Polarized Raman spectroscopy in low-symmetry 2D materials: angle-resolved experiments and complex number tensor elements.

In this perspective review, we discuss the power of polarized Raman spectroscopy to study optically anisotropic 2D materials, belonging to the orthorhombic, monoclinic and triclinic crystal families. We start by showing that the polarization dependence of the peak intensities is described by the Raman tensor that is unique for each phonon mode, and then we discuss how to determine the tensor elements from the angle-resolved polarized measurements by analyzing the intensities in both the parallel- and cross-polarized scattering configurations. We present specific examples of orthorhombic black phosphorus and monoclinic 1T'-MoTe2, where the Raman tensors have null elements and their principal axes coincide with the crystallographic ones, followed by a discussion on the results for triclinic ReS2 and ReSe2, where the axes of the Raman tensor do not coincide with the crystallographic axes and all elements are non-zero. We show that the Raman tensor elements are, in general, given by complex numbers and that phase differences between tensor elements are needed to describe the experimental results. We discuss the dependence of the Raman tensors on the excitation laser energy and thickness of the sample within the framework of the quantum model for the Raman intensities. We show that the wavevector dependence of the electron-phonon interaction is essential for explaining the distinct Raman tensor for each phonon mode. Finally, we close with our concluding remarks and perspectives to be explored using angle-resolved polarized Raman spectroscopy in optically anisotropic 2D materials.

Nonlinear Dark-Field Imaging of One-Dimensional Defects in Monolayer Dichalcogenides.

One-dimensional defects in two-dimensional (2D) materials can be particularly damaging because they directly impede the transport of charge, spin, or heat and can introduce a metallic character into otherwise semiconducting systems. Current characterization techniques suffer from low throughput and a destructive nature or limitations in their unambiguous sensitivity at the nanoscale. Here we demonstrate that dark-field second harmonic generation (SHG) microscopy can rapidly, efficiently, and nondestructively probe grain boundaries and edges in monolayer dichalcogenides (i.e., MoSe2, MoS2, and WS2). Dark-field SHG efficiently separates the spatial components of the emitted light and exploits interference effects from crystal domains of different orientations to localize grain boundaries and edges as very bright 1D patterns through a Cerenkov-type SHG emission. The frequency dependence of this emission in MoSe2 monolayers is explained in terms of plasmon-enhanced SHG related to the defect's metallic character. This new technique for nanometer-scale imaging of the grain structure, domain orientation and localized 1D plasmons in 2D different semiconductors, thus enables more rapid progress toward both applications and fundamental materials discoveries.

Comparative study of Raman spectroscopy in graphene and MoS2-type transition metal dichalcogenides.

CONSPECTUS: Raman spectroscopy is one of the most powerful experimental tools to study graphene, since it provides much useful information for sample characterization. In this Account, we show that this technique is also convenient to study other bidimensional materials beyond graphene, and we will focus on the semiconducting transition metal dichalcogenides (MX2), specifically on MoS2 and WS2. We start by comparing the atomic structure of graphene and 2H-MX2 as a function of the number of layers in the sample. The first-order Raman active modes of each material can be predicted on the basis of their corresponding point-group symmetries. We show the analogies between graphene and 2H-MX2 in their Raman spectra. Using several excitation wavelengths in the visible range, we analyze the first- and second-order features presented by each material. These are the E2g and 2TO(K) bands in graphene (also known as the G and 2D bands, respectively) and the A1', E', and 2LA(M) bands in 2H MX2. The double-resonance processes that originate the second-order bands are different for both systems, and we will discuss them in terms of the different electronic structure and phonon dispersion curves presented by each compound. According to the electronic structure of graphene, which is a zero band gap semiconductor, the Raman spectrum is resonant for all the excitation wavelengths. Moreover, due to the linear behavior of the electronic dispersion near the K point, the double-resonance bands of graphene are dispersive, since their frequencies vary when we change the laser energy used for the sample excitation. In contrast, the semiconducting MX2 materials present an excitonic resonance at the direct gap, and consequently, the double-resonance Raman bands of MX2 are not dispersive, and only their intensities depend on the laser energy. In this sense, resonant Raman scattering experiments performed in transition metal dichalcogenides using a wide range of excitation energies can provide information about the electronic structure of these materials, which is complementary to other optical spectroscopies, such as absorption or photoluminescence. Raman spectroscopy can also be useful to address disorder in MX2 samples in a similar way as it is used in graphene. Both materials exhibit additional Raman features associated with phonons within the interior of the Brillouin zone that are activated by the presence of defects and that are not observed in pristine samples. Such is the case of the well-known D band of graphene. MX2 samples present analogous features that are clearly observed at specific excitation energies. The origins of these double-resonance Raman bands in MX2 are still subjects of current research. Finally, we discuss the suitability of Raman spectroscopy as a strain or doping sensor. Such applications of Raman spectroscopy are being extensively studied in the case of graphene, and considering its structural analogies with MX2 systems, we show how this technique can also be used to provide strain/doping information for transition metal dichalcogenides.

