Excimer laser crystallization of microcrystalline silicon for TFTs on flexible substrate

Microcrystalline silicon (μc-Si) films have been deposited on PDMS as well as on PEN substrate. Excimer laser annealing was used to improve the crystalline structure and so to obtain high mobility TFTs. The effect of the laser annealing on the crystalline structure of silicon films is studied using different characterization techniques and discussed. Mobility values of 60 cm²/V s with PDMS and 46 cm²/V s with PEN are obtained.     

Characteristics of p-type nanocrystalline silicon thin films developed for window layer of solar cells

Different rf-power and chamber pressures have been used to deposit boron doped hydrogenated silicon films by the PECVD method. The optoelectronic and structural properties of the silicon films have been investigated. With the increase of power and pressure the crystallinity of the films increases while the absorption decreases. As a very thin p-layer is needed in p–i–n thin film solar cells the variation of properties with film thickness has been studied. The fraction of crystallinity and thus dark conductivity vary also with the thickness of the film. Conductivity as high as 2.46 S cm⁻¹ has been achieved for 400 Å thin film while for 3000 Å thick film it is 21 S cm⁻¹. Characterization of these films by XRD, Raman Spectroscopy, TEM and SEM indicate that the grain size, crystalline volume fraction as well as the surface morphology of p-layers depend on the deposition conditions as well as on the thickness of the film. Optical band gap varies from 2.19 eV to 2.63 eV. The thin p-type crystalline silicon film with high conductivity and wide band gap prepared under high power and pressure is suitable for application as window layer for Silicon thin film solar cells.     

Spectroscopic ellipsometry study of nickel induced crystallization of a-Si

The aim of this work is to present a spectroscopic ellipsometry study focused on the annealing time effect on nickel metal induced crystallization of amorphous silicon thin films. For this purpose silicon layers with 80 and 125 nm were used on the top of which a 0.5 nm Ni thick layer was deposited. The ellipsometry simulation using a Bruggemann Effective Medium Approximation shows that films with 80 nm reach a crystalline fraction of 72% after 1 h annealing, appearing to be full crystallized after 2 h. No significant structural improvement is detected for longer annealing times. On the 125 nm samples the crystalline volume fraction after 1 h is only around 7%, requiring 5 h to get a similar crystalline fraction than the one achieved with the thinner film. This means that the time required for full crystallization will be strongly determined by the Si layer thickness. Using a new fitting approach the Ni content within the films was also determined by SE and related to the silicon film thickness.     

Characterizations of pulsed laser deposited SiC thin films

Thin films of silicon carbide (SiC) were prepared using pulsed laser deposition (PLD) on Si(1 0 0) substrates at a temperature of 370 °C. Various structural characterizations showed the development of short-range SiC precipitates in the films. These films were annealed isochronally at temperatures of 800 °C, 1000 °C and 1200 °C for 2 h under an inert environment. Thermally induced crystalline ordering of SiC into β-SiC phase was investigated by X-ray diffraction (XRD), Raman spectroscopy and Fourier transforms infrared (FTIR) spectroscopic measurements. In addition to the crystallization of SiC films, high temperature annealing resulted in the dissolution of carbon clusters found in the as-grown films.     

Correlation between the method of preparation and the properties of the sol–gel HfO2 thin films

This work describes the preparation of HfO₂ thin films by the sol–gel method, starting with different precursors such as hafnium ethoxide, hafnium 2,4-pentadionate and hafnium chloride. From the solution prepared as mentioned above, thin films on silicon wafer substrates have been realized by ‘dip-coating’ with a pulling out speed of 5 cm min^?1. The films densification was achieved by thermal treatment for 10 min at 100 °C and 30 min at 450 °C or 600 °C, with a heating rate of 1 °C min^?1. The structural and optical properties of the films are determined employing spectroellipsometric (SE) measurements in the visible range (0.4–0.7 μm), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The main objective of this paper was to establish a correlation between the method of preparation (precursor, annealing temperature) and the properties of the obtained films. The samples prepared from pentadionate and ethoxide precursors are homogenous and uniform in thickness. The samples prepared starting from chloride precursor are thicker and proved to be less uniform in thickness. Higher non-uniformity develops in multi-deposition films or in crystallized films. A nano-porosity is present in the quasi-amorphous films as well in the crystallized one. For the samples deposited on silicon wafer, the thermal treatment induced the formation of a SiO₂ layer at the coating–substrate interface.     

