Improving dopant incorporation during femtosecond-laser doping of Si with a Se thin-film dopant precursor

We study the dopant incorporation processes during thin-film fs-laser doping of Si and tailor the dopant distribution through optimization of the fs-laser irradiation conditions. Scanning electron microscopy, transmission electron microscopy, and profilometry are used to study the interrelated dopant incorporation and surface texturing mechanisms during fs-laser irradiation of Si coated with a Se thin-film dopant precursor. We show that the crystallization of Se-doped Si and micrometer-scale surface texturing are closely coupled and produce a doped surface that is not conducive to device fabrication. Next, we use this understanding of the dopant incorporation process to decouple dopant crystallization from surface texturing by tailoring the irradiation conditions. A low-fluence regime is identified in which a continuous surface layer of doped crystalline material forms in parallel with laser-induced periodic surface structures over many laser pulses. This investigation demonstrates the ability to tailor the dopant distribution through a systematic investigation of the relationship between fs-laser irradiation conditions, microstructure, and dopant distribution.     

Polycrystalline silicon thin films prepared by Ni silicide induced crystallization and the dopant effects on the crystallization

Intrinsic and doped polycrystalline silicon thin films were grown by the Ni silicide seeds induced crystallization. The Ni first reacted to Si forming a silicide seeds, then these seeds act as nuclei, from which the grains start to grow laterally. Compared with traditional Ni induced lateral crystallization, polycrystalline silicon thin film was grown by Ni silicide induced crystallization with low Ni contamination and large grain sizes. It can be found that the Ni silicide induced crystallization rate is accelerated by p-type doping and is decelerated by n-type doping. And the slightly and strongly phosphorous-doped polycrystalline silicon can be obtained with different grain shapes. Also, the sheet resistance of doped polycrystalline silicon decreases with the increasing of the doping atoms. A reasonable explanation is presented for the dopant effects on the growth rate, microstructure and electronic properties of the samples.     

The role of diffusion in broadband infrared absorption in chalcogen-doped silicon

Sulfur doping of silicon beyond the solubility limit by femtosecond laser irradiation leads to near-unity broadband absorption of visible and infrared light and the realization of silicon-based infrared photodetectors. The nature of the infrared absorption is not yet well understood. Here we present a study on the reduction of infrared absorptance after various anneals of different temperatures and durations for three chalcogens (sulfur, selenium, and tellurium) dissolved into silicon by femtosecond laser irradiation. For sulfur doping, we irradiate silicon in SF₆ gas; for selenium and tellurium, we evaporate a film onto the silicon and irradiate in N₂ gas; lastly, as a control, we irradiated untreated silicon in N₂ gas. Our analysis shows that the deactivation of infrared absorption after thermal annealing is likely caused by dopant diffusion. We observe that a characteristic diffusion length—common to all three dopants—leads to the reduction of infrared absorption. Using diffusion theory, we suggest a model in which grain size of the resolidified surface layer can account for this characteristic diffusion length, indicating that deactivation of infrared absorptance may be caused by precipitation of the dopant at the grain boundaries.     

Boron doping of silicon by excimer laser irradiation in a reactive atmosphere

UV excimer lasers have been used to dope semiconductors by a one-step process in which the laser serves both to melt a controlled thickness of a sample placed in dopant ambient and to photodissociate the dopant molecules themselves. Here we report the boron doping of silicon by means of an ArF (193 nm) excimer laser. Dopant atoms are obtained by photolysis of BCl₃ or pyrolysis of BF₃ molecules. The doping is performed both in gas ambient and using only an adsorbed layer. We have investigated the dependence of doping parameters such as laser pulse repetition and gas pressure on the subsequent boron impurity profiles and the dopant incorporation rate. These results indicate that the laser doping process is dopant-flux limited for BF₃ and externally rate limited for BCl₃.     

The effect of silicon substrate on thickness of SiO2 thin film analysed by spectral reflectometry and interferometry

Techniques of spectral reflectometry and interferometry are used for measuring small changes in thickness of SiO₂ thin film grown by thermal oxidation on different silicon substrates. A slightly dispersive Michelson interferometer with one of its mirrors replaced by a thin-film structure is used to measure the reflectance and interferometric phase of the thin-film structure at the same time. The experimental data are used to determine precisely the thickness of the SiO₂ thin film on silicon wafers of two crystallographic orientations and different dopant concentrations. We confirmed very good agreement between the experimental data and theory and revealed that the thin-film thickness, which varies with the type of silicon substrate, depends linearly on the wavelength at which minimum in the spectral reflectance occurs. Similar behaviour was revealed for the interferometric phase.     

