Micro-Raman spectroscopy characterization of polycrystalline silicon films fabricated by excimer laser crystallization

The rapid recrystallization of amorphous silicon films utilizing excimer laser crystallization (ELC) is presented. The resulting poly-Si films are characterized by Raman spectroscopy. Polycrystalline silicon (poly-Si) films with higher crystallinity can be realized by a dehydrogenation process before ELC. Raman spectra as a function of various excimer laser energy densities are demonstrated. The crystallinity and residual stress of the poly-Si films are determined and discussed.     

A novel optical diagnostic technique for analyzing the recrystallization characteristics of polycrystalline silicon thin films following frontside and backside excimer laser irradiation

Excimer laser annealing (ELA) is a widely used technique for producing polycrystalline silicon (poly-Si) thin films. An optical inspection system with simple optical arrangements for rapid measurement of recrystallization results of poly-Si thin films is developed in this study. The recrystallization results after both frontside ELA and backside ELA can be easily visible from the profile of peak power density distribution using the optical inspection system developed with an optimized moving velocity of 0.312 mm/s of the specimen. The method of backside ELA is suggested for batch production of low-temperature polycrystalline silicon thin-film transistors due to higher laser beam utilization efficiency and lower surface roughness of poly-Si films.     

Evolution of microstructure in polycrystalline silicon thin films upon excimer laser crystallization

Polycrystalline silicon (poly-Si) films fabricated by pulsed excimer laser crystallization (ELC) have been investigated using time-resolved optical measurements, scanning-electron microscopy, and cross-sectional transmission-electron microscopy. Detailed crystallization mechanisms are proposed to interpret the microstructure evolution of poly-Si films for both frontside and backside ELC. It is found that the backside ELC is a good candidate for the manufacturing of low-temperature polycrystalline silicon because of the high laser efficiency and low surface roughness of the poly-Si films.     

Nickel-disilicide-assisted excimer laser crystallization of amorphous silicon

Polycrystalline silicon (poly-Si) thin film has been prepared by means of nickel-disilicide (NiSi多晶硅 受激准分子激光器结晶 结晶化 界面晶粒生长polycrystalline silicon, excimer laser crystallization,Ni-disilicide, Ni-metal-induced lateral crystallization, two-interface grain growthProject supported by the National High Technology Development Program of China (Grant No 2002AA303250) and by the National Natural Science Foundation of China (Grant No 60576056).9/7/2005 12:00:00 AM3/6/2006 12:00:00 AMPolycrystalline silicon （poly-Si） thin film has been prepared by means of nickel-disilicide （NiSi2） assisted excimer laser crystallization （ELC）. The process to prepare a sample includes two steps. One step consists of the formation of NiSi2 precipitates by heat-treating the dehydrogenated amorphous silicon （a-Si） coated with a thin layer of Ni. And the other step consists of the formation of poly-Si grains by means of ELC. According to the test results of scanning electron microscopy （SEM）, another grain growth model named two-interface grain growth has been proposed to contrast with the conventional Ni-metal-induced lateral crystallization （Ni-MILC） model and the ELC model. That is, an additional grain growth interface other than that in conventional ELC is formed, which consists of NiSi2 precipitates and a-Si. The processes for grain growth according to various excimer laser energy densities delivered to the a-Si film have been discussed. It is discovered that grains with needle shape and most of a uniform orientation are formed which grow up with NiSi2 precipitates as seeds. The reason for the formation of such grains which are different from that of Ni-MILC without migration of Ni atoms is not clear. Our model and analysis point out a method to prepare grains with needle shape and mostly of a uniform orientation. If such grains are utilized to make thin-film transistor, its characteristics may be improved.     

Characterization of polycrystalline Ge thin films fabricated by short-pulse XeF excimer laser crystallization

XeF excimer laser-induced melting and recrystallization dynamics of amorphous germanium are investigated using time-resolved optical reflection and transmission measurements with a nanosecond time resolution, field-emission scanning electron microscopy, and micro-Raman spectroscopy. It is found that the disc-shaped grain with a diameter of approximately 0.8 μm is located in the complete melting regime with a melt phase duration of approximately 141–200 ns. The significant change of transmissivity is a key phenomenon revealing the excessive excimer laser fluence during excimer laser crystallization by in-situ optical measurements. Differences between the melting and recrystallization phenomenon for Si and Ge thin films are also discussed.     

