B. Franta, D. Pastor, H. H. Gandhi, P. Rekemeyer, S. Gradečak, M. J. Aziz, and E. Mazur. 2015. “Simultaneous high crystallinity and optical absorptance in hyperdoped black silicon using nanosecond laser annealing.” J. Appl. Phys., 118, Pp. 225303–. Publisher's VersionAbstract
    Hyperdoped black siliconfabricated with femtosecond laserirradiation has attracted interest for applications in infrared photodetectors and intermediate band photovoltaics due to its sub-bandgap optical absorptance and light-trapping surface. However, hyperdoped black silicon typically has an amorphous and polyphasic polycrystalline surface that can interfere with carrier transport, electrical rectification, and intermediate band formation. Past studies have used thermal annealing to obtain high crystallinity in hyperdoped black silicon, but thermal annealing causes a deactivation of the sub-bandgap optical absorptance. In this study, nanosecond laser annealing is used to obtain high crystallinity and remove pressure-induced phases in hyperdoped black silicon while maintaining high sub-bandgap optical absorptance and a light-trapping surface morphology. Furthermore, it is shown that nanosecond laser annealing reactivates the sub-bandgap optical absorptance of hyperdoped black silicon after deactivation by thermal annealing. Thermal annealing and nanosecond laser annealing can be combined in sequence to fabricate hyperdoped black silicon that simultaneously shows high crystallinity, high above-bandgap and sub- bandgap absorptance, and a rectifying electrical homojunction. Such nanosecond laser annealing could potentially be applied to non- equilibrium material systems beyond hyperdoped black silicon.
    F. Fabbri, Y. Lin, G. Bertoni, F. Rossi, M. J. Smith, S. Gradecak, E. Mazur, and G. Salviati. 2015. “Origin of the visible emission of black silicon microstructures.” Appl. Phys. Lett., 107, Pp. 021907-1–021907-4. Publisher's VersionAbstract
    Silicon, the mainstay semiconductor in microelectronics, is considered unsuitable for optoelectronic applications due to its indirect electronic band gap that limits its efficiency as light emitter. Here, we univocally determine at the nanoscale the origin of visible emission in microstructured black silicon by cathodoluminescence spectroscopy and imaging. We demonstrate the formation of amorphous silicon oxide microstructures with a white emission. The white emission is composed by four features peaking at 1.98 eV, 2.24 eV, 2.77 eV, and 3.05 eV. The origin of such emissions is related to SiOx intrinsic point defects and to the sulfur doping due to the laser processing. Similar results go in the direction of developing optoelectronic devices suitable for silicon-based circuitry.
    Y. Lin, N. Mangan, S. Marbach, T. M. Schneider, G. Deng, S. Zhou, M. Brenner, and E. Mazur. 2015. “Creating femtosecond-laser-hyperdoped silicon with a homogeneous doping profile.” Appl. Phys. Lett., 106, Pp. 062105–. Publisher's VersionAbstract
    Femtosecond-laser hyperdoping of sulfur in silicon typically produces a concentration gradient that results in undesirable inhomogeneous material properties. Using a mathematical model of the doping process, we design a fabrication method consisting of a sequence of laser pulses with varying sulfur concentrations in the atmosphere, which produces hyperdoped silicon with a uniform concentration depth profile. Our measurements of the evolution of the concentration profiles with each laser pulse are consistent with our mathematical model of the doping mechanism, based on classical heat and solute diffusion coupled to the far-from-equilibrium dopant incorporation. The use of optimization methods opens an avenue for creating controllable hyperdoped materials on demand.
    M. Sher and E. Mazur. 2014. “Intermediate Band Conduction in Femtosecond-Laser Hyperdoped Silicon.” Appl. Phys. Lett., 105, Pp. 032103-1–032103-5. Publisher's VersionAbstract
    We use femtosecond-laser hyperdoping to introduce non-equilibrium concentrations of sulfur into silicon and study the nature of the resulting intermediate band. With increasing dopant concentration, the sub-bandgap absorption increases. To better understand the dopant energetics, we perform temperature-dependent Hall and resistivity measurements. We analyze the carrier concentration and the energetics of the intermediate band using a two- band model. The temperature-dependence of the carrier concentration and resistivity suggests that the dopant concentration is below the insulator-to-metal transition and that the samples have a localized intermediate band at 70 meV below the conduction band edge.
