High thermoelectric and reversible p-n-p conduction type switching integrated in dimetal chalcogenide.

The subject of the involved phase transition in solid materials has formed not only the basis of materials technology but also the central issue of solid-state chemistry for centuries. The ability to design and control the required changes in physical properties within phase transition becomes key prerequisite for the modern functionalized materials. Herein, we have experimentally achieved the high thermoelectric performance (ZT value reaches 1.5 at 700 K) and reversible p-n-p semiconducting switching integrated in a dimetal chalcogenide, AgBiSe(2) during the continuous hexagonal-rhombohedral-cubic phase transition. The clear-cut evidences in temperature-dependent positron annihilation and Raman spectra confirmed that the p-n-p switching is derived from the bimetal atoms exchange within phase transition, whereas the full disordering of bimetal atoms after the bimetal exchange results in the high thermoelectric performance. The combination of p-n-p switching and high thermoelectric performance enables the dimetal chalcogenides perfect candidates for novel multifunctional electronic devices. The discovery of bimetal atoms exchange during the phase transition brings novel phenomena with unusual properties which definitely enrich solid-state chemistry and materials science.

[1]  C. N. R. Rao,et al.  Phase transitions and the chemistry of solids , 1984 .

[2]  J. Jiang,et al.  Structural and phase changes in amorphous solid water films revealed by positron beam spectroscopy. , 2010, Physical Review Letters.

[3]  Andreas Kornowski,et al.  Synthesis and Thermoelectric Characterization of Bi2Te3 Nanoparticles , 2009, 1003.0621.

[4]  Kun Li,et al.  Superionic phase transition in silver chalcogenide nanocrystals realizing optimized thermoelectric performance. , 2012, Journal of the American Chemical Society.

[5]  G. J. Snyder,et al.  Copper ion liquid-like thermoelectrics. , 2012, Nature materials.

[6]  O. Delaire,et al.  Phonon softening and metallization of a narrow-gap semiconductor by thermal disorder , 2011, Proceedings of the National Academy of Sciences.

[7]  Xiujian Zhao,et al.  Formation of AgI/TiO2 nanocomposite leads to excellent thermochromic reversibility and photostability , 2011 .

[8]  H. Gossmann,et al.  Vacancy-impurity complexes in highly Sb-doped Si grown by molecular beam epitaxy. , 2005, Physical review letters.

[9]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[10]  L. Bell Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems , 2008, Science.

[11]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[12]  Gabor A. Somorjai,et al.  Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect , 2004, Science.

[13]  Oliver Gutfleisch,et al.  Giant magnetocaloric effect driven by structural transitions. , 2012, Nature materials.

[14]  Mingxing Zhang,et al.  Crystallographic features of phase transformations in solids , 2009 .

[15]  Kun Li,et al.  Solid-solutioned homojunction nanoplates with disordered lattice: a promising approach toward "phonon glass electron crystal" thermoelectric materials. , 2012, Journal of the American Chemical Society.

[16]  J. Schumann,et al.  Precise control of thermal conductivity at the nanoscale through individual phonon-scattering barriers. , 2010, Nature materials.

[17]  J. Heremans,et al.  Measurements of the energy band gap and valence band structure of AgSbTe 2 , 2008 .

[18]  D. Morelli,et al.  Intrinsically minimal thermal conductivity in cubic I-V-VI2 semiconductors. , 2008, Physical review letters.

[19]  G. J. Snyder,et al.  Complex thermoelectric materials. , 2008, Nature materials.

[20]  G. J. Snyder,et al.  Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties , 2004, Nature materials.

[21]  Ali Shakouri,et al.  Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features , 2010, Advanced materials.

[22]  Teppei Yamada,et al.  Size-controlled stabilization of the superionic phase to room temperature in polymer-coated AgI nanoparticles. , 2009, Nature materials.

[23]  Yi Xie,et al.  New Vanadium Oxide Nanostructures: Controlled Synthesis and Their Smart Electrical Switching Properties , 2010, Advanced materials.

[24]  Zircon to monazite phase transition in CeVO4: X-ray diffraction and Raman-scattering measurements , 2011, 1105.0272.

[25]  C. Manolikas,et al.  Electron microscopic study of polymorphism and defects in AgBiSe2 and AgBiS2 , 1977 .

[26]  P. Nambissan,et al.  Positron annihilation studies of some anomalous features of Ni Fe 2 O 4 nanocrystals grown in Si O 2 , 2005 .

[27]  M. Kanatzidis,et al.  First-principles study of the electronic, optical, and lattice vibrational properties of AgSbTe 2 , 2008 .

[28]  O. Lebedev,et al.  Highly Disordered Crystal Structure and Thermoelectric Properties of Sn3P4 , 2008 .

[29]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[30]  S. Raoux,et al.  Size-dependent polar ordering in colloidal GeTe nanocrystals. , 2011, Nano letters.

[31]  K. Hashimoto,et al.  Synthesis of a metal oxide with a room-temperature photoreversible phase transition. , 2010, Nature chemistry.

[32]  K. Hashimoto,et al.  Electronic nematicity above the structural and superconducting transition in BaFe2(As1−xPx)2 , 2012, Nature.

[33]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[34]  S. Blundell,et al.  Coexistence of superconductivity and magnetism by chemical design. , 2010, Nature chemistry.

[35]  Fujio Izumi,et al.  VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data , 2011 .

[36]  K. Koumoto,et al.  Development of novel thermoelectric materials by reduction of lattice thermal conductivity , 2010, Science and technology of advanced materials.

[37]  D. Rowe CRC Handbook of Thermoelectrics , 1995 .

[38]  M. Janssen,et al.  Reversible switching between p- and n-type conduction in the semiconductor Ag10Te4Br3. , 2009, Nature materials.

[39]  Jun Zhang,et al.  Raman spectroscopy of few-quintuple layer topological insulator Bi2Se3 nanoplatelets. , 2011, Nano letters.