多晶硅薄膜低温生长中晶粒大小的控制

以SiCl4H2为气源,用等离子体增强化学气相沉积(PECVD)方法低温快速沉积多晶硅薄膜.实验发现,在多晶硅薄膜的生长过程中,气相空间各种活性基团的相对浓度是影响晶粒大小的重要因素,随功率、H2/SiCl4流量比的减小和反应室气压的增加,晶粒增大.而各种活性基团的相对浓度依赖于PECVD工艺参数,通过工艺参数的改变,分析生长过程中空间各种活性基团相对浓度的变化,指出“气相结晶”过程是晶粒长大的一个重要因素. 关键词： 气相结晶 多晶硅薄膜 晶粒生长 SiCl4     

On-line determination of average grain size of polycrystalline silicon from melt duration of molten silicon

We demonstrate a method of on-line determination of the average grain size of polycrystalline silicon (poly-Si) deduced from the melt duration of molten silicon during the phase transformation using an in-situ optical measurement system. Optical measurements revealed that the entire phase transformation processes are melting, nucleation, and resolidification. The average grain size of poly-Si can be directly deduced from the melt duration of molten Si under a thickness uniformity of precursor a-Si thin films below ±5%, a pulse-to-pulse variation in the excimer-laser-beam energy below 2% (standard deviation), and a laser-beam spatial homogeneity below 2.5%.     

Raman microprobe technique diagnostic of YBCO films produced by laser ablation

Summary We have used a Raman microprobe technique for the characterisation and the diagnostic of YBCO superconducting thin films deposited by Pulsed-Laser Ablation (PLA) on MgO insulating substrates. Using polarisation analysis associated with sample rotations we developed a method for films orientation determination without any request for absolute calibration of the Raman spectra. The use of a bidimensional multichannel detector (OMA 4) allowed an overall detection time of 40 minutes. Each spectrum (shift range from 100 cm⁻¹ to 700 cm⁻¹) takes about 600 seconds. The results of this detection were used to determine the oxygen content, from the position of the Raman mode at 500 cm⁻¹ Homogeneity was checked with the spatial resolution allowed by the dimension of the focused laser beam (10 μm). Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.     

A simple technique for quickly measuring the spot size of Gaussian laser beams

A simple and accurate technique for measuring the spot size of Gaussian laser beams by scanning the beam with an opaque ribbon is proposed. The usefulness of this technique is verified experimentally.     

Surface control of optical properties in silicon nanocrystals produced by laser pyrolysis

Macroscopic quantities (g/h) of Si nanoparticles were prepared by laser pyrolysis of silane and showed photoluminescence (PL) emission in the range 700-1050 nm after oxidation in air at a temperature T ≥ 700 °C. Two different strategies were followed to reduce as-produced particle agglomeration which hinders most of the applications, namely etching with either acid or alkaline solutions. Well isolated single particles were detected after acid etching in HF. Disaggregation was also achieved by the combined effect of the high power sonication and alkaline etching by tetra-methyl ammonium hydroxide (TMAH), which leaves OH terminated surfaces. However, in both cases re-aggregation was observed within a few hours after oxide removal. Stable dispersions of Si nanoparticles in different solvents were obtained by treatments of H-terminated surfaces with the surfactant TOPO (C₂₄H₅₁PO, trioctylphospine oxide) and by treatment of OH-terminated surfaces with Na₃PO₄.     

