Strain-engineered interaction of quantum polar and superconducting phases

Much of the focus of modern condensed matter physics concerns control of quantum phases with examples that include flat band superconductivity in graphene bilayers, the interplay of magnetism and ferroelectricity, and induction of topological transitions by strain. Here we report the first observation of a reproducible and strong enhancement of the superconducting critical temperature, $T_c$, in strontium titanate (SrTiO3) obtained through careful strain engineering of interacting superconducting phase and the polar quantum phase (quantum paraelectric). Our results show a nearly 50% increase in $T_c$ with indications that the increase could become several hundred percent. We have thus discovered a means to control the interaction of two quantum phases through application of strain, which may be important for quantum information science. Further, our work elucidates the enigmatic pseudogap-like and preformed electron pairs phenomena in low dimensional strontium titanate as potentially resulting from the local strain of jammed tetragonal domains.Comment: Figure 4 - error correcte

Layered BiOI single crystals capable of detecting low dose rates of X-rays

Detecting low dose rates of X-rays is critical for making safer radiology instruments, but is limited by the absorber materials available. Here, we develop bismuth oxyiodide (BiOI) single crystals into effective X-ray detectors. BiOI features complex lattice dynamics, owing to the ionic character of the lattice and weak van der Waals interactions between layers. Through use of ultrafast spectroscopy, first-principles computations and detailed optical and structural characterisation, we show that photoexcited charge-carriers in BiOI couple to intralayer breathing phonon modes, forming large polarons, thus enabling longer drift lengths for the photoexcited carriers than would be expected if self-trapping occurred. This, combined with the low and stable dark currents and high linear X-ray attenuation coefficients, leads to strong detector performance. High sensitivities reaching 1.1  × 103 μC Gyair−1 cm−2 are achieved, and the lowest dose rate directly measured by the detectors was 22 nGyair s−1. The photophysical principles discussed herein offer new design avenues for novel materials with heavy elements and low-dimensional electronic structures for (opto)electronic applications

Ambipolar and Robust WSe2 Field‐Effect Transistors Utilizing Self‐Assembled Edge Oxides

Transition metal oxides (TMOs) with high work function (WF) show promising properties as unipolar p‐type contacts for transition metal dichalcogenides. Here, ambipolar field‐effect transistors (FETs) enabled by bilayer WSe2 with self‐assembled TMOs (WO2.57) as contacts are reported. Systematic material characterizations demonstrate the formation of WO2.57/WSe2 heterojunctions around nanoflake edges with Se atoms substituted by O atoms after air‐exposure, while pristine properties of WSe2 almost sustain in inner domains. As‐fabricated FETs exhibit both polarities, implying WO2.57 with lowered WF at edges can serve as both the p‐type and n‐type contact for inner WSe2. Noteworthy, greatly reduced contact resistance and enhanced channel current are achieved, compared to the devices without WO2.57 contacts. Linear drain–source current relationship from 77 to 300 K indicates the ohmic contact between edge WO2.57 and inner WSe2. Density functional theory calculations further reveal that the WO2.57/WSe2 heterojunction forms a barrier‐less charge distribution. These nm‐scale FETs possess remarkable electrical conductivity up to ≈2600 S m−1, ultra‐low leakage current down to ≈10−12 A, robustness for high voltage operation, and air stability, which even outperform pristine WSe2 FETs. Theoretical calculations reveal that the high conductivity is exclusively attributed to the air‐induced WO2.57 and its further carrier injection to WSe2

Crescimento e caracterização de grafeno de grande área e de dissulfureto de molibdénio por deposição química em fase de vapor (CVD)

