Skip to main content

Selenium Segregation in Femtosecond-Laser Hyperdoped Silicon Revealed by Electron Tomography

  • Georg Haberfehlner (a1), Matthew J. Smith (a2), Juan-Carlos Idrobo (a3), Geoffroy Auvert (a4), Meng-Ju Sher (a5), Mark T. Winkler (a5), Eric Mazur (a5), Narciso Gambacorti (a1), Silvija Gradečak (a2) and Pierre Bleuet (a1)...

Doping of silicon with chalcogens (S, Se, Te) by femtosecond laser irradiation to concentrations well above the solubility limit leads to near-unity optical absorptance in the visible and infrared (IR) range and is a promising route toward silicon-based IR optoelectronics. However, open questions remain about the nature of the IR 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 three-dimensional 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.

Corresponding author
* Corresponding author. E-mail:
Hide All
Adams R. & Bischof L. (1994). Seeded region growing. IEEE Trans Pattern Anal Mach Intell 16, 641647.
Bals S., Batenburg K.J., Verbeeck J., Sijbers J. & Van Tendeloo G. (2007). Quantitative three-dimensional reconstruction of catalyst particles for bamboo-like carbon nanotubes. Nano Lett 7, 36693674.
Bals S., Casavola M., van Huis M.A., Van Aert S., Batenburg K.J., Van Tendeloo G. & Vanmaekelbergh D.L. (2010). Three-dimensional atomic imaging of colloidal core-shell nanocrystals. Nano Lett 11, 34203424.
Batenburg K.J., Bals S., Sijbers J., Kübel C., Midgley P.A., Hernandez J.C., Kaiser U., Encina E.R., Coronado E.A. & Van Tendeloo G. (2009). 3D imaging of nanomaterials by discrete tomography. Ultramicroscopy 109, 730740.
Carey J.E., Crouch C.H., Shen M. & Mazur E. (2005). Visible and near-infrared responsivity of femtosecond-laser microstructured silicon photodiodes. Opt Lett 30, 17731775.
Duguay S., Colin A., Mathiot D., Morin P. & Blavette D. (2010). Atomic-scale redistribution of dopants in polycrystalline silicon layers. J Appl Phys 108, 034911.
Fernandez J.-J. (2012). Computational methods for electron tomography. Micron 43, 10101030.
Fernandez J.J. & Sam L. (2005). Anisotropic nonlinear filtering of cellular structures in cryoelectron tomography. Comput Sci Eng 7, 5461.
Fernández-Busnadiego R., Zuber B., Maurer U.E., Cyrklaff M., Baumeister W. & Lučić V. (2010). Quantitative analysis of the native presynaptic cytomatrix by cryoelectron tomography. J Cell Biol 188, 145156.
Frangakis A.S. & Hegerl R. (2001). Noise reduction in electron tomographic reconstructions using nonlinear anisotropic diffusion. J Struct Biol 135, 239250.
Gilbert P. (1972). Iterative methods for the three-dimensional reconstruction of an object from projections. J Theor Biol 36, 105117.
Goris B., Bals S., Van den Broek W., Carbó-Argibay E., Gómez-Graña S., Liz-Marzán L.M. & Van Tendeloo G. (2012a). Atomic-scale determination of surface facets in gold nanorods. Nat Mater 11, 930935.
Goris B., Van den Broek W., Batenburg K.J., Heidari Mezerji H. & Bals S. (2012b). Electron tomography based on a total variation minimization reconstruction technique. Ultramicroscopy 113, 120130.
Hyun J.K., Ercius P. & Muller D.A. (2008). Beam spreading and spatial resolution in thick organic specimens. Ultramicroscopy 109, 17.
Jin S., Jones K.S., Law M.E. & Camillo-Castillo R. (2012). B segregation to grain boundaries and diffusion in polycrystalline Si with flash annealing. J Appl Phys 111, 044508.
Kaneko K., Inoke K., Sato K., Kitawaki K., Higashida H., Arslan I. & Midgley P.A. (2008). TEM characterization of Ge precipitates in an Al-1.6 at% Ge alloy. Ultramicroscopy 108, 210220.
Kawase N., Kato M., Nishioka H. & Jinnai H. (2007). Transmission electron microtomography without the “missing wedge” for quantitative structural analysis. Ultramicroscopy 107, 815.
Ke X., Bals S., Cott D., Hantschel T., Bender H. & Van Tendeloo G. (2010). Three-dimensional analysis of carbon nanotube networks in interconnects by electron tomography without missing wedge artifacts. Microsc Microanal 16, 210217.
Midgley P.A. & Dunin-Borkowski R.E. (2009). Electron tomography and holography in materials science. Nat Mater 8, 271280.
Midgley P.A. & Weyland M. (2003). 3D electron microscopy in the physical sciences: The development of Z-contrast and EFTEM tomography. Ultramicroscopy 96, 413431.
Narasimha R., Aganj I., Bennett A.E., Borgnia M.J., Zabransky D., Sapiro G., McLaughlin S.W., Milne J.L.S. & Subramaniam S. (2008). Evaluation of denoising algorithms for biological electron tomography. J Struct Biol 164, 717.
Newman B.K., Sullivan J.T., Winkler M.T., Sher M.J., Marcus M.A., Fakra S., Smith M.J., Gradečak S., Mazur E. & Buonassisi T. (2009). Illuminating the mechanism for sub-bandgap absorption in chalcogen doped silicon materials for PV applications. In 24th European Photovoltaic Solar Energy Conference, pp. 236238.