Erratum: Symmetry-Dependent Exciton-Phonon Coupling in 2D and Bulk MoS_{2} Observed by Resonance Raman Scattering [Phys. Rev. Lett. 114, 136403 (2015)].

This corrects the article DOI: 10.1103/PhysRevLett.114.136403.

Low-Temperature Solution Synthesis of Few-Layer 1T '-MoTe2 Nanostructures Exhibiting Lattice Compression.

Molybdenum ditelluride, MoTe2 , is emerging as an important transition-metal dichalcogenide (TMD) material because of its favorable properties relative to other TMDs. The 1T ' polymorph of MoTe2 is particularly interesting because it is semimetallic with bands that overlap near the Fermi level, but semiconducting 2H-MoTe2 is more stable and therefore more accessible synthetically. Metastable 1T '-MoTe2 forms directly in solution at 300 °C as uniform colloidal nanostructures that consist of few-layer nanosheets, which appear to exhibit an approx. 1 % lateral lattice compression relative to the bulk analogue. Density functional theory calculations suggest that small grain sizes and polycrystallinity stabilize the 1T ' phase in the MoTe2 nanostructures and suppress its transformation back to the more stable 2H polymorph through grain boundary pinning. Raman spectra of the 1T '-MoTe2 nanostructures exhibit a laser energy dependence, which could be caused by electronic transitions.

Symmetry-dependent exciton-phonon coupling in 2D and bulk MoS2 observed by resonance Raman scattering.

This work describes a resonance Raman study performed on samples with one, two, and three layers (1L, 2L, 3L), and bulk MoS2, using more than 30 different laser excitation lines covering the visible range, and focusing on the intensity of the two most pronounced features of the Raman scattering spectrum of MoS2 (E2g(1) and A1g bands). The Raman excitation profiles of these bands were obtained experimentally, and it is found that the A1g feature is enhanced when the excitation laser is in resonance with A and B excitons of MoS2, while the E2g1 feature is shown to be enhanced when the excitation laser is close to 2.7 eV. We show from the symmetry analysis of the exciton-phonon interaction that the mode responsible for the E2g(1) resonance is identified as the high energy C exciton recently predicted [D. Y. Qiu, F. H. da Jornada, and S. G. Louie, Phys. Rev. Lett. 111, 216805 (2013)].

First pregnancy and live birth from ex vivo-retrieved metaphase II oocytes from a woman with bilateral ovarian carcinoma: a case report.