Doutoramento em Nanociências e NanotecnologiaThe present work is aimed to provide description of experimental part of graphene and two-dimensional structures. State-of-the-art techniques employing chemical vapor deposition (CVD) were used to deposit graphene and two-dimensional structures for their multidisciplinary applications including nano-electronics and semi-conducting industries. All the problems, suggestions and other important issues related to the growth and parameterizing the optimum condition for strictly monolayer to few layers have been briefly discussed. This may give double benefits such as realizing 2D electronic devices with high carrier motilities and understanding the behaviour of these 2D materials upon small ion intercalation. The as synthesized graphene grown on copper (Cu) substrate showed the ideal Raman spectrum with least defect concentration. The presence of very small D peaks confirmed the high quality of graphene crystals with strictly monolayer to few layers. Moreover, High Resolution X-rays Spectroscopy (HR-XPS) analysis showed the high quality graphene with C 1s in sp2 configuration (with binding energy at ~284.8 eV). The absence of other components resembled the purity of graphene and again reconfirmed the good quality of synthesized graphene. The Raman image mapping, demonstrated the full coverage of large area graphene on copper substrate. Additionally, the High Resolution Transmission Electron Microscopy (HRTEM) results reconfirmed that the high crystalline nature with two-type of rotational planes, which may attributed to the presence of wrinkles formed during the transfer of graphene sheet on TEM grids. This thesis is also devoted to the heteroatom doping in order to tune the electronic properties of graphene. Ammonia (NH3) was used herein to provide nitrogen (N) as a source for foreign atom for the doping of pure graphene. Here again, efforts were made to discuss all the problems, suggestions and other important issues related to growth and parameterizing the optimum conditions for in-situ ammonia doping of graphene on Cu. The substrate (thickness of films) playing role in the defect creations was also discussed. Raman results showed the enhanced D and D’ peaks, which confirmed the doping of graphene by NH3. HRXPS showed the C 1s core level centred at a BE of 284.5 eV, ascribed to C sp2 can be co-related with the good quality of C. Thus, in context with the XPS, the graphene grown on 20 µm Cu substrate showed the better nitrogen intercalation in the graphene sheets under the same growing conditions. Two components (substitutional at BE of 401.7 eV and pyridinic at BE of 398.5 eV) were clearly distinguished in the respective N 1s core level. The doping with substitutional type of configuration, involves three nitrogen valence electron forming three σ– bonds, one electron filling the π–states, and the fifth electron entering the π*–states of the conduction band, and altogether provide a strong doping effect. The presented work also reported a study demonstrating an in-situ method for the quantitative characterization of nanoscale electrostatic properties of as-grown multilayer-graphene (MLG) sheets on nickel (Ni) by combining atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). Large area epitaxial MLG sheets were grown on Ni by using CVD technique. The high crystalline nature of MLG sheets on Ni was confirmed by Raman spectroscopy with the FWHM value as low as ~20 cm-1 for G peak. We performed the charge injection (and subsequent charge diffusion over time) on the as synthesized graphene on Ni. The results unveiled that: (i) MLG surface can be either positively or negatively charged through injection process using Pt coated Si-based AFM probes; (ii) the charges can be accumulated and eventually reached to saturated concentrations of (+4.45±0.1) μC/m2 and (−1.3±0.1) μC/m2 , respectively; and (iii) the charge diffusion coefficients on graphene surface were measured to be (1.50±0.05) × 10−16 m2 /s and (0.64±0.05) × 10−16 m2 /s for the positive and the negative charges, respectively. The concerned experiment