A simple KPFM-based approach for electrostatic-free topographic measurements: the case of MoS2_2 on SiO2_2

A simple implementation of Kelvin probe force microscopy is reported that enables recording topographic images in the absence of any component of the electrostatic force. Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum, the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that defects at the TMD/oxide interface can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to non-defective sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxide

Heat dissipation in few-layer MoS2and MoS2/hBN heterostructure

State-of-the-art fabrication and characterisation techniques have been employed to measure the thermal conductivity of suspended, single-crystalline MoS2 and MoS2/hBN heterostructures. Two-laser Raman scattering thermometry was used combined with real time measurements of the absorbed laser power. Measurements on MoS2 layers with thicknesses of 5 and 14 nm exhibit thermal conductivity in the range between 12 Wm-1 K-1 and 24 Wm-1 K-1. Additionally, after determining the thermal conductivity of the latter MoS2 sample, an hBN flake was transferred onto it and the effective thermal conductivity of the heterostructure was subsequently measured. Remarkably, despite that the thickness of the hBN layer was less than a hal of the thickness of the MoS2 layer, the heterostructure showed an almost eight-fold increase in the thermal conductivity, being able to dissipate more than ten times the laser power without any visible sign of damage. These results are consistent with a high thermal interface conductance G between MoS2 and hBN and an efficient in-plane heat spreading driven by hBN. Indeed, we estimate G ∼ 70 MW m-2 K-1 for hBN layer thermal conductivity of 450 Wm-1 K-1 which is significantly higher than previously reported values. Our work therefore demonstrates that the insertion of hBN layers in potential MoS2-based devices holds the promise for efficient thermal management.This work was partially funded by the European Union under the H2020 FET-OPEN NANOPOLY (GA 289061) and Spanish Ministry of Science projects SIP (PGC2018-101743-B-I00), ADAGIO (PGC2018-094490-B-C22), 2DTecBio (FIS2017-85787-R) and 2DENGINE (PID2019-111773RB- I00/AEI/10.13039/501100011033). E D C acknowledges the Spanish Ministry of Science for the Juan de la Cierva Fellowship (JC-2015-25201) and the Ramon y Cajal fellowship (RYC2019-027879-I). D N U and J F S acknowledge the Ramón y Cajal fellowships RYC2014-15392 and RYC2019-028368-I/AEI/10.13039/501100011033. M V C acknowledges project (Reference No. 103739) funded by the Agencia Estatal de Investigación through the PCI 2019 call. The Catalan Institute of Nanoscience and Nanotechnology (ICN2) is funded by the CERCA program/Generalitat de Catalunya, and is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706). K W and T T acknowledge support from the Elemental Strategy Initiative conducted by the MEXT, Japan (Grant Number JPMXP0112101001) and JSPS KAKENHI (Grant Numbers 19H05790 and JP20H00354)

Strongly anisotropic spin relaxation in graphene/transition metal dichalcogenide heterostructures at room temperature

Graphene has emerged as the foremost material for future two-dimensional spintronics due to its tuneable electronic properties. In graphene, spin information can be transported over long distances and, in principle, be manipulated by using magnetic correlations or large spin-orbit coupling (SOC) induced by proximity effects. In particular, a dramatic SOC enhancement has been predicted when interfacing graphene with a semiconducting transition metal dechalcogenide, such as tungsten disulphide (WS$_2$). Signatures of such an enhancement have recently been reported but the nature of the spin relaxation in these systems remains unknown. Here, we unambiguously demonstrate anisotropic spin dynamics in bilayer heterostructures comprising graphene and WS$_2$. By using out-of-plane spin precession, we show that the spin lifetime is largest when the spins point out of the graphene plane. Moreover, we observe that the spin lifetime varies over one order of magnitude depending on the spin orientation, indicating that the strong spin-valley coupling in WS$_2$ is imprinted in the bilayer and felt by the propagating spins. These findings provide a rich platform to explore coupled spin-valley phenomena and offer novel spin manipulation strategies based on spin relaxation anisotropy in two-dimensional materials