OBJECTIVE: To report pregnancy and live birth resulting from intracytoplasmic sperm injection of ex vivo-retrieved mature oocytes from a woman with bilateral ovarian carcinoma. DESIGN: Case report. SETTING: Fertility clinic. PATIENT: A 34-year-old nulliparous woman with bilateral ovarian tumor, with a risk of malignancy of 96.1% according to International Ovarian Tumor Analysis Group recommendations for adnexal tumors, who desired fertility preservation before definitive surgical treatment. INTERVENTION(S): Cryopreservation of ex vivo-retrieved mature metaphase II oocytes is followed by fertilization with donor sperm and embryo transfer to a gestational carrier. MAIN OUTCOME MEASURE(S): Fertility preservation. RESULTS: After controlled ovarian stimulation, 12 metaphase II oocytes were retrieved from oophorectomized specimens and vitrified. Intracytoplasmic sperm injection with donor sperm was performed in remission, resulting in 9 cleavage-stage embryos, 2 of which were transferred to a gestational carrier, resulting in a normal, healthy singleton pregnancy, and the live birth of a healthy infant. CONCLUSION(S): Ex vivo oocyte retrieval after oophorectomy may be a safe alternative to standard oocyte retrieval for fertility preservation in women with ovarian malignancies.

Raman spectroscopy of a few layers of bismuth telluride nanoplatelets.

We can shape the electronic and phonon properties of Bi2Te3 crystals via the variation of the number of layers. Here, we report a Raman study with the aid of first-principles calculations on few-layered Bi2Te3 systems ranging from 5 to 24 nm layer thickness using 1.92, 2.41 and 2.54 eV excitation energies. We examine how the frequency position, intensity and lineshape of the main Raman modes (A11g, E2g, and A21g) behave by the variation of the layer thickness and excitation energy. We observed a frequency dispersion on the number of layers of the main modes, indicating changes in the inter- and intra-layers interaction. A resonant Raman condition is reached for all modes for samples with 11 and 18 nm thickness because of van Hove singularities at the electronic density of states. Also, the Breit-Wigner-Fano line shape of the A21g mode shows an increase of electron-phonon coupling for thick layers. These results suggest a relevant influence of numbers of layers on the Raman scattering mechanics in Bi2Te3 systems.

Selective Electron-Phonon Coupling in Dimerized 1T-TaS2 Revealed by Resonance Raman Spectroscopy.

The layered transition-metal dichalcogenide material 1T-TaS2 possesses successive phase transitions upon cooling, resulting in strong electron-electron correlation effects and the formation of charge density waves (CDWs). Recently, a dimerized double-layer stacking configuration was shown to form a Peierls-like instability in the electronic structure. To date, no direct evidence for this double-layer stacking configuration using optical techniques has been reported, in particular through Raman spectroscopy. Here, we employ a multiple excitation and polarized Raman spectroscopy to resolve the behavior of phonons and electron-phonon interactions in the commensurate CDW lattice phase of dimerized 1T-TaS2. We observe a distinct behavior from what is predicted for a single layer and probe a richer number of phonon modes that are compatible with the formation of double-layer units (layer dimerization). The multiple-excitation results show a selective coupling of each Raman-active phonon with specific electronic transitions hidden in the optical spectra of 1T-TaS2, suggesting that selectivity in the electron-phonon coupling must also play a role in the CDW order of 1T-TaS2.

Electronic Band Tuning and Multivalley Raman Scattering in Monolayer Transition Metal Dichalcogenides at High Pressures.

Transition metal dichalcogenides (TMDs) possess spin-valley locking and spin-split K/K' valleys, which have led to many fascinating physical phenomena. However, the electronic structure of TMDs also exhibits other conduction band minima with similar properties, the Q/Q' valleys. The intervalley K-Q scattering enables interesting physical phenomena, including multivalley superconductivity, but those effects are typically hindered in monolayer TMDs due to the large K-Q energy difference (ΔEKQ). To unlock elusive multivalley phenomena in monolayer TMDs, it is desirable to reduce ΔEKQ, while being able to sensitively probe the valley shifts and the multivalley scattering processes. Here, we use high pressure to tune the electronic properties of monolayer MoS2 and WSe2 and probe K-Q crossing and multivalley scattering via double-resonance Raman (DRR) scattering. In both systems, we observed a pressure-induced enhancement of the double-resonance LA and 2LA Raman bands, which can be attributed to a band gap opening and ΔEKQ decrease. First-principles calculations and photoluminescence measurements corroborate this scenario. In our analysis, we also addressed the multivalley nature of the DRR bands for WSe2. Our work establishes the DRR 2LA and LA bands as sensitive probes of strain-induced modifications to the electronic structure of TMDs. Conversely, their intensity could potentially be used to monitor the presence of compressive or tensile strain in TMDs. Furthermore, the ability to probe K-K' and K-Q scattering as a function of strain shall advance our understanding of different multivalley phenomena in TMDs such as superconductivity, valley coherence, and valley transport.