related to the discovery of charge injection in MLG may pave the way for designing a new class of energy harvesting devices. In addition to this, study also demonstrated a technique for nano-patterning/charge lithography of surface charges by contact electrification, which could be a promising application to create charged nanostructures for next generation graphene based nano-electronic devices. A brief description on the quality of transferred substrate has also been noted. Various substrates such as SiO2/Si and Au substrate have been used. A relative quality comparison between before and after transfer of graphene has been critically described. Results from HRXPS show the iron monolayer interaction with graphene. Lastly, this research also showed the major parameterizing and synthesizing steps, and the work flow for the high quality TMDs materials (such as MoS2) by modifying the current CVD equipment. A thorough review of the fundamental properties as well as methods of synthesis, properties and problems related to the growth of 2D materials was also highlighted. The effect of pressure and other conditions for the growth of high quality were fully described. This study found 50mbar as an optimum pressure for the growth of large area MoS2 having a direct bandgap of 1.6eV. Micro-Raman results clearly showed distinguish E1 2g and A1 g peaks and HRXPS re-confirmed its high quality by the different Mo and S core-level peaks. Additionally, employing Focused ion beam equipped with SEM (scanning electron microscopy) technique (FIB), the present study prepared platinum (Pt) electrodes required for the electrical measurements. The result showed: (i) the ohmic and semi-conducting behavior of the crystals; (ii) the importance of high-quality singlelayer (SL) MoS2 in the semi-conducting industries; and (iii) the potential of high quality SL MoS2 for replacing graphene in near future.O presente trabalho, tem com objetivo promover a descrição da parte experimental da síntese de grafeno e de estruturas bidimensionais (2D). Foram usadas as técnicas já existentes, que aplicam deposição química na fase de vapor (CVD), para a síntese de grafeno e estruturas bidimensionais com aplicações multidisciplinares, como indústrias de nano-eletrónicos e de semicondutores. Todos os problemas, sugestões e questões importantes relacionados com o crescimento e parametrização da condição ótima para formação de estritamente monocamadas a pequenas camadas foram brevemente discutidas. Isto pode trazer benefícios duplos como a produção de dispositivos eletrónicos 2D com altas motilidades de transporte e o entendimento do comportamento dos materiais 2D sujeitos a intercalação iónica. Os grafenos sintetizados no substrato cobre (Cu) apresentaram um espectro ideal de Raman com uma concentração de defeitos menor. A presença de pequenos picos D confirmou a elevada qualidade dos cristais de grafeno com estritamente monocamadas a pequenas cadeias. Além disso, a espectroscopia de Raios-X de alta resolução (HR-XPS) mostrou o grafeno de elevada qualidade com C 1s em configuração sp2 (com energia de ligação a ~284.8 eV). A ausência de outros componentes reforça a pureza e a qualidade do grafeno sintetizado. As imagens de mapping Raman demonstraram a cobertura total do grafeno de elevada área no substrato cobre. Adicionalmente, os resultados de microscopia de transmissão eletrónica de alta resolução (HRTEM) confirmaram a elevada natureza cristalina com dois tipos de planos rotacionais que podem ser atribuídos à presença de rugas durante a transferência de folhas de grafeno nas grelhas de TEM. Esta tese dedica-se também à dopagem heteroatómica do grafeno com o objetivo de alterar as suas propriedades eletrónicas. A amónia (NH3) foi usada como fonte de azoto (N) como átomo externo para a dopagem do grafeno puro. Mais uma vez, foram feitos esforços para discutir todos os problemas, sugestões e outras questões importantes relacionadas com o crescimento e parametrização das condições ótimas para a dopagem in-situ de amónia do grafeno no cobre. O papel do substrato (espessura do filme) na criação