Perona P. & Malik J. (1990). Scale-space and edge detection using anisotropic diffusion. IEEE Trans Pattern Anal Mach Intell 12, 629639.
Saghi Z., Holland D.J., Leary R., Falqui A., Bertoni G., Sederman A.J., Gladden L.F. & Midgley P.A. (2011). Three-dimensional morphology of iron oxide nanoparticles with reactive concave surfaces. A compressed sensing-electron tomography (CS-ET) approach. Nano Lett 11, 46664673.
Salvi E., Cantele F., Zampighi L., Fain N., Pigino G., Zampighi G. & Lanzavecchia S. (2008). JUST (Java User Segmentation Tool) for semi-automatic segmentation of tomographic maps. J Struct Biol 161, 287297.
Schierning G., Theissmann R., Stein N., Petermann N., Becker A., Engenhorst M., Kessler V., Geller M., Beckel A., Wiggers H. & Schmechel R. (2011). Role of oxygen on microstructure and thermoelectric properties of silicon nanocomposites. J Appl Phys 110, 113515.
Scott M.C., Chen C.-C., Mecklenburg M., Zhu C., Xu R., Ercius P., Dahmen U., Regan B.C. & Miao J. (2012). Electron tomography at 2.4-angstrom resolution. Nature 483, 444447.
Sheehy M.A., Tull B.R., Friend C.M. & Mazur E. (2007). Chalcogen doping of silicon via intense femtosecond-laser irradiation. Mater Sci Eng B 137, 289294.
Sher M.J., Winkler M.T. & Mazur E. (2011). Pulsed-laser hyperdoping and surface texturing for photovoltaics. MRS Bull 36, 439445.
Smith M., Winkler M., Sher M.-J., Lin Y.-T., Mazur E. & Gradečak S. (2011a). The effects of a thin film dopant precursor on the structure and properties of femtosecond-laser irradiated silicon. Appl Phys A 105, 795800.
Smith M.J., Lin Y.-T., Sher M.-J., Winkler M.T., Mazur E. & Gradečak S. (2011b). Pressure-induced phase transformations during femtosecond-laser doping of silicon. J Appl Phys 110, 053524.
Smith M.J., Sher M.-J., Franta B., Lin Y.-T., Mazur E. & Gradečak S. (2012). The origins of pressure-induced phase transformations during the surface texturing of silicon using femtosecond laser irradiation. J Appl Phys 112, 083518.
Thompson K., Booske J.H., Larson D.J. & Kelly T.F. (2005). Three-dimensional atom mapping of dopants in Si nanostructures. Appl Phys Lett 87, 052108.
Tull B., Winkler M. & Mazur E. (2009). The role of diffusion in broadband infrared absorption in chalcogen-doped silicon. Appl Phys A 96, 327334.
Tull B.R., Carey J.E., Mazur E., McDonald J.P. & Yalisove S.M. (2006). Silicon surface morphologies after femtosecond laser irradiation. MRS Bull 31, 626633.
Van Aert S., Batenburg K.J., Rossell M.D., Erni R. & Van Tendeloo G. (2011). Three-dimensional atomic imaging of crystalline nanoparticles. Nature 470, 374377.
Van Aert S., Verbeeck J., Erni R., Bals S., Luysberg M., Dyck D.V. & Tendeloo G.V. (2009). Quantitative atomic resolution mapping using high-angle annular dark field scanning transmission electron microscopy. Ultramicroscopy 109, 12361244.
Van den Broek W., Rosenauer A., Goris B., Martinez G.T., Bals S., Van Aert S. & Van Dyck D. (2012). Correction of non-linear thickness effects in HAADF STEM electron tomography. Ultramicroscopy 116, 812.
Volkmann N. (2002). A novel three-dimensional variant of the watershed transform for segmentation of electron density maps. J Struct Biol 138, 123129.
Vydyanath H.R., Lorenzo J.S. & Kroger F.A. (1978). Defect pairing diffusion, and solubility studies in selenium-doped silicon. J Appl Phys 49, 59285937.
Wu C., Crouch C.H., Zhao L., Carey J.E., Younkin R., Levinson J.A., Mazur E., Farrell R.M., Gothoskar P. & Karger A. (2001). Near-unity below-band-gap absorption by microstructured silicon. Appl Phys Lett 78, 18501852.
Yaguchi T., Konno M., Kamino T. & Watanabe M. (2008). Observation of three-dimensional elemental distributions of a Si device using a 360°-tilt FIB and the cold field-emission STEM system. Ultramicroscopy 108, 16031615.
Younkin R., Carey J.E., Mazur E., Levinson J.A. & Friend C.M. (2003). Infrared absorption by conical silicon microstructures made in a variety of background gases using femtosecond-laser pulses. J Appl Phys 93, 26262629.
Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Microscopy and Microanalysis
  • ISSN: 1431-9276
  • EISSN: 1435-8115
  • URL: /core/journals/microscopy-and-microanalysis
Please enter your name
Please enter a valid email address
Who would you like to send this to? *


Type Description Title
Supplementary Materials

Haberfehlner supplementary material
Haberfehlner supplementary material

 PDF (2.1 MB)
2.1 MB
Movie 2

Haberfehlner supplementary movie 2
Haberfehlner supplementary movie 2

 Video (3.9 MB)
3.9 MB
Movie 1

Haberfehlner supplementary movie 1
Haberfehlner supplementary movie 1

 Video (6.0 MB)
6.0 MB


Full text views

Total number of HTML views: 1
Total number of PDF views: 11 *
Loading metrics...

Abstract views

Total abstract views: 214 *
Loading metrics...

* Views captured on Cambridge Core between September 2016 - 25th November 2017. This data will be updated every 24 hours.