Quantification and Healing of Defects in Atomically Thin Molybdenum Disulfide: Beyond the Controlled Creation of Atomic Defects.

Atomically thin 2D materials provide an opportunity to investigate the atomic-scale details of defects introduced by particle irradiation. Once the atomic configuration of defects and their spatial distribution are revealed, the details of the mesoscopic phenomena can be unveiled. In this work, we created atomically small defects by controlled irradiation of gallium ions with doses ranging from 4.94 × 1012 to 4.00 × 1014 ions/cm2 on monolayer molybdenum disulfide (MoS2) crystals. The optical signatures of defects, such as the evolution of defect-activated LA-bands and a broadening of the first-order (E' and A'1) modes, can be studied by Raman spectroscopy. High-resolution scanning transmission electron microscopy (HR-STEM) analysis revealed that most defects are vacancies of few-molybdenum atoms with surrounding sulfur atoms (VxMo+yS) at a low ion dose. When increasing the ion dose, the atomic vacancies merge and form nanometer-sized holes. Utilizing HR-STEM and image analysis, we propose the estimation of the finite crystal length (Lfc) via the careful quantification of 0D defects in 2D systems through the formula Lfc = 4.41/ηion, where ηion corresponds to the ion dose. Combining HR-STEM and Raman spectroscopy, the formula to calculate Lfc from Raman features, I(LA)/I(A'1) = 5.09/Lfc2, is obtained. We have also demonstrated an effective route to healing the ion irradiation-induced atomic vacancies by annealing defective MoS2 in a hydrogen disulfide (H2S) atmosphere. The H2S annealing improved the crystal quality of MoS2 with Lfc greater than the calculated size of the A exciton wave function, which leads to a partial recovery of the photoluminescence signal after its quenching by ion irradiation.

Magnetic Response Dependence of ZnO Based Thin Films on Ag Doping and Processing Architecture.

Multifunctional and multiresponsive thin films are playing an increasing role in modern technology. This work reports a study on the magnetic properties of ZnO and Ag-doped ZnO semiconducting films prepared with a zigzag-like columnar architecture and their correlation with the processing conditions. The films were grown through Glancing Angle Deposition (GLAD) co-sputtering technique to improve the induced ferromagnetism at room temperature. Structural and morphological characterizations have been performed and correlated with the paramagnetic resonance measurements, which demonstrate the existence of vacancies in both as-cast and annealed films. The magnetic measurements reveal changes in the magnetic order of both ZnO and Ag-doped ZnO films with increasing temperature, showing an evolution from a paramagnetic (at low temperature) to a diamagnetic behavior (at room temperature). Further, the room temperature magnetic properties indicate a ferromagnetic order even for the un-doped ZnO film. The results open new perspectives for the development of multifunctional ZnO semiconductors, the GLAD co-sputtering technique enables the control of the magnetic response, even in the un-doped semiconductor materials.

Immediate post-insertion tip migration of peripherally inserted central catheters dependent on arm position and depth of inspiration.

