Impact of Stoichiometry on the Structure of van der Waals Layered GeTe/Sb2 Te3 Superlattices Used in Interfacial Phase-Change Memory (iPCM) Devices.

Van der Waals layered GeTe/Sb2 Te3 superlattices (SLs) have demonstrated outstanding performances for use in resistive memories in so-called interfacial phase-change memory (iPCM) devices. GeTe/Sb2 Te3 SLs are made by periodically stacking ultrathin GeTe and Sb2 Te3 crystalline layers. The mechanism of the resistance change in iPCM devices is still highly debated. Recent experimental studies on SLs grown by molecular beam epitaxy or pulsed laser deposition indicate that the local structure does not correspond to any of the previously proposed structural models. Here, a new insight is given into the complex structure of prototypical GeTe/Sb2 Te3 SLs deposited by magnetron sputtering, which is the used industrial technique for SL growth in iPCM devices. X-ray diffraction analysis shows that the structural quality of the SL depends critically on its stoichiometry. Moreover, high-angle annular dark-field-scanning transmission electron microscopy analysis of the local atomic order in a perfectly stoichiometric SL reveals the absence of GeTe layers, and that Ge atoms intermix with Sb atoms in, for instance, Ge2 Sb2 Te5 blocks. This result shows that an alternative structural model is required to explain the origin of the electrical contrast and the nature of the resistive switching mechanism observed in iPCM devices.

[1]  T. Walther A new experimental procedure to quantify annular dark field images in scanning transmission electron microscopy , 2006, Journal of microscopy.

[2]  Wei Zhang,et al.  Metal - Insulator Transition Driven by Vacancy Ordering in GeSbTe Phase Change Materials , 2016, Scientific reports.

[3]  P Fons,et al.  Interfacial phase-change memory. , 2011, Nature nanotechnology.

[4]  Raffaella Calarco,et al.  Intermixing during Epitaxial Growth of van der Waals Bonded Nominal GeTe/Sb2Te3 Superlattices , 2016 .

[5]  Wei Zhang,et al.  Role of vacancies in metal-insulator transitions of crystalline phase-change materials. , 2012, Nature materials.

[6]  Agostino Pirovano,et al.  Phase Change Memories have taken the field , 2013, 2013 5th IEEE International Memory Workshop.

[7]  H. Krause,et al.  Refinement of the Sb2Te3 and Sb2Te2Se structures and their relationship to nonstoichiometric Sb2Te3−ySey compounds , 1974 .

[8]  Junji Tominaga,et al.  Self‐organized van der Waals epitaxy of layered chalcogenide structures , 2015 .

[9]  L. Erra,et al.  Temperature dependent resonant X-ray diffraction of single-crystalline Ge2Sb2Te5 , 2013 .

[10]  Bernd Rauschenbach,et al.  Van der Waals interfacial bonding and intermixing in GeTe-Sb2Te3-based superlattices , 2018, Nano Research.

[11]  Christophe Vallée,et al.  Phase-change materials for non-volatile memory devices: from technological challenges to materials science issues , 2017 .

[12]  K. Shiraishi,et al.  GeTe sequences in superlattice phase change memories and their electrical characteristics , 2014 .

[13]  Honggang Zhou,et al.  Problems and Solutions in Click Chemistry Applied to Drug Probes , 2016, Scientific Reports.

[14]  Epitaxial formation of cubic and trigonal Ge-Sb-Te thin films with heterogeneous vacancy structures , 2017 .

[15]  M. Wuttig,et al.  Phase-change materials for rewriteable data storage. , 2007, Nature materials.

[16]  A. V. Kolobov,et al.  Ferroelectric Order Control of the Dirac‐Semimetal Phase in GeTe‐Sb2Te3 Superlattices , 2014 .

[17]  Marcel A. Verheijen,et al.  Interface formation of two- and three-dimensionally bonded materials in the case of GeTe-Sb₂Te₃ superlattices. , 2015, Nanoscale.

[18]  N. Yamada,et al.  Structures of stable and metastable Ge2Sb2Te5, an intermetallic compound in GeTe-Sb2Te3 pseudobinary systems. , 2004, Acta crystallographica. Section B, Structural science.

[19]  J. Tominaga,et al.  A two-step process for growth of highly oriented Sb2Te3 using sputtering , 2016 .

[20]  Marcel A. Verheijen,et al.  Dynamic reconfiguration of van der Waals gaps within GeTe-Sb2Te3 based superlattices. , 2017, Nanoscale.

[21]  A. Lotnyk,et al.  Microstructure evolution in pulsed laser deposited epitaxial Ge-Sb-Te chalcogenide thin films , 2016 .

[22]  J. Kowal,et al.  Robust image alignment for cryogenic transmission electron microscopy. , 2017, Journal of structural biology.

[23]  Junji Tominaga,et al.  A Magnetoresistance Induced by a Nonzero Berry Phase in GeTe/Sb2Te3 Chalcogenide Superlattices , 2017 .

[24]  J. Tominaga,et al.  THz Pulse Detection by Multilayered GeTe/Sb2Te3. , 2016, ACS applied materials & interfaces.

[25]  X. Miao,et al.  Logic gates realized by nonvolatile GeTe/Sb2Te3 super lattice phase-change memory with a magnetic field input , 2016 .

[26]  K. Takeuchi,et al.  Investigation of multi-level-cell and SET operations on super-lattice phase change memories , 2014 .

[27]  Thermal annealing studies of GeTe-Sb2Te3 alloys with multiple interfaces , 2017 .

[28]  S. Murakami,et al.  Mirror-symmetric Magneto-optical Kerr Rotation using Visible Light in [(GeTe)2(Sb2Te3)1]n Topological Superlattices , 2014, Scientific Reports.

[29]  An Chen,et al.  A review of emerging non-volatile memory (NVM) technologies and applications , 2016 .

[30]  M. Wuttig,et al.  Atomic stacking and van-der-Waals bonding in GeTe–Sb_2Te_3 superlattices , 2016 .

[31]  K. Takeuchi,et al.  Reliable, low-power super-lattice phase-change memory without melting and write-pulse down slope , 2013, 2013 IEEE International Reliability Physics Symposium (IRPS).

[32]  Textured Sb2Te3 films and GeTe/Sb2Te3 superlattices grown on amorphous substrates by molecular beam epitaxy , 2017 .

[33]  John Robertson,et al.  Modeling of switching mechanism in GeSbTe chalcogenide superlattices , 2015, Scientific Reports.

[34]  M. Cecchini,et al.  Ultrastructural Characterization of the Lower Motor System in a Mouse Model of Krabbe Disease , 2016, Scientific Reports.

[35]  L. E. Shelimova,et al.  An X-ray study of the mixed-layered compounds of (GeTe)n (Sb2Te3)m homologous series , 1998 .

[36]  Zhitang Song,et al.  Phase‐Change Memory Materials by Design: A Strain Engineering Approach , 2016, Advanced materials.

[37]  Avalanche atomic switching in strain engineered Sb2Te3–GeTe interfacial phase-change memory cells , 2017 .

[38]  T. Chattopadhyay,et al.  Neutron diffraction study on the structural phase transition in GeTe , 1987 .

[39]  Role of interfaces on the stability and electrical properties of Ge2Sb2Te5 crystalline structures , 2017, Scientific Reports.

[40]  Shuichi Murakami,et al.  Giant multiferroic effects in topological GeTe-Sb2Te3 superlattices , 2015, Science and technology of advanced materials.

[41]  Simon Wall,et al.  Strain-engineered diffusive atomic switching in two-dimensional crystals , 2016, Nature Communications.