Thermal and thermoelectric properties of two-dimensional materials

La gestió tèrmica és un problema crític en el disseny de dispositius nanoelectrònics. Les solucions de refredament avançades i la recol·lecció eficient d'energia són clau per mantenir la tendència de productes electrònics cada vegada més petits i ràpids. Aquesta tesi se centra en la gestió tèrmica i l'ús de calor dissipada en materials emergents per a l'electrònica. En particular, els materials bidimensionals (2DM) i heteroestructures d'aquests són dels candidats més interessants per al futur de l'electrònica i s'estan investigant intensament. En aquesta tesi, s'exploren dos temes principals: (i) el transport tèrmic de 2DMs suspesos, inclòs el grafè CVD, dicalcògens de metalls de transició (TMDC) i heteroestructures de TMDC amb nitrur de bor hexagonal (hBN); i (ii) les propietats tèrmiques i de termoelectricitat de les pel·lícules primes (Bi1-xSbx)2Te3 (BST). Aquests materials s'estan considerant per interconnexions i transistors fins als THz (grafè), per a electrònica digital (TMDCs) i per a aïllament elèctric (hBN) i són ben coneguts com a generadors termoelèctrics, com ho són també materials recentment identificats com a aïllants topològics (BST). En primer lloc, l'objectiu era mesurar la conductivitat tèrmica de 2DMs utilitzant el mètode d'espectroscòpia Raman de dos làsers, recentment desenvolupat. La implementació fou dificultada per l'ús de membranes relativament petites obtingudes dels materials investigats i la seva alta conductivitat tèrmica. Demostràrem que la conductivitat tèrmica del grafè CVD és d'aproximadament 300 W/(m·K). Encara que menor que en el grafè exfoliat, això podria ser degut a les fronteres de gra i al desordre en el grafè CVD. Demostràrem també que les conductivitats tèrmiques de MoS2 i MoSe2 exfoliats (dos TMDC) són de 12 a 24 W/(m·K) i 60 W/(m·K), respectivament. I que per a membranes primes (de poques monocapes) de MoS2, la conductivitat incrementa amb el gruix. Afegint una membrana de hBN exfoliada sobre una mostra de MoS2 prèviament caracteritzada demostràrem un augment notable de la conductivitat tèrmica en l'heteroestructura de hBN/MoS2, quan s'introdueix calor al MoS2. Aquesta presenta una conductivitat tèrmica de 185 W/(m·K), gairebé un ordre de magnitud més gran que el MoS2 sol. En segon lloc, capes primes de BST crescudes mitjançant epitàxia de feix molecular s'estudiaren amb l'objectiu de correlacionar-ne les propietats termoelèctriques amb el seu nivell de Fermi, que sintonitzaria el pes relatiu del transport de volum i dels estats topològics de superfície (TSS). Primer demostràrem que és possible dissenyar l'estructura de la banda i ajustar el nivell de Fermi des de la valència fins a la banda de conducció simplement controlant la concentració de Sb. La demostració s'aconseguí utilitzant espectroscòpia de fotoemissió amb resolució angular en combinació amb conductivitat elèctrica i mesures d'efecte Hall en pel·lícules relativament primes (10 nm). S'identificà la concentració de Sb a la qual els TSSs dominen el transport i es dugueren a terme experiments termoelèctrics en les mateixes capes. No es trobà una correlació clara entre l'energia termoelèctrica i la naturalesa dels portadors de càrrega quan els TSSs eren dominants. Això indica que el transport dels TSSs té una influència limitada en les propietats termoelèctriques d'aquest material, i que per tal d'observar els efectes de superfície es necessitarien capes encara més primes. Finalment, una caracterització de les capes primes de BST usant espectroscòpia Raman demostrà variacions específiques en el comportament associat a la concentració de Sb. En particular, l'augment de la potència del làser va donar lloc a l'aparició de pics Raman no actius d'origen indeterminat. Aquests pics poden indicar la ruptura de simetries estructurals, modes de fonó de superfície o altres efectes com ara ressonàncies plasmòniques que són d'alt