de defeitos foi também discutida. Os resultados de Raman mostram o aumento dos picos D e D’, o que confirma a dopagem do grafeno por NH3. Os dados de HRXPS mostraram o pico C 1s centrado a uma energia de ligação (BE) de 284.5 eV, atribuído ao C sp2 que pode ser correlacionado com a boa qualidade do C. Então, de acordo com o XPS, o grafeno que cresceu no substrato Cu 20 µm apresentou uma melhor intercalação do azoto nas folhas de grafeno sob as mesmas condições de crescimento. As duas componentes (substitucional a BE de 401.7 eV e piridínica de 398.5 eV) foram claramente distinguidas no respetivo pico N 1s. A dopagem com o tipo de configuração substitucional envolve três eletrões de valência do nitrogénio formando três ligações σ, um eletrão a preencher os estados π e o quinto eletrão no estado π* da banda de condução que conduzem, no total, a um forte efeito de doping. O presente trabalho também reporta um método in-situ para a caraterização quantitativa das propriedades eletrostáticas na escala nano das folhas de grafeno multicamada (MLG) crescidas no níquel (Ni) por combinação de dados de microscopia de força atómica (AFM) e microscopia de força atómica Kelvin (KPFM). Folhas MLG de larga área epitaxial cresceram no Ni usando a técnica CVD. A elevada natureza cristalina das folhas MLG no níquel foi confirmada por espectroscopia Raman com valor de FWHM tão baixo como ~20 cm-1 para o pico G. Foi feita a injeção de carga (e subsequente difusão de carga com o tempo) no recém sintetizado grafeno no Ni. Os resultados revelaram que : (i) a superfície MLG pode ser carregada quer positivamente quer negativamente pelo processo de injeção usando sondas de Si revestidas de Pt; (ii) as cargas podem ser acumuladas e eventualmente atingir concentrações de saturação de (+4.45±0.1) μC/m2 e (−1.3±0.1) μC/m2 , respetivamente; e (iii) os coeficientes de difusão de carga na superfície medidos foram de (1.50±0.05) × 10−16 m2 /s e (0.64±0.05) × 10−16 m2 /s para as cargas positivas e negativas, respetivamente. As experiências relacionadas com a descoberta de injeção de carga no MLG podem conduzir a uma maneira de desenhar uma nova classe de dispositivos de recolha de energia. Além disso, este estudo também demonstra uma técnica para nano-modelação/litografia de carga das superfícies de carga por eletrificação do contacto, que pode vir a ser uma aplicação promissora para criar nanoestruturas carregadas para a próxima geração de dispositivos nanoeletrónicos baseados em grafeno. Uma breve descrição da qualidade dos substratos transferidos foi também explorada. Foram usados vários substratos, como SiO2/Si e Au. Uma comparação qualitativa da qualidade entre a transferência do grafeno antes e depois foi criticamente descrita. Os resultados de HRXPS mostram a interação da camada de ferro com o grafeno. Por fim, esta pesquisa também mostrou as principais etapas de parametrização e síntese, e o fluxo de trabalho para materiais de elevada qualidade TMDs (como MoS2), por modificação do actual aparelho de CVD. Uma revisão completa das propriedades fundamentais, assim como do método de síntese, propriedades e problemas relacionados com o crescimento de materiais 2D foram também salientados. O efeito da pressão e outras condições para o crescimento de elevada qualidade foram completamente descritos. Este estudo indica que a pressão ótima para o crescimento de uma larga área MoS2 com uma bandgap direta de 1.6 eV é de 50 mbar. Os resultados de micro-Raman mostram claramente a distinção de picos E1 2g e A1 g picos e os dados de HR-XPS reconfirmam a sua elevada qualidade através de diferentes picos de nível interno de Mo and S. Além disso, através do uso da técnica microscopia eletrónica de varrimento (SEM) com feixe de iões focalizados (FIB), foram preparados elétrodos de platina necessários para medidas elétricas. O resultado mostrou: (i) o comportamento óhmico e semi-condutor dos cristais; (ii) a importância das monocamadas de elevada qualidade (SL) MoS2 nas indústrias de semi-condutores e (iii) o potencial das SL MoS2 de elevada qualidade para substituir o grafeno num futuro próximo

