glass substrate at the substrate temperature of 300 °C. The effect of the ratio N₂O/SiH₄ on the oxidation, microstructures and photoluminescence (PL) of the as-deposited Si-rich silicon oxide films was investigated with FTIR, XRD and HRTEM. The results reveal that with the increasing ratio of N₂O/SiH₄, more amounts of oxygen are incorporated in the as-deposited films and more nanosized silicon particles are embedded in the films, forming nanocrystalline Si-rich silicon oxide films. The quantum confinement effect or the cooperation of quantum confinement and luminescence center results in the nanocrystalline Si-rich silicon oxide films of higher PL intensity.     

Copper doped nickel oxide transparent p-type conductive thin films deposited by pulsed plasma deposition

Transparent p-type conductive Ni_0.9Cu_0.1O thin films were prepared by pulsed plasma deposition (PPD) method. The effects of substrate temperature and oxygen pressure on the structural, electrical and optical properties of the films were investigated respectively. The film deposited at room temperature exhibits the highest conductivity of 5.17 S cm⁻¹, with an average transmittance of 60% in the visible region. A transparent p-Ni_0.9Cu_0.1O/n-In₂O₃:W (IWO) hetero-junction diode was fabricated exhibiting rectifying current-voltage characteristics.     

螺旋波等离子体沉积纳米硅薄膜结构特性

采用螺旋波等离子体化学气相沉积(HWPCVD)技术,以SiH4作为源反应气体在Si(100)和玻璃衬底上制备了纳米Si薄膜。通过X射线衍射(XRD)、Raman光谱、原子力显微镜(AFM)对所制备的材料结构和形貌等特性进行表征,分析了纳米Si薄膜结构随衬底温度变化的规律。实验结果表明,在较低的衬底温度(100-300℃)范围内,可以实现高晶化度纳米Si薄膜的沉积,颗粒大小在4-8nm之间,样品的晶化度随着衬底温度升高而升高,晶粒大小也随之增大,样品表面光滑,晶粒分布均匀。     

Hot wire configuration for depositing device grade nano-crystalline silicon at high deposition rate

The University of Barcelona is developing a pilot-scale hot wire chemical vapor deposition (HW-CVD) set up for the deposition of nano-crystalline silicon (nc-Si:H) on 10 cm × 10 cm glass substrate at high deposition rate. The system manages 12 thin wires of 0.15-0.2 mm diameter in a very dense configuration. This permits depositing very uniform films, with inhomogeneities lower than 2.5%, at high deposition rate (1.5-3 nm/s), and maintaining the substrate temperature relatively low (250 °C). The wire configuration design, based on radicals’ diffusion simulation, is exposed and the predicted homogeneity is validated with optical transmission scanning measurements of the deposited samples. Different deposition series were carried out by varying the substrate temperature, the silane to hydrogen dilution and the deposition pressure. By means of Fourier transform infrared spectroscopy (FTIR), the evolution in time of the nc-Si:H vibrational modes was monitored. Particular importance has been given to the study of the material stability against post-deposition oxidation.     

Optical properties of nanocrystalline ZnS films prepared by high pressure magnetron sputtering

Nanocrystalline ZnS films with different thickness (10–40 nm) were deposited onto quartz and NaCl substrates by magnetron sputtering of a ZnS target in argon plasma. All the films showed a zinc blende structure and the photoluminescence peak positions depended on the surface to volume ratio of the films. The optical absorption in these films could be explained by the combined effects of phonon and inhomogeneity broadening along with optical loss due to light scattering at the nanocrystallites.     

Highly conductive microcrystalline silicon carbide films deposited by the hot wire cell method and its application to amorphous silicon solar cells

Microcrystalline silicon carbide (μc-Si_1−xC_x) films were successfully deposited by the hot wire cell method using a gas mixture of SiH₄, H₂ and C₂H₂. It was confirmed by Fourier transform infrared and X-ray diffraction analyses that the films consisted of μc-Si grains embedded in a-Si_1−xC_x tissue. The p-type μc-Si_1−xC_x films were deposited using B₂H₆ as a doping gas. A dark conductivity of 0.2 S/cm and an activation energy of 0.067 eV were obtained. The p-type μc-Si_1−xC_x was used as a window layer of a-Si solar cells, in which the intrinsic layer was deposited by photo-chemical vapor deposition, and an initial conversion efficiency of 10.2% was obtained.     

Residual stress on nanocrystalline silicon thin films deposited under energetic ion bombardment by using internal ICP-CVD

Nano/microcrystalline silicon thin films were deposited using an internal-type, inductively coupled, plasma-chemical vapor deposition (ICP-CVD) at room temperature by varying the bias power to the substrate. The structural characteristics of the deposited thin film were investigated. The deposition rate was increased by the application of a small RF bias power of 30 W (12.56 MHz), but was then decreased as the bias power was increased above 30 W. In addition, the application of bias power generally increased the residual compressive stress, which was attributed to the increased defect formation in the thin film due to the formation of interstitial atoms. The crystalline volume fraction was also decreased with increasing bias power. However, in the low bias power range of 0-60 W, the compressive stress in the deposited thin film was in the range of − 34 to − 77 MPa, which was lower than the residual stress in the range of − 150 to − 1050 MPa that is observed for the nano/microcrystalline silicon thin films deposited by capacitively coupled plasma.     

Highly reflective nc-Si:H/a-CNx:H multilayer films prepared by r.f. PECVD technique

Multilayer thin films consisting of a-CN_x:H/nc-Si:H layers prepared by radio-frequency plasma enhanced chemical vapour (r.f. PECVD) deposition technique were studied. High optical reflectivity at a specific wavelength is one of major concern for its application. By using this technique, a-CN_x:H/nc-Si:H multilayered thin films (3-11 periods) were deposited on substrates of p-type (111) crystal silicon and quartz. These films were characterized using ultra-violet-visible-near infrared (UV-Vis-NIR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, field effect scanning electron microscopy (FESEM) and AUGER electron spectroscopy (AES). The multilayered films show high reflectivity and wide stop band width at a wavelength of approximately 650 ± 60 nm. The FTIR spectrum of this multilayered structure showed the formation of Si-H and Si-H₂ bonds in the nc-Si:H layer and CC and N-H bonds in a-CN_x:H layer. SEM image and AES reveal distinct formation of a-CN_x:H and nc-Si:H layers in the cross section image with a decrease in interlayer cross contamination with increasing number of periods.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

射频PECVD法高压快速制备纳米晶硅薄膜

采用传统的射频等离子体增强化学气相沉积技术,在较高的工作气压(133～266Pa)下,以0.4nm/s速率制备出优质的氢化纳米晶硅薄膜.薄膜的晶化率约60%,平均晶粒尺寸约6.0nm,暗电导率为10-3～104/Ω·cm.红外吸收谱显示,薄膜中没有Si-O、Si-C、Si-N等杂质键,随晶化率的提高,Si-H键也逐渐消失.