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     

Enhanced photocatalytic activity of TiO2 thin film coating on microstructured silicon substrate

Photocatalytic TiO2 thin film is prepared by sol–gel technique on microstructured silicon substrate produced by femtosecond laser cumulative irradiation. The photocatalytic activity is evaluated by the degradation of methylene blue (MB) solution under ultraviolet (UV) irradiation. For 6-ml MB solution with initial concentration of 3.0×10~-5 mol/L, the degradation rate caused by TiO2 thin film of 2-cm~2 area is higher than 70% after 10-h UV irradiation. Microstructured silicon substrate is found to enhance photocatalytic activity of the TiO2 thin film remarkably. The femtosecond laser microstructured silicon substrate is suitable to support TiO2 thin film photocatalysts.     

Structural,electrical and optical studies on spray-deposited aluminium-doped ZnO thin films

Thin films of zinc oxide (ZnO) were deposited on cleaned glass substrates by chemical spray pyrolysis technique using Zn(CH₃COO)₂ as precursor solution. Also, aluminium-doped thin films of ZnO were prepared by using AlCl₃ as doping solution for aluminium. The dopant concentration [Al/Zn atomic percentage (at%)] was varied from 0 to 1.5 at% in thin films of ZnO prepared in different depositions. Structural characterization of the deposited films was performed with X-ray diffraction (XRD) studies. It confirmed that all the films were of zinc oxide having polycrystalline nature and possessing typical hexagonal wurtzite structure with crystallite size varying between 100.7 and 268.6 nm. The films exhibited changes in relative intensities and crystallite size with changes in the doping concentration of Al. The electrical studies established that 1 at% of Al-doping was the optimum for enhancing electrical conduction in ZnO thin films and beyond that the distortion caused in the lattice lowered the conductivity. The films also exhibited distinct changes in their optical properties at different doping concentrations, including a blue shift and slight widening of bandgap with increasing Al dopant concentration.     

Surface smoothening mechanism of amorphous silicon thin films

An important concern in the deposition of thin hydrogenated amorphous silicon () films is to obtain smooth surfaces. Herein, we combine molecular-dynamics simulations with first-principles density functional theory calculations to elucidate the smoothening mechanism of plasma deposited thin films. We show that the deposition precursor may diffuse rapidly on the film surface via overcoordinated surface Si atoms and incorporate into the film preferentially in surface valleys, with activation barriers for incorporation dependent on the local surface morphology. Experimental data on smoothening and precursor diffusion are accounted for.     

Influence of Boron doping on microcrystalline silicon growth

Microcrystalline silicon (μc-Si:H) thin films with and without boron doping are deposited using the radio-frequency plasma-enhanced chemical vapour deposition method. The surface roughness evolutions of the silicon thin films are investigated using ex situ spectroscopic ellipsometry and an atomic force microscope. It is shown that the growth exponent β and the roughness exponent α are about 0.369 and 0.95 for the undoped thin film, respectively. Whereas, for the boron-doped μc-Si:H thin film, β increases to 0.534 and α decreases to 0.46 due to the shadowing effect.     

氢化硅薄膜介观力学行为及其与微结构内禀关联特性

使用等离子体增强化学气相沉积系统，在射频和直流负偏压的双重激励下制备了本征和掺杂后的氢化硅薄膜.利用拉曼谱对薄膜进行了微结构分析，用纳米压痕系统研究了薄膜的介观力学行为.研究表明：制备于玻璃衬底上的氢化硅薄膜，由于存在非晶态的过渡缓冲层，弹性模量小于相应的制备于单晶硅衬底的薄膜.对于掺杂的氢化硅薄膜，由于磷的掺入使得薄膜晶粒细化、有序度提高，薄膜的晶态比一般在40％以上.而硼的掺入，薄膜晶态比减小，一般低于40％.同时发现，掺磷、本征和掺硼的氢化硅薄膜分别在晶态比为45％，30％和15％左右处，弹性模量较 关键词： 氢化硅薄膜 拉曼谱 弹性模量 晶态比     

Mechanisms and application of the Excimer laser doping from spin-on glass sources for USJ fabrication

In this work was investigated numerically and experimentally a simple laser doping method employing borosilicate (BSG) glass films as dopant sources which are deposited onto Si by the spin-coating technique. Both short (20 ns) and long (200 ns) pulse duration Excimer laser beams were used to deposit a large amount of energy in short time onto the near-surface region. Under suitable conditions, the irradiation leads to surface melting and dopant incorporation by liquid phase diffusion from the surface. Boron distribution profiles in the two-pulse duration regimes were studied as well as their electrical properties, and the junction formation of less than 25 nm in depth was demonstrated.     