In situ time-resolved optical measurements of a-Si thin films during excimer laser crystallization

An in situ time-resolved optical reflection and transmission (TRORT) monitoring system combining two He-Ne probe lasers, a digital oscilloscope and three fast photodetectors is developed to investigate the crystallization processes of Si thin films during excimer laser crystallization (ELC). The physical meaning of optical spectra obtained by TRORT measurements has been interpreted in detail. The melt duration and transient phase transformation dynamics of Si thin films can be determined and interpreted immediately. A high efficiency and non-destructive evaluation approach is proposed for determining the grain size of polycrystalline Si after ELC directly and immediacy under appropriate experimental conditions.     

Rapid determination of surface roughness of polycrystalline silicon following frontside and backside excimer laser irradiation

Excimer-laser crystallization (ELC) is the most commonly employed technology for fabricating low-temperature polycrystalline silicon (LTPS). Investigations on the surface roughness of polycrystalline silicon (poly-Si) thin films have become an important issue because the surface roughness of poly-Si thin films is widely believed to be related to its electrical characteristics. In this study, we develop a simple optical measurement system for rapid surface roughness measurements of poly-Si thin films fabricated by frontside ELC and backside ELC. We find that the incident angle of 20° is a good candidate for measuring the surface roughness of poly-Si thin films. The surface roughness of polycrystalline silicon thin films can be determined rapidly from the reflected peak power density measured by the optical system developed using the prediction equation. The maximum measurement error rate of the optical measurement system developed is less than 9.71%. The savings in measurement time of the surface roughness of poly-Si thin films is up to 83%. The method of backside ELC is suggested for batch production of low-temperature polycrystalline silicon thin-film transistors due to the lower surface roughness of poly-Si films and higher laser-beam utilization efficiency.     

A high-sensitivity in situ optical diagnostic technique for laser cleaning of transparent substrates

A differential optical transmission technique has been used to monitor in situ the efficiency of laser cleaning for the removal of sub-micrometer-sized particles on substrates transparent at the monitoring wavelength. This technique has been applied to the removal of sub-micrometer polystyrene particles on polyimide substrates using laser pulses of 30 ps duration at 292 nm while probing the material transmission at 633 nm. The sensitivity achieved -1/10⁴ for the transmission changes induced upon single-pulse laser exposure – allows us to monitor the removal of just a few sub-micron-sized particles from the probed region inside the irradiated area. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-3/87844082, E-mail: nchaoui@iut.univ-metz.fr RID="**" ID="**"Present address: Laboratoire de Chimie et Applications, Institut Universitaire de Technologie de Metz, Département Chimie, Rue Victor Demange, 57500 Saint-Avold, France     

Growth,optical, and electrical properties of silicon films produced by the metal-induced crystallization process

Amorphous Si (a-Si) and Ni films were deposited by electron beam evaporation on to borosilicate glass (BSG) substrate maintained at ambient temperature. The BSG/a-Si/Ni stack was subjected to post deposition annealing in air at various temperatures from 200 to 500 °C for 1 h. Electron diffraction was employed to characterize the crystallographic phases appearing on the stacks that were depending on initial conditions. Clear evidence of the formation of hexagonal Si and fcc NiSi₂ was shown by TEM. In parallel, an increase of refraction index was observed. Electrical resistivity measurements showed that resistance is of the order of kilo ohms in the as-deposited films, increasing sharply to giga ohms in films annealed at T higher than 300 °C. A large band gap of 2.23 eV which is the combined contribution from a-Si, wurtzite-Si, and Ni silicide phases, is observed.     

Partial crystallization of silicon by high intensity laser irradiation

Commercial single crystal silicon wafers and amorphous silicon films piled on single crystal silicon wafers were irradiated with a femtosecond pulsed laser and a nanosecond pulsed laser at irradiation intensities between 10¹⁷ W/cm² and 10⁹ W/cm². In the single crystal silicon substrate, the irradiated area was changed to polycrystalline silicon and the piled silicon around the irradiated area has spindly column structures constructed of polycrystalline and amorphous silicon. In particular, in the case of the higher irradiation intensity of 10¹⁶ W/cm², the irradiated area was oriented to the same crystal direction as the substrate. In the case of the lower irradiation intensity of 10⁸ W/cm², only amorphous silicon was observed around the irradiated area, even when the target was single crystal silicon. In contrast, only amorphous silicon particles were found to be piled on the amorphous silicon film, irrespective of the intensity and pulse duration.Three-dimensional thermal diffusion equation for the piled particles on the substrate was solved by using the finite difference methods. The results of our heat-flow simulation of the piled particles almost agree with the experimental results.     