Electron and hole transport in microcrystalline silicon solar cells studied by time-of-flight photocurrent spectroscopy

A photocurrent time-of-flight study of carrier transport in microcrystalline silicon pin diodes prepared over a range of crystallinities is presented. Electron and hole drift mobilities at a crystalline volume fraction >0.35 are typically 3.8 and 1.3 cm²/(V s) respectively at 300 K and a thickness to electric field ratio of 1.8 × 10⁻⁷ cm²/V. A factor of five enhancement in hole mobility over amorphous silicon persists at a crystalline volume fraction as low as 0.1. Current decays are dispersive and mobilities are thermally activated, although detailed field-dependence is still under investigation. Evidence for a sharp fall in the density of states at 0.13 eV above the valence band edge is presented. Similarities in behaviour with certain amorphous and polymorphous silicon samples are identified.     

Optical characterization of sputtered amorphous aluminum nitride thin films by spectroscopic ellipsometry

We have measured and analyzed the optical constants and polarized optical properties of amorphous aluminum nitride (a-AlN) thin films deposited by RF reactive magnetron sputtering onto silicon(1 1 1) and glass substrates. The optical constants were obtained by analysis of the measured ellipsometric spectra in the wavelength range 300–1400 nm, using the Cauchy–Urbach model. Refractive indices and extinction coefficients of the films were determined to be in the range 1.80–2.11 and 8.6 × 10⁻³–1.5 × 10⁻⁵, respectively. Analysis of the absorption coefficient, in the wavelength range 200–1400 nm, shows the bandgap of a-AlN thin films to be 5.84 ± 0.05 eV. From the angle dependence of the p-polarized reflectivity we deduce a Brewster angle of 61° and a principal angle of 64°. Measurement of the polarized optical properties reveals a high transmissivity and very low absorptivity for a-AlN films in the visible and near infrared regions. X-ray diffraction analysis confirmed the amorphous nature of the films under study.     

Nanocrystalline silicon TFT process using silane diluted in argon–hydrogen mixtures

We have investigated the effect of Ar dilution on the deposition process of intrinsic nc-Si:H (hydrogenated nanocrystalline silicon) thin films used as active layers of top-gate TFTs, in order to improve the TFTs performances. The nc-Si:H films were deposited by plasma enhanced chemical vapor deposition (PECVD) at low temperature (165 °C) and the related TFTs were fabricated with a maximum process temperature of 200 °C. During the nc-Si:H films deposition, the SiH₄ fraction and the total flow of the diluting gases Ar + H₂ mixture was kept constant, H₂ being substituted by Ar. We have pointed out the active role played by the metastable states of excited Ar atoms in both the dissociation of SiH₄ and H₂ by quenching reactions in the plasma. The role of the atomic hydrogen during the film deposition seems to be promoted by the addition of argon into the discharge, leading to an increase of the deposition rate by a factor of about three and an enhancement of the crystalline quality of the nc-Si:H films. This effect is maximized when the Ar fraction in the Ar + H₂ gases mixture reaches 50%. The evolution with Ar addition of the carriers mobility of the related TFTs is closely connected to the evolution of the crystalline fraction of the intrinsic nc-Si:H film. Mobilities values as high as 8 cm² V^?1 s^?1 are obtained at the Ar fraction of 50%. For higher Ar fractions, the fall of the mobility comes with a degradation of the I_D–V_G transfer characteristics of the processed TFTs due to a degradation of the nc-Si:H films quality. OES measurements show that the evolution of the H_α intensity is closely connected to the evolution of the deposition rate, intrinsic films crystalline fraction and TFTs mobility, providing an interesting tool to monitor the TFTs performances.     