    Y. Lin. 2014. “Femtosecond-laser hyperdoping and texturing of silicon for photovoltaic applications”. Publisher's VersionAbstract
    This dissertation explores strategies for improving photolvoltaic efficiency and reduc- ing cost using femtosecond-laser processing methods including surface texturing and hyperdoping. Our investigations focus on two aspects: 1) texturing the silicon sur- face to create efficient light-trapping for thin silicon solar cells, and 2) understanding the mechanism of hyperdoping to control the doping profiles for fabricating efficient intermediate band materials.> We first discuss the light-trapping properties in laser-textured silicon and its benefit to thin silicon heterojunction solar cells. We report a nearly 15% improvement in the short circuit current and device efficiency after surface texturing, which is attributed to the enhancement of absorption due to the formation of Lambertian surfaces. We next present studies on the hyperdoping mechanism using a pump-probe method. We measure in situ the change in surface reflectivity during hyperdoping and extract the dynamics of the melt front. Understanding the melt dynamics allows us to constrain the physical parameters in a numerical model, which we use to simulate the doping profile with a simplified classical picture. We then demonstrate the successful fabrication of homogeneously doped silicon by manipulating the hyperdoping process based on theoretically predicted design principles.
    M. Sher. 2013. “Intermediate Band Properties of Femtosecond-Laser Hyperdoped Silicon”. Publisher's VersionAbstract
    This thesis explores using femtosecond-laser pulses to hyperdope silicon with chalcogen dopants at concentrations above the maximum equilibrium solubility. Hyperdoped silicon is promising for improving efficiencies of solar cells: the material exhibits broad-band light absorption to wavelengths deep below the corresponding bandgap energy of silicon. The high concentration of dopants forms an intermediate band (IB), instead of discrete energy levels, and the IB enables sub-bandgap light absorption. This thesis is divided into two primary studies: the dopant incorporation and the IB properties. First, we study dopant incorporation with a gas- phase dopant precursor (SF6) using secondary ion mass spectrometry. By varying the pressure of SF6, we find that the surface adsorbed molecules are the dominant source of the dopant. Furthermore, we show the hyperdoped layer is single crystalline. The results demonstrate that the dopant incorporation depth, concentration, and crystallinity are controlled respectively by the number of laser pulses, pressure of the dopant precursor, and laser fluence. Second, we study the IB properties of hyperdoped silicon using optical and electronic measurements. We use Fourier transform infrared spectroscopy to study light absorption. The absorption extends to wavelengths as far as 6 µm before thermal annealing and we find the upper bound of the IB location at 0.2 eV below the conduction band edge. For electronic measurements, we anneal the samples to form a diode between the hyperdoped layer and the substrate, allowing us to probe the IB using temperature-dependent electronic transport measurements. The measurement data indicate that these samples form a localized IB at concentrations below the insulator-to-metal transition. Using a two-band model, we obtain the location of the localized IB at >0.07 eV below the conduction band edge. After femtosecond-laser hyperdoping, annealing is necessary to reduce the laser-induced defects; however annealing decreases the sub-bandgap absorption. As we are interested in the IB that contributes to sub-bandgap absorption, we explore methods to reactivate the sub-bandgap absorption. We show that the sub-bandgap absorption is reactivated by annealing at high temperatures between 1350 and 1550 K followed by fast cooling (>50 K/s). Our results demonstrate an ability to control sub-bandgap absorption using thermal processing.
    G. Haberfehlner, M. J. Smith, J. Idrobo, G. Auvert, M. Sher, M. T. Winkler, E. Mazur, N. Gambacorti, S. Gradečak, and P. Bleuet. 2013. “Selenium segregation in femtosecond-laser hyperdoped silicon revealed by electron tomography.” Microscopy and Microanalysis, 19, Pp. 716–725. Publisher's VersionAbstract
    Doping of silicon with chalcogens (S, Se, Te) by femtosecond laser irradiation leads to nearunity optical absorptance in the visible and infrared range and is a promising route towards siliconbased infrared optoelectronics. However, open questions remain about the nature of the infrared absorptance and in particular about the impact of the dopant distribution and possible role of dopant diffusion. Here we use electron tomography using a high-angle annular dark field (HAADF) detector in a scanning transmission electron microscope (STEM) to extract information about the threedimensional distribution of selenium dopants in silicon and correlate these findings with the optical properties of selenium- doped silicon. We quantify the tomography results to extract information about the size distribution and density of selenium precipitates. Our results show correlation between nanoscale distribution of dopants and the observed sub- band gap optical absorptance, and demonstrate the feasibility of HAADF-STEM tomography for the investigation of dopant distribution in highly-doped semiconductors.