Evaluation of probe lasers employed in optical diagnostics for phase transformation of thin films during excimer laser crystallization

The stability and reliability of probe laser is an important factor affecting the inspection of the phase transformation process of Si thin films during excimer laser crystallization using in-situ time-resolved optical measurements. The changes in 2D intensity profile, peak power density, and beam wander of the commonly used helium–neon (He–Ne) and diode laser are investigated experimentally. It is found that the peak power density of He–Ne laser is higher than that of diode laser, while the total power of He–Ne laser is lower than that of diode laser. Although the instability in the peak power density of He–Ne laser will increase with increasing the operation time, the beam stability of He–Ne laser is better than that of diode laser. For long-time operation (>24 h) of optical measurements, the diode laser is a good candidate of probe laser. Conversely, the diode laser is suitable for the short-time operation (<24 h) of optical measurements because the beam-wander is higher than that of He–Ne laser.     

Silicon grain arrays prepared using a pattern crystallization technique of pulsed-excimer laser irradiation

Silicon grain arrays were prepared using a pattern crystallization technique of pulsed KrF excimer laser irradiation. The precursor material was hydrogenated amorphous silicon (a-Si:H) thin films deposited on single crystal Si wafers by plasma-enhanced chemical vapor deposition. It was shown that Si grains with a uniform size and a well-defined periodicity embedded in the a-Si:H matrix were obtained by this simple technique. The grain size was less than 2 μm. Relativly strong photo-luminescence with two peaks at 720 and 750 nm was observed at room temperature. We expect to reduce Si grain sizes by optimizing the growth conditions of a-Si:H thin films and controlling the temperature distribution in the film during laser irradiation. Received: 21 November 2000 / Accepted: 12 December 2000 / Published online: 9 February 2001     

Low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation

The low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation has been studied. Two fabrication methods are presented. One is photoenhanced direct nitridation of a silicon surface with NH₃ for very thin gate insulators, and the other is photo-enhanced deposition of silicon nitride films with Si₂H₆ and NH₃ gases for stable passivation films. The ArF excimer laser irradiation dissociates the NH3 gas producing NH and NH₂ radicals which proved effective in instigating the nitridation reaction. The quality of both films has been much improved and the growth temperature has been lowered by using laser irradiation. These photo-enhanced processes seem to be promising ULSI techniques because they do not depend on high temperatures and are free from possible reactor contamination.     

Development of polycrystalline silicon films on flexible metallic substrates by aluminium induced crystallization

Thin film silicon solar cells on low cost foreign substrates could be attractive for highly efficient and low cost production of photovoltaic electricity. An attempt has been made to synthesise high-quality continuous polycrystalline silicon (pc-Si) layers on flexible metallic substrates using aluminium induced crystallization (AIC) for the first time. Amorphous silicon films deposited by ECR-PECVD were crystallized on diffusion barrier coated metallic substrates at lower temperatures (<577°C). The crystallization was studied using Raman as well as UV reflectance spectroscopy. The as-grown AIC pc-Si films were found to be continuous and densely packed without amorphous phase. The migration of impurities from the substrate to the pc-Si films and the conformability of the barrier layer with the substrate and pc-Si films were studied systematically in terms of chemical and stress level analysis, which are the important aspects to be considered when metallic foils are used as substrates. It was observed that the barrier layer also serves as a buffer layer to minimise the stress level enormously in the AIC grown pc-Si layer, though the supporting material has a thermal expansion coefficient of higher order at higher annealing temperatures. The present investigation proves the possibility to grow better-quality polycrystalline silicon films on flexible metallic foils and further demonstrates the steps that need to be considered to improve the quality of AIC pc-Si films as well as the strength of the barrier layer.