INTRODUCTION: The purpose of this study is to assess the degree of PICC tip migration with breathing and arm movement to determine whether accurate positioning is feasible or futile. METHODS: A prospective cohort of 218 consecutive patients undergoing PICC insertion at our institution between January and August 2015 was selected, of which 129 met inclusion criteria. The position of insertion was used as control with the arm at 90° during inspiration, followed by three study images: expiration with arm unchanged, inspiration with arm fully adducted and inspiration with arm fully abducted. Mean and standard deviations (SD) of change in PICC position were determined. ANOVA, Pearson correlation coefficients and Chi-square tests were used to assess the effects of vessel choice, PICC calibre and angle of arm abduction. Complications were recorded. RESULTS: Movement was predominantly caudal with a mean of 10.4 mm (SD 16.5) with similar degrees of movement in the expiration (12.3 mm) and adduction (12.9 mm) views (P = 0.709). Arm abduction resulted in a mean caudal movement of 6.5 mm. (SD 18.6); however, the degree of abduction had no predictable effect on PICC movement. Thirty-two per cent of cases demonstrated movement into the right atrium. Neither vessel choice nor type of PICC was shown to have a significant effect on PICC movement. CONCLUSION: There is large amplitude of PICC tip position change with depth of inspiration and arm position resulting in frequent right atrial position. Despite this there were no associated complications in our cohort which compliments emerging international opinion regarding intra-atrial PICC tip position.

Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy.

Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2.

Embryo stage of development is not decisive for reproductive outcomes in frozen-thawed embryo transfer cycles.

OBJECTIVE: To evaluate if the outcomes of IVF/ICSI in frozen-thawed embryo transfer and fresh embryo transfer cycles differ in relation to cleavage and blastocyst stages. METHODS: Retrospective cohort study to compare IVF/ICSI outcomes between fresh embryo transfer and frozen-thawed embryo transfer cycles, according to the stage of embryo development. Analysis was carried out on 443 consecutive embryo transfer cycles performed between January 1st and December 31st, 2014. Women aged up to 38 and submitted to embryo transfer cycles with fresh (n = 309) or frozen-thawed (n = 134) embryos at a private center for assistance in human reproduction were considered for analysis. Results in each group were stratified according to the stage of embryo development: cleavage stage and blastocyst stage. Main outcome measures were implantation rate, clinical pregnancy rate, ongoing pregnancy rate and live birth rate per cycle. RESULTS: In the fresh embryo transfer group, for cleavage stage versus blastocyst stage, respectively, implantation rates were 22% and 47% (p = 0.0005); clinical pregnancy rates were 34% and 64% (p = 0.0057); the ongoing pregnancy rates were 30% and 61% (p = 0.0046) and live birth rates were 28% and 55% (p = 0.0148). There were no significant differences in the rates between cleavage and blastocyst stages in the frozen-thawed group, neither between fresh and frozen-thawed cleavage embryo transfers nor between fresh and frozen-thawed blastocyst transfers. CONCLUSION: Our results confirm that blastocyst transfer is better than cleavage stage in fresh embryo transfer cycles. In frozen-thawed cycles, cleavage or blastocyst stages seem to offer similar reproductive outcomes.

Optical identification of sulfur vacancies: Bound excitons at the edges of monolayer tungsten disulfide.

Defects play a significant role in tailoring the optical properties of two-dimensional materials. Optical signatures of defect-bound excitons are important tools to probe defective regions and thus interrogate the optical quality of as-grown semiconducting monolayer materials. We have performed a systematic study of defect-bound excitons using photoluminescence (PL) spectroscopy combined with atomically resolved scanning electron microscopy and first-principles calculations. Spatially resolved PL spectroscopy at low temperatures revealed bound excitons that were present only on the edges of monolayer tungsten disulfide and not in the interior. Optical pumping of the bound excitons was sublinear, confirming their bound nature. Atomic-resolution images reveal that the areal density of monosulfur vacancies is much larger near the edges (0.92 ± 0.45 nm-2) than in the interior (0.33 ± 0.11 nm-2). Temperature-dependent PL measurements found a thermal activation energy of ~36 meV; surprisingly, this is much smaller than the bound-exciton binding energy of ~300 meV. We show that this apparent inconsistency is related to a thermal dissociation of the bound exciton that liberates the neutral excitons from negatively charged point defects. First-principles calculations confirm that sulfur monovacancies introduce midgap states that host optical transitions with finite matrix elements, with emission energies ranging from 200 to 400 meV below the neutral-exciton emission line. These results demonstrate that bound-exciton emission induced by monosulfur vacancies is concentrated near the edges of as-grown monolayer tungsten disulfide.