interès. La inesperada resposta observada en l'espectre Raman hauria de motivar investigacions addicionals.La gestión térmica es un problema crítico en el diseño de dispositivos nanoelectrónicos. Las soluciones de enfriamiento avanzadas y la recolección eficiente de energía son clave para mantener la tendencia de productos electrónicos cada vez más pequeños y rápidos. Esta tesis se centra en la gestión térmica y el uso de calor disipado en materiales emergentes para la electrónica. En particular, los materiales bidimensionales (2DM) y las heteroestructuras basadas en ellos son candidatos muy interesantes para el futuro de la electrónica y se están investigando intensamente. La tesis trata dos temas principales: (i) el transporte térmico de 2DMs suspendidos, incluido el grafeno CVD, dicalcogenuros de metales de transición (TMDC) y heteroestructuras de TMDC con nitruro de boro hexagonal (hBN); y (ii) las propiedades térmicas y de termoelectricidad de películas delgadas de (Bi1-xSbx)2Te3(BST). Estos materiales están siendo considerados para interconexiones y transistores hasta THz (grafeno), electrónica digital (TMDCs) y aislamiento eléctrico (hBN) y son bien conocidos como generadores termoeléctricos, como también lo son materiales recientemente identificados como aislantes topológicos (BST). En primer lugar, el objetivo fue medir la conductividad térmica de 2DMs utilizando el método de espectroscopia Raman de dos láser, recientemente desarrollado. El desafío fue el uso de membranas relativamente pequeñas obtenidas y su alta conductividad térmica. Demostramos que la conductividad térmica del grafeno CVD es de aproximadamente 300 W/(m·K). Aunque menor que en el grafeno exfoliado, esto podría deberse a los bordes de grano y al desorden en grafeno CVD. Demostramos también que las conductividades térmicas de MoS2 y MoSe2 exfoliados (dos TMDC) son 12 a 24 W/(m·K) y 60 W/(m·K), respectivamente. Y que para membranas delgadas (pocas monocapas) la conductividad incrementa con su grosor. Agregando una membrana de hBN exfoliada sobre una muestra de MoS2 previamente caracterizada nos permitió demostrar un notable aumento de la conductividad térmica en la heteroestructura de hBN/MoS2, cuando se introduce calor en MoS2. Esta presenta una conductividad térmica de 185 W/(m·K), casi un orden de magnitud mayor que para MoS2. En segundo lugar, se estudiaron películas delgadas de BST crecidas mediante epitaxia de haz molecular con el objetivo de correlacionar sus propiedades termoeléctricas con su nivel de Fermi, que sintonizaría el peso relativo del transporte de volumen y de los estados topológicos de superficie (TSS). Primero demostramos que es posible diseñar la estructura de la banda y ajustar el nivel de Fermi desde la valencia hasta la banda de conducción simplemente controlando la concentración de Sb. Para ello se utilizó espectroscopia de fotoemisión con resolución angular en combinación con conductividad eléctrica y mediciones de Hall en películas relativamente delgadas (10 nm). También se identificó la concentración de Sb a la que los TSSs dominan el transporte y se llevaron a cabo experimentos termoeléctricos en las mismas películas. No se encontró una correlación clara entre la energía termoeléctrica y la naturaleza de los portadores de carga cuando los TSSs eran dominantes, indicando que el transporte de los TSSs tiene una influencia limitada en las propiedades termoeléctricas de este material y que para observar los efectos de superficie se necesitarían películas más delgadas. Finalmente, una caracterización de las películas delgadas de BST usando espectroscopia Raman demostró variaciones específicas en el comportamiento asociado a la concentración de Sb. En particular, el aumento de la potencia del láser dio lugar a la aparición de picos Raman no activos de origen indeterminado. Estos picos pueden indicar la ruptura de simetrías estructurales, modos de fonón de superficie u otros efectos tales como