Modification of the surface state and doping of CdTe and CdZnTe crystals by pulsed laser irradiation

The photoelectric and electrical properties of high-resistivity p-like CdTe and Cd_0.96Zn_0.04Te single crystals and barrier structures on their base before and after laser irradiation in different conditions are studied. Irradiation of samples with nanosecond ruby laser pulses was carried out in two different ways. In the first case, the Cd(Zn)Te crystals were subjected to laser action directly from the surface and irradiation within a certain range of intensities resulted in a decrease in the surface recombination rate and increase in the photoconductivity signal. The surface region with a wider bandgap in CdZnTe crystals was formed. In the second case, the samples were irradiated from the side pre-coated with a relatively thick In dopant film and it caused rectification in the I-V characteristics as a result of laser-induced doping of the thin Cd(Zn)Te surface region and formation of a built-in p-n junction. The application of the fabricated M-p-n structured In/Cd(Zn)Te/Au diodes for X-ray and γ-ray detectors is discussed.     

Surface doping of semiconductors by pulsed-laser irradiation in reactive atmosphere

Intense pulsed-laser irradiation in a suitable chemical atmosphere can produce a significant incorporation of chemical species from the environment to the surface molten layer. This process has been used to produce p-n junctions in silicon and GaAs irradiated, respectively, in PCl₃ and SiH₄ atmospheres. A modelling of the incorporation process, taking into account the solid-liquid-solid transition of the surface layer, has been developed following both a numerical and a semi-analytical approach. The modelling of the doping process gives results in a reasonably good agreement with the experimental doping profiles, obtained by irradiating Si samples in PCl₃ atmosphere.     

Si molecular beam Epitaxy: A model for temperature dependent incorporation probabilities and depth distributions of dopants exhibiting strong surface segregation

A model describing the incorporation of thermal dopants into single crystal films grown by molecular beam epitaxy (MBE) is presented. The model is general, accounts for dopant surface segregation during deposition, and allows dopant incorporation probabilities and depth profiles to be calculated as a function of film growth conditions (e.g. deposition rate, dopant beam flux, and growth temperature T_s). Input data to the model include thermodynamic parameters such as the free energy of segregation and dopant-surface binding energies together with kinetic parameters such as incident fluxes and dopant diffusivities. The model is applied here to Si MBE in which common dopants are typically characterized by strong surface segregation and temperature-dependent incorporation probabilities σ. Calculated values of σ(T_s) and calculated depth profiles were found to agree very well with available experimental data for both group-III acceptors and group-V donors in Si. In addition, the model predicts, in agreement with limited experimental data, that a growth parameter range exists in which abrupt doping profiles can be obtained, even for dopants which exhibit strong surface segregation. Finally, transition temperatures from equilibrium to kinetically-limited segregation are determined for several dopants.     

氮流量在高氢氛围中对富硅氮化硅薄膜材料结构及其发光特性的影响

采用等离子体增强化学气相沉积技术,以N₂掺入到SiH₄和H₂的沉积方式,分别在玻璃和N型单晶硅片(100)衬底上制备富硅氮化硅薄膜。通过紫外-可见光吸收光谱、傅里叶变换红外吸收光谱(FTIR光谱)、拉曼光谱和光致发光谱(PL谱)分别表征掺氮硅薄膜材料的带隙、结构及其发光特性的变化。结果表明：在氢气的氛围中,随着氮气流量的增加,氢原子能够对薄膜缺陷起到抑制作用,并使较低的SiH₄/N₂流量比下呈现富硅态,但却不利于硅团簇的形成。随着氮原子的掺入,Si—N键的含量增大,带隙增大,薄膜内微结构的无序度也增大,薄膜出现了硅与氮缺陷相关的缺陷态发光;随着氮原子进一步增加,出现了带尾态发光,进一步讨论了发光与结构之间的关联。这些结果有助于采用PECVD制备富硅氮化硅对材料发光与结构特性的优化。     

