Ultrathin PbS Sheets by Two-Dimensional Oriented Attachment

Manufacturing Nanomaterials The exploration of many materials at the nanoscale has revealed properties that only emerge when working at these small dimensions. For device manufacture, materials need to be deposited or assembled in specific patterns. Schliehe et al. (p. 550; see the cover) show the oriented attachment of lead sulfide nanocrystals into two-dimensional sheets. The packing is driven by the choice of solvents that influence the interactions between the nanocrystals. The nanocrystals have excellent photoconductive properties and were incorporated into a photodetector without any additional chemical processing. Self-assembled two-dimensional nanocrystals of lead sulfide have excellent photoconductive properties. Controlling anisotropy is a key concept in the generation of complex functionality in advanced materials. For this concept, oriented attachment of nanocrystal building blocks, a self-assembly of particles into larger single-crystalline objects, is one of the most promising approaches in nanotechnology. We report here the two-dimensional oriented attachment of lead sulfide (PbS) nanocrystals into ultrathin single-crystal sheets with dimensions on the micrometer scale. We found that this process is initiated by cosolvents, which alter nucleation and growth rates during the primary nanocrystal formation, and is finally driven by dense packing of oleic acid ligands on {100} facets of PbS. The obtained nanosheets can be readily integrated in a photodetector device without further treatment.

[1]  P. Yang,et al.  Shape, size, and assembly control of PbTe nanocrystals. , 2007, Journal of the American Chemical Society.

[2]  R. Koole,et al.  The hidden role of acetate in the PbSe nanocrystal synthesis. , 2006, Journal of the American Chemical Society.

[3]  H. Yang,et al.  Self-construction of hollow SnO(2) octahedra based on two-dimensional aggregation of nanocrystallites. , 2004, Angewandte Chemie.

[4]  C. Klinke,et al.  Carbon supported CdSe nanocrystals. , 2008, Journal of the American Chemical Society.

[5]  Jin-Sil Choi,et al.  Shape control of semiconductor and metal oxide nanocrystals through nonhydrolytic colloidal routes. , 2006, Angewandte Chemie.

[6]  M. Antonietti,et al.  Ligand‐Directed Assembly of Preformed Titania Nanocrystals into Highly Anisotropic Nanostructures , 2004 .

[7]  J. Banfield,et al.  Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. , 2000, Science.

[8]  Banfield,et al.  Imperfect oriented attachment: dislocation generation in defect-free nanocrystals , 1998, Science.

[9]  Jung Ho Yu,et al.  Large-scale soft colloidal template synthesis of 1.4 nm thick CdSe nanosheets. , 2009, Angewandte Chemie.

[10]  Xiaofeng Zhang,et al.  Self-organized ultrathin oxide nanocrystals. , 2009, Nano letters.

[11]  K. Schwarzhans,et al.  207Pb-NMR-Untersuchungen an Bleiorganylen , 1987 .

[12]  Dmitri V Talapin,et al.  PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors , 2005, Science.

[13]  P. Prasad,et al.  Shape Control of CdS Nanocrystals in One-Pot Synthesis , 2007 .

[14]  M. Bawendi,et al.  On the mechanism of lead chalcogenide nanocrystal formation. , 2006, Journal of the American Chemical Society.

[15]  Y. Matsuura,et al.  Structure and Crystallization Behavior of the Phase of Oleic Acid , 1997 .

[16]  Kyung-Sang Cho,et al.  Designing PbSe nanowires and nanorings through oriented attachment of nanoparticles. , 2005, Journal of the American Chemical Society.

[17]  M. Kovalenko,et al.  Colloidal Nanocrystals with Molecular Metal Chalcogenide Surface Ligands , 2009, Science.

[18]  G. Konstantatos,et al.  Ultrasensitive solution-cast quantum dot photodetectors , 2006, Nature.

[19]  S. Abrahamsson,et al.  The crystal structure of the low‐melting form of oleic acid , 1962 .

[20]  R. Schubert,et al.  Micelle and vesicle formation of amphiphilic nanoparticles. , 2009, Angewandte Chemie.

[21]  A. Kornowski,et al.  Synthesis of Monodisperse PbS Nanoparticles and Their Assembly into Highly Ordered 3D Colloidal Crystals , 2007 .

[22]  Matt Law,et al.  Structural, optical, and electrical properties of self-assembled films of PbSe nanocrystals treated with 1,2-ethanedithiol. , 2008, ACS nano.

[23]  J. Ashby References and Notes , 1999 .

[24]  Ariel Kigel,et al.  Synthesis and Characterization of PbSe Quantum Wires, Multipods, Quantum Rods, and Cubes , 2003 .

[25]  M. Kastner,et al.  Charge transport in PbSe nanocrystal arrays , 2008 .

[26]  Dmitri V Talapin,et al.  Self-assembly of PbTe quantum dots into nanocrystal superlattices and glassy films. , 2006, Journal of the American Chemical Society.

[27]  Zhiyong Tang,et al.  Self-Assembly of CdTe Nanocrystals into Free-Floating Sheets , 2006, Science.

[28]  R. Cernik,et al.  Using in-situ synchrotron radiation powder diffraction to characterize growth-related structural polymorphic phase transformations in cis-9-c0-octadecenoic acid , 1993 .

[29]  Q. Xue,et al.  Size-controlled synthesis of orderly organized cube-shaped lead sulfide nanocrystals via a solvothermal single-source precursor method , 2007 .

[30]  Giovanni Luigi Carlo Bongiovanni,et al.  Solution‐Processable Near‐IR Photodetectors Based on Electron Transfer from PbS Nanocrystals to Fullerene Derivatives , 2009 .