resonancias plasmónicas que son de alto interés, una respuesta que debería motivar investigaciones adicionales.Thermal management is becoming a critical issue in the packaging and design of nanoelectronics. Advanced cooling solutions and efficient energy harvesting are key aspects to help keep the trend for ever smaller and faster electronics. This thesis is focused on thermal management and the use of heat waste in emerging materials for electronics. In particular, two-dimensional materials (2DM), and related heterostructures, are amongst the most intriguing prospects for future electronics and are being intensively investigated. Here, two main subjects were explored. First, the thermal transport of suspended 2DMs, including CVD graphene, transition metal dichalcogenides (TMDCs) and heterostructures of TMDCs with hexagonal boron nitride (hBN) and, second, the thermal properties and thermoelectricity of (Bi1-xSbx)2Te3 (BST) thin films. These materials are being considered for interconnects and THz transistors (graphene), digital electronics (TMDCs) and electrical insulation (hBN) and are well known as thermoelectric generators, as are also materials that have recently been identified as topological insulators (BST). In the first part, the objective was to demonstrate the measurement of the thermal conductivity of 2DMs using the recently developed two-laser Raman spectroscopy method. Its implementation was rendered difficult by the relatively small exfoliated flakes of the materials investigated and their high thermal conductivity. The thermal conductivity of CVD graphene was found to be about 300 W/(m·K). Although smaller than exfoliated graphene, it is argued that this could be due to grain boundaries and disorder. Exfoliated MoS2 and MoSe2 (two well-known TMDCs) presented thermal conductivities of 12 to 24 W/(m·K) and 60 W/(m·K). Measurements on different membranes of MoS2 further showed that the conductivity increases with the thickness in thin membranes (few monolayers). Furthermore, stacking an exfoliated hBN membrane on top of a previously characterized MoS2 sample allowed us to demonstrate a notorious increase of the thermal conductivity in the hBN/MoS2 heterostructure, when heat is introduced on MoS2. Indeed, when compared with MoS2 alone the thermal conductivity is found to be almost one order of magnitude larger, 185 W/(m·K). For the second part, BST thin films were grown by molecular beam epitaxy. The main objective was to investigate the correlation of the thermoelectric properties of these materials with the Fermi level, which would tune the relative weight of bulk and topological surface state (TSS) transport. It was first demonstrated that controlling the concentration of Sb we could engineer the band structure and tune the Fermi level from the valence to the conduction band. Such demonstration was achieved by using angle-resolved photoemission spectroscopy in combination with conductivity and Hall measurements in relatively thin (10 nm) films. The Sb concentration at which TSS dominated the transport was also identified. Thermoelectric experiments on the same films were then carried out but no clear correlation between the thermopower and the carrier nature was found when the TSSs were dominant. These results indicate that TSS transport has limited influence on the thermoelectric properties. Further studies should be carried our using even thinner films. Finally, a side characterization of the BST thin films using Raman spectroscopy demonstrated specific variations in the behaviour associated to Sb concentration. An increase of the laser power showed the emergence of non-active Raman peaks of undetermined origin. However, they can indicate the presence of broken structural symmetries, surface phonon modes or other effects such as plasmonic resonances. This interesting response is worthy of for further investigation.Universitat Autònoma de Barelona. Programa de Doctorat en Físic