    M. Sher, K. Charles Hammond, L. Christakis, and E. Mazur. 2013. “The photovoltaic potential of femtosecond-laser textured amorphous silicon.” In . SPIE 2013 Photonics West. Publisher's VersionAbstract
    Femtosecond laser texturing of silicon yields micrometer scale surface roughness that reduces reflection and enhances light absorption. In this work, we study the potential of using this technique to improve efficiencies of amorphous silicon-based solar cells by laser texturing thin amorphous silicon films. We use a Ti:Sapphire femtosecond laser system to texture amorphous silicon, and we also study the effect of laser texturing the substrate before depositing amorphous silicon. We report on the material properties including surface morphology, light absorption, crystallinity, as well as solar cell efficiencies before and after laser texturing.
    T. Sarnet, T. J. - Derrien, R. Torres, P. Delaporte, F. Torregrosa, M. Sher, Y. Lin, B. Franta, G. Deng, and E. Mazur. 2013. “Black silicon for photovoltaic cells: towards a high-efficiency silicon solar cell.” In . EU PVSEC 2013, 28th European Photovoltaic Solar Energy Conference and Exhibition. Publisher's VersionAbstract
    Laser-created Black Silicon has been developed since 1998 at Harvard University. The unique optical and semiconducting properties of black silicon first led to interesting applications for sensors (photodetectors, thermal imaging cameras, etc.) Other applications like photovoltaic solar cells have been rapidly identified, but it took more than ten years of research and development before demonstrating a real improvement of the photovoltaic efficiency on an industrial multi-crystalline solar cell. This paper is a short review on recent research on the use of black silicon for photovoltaic cells.
    M. Sher, Y. Lin, M. T. Winkler, E. Mazur, C. Pruner, and A. Asenbaum. 2013. “Mid-infrared absorptance of silicon hyperdoped with chalcogen via fs-laser irradiation.” J. Appl. Phys., 113, Pp. 063520–. Publisher's VersionAbstract
    Silicon hyperdoped with heavy chalcogen atoms via femtosecond- laser irradiation exhibits strong broadband, sub-bandgap light absorption. Understanding the origin of this absorption could enable applications for hyperdoped-silicon based optoelectronic devices. In this work, we measure absorption to wavelengths up to 14 μm using Fourier transform infrared spectroscopy and study sulfur-, selenium- and tellurium- hyperdoped Si before and after annealing. We find that absorption in the samples extends to wavelengths as far as 6 μm. After annealing, the absorption spectrum exhibits features that are consistent with free-carrier absorption. Although the surface morphology influences the shape of the absorption curves, the data permit us to place an upper bound on the position of the chalcogen dopant energy levels.
    B. K. Newman, E. Ertekin, J. Timothy Sullivan, M. T. Winkler, M. A. Marcus, S. Fakra, M. Sher, E. Mazur, J. C. Grossman, and T. Buonassisi. 2013. “Extended X-ray absorption fine structure spectroscopy of selenium-hyperdoped silicon.” J. Appl. Phys., 114, Pp. 133507–133507-8. Publisher's VersionAbstract
    Silicon doped with an atomic percent of chalcogens exhibits strong, uniform sub-bandgap optical absorptance and is of interest for photovoltaic and infrared detector applications. This sub-bandgap absorptance is reduced with subsequent thermal annealing indicative of a diffusion mediated chemical change. However, the precise atomistic origin of absorptance and its deactivation is unclear. Herein, we apply Se K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy to probe the chemical states of selenium dopants in selenium-hyperdoped silicon annealed to varying degrees. We observe a smooth and continuous selenium chemical state change with increased annealing temperature, highly correlated to the decrease in sub-bandgap optical absorptance. In samples exhibiting strong sub-bandgap absorptance, EXAFS analysis reveals that the atoms nearest to the Se atom are Si at distances consistent with length scales in energetically favorable Se substitutional-type point defect complexes as calculated by density functional theory. As the sub- bandgap absorptance increases, EXAFS data indicate an increase in the Se-Si bond distance. In specimens annealed at 1225 K exhibiting minimal sub- bandgap absorptance, fitting of the EXAFS spectra indicates that Se is predominantly in a silicon diselenide (SiSe2) precipitate state. The EXAFS study supports a model of highly optically absorbing point defects that precipitate during annealing into structures with no sub-bandgap absorptance.