Direct conversion of a metal organic compound to epitaxial Sb-doped SnO2 film on a (0 0 1) TiO2 substrate using a KrF laser, and its resulting electrical properties

Epitaxial Sb-doped SnO₂ (0 0 1) thin film on a TiO₂ (0 0 1) substrate was successfully prepared by laser-assisted metal organic deposition at room temperature. The effects of the precursor thin film and laser fluence on the resistivity, carrier concentration, and mobility of the Sb-doped SnO₂ film were investigated. The resistivity of the Sb-doped SnO₂ film prepared by direct irradiation to metal organic film is one order of magnitude lower than that of film prepared by irradiation to amorphous Sb-doped SnO₂ film. From an analysis of Hall measurements, the difference between the resistivity of the Sb-doped SnO₂ film prepared using the metal organic precursor film and that of amorphous precursor film appears to be caused by the mobility. Direct conversion of the metal organic compound by excimer laser irradiation was found to be effective for preparing epitaxial Sb-doped SnO₂ film with low resistivity.     

Effect of swift heavy ion irradiation on dilute Fe-doped Sb0.95Se0.05 magnetic semiconductor

A thin film of dilute Fe (0.008)-doped Sb_0.95Se_0.05 alloy was grown on silicon substrate using the thermal evaporation technique. This film was irradiated with swift heavy ions (SHIs) Ag⁺¹⁵ having 200?MeV energy at ion fluences of 1?×?10¹² and 5?×?10¹² ions per cm², respectively. The thickness of the thin film was ～500?nm. We study the effect of irradiation on structural, electrical, surface morphology and magnetic properties of this film using grazing angle XRD (GAXRD), DC resistivity, atomic force microscopy (AFM) and magnetic force microscopy (MFM), respectively. GAXRD suggests that no significant change is observed in this system due to SHI irradiation. The average crystallite size increases with fluence, whereas the AFM image shows the rms roughness decreases due to irradiation with respect to the un-irradiated thin film. The MFM image shows that the magnetic interaction in irradiated film decreases due to the irradiation effect. Although the un-irradiated sample shows metal to semiconducting transition, but after irradiation with fluence of 5?×?10¹² ions per cm², the sharpness of the metal to semiconducting phase transition is observed to increase dramatically at ～300?K. This characteristic of the thin film makes it a promising candidate for an electrical switching device after irradiation.     

Space-selective modification of the magnetic properties of transparent Fe3+-doped glass by femtosecond-laser irradiation

We have demonstrated spatially selective modification of the magnetic properties of transparent iron-oxide-doped glass by femtosecond- (fs-) laser irradiation and subsequent annealing. A near-infrared fs-laser beam with a wavelength of 775 nm was focused 1 mm below the surfaces of glass samples. This produces absorption peaks due to the formation of hole-trap centers in the irradiated region. Transparency was recovered after annealing at 450°C. A ferrimagnetic component was observed in the M–H curve even at room temperature, whereas the diamagnetic component dominated in the M–H curve of the as-prepared glass sample. This indicates that fs-laser irradiation enhanced the magnetization in the irradiated area. The irradiated and annealed glass sample also exhibited superparamagnetic blocking in the temperature dependence of the magnetization with a blocking temperature higher than room temperature. This change in magnetism is presumably due to local crystallization of ferrimagnetic nanoparticles, such as magnetite, induced by fs-laser irradiation and annealing. The magnetic and optical properties of glass that had been annealed but not irradiated by a fs-laser beam remained unchanged.     

Electrochromic properties of spray deposited TiO2-doped WO3 thin films

TiO₂-doped WO₃ thin films were deposited onto fluorine-doped tin oxide coated conducting glass substrates using spray pyrolysis technique at 525 °C. The volume percentage of TiO₂ dopant was varied from 13% to 38%. The thin film samples were transparent, uniform and strongly adherent to the substrates. Electrochromical properties of TiO₂-doped WO₃ thin films were studied with the help of cyclic voltammetry (CV), chronoamperometry (CA) and chronocoulometry (CC) techniques. It has been found that TiO₂ doping in WO₃ enhances its electrochromic performance. Colouration efficiency becomes almost double and samples exhibit increasingly high reversibility with TiO₂ doping concentrations, in the studied range.