Reproductive planning in times of Zika: getting pregnant or delaying plans? The opinion of the Brazilian Society of Assisted Reproduction Committee - a basis for a bioethical discussion.

Although the causality between Zika virus, microcephaly, and other central nervous system disorders has been taken for granted by the scientific community, many uncertainties remain. The gap of knowledge at the moment is large enough to remove part of the confidence physicians have on the advice given to patients - and infertile women in particular - on their reproductive plans. Pretreatment serologic screening is a possible strategy to offer more confidence for individuals choosing to bear children regardless of the Zika virus, but the tests currently available do not seem to be sufficiently adequate. Until now, there is no formal recommendation to avoid pregnancy solely because of the Zika virus outbreak, and the choice of becoming pregnant has been regarded as a personal decision to be made by each woman and her family.

Ultrasensitive molecular sensor using N-doped graphene through enhanced Raman scattering.

As a novel and efficient surface analysis technique, graphene-enhanced Raman scattering (GERS) has attracted increasing research attention in recent years. In particular, chemically doped graphene exhibits improved GERS effects when compared with pristine graphene for certain dyes, and it can be used to efficiently detect trace amounts of molecules. However, the GERS mechanism remains an open question. We present a comprehensive study on the GERS effect of pristine graphene and nitrogen-doped graphene. By controlling nitrogen doping, the Fermi level (E F) of graphene shifts, and if this shift aligns with the lowest unoccupied molecular orbital (LUMO) of a molecule, charge transfer is enhanced, thus significantly amplifying the molecule's vibrational Raman modes. We confirmed these findings using different organic fluorescent molecules: rhodamine B, crystal violet, and methylene blue. The Raman signals from these dye molecules can be detected even for concentrations as low as 10(-11) M, thus providing outstanding molecular sensing capabilities. To explain our results, these nitrogen-doped graphene-molecule systems were modeled using dispersion-corrected density functional theory. Furthermore, we demonstrated that it is possible to determine the gaps between the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO) of different molecules when different laser excitations are used. Our simulated Raman spectra of the molecules also suggest that the measured Raman shifts come from the dyes that have an extra electron. This work demonstrates that nitrogen-doped graphene has enormous potential as a substrate when detecting low concentrations of molecules and could also allow for an effective identification of their HOMO-LUMO gaps.

Strategies to preserve the reproductive future of women after cancer.

Malignant and cardiovascular diseases are the main causes of death in Brazil. Estimates for 2013 predict the occurrence of 189,150 new cases of cancer in Brazilian women. With advanced detection tools, patients are diagnosed and treated for cancer at a younger age and are more likely to survive. The cytotoxic action of chemotherapeutic agents and radiotherapy very frequently implies serious damage to the gonads, and consequences due to the hypoestrogenism, such as osteoporosis, infertility and premature ovarian failure, are expected. Oncofertility, then, appears as a new area of reproductive medicine, which is dedicated to the development of strategies for the reduction of therapeutic sequels in cancer survivals, ultimately aiming the maintenance of their quality of life and the possibility of biological maternity. This article aims to present an overview of possible options for female fertility preservation after cancer and future perspectives in oncofertility.

Modular versus all-polyethylene tibial components: comparison of pre- and early post-operative patient scores in total knee replacement.

INTRODUCTION: All-polyethylene (AP) tibial components of total knee replacement (TKR) are substantially cheaper than their modular counterparts. It is well established that their survivorship and radiographic outcomes are comparable. In this study, patient-derived outcome measures were used to compare these two implant types. METHODS: A cohort of 456 primary TKRs (142 AP, 314 modular) were assessed with preoperative and 1-year post-operative Oxford Knee Score, Western Ontario and McMaster Universities Arthritis Index and Short Form - 12 scores. RESULTS: Both groups performed well with no significant difference in improvement and final scores at 1 year. Although there was a significant difference in mean age among the groups (P < 0.001) age-adjusted scores continued to show no significant difference between the two groups. DISCUSSION: Our results support the more frequent use of AP tibial components for uncomplicated TKR.