Improving the performance of amorphous and crystalline silicon heterojunction solar cells by monitoring surface passivation

The influence of thermal annealing on the crystalline silicon surface passivating properties of selected amorphous silicon containing layer stacks (including intrinsic and doped films), as well as the correlation with silicon heterojunction solar cell performance has been investigated. All samples have been isochronally annealed for 1 h in an N₂ ambient at temperatures between 150 °C and 300 °C in incremental steps of 15 °C. For intrinsic films and intrinsic/n-type stacks, an improvement in passivation quality is observed up to 255 °C and 270 °C, respectively, and a deterioration at higher temperatures. For intrinsic/n-type a-Si:H layer stacks, a maximum minority carrier lifetime of 13.3 ms at an injection level of 10¹⁵ cm^? 3 has been measured. In contrast, for intrinsic/p-type a-Si:H layer stacks, a deterioration in passivation is observed upon annealing over the whole temperature range. Comparing the lifetime values and trends for the different layer stacks to the performance of the corresponding cells, it is inferred that the intrinsic/p-layer stack is limiting device performance. Furthermore, thermal annealing of p-type layers should be avoided entirely. We therefore propose an adapted processing sequence, leading to a substantial improvement in efficiency to 16.7%, well above the efficiency of 15.8% obtained with the ‘standard’ processing sequence.     

Characterization of mixed phase silicon by Raman spectroscopy

We have examined the common methods for determination of the crystallinity of mixed phase silicon thin films from the TO–LO phonon band in Raman spectra. Spectra are decomposed into contributions of amorphous and crystalline phase and empirical formulas are used to obtain crystallinity either from the integral intensities (peak areas) or from magnitudes (peak maxima). Crystallinity values obtained from Raman spectra excited by Ar⁺ laser green line (514.5 nm) for a special sample with a profile of structure from amorphous to fully microcrystalline were compared with surface crystallinity obtained independently from atomic force microscopy (AFM). Analysis of the Raman collection depth in material composed of grains with absorption depth 1000 nm in an amorphous matrix (absorption depth 100 nm), was used to explain reasons for systematic difference between surface and Raman crystallinities. Recommendations are given for obtaining consistent results.     

Plasma enhanced chemical vapor deposition of ZnO thin films

Zinc oxide thin films were deposited on silicon and corning-7059 glass substrates by plasma enhanced chemical vapor deposition at different substrate temperatures ranging from 36 to 400 °C and with different gas flow rates. Diethylzinc as the source precursor, H₂O as oxidizer and argon as carrier gas were used for the preparation of ZnO films. Structural and optical properties of these films were investigated using X-ray diffraction, reflection high energy electron diffraction, atomic force microscopy and photoluminescence. Highly oriented films with (0 0 2) preferred planes were obtained on silicon kept at 300 °C with 50 ml/min flow rate of diethylzinc without any post annealing. Reflection high energy electron diffraction pattern also showed the crystalline nature of these films. A textured surface with rms roughness ∼28 nm was observed by atomic force microscopy for the films deposited at 300 °C. A sharp peak at 380 nm in the PL spectra indicated the UV band-edge emission.     

Microstructures of high-growth-rate (up to 8.3 nm/s) microcrystalline silicon photovoltaic layers and their influence on the photovoltaic performance of thin-film solar cells

Microstructures of microcrystalline silicon (μc-Si) deposited at a high-growth-rate have been investigated in order to apply to the photovoltaic i-layer. μc-Si films were prepared by very-high-frequency (100 MHz) plasma-enhanced chemical vapor deposition at 180 °C. High growth rates of 3.3–8.3 nm/s have been achieved utilizing high deposition pressures up to 24 Torr and large input powers. Applying μc-Si to n–i–p junction solar cells, as the optimum result in this experimental series, a conversion efficiency of 6.30% (J_SC: 22.1 mA/cm², V_OC: 0.470 V, and FF: 60.7%) has been achieved employing the i-layer deposited at 8.1 nm/s. Raman scattering and X-ray diffraction measurements revealed the crystalline volume fraction of around 50% with the (2 2 0) crystallographic preferential orientation, respectively. The cross-sectional transmission electron microscope image shows densely columnar structure grown directly on the underlying n-layer. These structural features are basically in good agreement those of low-growth-rate μc-Si used for a high efficiency solar cell as previously reported, implying advantages of the use of high pressures with regard to providing the photovoltaic i-layers. Finally, the implication is discussed from the photovoltaic performance as a function of the crystalline volume fraction of i-layer, and current problems in improving the photovoltaic performance are extracted.     