A simple KPFM-based approach for electrostaticfree topographic measurements: the case of MoS2 on SiO2

A simple implementation of Kelvin probe force microscopy is reported that enables recording topographic images in the absence of any component of the electrostatic force. Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum, the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that defects at the TMD/oxide interface can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to non-defective sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxide

A simple KPFM-based approach for electrostaticfree topographic measurements: the case of MoS2_2 on SiO2_2

A simple implementation of Kelvin probe force microscopy is reported that enables recording topographic images in the absence of any component of the electrostatic force. Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum, the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that defects at the TMD/oxide interface can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to non-defective sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxide

A simple KPFM-based approach for electrostaticfree topographic measurements: the case of MoS2 on SiO2

A simple implementation of Kelvin probe force microscopy is reported that enables recording topographic images in the absence of any component of the electrostatic force. Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum, the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that defects at the TMD/oxide interface can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to non-defective sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxide

Thermoelectric properties of topological insulators

Resumen del póster presentado al 1st Workshop Spain-Taiwan: "2D Materials and Interfaces for Spintronics", celebrado en Barcelona (España) del 23 al 25 de octubre de 2017.Topological Insulators (TIs) are some of the best thermoelectric materials. They are made of heavy elements that give a low phonon thermal conductivity and a small bandgap. Bi2Te3 is one of the best with a large figure of merit ZT. In this work, we take into account the Dirac states of TIs in the study case of thermoelectric properties. This can lead to improve the power factor. Different alloys of (Bi1-xSbx)2Te3 have been grown by MBE on a (111) Barium Fluoride substrate. Usual XPS measurements were made in order to see the different concentration. In addition, ARPES and Hall measurements combined to define the surface states. Finally, thermoelectric devices were designed by lithography in the objective to measure the Seebeck coefficient.Peer reviewe

Heat transport in two-dimensional heterostructures studied using Raman thermometry

Resumen del póster presentado a la 6th edition of Graphene Conference series, the largest European Event in Graphene and 2D Materials, celebrada en Genova (Italia) del 19 al 22 de abril de 2016.In order to study the thermal properties of 2-dimensional materials such as graphene and h-BN we have fabricated a series of free-standing samples adapting a standard mechanical transfer method to a free-standing geometry. Several transfer processes based on different polymers have been tested as for example PMMA, PPC. As support platform we have designed and fabricated a series of holy Si substrates with holes of circular geometry and different diameters ranging from 5 to 50um. Whereas the BN samples were fabricated by direct exfoliation, the grapheme samples were grown on Cu substrates using chemical vapor deposition and subsequently transferred to the hoy substrates. The thermal conductivity of the samples was measured using a state-of-the art thermal characterization technique, two-laser Raman thermometry, a contactless method based on a two laser approach. In addition to the thermal conductivity we could also obtain thermal maps which directly show how heat is dissipated, upon a localized excitation, to the 2-dimensional flakes and to the substrate. In addition, this technique allowed us to study the higher temperature regime close to 1000 ºK, which results almost impossible using alternative approaches.Peer reviewe

Fracturing of polycrystalline MoS2 nanofilms

The possibility of tailoring the critical strain of two-dimensional (2D) materials will be crucial for the fabrication of flexible and stretchable devices. While crystalline MoS2 monolayer shows tensile strength comparable to that of steel, a large concentration of defects and grain boundaries in polycrystalline MoS2 significantly degrades its mechanical properties. In this paper, the fracture in polycrystalline MoS2 films with an average grain size below 10 nm is studied at the micro- and nanoscale using electron microscopy. Two samples with different thicknesses and grain orientations horizontal and vertical to the sample plane are measured. The critical uniaxial strain is determined to be approximately 5% and independent of the sample morphology. However, electron beam irradiation is found to enhance the interaction between MoS2 and polydimethylsiloxane (PDMS) substrates, leading to an increased critical strain that can exceed 10%. This enhancement of strain resistance was used to fabricate a mechanically robust array of MoS2 lines 1 mm in length. Finally, nanoscale crack propagation studied by transmission electron microscopy showed that cracks propagate along the grain boundaries as well as through the grains, preferentially along van der Waals planes. These results provide insight into the fracture of polycrystalline 2D materials and a method to enhance the critical strain.ICN2 is funded by the CERCA program/Generalitat de Catalunya and supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706). We acknowledge support from the EU Project NANOPOLY (GA 289061) and the Spanish MICINN project SIP (PGC2018-101743-BI00). M.S. thanks D. Torres Navarro for his support in figure preparation. M.P. acknowledges the support from Spanish Ministry of Science, Innovation and Universities within the Ramon y Cajal Program (RYC-2017-23758). P.X. is supported by a M. Sklodowska-Curie Fellowship (COFUND BIST Predoctoral Programme, PREBIST project, Grant No. 754558).Peer reviewe