Photoinduced anisotropic lattice dynamic response and domain formation in thermoelectric SnSe

Identifying and understanding the mechanisms behind strong phonon–phonon scattering in condensed matter systems is critical to maximizing the efficiency of thermoelectric devices. To date, the leading method to address this has been to meticulously survey the full phonon dispersion of the material in order to isolate modes with anomalously large linewidth and temperature-dependence. Here we combine quantitative MeV ultrafast electron diffraction (UED) analysis with Monte Carlo based dynamic diffraction simulation and first-principles calculations to directly unveil the soft, anharmonic lattice distortions of model thermoelectric material SnSe. A small single-crystal sample is photoexcited with ultrafast optical pulses and the soft, anharmonic lattice distortions are isolated using MeV-UED as those associated with long relaxation time and large displacements. We reveal that these modes have interlayer shear strain character, induced mainly by c-axis atomic displacements, resulting in domain formation in the transient state. These findings provide an innovative approach to identify mechanisms for ultralow and anisotropic thermal conductivity and a promising route to optimizing thermoelectric devices

Quantum Monte Carlo study of low dimensional materials

This thesis addresses several challenging problems in low-dimensional systems, which have rarely or never been studied using quantum Monte Carlo methods. It begins with an investigation into weak van der Waals-like interactions in bilayer graphene and extends to graphene placed on top of boron nitride at four different stacking configurations. The in-plane optical phonon frequencies for the latter heterostructure as well as the out-of-plane phonon frequencies for both structures are calculated. We find that the binding energies (BEs) of these structures are almost within the same range and are less than 20 meV/atom. Although the phonon vibrations are comparable within both the diffusion quantum Monte Carlo (DMC) method and density functional theory (DFT), DFT gives quantitatively wrong BEs for vdW structures. Next, the BEs of 2D biexcitons are studied at different mass ratios and a variety of screening lengths. Our exact DMC results show that the BEs of biexcitons in different kinds of transition-metal dichalcogenides are in the range 15 − 30 meV bound at room temperature. Besides 2D systems, the electronic properties of 1D hydrogen-terminated oligoynes and polyyne are studied by calculating their DMC quasiparticle and excitonic gaps. By minimising the DMC energy of free-standing polyyne with respect to the lattice constant and the bond-length alternation, DMC predicts geometry in agreement with that obtained by accurate quantum chemistry methods. The DMC longitudinal optical phonon is within the range of experimental values. Our results confirm that DMC is capable of accurately describing Peierls-distorted materials

Bond-Order Potential for Molybdenum: Application to Dislocation Behavior

The bond-order potential (BOP) for transition metals is a real-space semiempirical description of interactions between the atoms, which is based on the tight-binding approximation and the d-band model. This scheme provides a direct bridge between the electronic level modeling and the atomistic modeling, where the electronic degrees of freedom have been coarse grained into many-body interatomic potentials. In this paper we construct BOP in which both the attractive and the repulsive contributions to the binding energy are environmentally dependent due to both the nonorthogonality of the orbitals and the breathing of the screening charges. The construction of the BOP is described and tested in detail. First, the energies of alternative crystal structures (A15, fcc, hcp, simple cubic) are calculated and compared with those evaluated ab initio. The transferability of the BOP to atomic configurations that deviate significantly from the bcc lattice is studied by computing the energies along tetragonal, trigonal, and hexagonal transformation paths. Next, the phonon spectra are evaluated for several symmetrical crystallographic directions and compared with available experiments. All these calculations highlight the importance of directional bonding and the investigation of phonons demonstrates that the environmental dependence of the bond integrals is crucial for the phonons of the N branch not to be unphysically soft. Finally, the constructed BOP was applied in the modeling of the core structure and glide of the 1/2⟨111⟩ screw dislocation. The calculated structure of the core agrees excellently with that found in the recent ab initio calculations and the observed glide behavior not only agrees with available ab initio data but is in agreement with many experimental observations and explains the primary reason for the breakdown of the Schmid law in bcc metals