Linear and nonlinear optical properties of the optical fiber doped with silicon nano-particles

We report for the first time the realization of the optical fiber doped with silicon nano-particles. Silica glass optical fibers incorporated with silicon nano-particles were fabricated by the modified chemical vapor deposition and the solution doping technique. We found that a broadband absorption appeared at 450–1300 nm and a photoluminescence band appeared at 600–1100 nm upon pumping with the Ar-ion laser, indicating that silicon nano-particles were successfully incorporated in the fiber core. We also estimated the third-order optical nonlinearity of the optical fibers by measuring the fringe shift obtained from the long-period gratings upon pumping with the Ar-ion laser from 477 to 512 nm. Importantly the optical nonlinearity at 1550 nm was found to be ～1.5 × 10^?15 m²/W and we believe that this large optical nonlinearity is caused by the exciton absorption of the silicon particles.     

Study of the oxygen role in the photoluminescence of erbium doped nanocrystalline silicon embedded in a silicon amorphous matrix

We have produced and studied erbium doped nanocrystalline silicon thin films with different oxygen and hydrogen content in order to evaluate the influence of the matrix on the Er³⁺ emission and on the 0.89 eV and 1.17 eV bands. Films were grown by reactive magnetron sputtering on glass substrates under several different conditions (RF power, Er content and gas mixture composition) in order to obtain different microstructures. The structural parameters and the chemical composition of the samples were obtained by X-ray in the grazing incidence geometry, Raman spectroscopy and Rutherford back scattering analysis. Using X-ray technique combined with Raman spectroscopy information on the crystalline fraction and the average crystallite size of Si nanocrystals was obtained. Dependence of the 0.89 eV and 1.17 eV peaks in Si heterogeneous matrixes on the films crystallinity and O/H ratio has been analyzed.     

Influence of crystalline volume fraction on the performance of high mobility microcrystalline silicon thin-film transistors

The influence of the crystalline volume fraction of hydrogenated microcrystalline silicon on the device performance of thin-film transistors fabricated at temperatures below 200 °C was investigated. Transistors employing microcrystalline silicon channel material prepared close to the transition to amorphous growth regime exhibit the highest charge carrier mobilities exceeding 50 cm²/V s. The device parameters like the charge carrier mobility, the threshold voltage and the subthreshold slope will be discussed with respect to the crystalline volume fraction of the intrinsic microcrystalline silicon material.     

Structural change of laser-irradiated Ge2Sb2Te5 films studied by electrical property measurement

Sheet resistance of laser-irradiated Ge₂Sb₂Te₅ thin films prepared by magnetron sputtering was measured by the four-point probe method. With increasing laser power the sheet resistance undergoes an abrupt drop from 10⁷ to 10³ Ω/□ at about 580 mW. The abrupt drop in resistance is due to the structural change from amorphous to crystalline state as revealed by X-ray diffraction (XRD) study of the samples around the abrupt change point. Crystallized dots were also formed in the amorphous Ge₂Sb₂Te₅ films by focused short pulse laser-irradiated, the resistivities at the crystallized dots and the non-crystallized area are 3.375 × 10^?3 and 2.725 Ω m, sheet resistance is 3.37 × 10⁴ and 2.725 × 10⁷ Ω/□ respectively, deduced from the I–V curves that is obtained by conductive atomic force microscope (C-AFM).     

Hydrogenated amorphous and nanocrystalline silicon solar cells deposited by HWCVD and RF-PECVD on plastic substrates at 150 °C