    M. T. Winkler, M. Sher, Y. Lin, M. J. Smith, H. Zhang, S. Gradečak, and E. Mazur. 2012. “Studying femtosecond-laser hyperdoping by controlling surface morphology.” Journal of Applied Physics, 111, Pp. 093511–. Publisher's VersionAbstract
    We study the fundamental properties of femtosecond-laser (fs-laser) hyperdoping by developing techniques to control the surface morphology following laser irradiation. By decoupling the formation of surface roughness from the doping process, we study the structural and electronic properties of fs-laser doped silicon. These experiments are a necessary step toward developing predictive models of the doping process. We use a single fs-laser pulse to dope silicon with sulfur, enabling quantitative secondary ion mass spectrometry, transmission electron microscopy, and Hall effect measurements. These measurements indicate that at laser fluences at or above 4 kJ m-2, a single laser pulse yields a sulfur dose > (3 ± 1) x 1013 cm–2 and results in a 45-nm thick amorphous surface layer. Based on these results, we demonstrate a method for hyperdoping large areas of silicon without producing the surface roughness.
    E. Landis, K. Phillips, E. Mazur, and C. M. Friend. 2012. “Formation of nanostructured TiO2 by femtosecond laser irradiation of titanium in O2.” J. Appl. Phy., 112, Pp. –. Publisher's VersionAbstract
    We use femtosecond laser irradiation of titanium metal to create nanometer scale laser-induced periodic surface structures and study the influence of atmospheric composition on these surface structures. We find that gas composition and pressure affect the chemical composition of the films, but not the surface morphology. We demonstrate that irradiation of titanium in oxygen containing atmospheres forms a highly stable surface layer of nanostructured amorphous titanium dioxide.
    M. J. Smith, M. Sher, B. Franta, Y. Lin, E. Mazur, and S. Gradečak. 2012. “The origins of pressure-induced phase transformations during the surface texturing of silicon using femtosecond laser irradiation.” J. Appl. Phys., 112, Pp. 083518–. Publisher's VersionAbstract
    Surface texturing of silicon using femtosecond (fs) laser irradiation can reduce the surface reflectivity to less than 5%, enables control over the resulting surface morphology, and uses little material. The laser-induced damage that occurs in parallel with surface texturing, however, can result in increased recombination currents that inhibit device performance. In this work, we investigate the light- material interaction during the texturing of silicon by directly correlating the formation of pressure-induced silicon polymorphs, fs-laser irradiation conditions, and the resulting morphology and microstructure using scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy. We identify resolidification-induced stresses as the mechanism responsible for driving sub- surface phase transformations during the surface texturing of silicon, the understanding of which is an important first step towards reducing laser-induced damage during the texturing of silicon with fs-laser irradiation.
    T. Sarnet, J. E. Carey, and E. Mazur. 2012. “From black silicon to photovoltaic cells, using short pulse lasers.” In . International Symposium on High Power Laser Ablation 2012. Publisher's VersionAbstract
    Laser created Black Silicon has been developed since 1998 at Harvard University. The unique optical and semiconducting properties of the black silicon first lead to interesting applications for sensors (photodetectors, thermal imaging cameras…). Other applications like Photovoltaic solar cells have been rapidly identified, but it took more than ten years of research and development before demonstrating a real improvement of the photovoltaic efficiency on an industrial multi-crystalline solar cell. This paper is a brief review of the use of black silicon for photovoltaic cells.
    B. K. Newman, M. Sher, E. Mazur, and T. Buonassisi. 2011. “Reactivation of sub-bandgap absorption in chalcogen-hyperdoped silicon.” Appl. Phys. Lett., 98, Pp. 251905–. Publisher's VersionAbstract
    Silicon doped with non-equilibrium concentrations of chalcogens using a femtosecond laser exhibits near-unity absorption of sub-bandgap photons to wavelengths of at least 2500 nm. Previous studies have shown that sub-bandgap absorptance decreases with thermal annealing up to 1175 K, and that the absorption deactivation correlates with chalcogen diffusivity. In this work, we show that sub-bandgap absorptance can be reactivated by annealing at temperatures between 1350 K and 1550 K followed by fast cooling (> 50 K/s). Our results suggest that the defects responsible for sub-bandgap absorptance are in equilibrium at high-temperatures in hyperdoped Si:chalcogen systems.