Relaxation and Coherent Control of Quantum Dots

歪誘起InGaAs/GaAs量子ドットの共鳴二次発光の干渉を用いた位相緩和測定法を実証し、また、蓄積フォトンエコー法によりCdSeおよびCuBr量子ドットにおける励起子位相緩和を測定した。ドットにおける低温均一幅は、温度に依存しない成分、励起子一母体の二準位系間の相互作用、励起子一閉じ込め音響フォノン間の2フォノンラマン過程の3つの和で統一的・普遍的に記述できる。 InPやInGaAs自己形成量子ドットに負の電気バイアスをかけ、ドットから光励起された正孔を抜き取る非輻射緩和速度を制御し、定常・時間分解発光の両面から競合するフォノン緩和が明らかにされた。フォノンボトルネック効果は、予想に比べ十分速いフォノン緩和の観測により否定された。単層の歪み誘起GaAs量子ドットと電場印加InP量子ドットのヘテロダイン検出フォトンエコー測定に成功し、前者では井戸に比ベドット中の励起子分子の束縛エネルギーの増大、後者では、電場により正孔をトンネル過程でドットから引き抜く過程を観測した。トリオン発光の量子ビートをInP量子ドットで見出し、:更に、量子ドットの4種類の量子ビートを発見した。これらの研究はチャージチューナブル量子ドットの概念を生み出した。 InP量子ドット中のドープ電子のスピン緩和時間がサブミリ秒からミリ秒に達することを示した。正孔ドープInAs量子ドットにおいて、無磁場で500psの光励起電子スピンの緩和時間が、0.1Tの磁場で4nsに伸びる、核スピン揺らぎの凍結効果を実証した。(1) Dephasing of the lowest-energy electronic transition of stress-induced InGaAs quantum dots was measured by the interferometric double pulse excitation and time-integrated detection of optical-phonon sideband in their resonant-photoluminescence spectra. Homogeneous linewidth of confined excitons in CdSe and CuBr quantum dots was investigated at low temperatures by means of accumulated photon echo. Homogeneous width is universally given by the sum of "temperature-independent" term, "exciton-two level system interaction" term and "exciton-confined acoustic phonon interaction" term.(2) Spectral and temporal behavior of photoluminescence of site-selectively excited InP and InGaAs quantum dots in external electric field showed fast phonon mediated relaxation processes is much faster than predicted theoretically. This observation demonstrates the breakdown of the predicted phonon bottleneck effect.(3) Highly sensitive heterodyne-detected photon echo enabled us to observe the signal from one layer of strain-induced GaAs quantum dots and InP quantum dots. A biexcitonic beat observed in GaAs quantum dots formed in the quantum well shows the additional increase in the biexciton binding energy compared with that of the quantum well. The photon echo in InP quantum dots under the electric field showed tunneling-induced dephasing and decayed nonexponentially, reflecting its non-Markovian nature.(4) Trionic quantum beat was discovered in eletron-doped InP quantum dots and 4 kinds of quantum beats were observed in quantum dots. The study created the concept of change tunable quantum dots.(5) Electron spin relaxation in electron-doped InP quantum dots was investigated and found to reach the submillisecond range.(6) It was shown that electron spin relaxation time of 500 ps observed in p-InAs quantum dots was elongated to 4 ns under the magnetic field of 0.1 T. This shows the efficient suppression of electron spin relaxation caused by randomly oriented nuclear spins.課題番号:1385200

Approaching the quantitative description of enantioselective adsorption by the density functional theory means

The applications of enantiopure organic compounds range from medicine to green agrochemistry. Their racemic or enantioselective synthesis permits their acquisition beyond the extraction from life forms. These procedures need chiral resolution steps to achieve the required degrees of enantiomeric purity, though. Many research endeavours are addressed at finding chiral materials able to separate the enantiomers by their selective adsorption upon. Transition metal chiral surfaces have been found to reach enantiomeric excess degrees of purity outperforming surfaces of naturally existing chiral materials. Future research can be driven by high-throughput computational screening, given the employed methodology is able to discern the subtle enantiomeric differences of free energies of adsorption. The capabilities of density functional theory methods are here evaluated on the textbook case of D/L-aspartic acid adsorption on chiral Cu(3,1,17)R&S metal surfaces. Results show that dispersive forces are a prerequisite to properly describe the enantioselective adsorption, whereas the inclusion of fundamental vibrational energy and adsorbate vibrational free energies are key ingredients to approach a quantitative description. Simulated X-ray photoemission and infrared spectra indicate that the adsorption conformations can be qualitatively recognized