In this work we present a study of the structural, optoelectronic and transport properties of a series of Si films deposited in a parameter region (namely hydrogen dilution) corresponding to a transition from amorphous-to-nanocrystalline silicon by hot-wire (HW) and radio-frequency plasma enhanced chemical vapor deposition (RF) on plastic substrates at 150 °C. To achieve a higher deposition rate of Si films by RF we used a relatively high power density (350 mW/cm²) and deposition pressure (1.5 Torr). For certain hydrogen dilution values, these deposition conditions can lead to the formation of Si crystals in the silane plasma and to a growth of polymorphous silicon film. This material has improved carrier transport properties (ambipolar diffusion length = 220 nm) and very high photosensitivity (>5 × 10⁶). The best HW amorphous silicon films exhibited lower photosensitivity (7 × 10⁴) and an ambipolar diffusion length of only 100 nm. For solar cell fabrication, we optimized the RF deposition conditions to produce very thin amorphous and nanocrystalline phosphorous and boron doped silicon layers. Our best n–i–p solar cell, with a polymorphous Si intrinsic layer deposited on plastic, has an efficiency of 5.5%, FF = 52.5%, V_OC = 920 mV, J_SC = 11.6 mA/cm². For solar cells with a nanocrystalline Si active layer deposited on glass the following results were achieved: efficiency = 3.4%, FF = 43.5%, V_OC = 460 mV, J_SC = 17.2 mA/cm²; and on plastic substrate: efficiency = 2.2%, FF = 32.7%, V_OC = 397 mV, J_SC = 17.2 mA/cm².     

Absorption and luminescence in amorphous SixGe1-xO2 films fabricated by SPCVD

Optical absorption and photoluminescence of Ge-doped silica films fabricated by the surface-plasma chemical vapor deposition (SPCVD) are studied in the 2–8 eV spectral band. The deposited on silica substrate films of about 10 μm in thickness are composed as x·GeO₂-(1-x)·SiO₂ with x ranging from 0.02 to 1. It is found that all as‐deposited films do not luminesce under the excitation by a KrF (5 eV) excimer laser, thus indicating lack of oxygen deficient centers (ODCs) in them. After subsequent fusion of silicon containing (x < 1) films by a scanning focused CO₂ laser beam absorption band centered at 5 eV as well as two luminescence bands centered at blue (3.1 eV) and UV (4.3 eV) wavelengths arise, highlighting the formation of the ODCs. The excitation of unfused SPCVD films by an ArF (6.4 eV) excimer laser yields a luminescence spectrum with two bands typical for the ODCs, but with a faster decay kinetics. Intensities of these bands grow up with samples cooling down to a temperature of 80–60 K. Unfused films excited by the ArF laser also demonstrate luminescence due to recombination of a trapped charge resulted from the excitation of localized electron states of the glass network. In the unfused GeO₂ film luminescence related to a self-trapped exciton (STE) typical for GeO₂ crystals with α-quartz structure is observed. The observed STE luminescence can be indicative of the crystalline fraction availability in the film. Whereas GeO₂ crystals are known as not containing twofold coordinated germanium, a polycrystalline inclusion in the SPCVD GeO₂ film serves as a factor explaining the absence of any spectroscopic manifestation of this type of defects in it even after fusion. On the other hand, lack of STE luminescence in other unfused films with x < 1 testifies truly amorphous state of the matter in them.     

Silicon nanowire solar cells grown by PECVD

Silicon nanowires offer an opportunity to improve light trapping in low-cost silicon photovoltaic cells. We have grown radial junctions of hydrogenated amorphous silicon over p-doped crystalline silicon nanowires in a single pump-down plasma enhanced chemical vapor deposition process on glass substrates. By using Sn catalysts and boosting p-type doping in the nanowires, the open-circuit voltage of the devices increased from 200 to 800 mV. Light trapping was optimized by extending the length of nanowires in these devices from 1 to 3 μm, producing currents in excess of – 13 mA cm^? 2 and energy conversion efficiencies of 5.6%. The advantages of using thinner window layers to increase blue spectral response were also assessed.     

Cw argon laser crystallization of silicon films: Structural properties

This paper deals with the structural characterization of amorphous silicon films deposited on glass in the amorphous state and then post-crystallized using a continuous wave argon laser. In opposite to the excimer laser crystallization method, the processing window is wider. Due to the low cooling rate induced by the continuous irradiation, very large grains are obtained. With an epitaxial growth induced by an adequate overlapping of the laser traces, grains as large as 100 μm can be reached. Electron back-scattered diffraction analysis highlights the single crystalline character of the large size grains crystallized with this kind of laser. The technique is able to produce large area single crystalline regions, suitable to fabricate high speed circuits.