    M. Sher, M. T. Winkler, and E. Mazur. 2011. “Pulsed-laser hyperdoping and surface texturing for photovoltaics.” MRS Bulletin, 36, Pp. 439–445. Publisher's VersionAbstract
    We describe two ways in which pulsed lasers can be used to increase efficiency in photovoltaic devices. First, pulsed-laser hyperdoping can introduce dopants into a semiconductor at non-equilibrium concentrations, which creates an intermediate band within the bandgap of the material and modifies the absorption coefficient. Second, pulsed-laser irradiation can enhance geometric light trapping by increasing surface roughness. Hyperdoping in silicon enables absorption of photons to wavelengths of at least 2.5 μm, while texturing enhances the absorptance to near unity at all absorbing wavelengths. In this paper, we review both effects and comment on outstanding questions and challenges in applying each to increasing the efficiency of photovoltaic devices.
    M. J. Smith, M. T. Winkler, M. Sher, Y. Lin, E. Mazur, and S. Gradečak. 2011. “The Effects of a Thin Film Dopant Precursor on the Structure and Properties of Femtosecond-laser Irradiated Silicon.” Appl. Phys. A, 105, Pp. 795–800. Publisher's VersionAbstract
    Femtosecond (fs) laser irradiation of a silicon substrate coated with a thin film is a flexible approach to producing metastable alloys with unique properties, including near-unity sub-band gap absorptance extending into the infrared. However, dopant incorporation from a thin film during fs-laser irradiation is not well understood. We study the thin film femtosecond-laser doping process through optical and structural characterization of silicon fs-laser doped using a selenium thin film, and compare the resulting microstructure and dopant distribution to fs-laser doping with sulfur from a gaseous precursor. We show that a thin film dopant precursor significantly changes the laser-material interactions, modifying both the surface structuring and dopant incorporation processes and in turn affecting p-n diode behavior.
    M. J. Smith, Y. Lin, M. Sher, M. T. Winkler, E. Mazur, and S. Gradecak. 2011. “Pressure-induced phase transformations during femtosecond-laser doping of silicon.” J. Appl. Phys., 110, Pp. 053524–. Publisher's VersionAbstract
    Silicon hyperdoped with chalcogens via femtosecond-laser irradiation exhibits unique near-unity sub-bandgap absorptance extending into the infrared region. The intense light-matter interactions that occur during femtosecond-laser doping produce pressure waves sufficient to induce phase transformations in silicon, resulting in the formation of metastable polymorphic phases, but their exact formation mechanism and influence on the doping process are still unknown. We report direct observations of these phases, describe their formation and distribution, and consider their potential impact on sub-bandgap absorptance. Specifically, the transformation from diamond cubic Si-I to pressure-induced polymorphic crystal structures (amorphous Si, Si-XII, and Si-III) during femtosecond-laser irradiation was investigated using scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy. Amorphous Si, Si-XII, and Si-III were found to form in femtosecond-laser doped silicon regardless of the presence of a gaseous or thin-film dopant precursor. The rate of pressure loading and unloading induced by femtosecond-laser irradiation kinetically limits the formation of pressure-induced phases, producing regions of amorphous Si 20 to 200 nm in size and nanocrystals of Si- XII and Si-III. The surface texturing that occurs during femtosecond-laser irradiation produces inhomogeneous pressure distributions across the surface and causes delayed development of high-pressure silicon polymorphs over many laser pulses. Finally, we find that the polymorph phases disappear during annealing more rapidly than the sub-bandgap absorptance decreases, enabling us to decouple these two processes through post-treatment annealing.
    M. T. Winkler, D. Recht, M. Sher, A. J. Said, E. Mazur, and M. J. Aziz. 2011. “Insulator-to-metal transition in sulfur-doped silicon.” Phys. Rev. Lett., 106, Pp. 178701–. Publisher's VersionAbstract
    We observe an insulator-to-metal (I–M) transition in crystalline silicon doped with sulfur to non-equilibrium concentrations using ion implantation followed by pulsed laser melting and rapid resolidification. This I–M transition is due to a dopant known to produce only deep levels at equilibrium concentrations. Temperature-dependent conductivity and Hall effect data measured for temperatures T > 1.7 K both indicate that a transition from insulating to metallic conduction occurs at a peak sulfur concentration between 1.8 and 4.3 × 1020 cm–3. Conduction in insulating samples is consistent with variable range hopping with a Coulomb gap. The capacity for deep states to effect metallic conduction by delocalization is the only known route to bulk intermediate band photovoltaics in silicon.