Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moir\ue9 pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moir\ue9 engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field

Independent and combined effects of improved water, sanitation, and hygiene, and improved complementary feeding, on child stunting and anaemia in rural Zimbabwe: a cluster-randomised trial.

BACKGROUND: Child stunting reduces survival and impairs neurodevelopment. We tested the independent and combined effects of improved water, sanitation, and hygiene (WASH), and improved infant and young child feeding (IYCF) on stunting and anaemia in in Zimbabwe. METHODS: We did a cluster-randomised, community-based, 2 × 2 factorial trial in two rural districts in Zimbabwe. Clusters were defined as the catchment area of between one and four village health workers employed by the Zimbabwe Ministry of Health and Child Care. Women were eligible for inclusion if they permanently lived in clusters and were confirmed pregnant. Clusters were randomly assigned (1:1:1:1) to standard of care (52 clusters), IYCF (20 g of a small-quantity lipid-based nutrient supplement per day from age 6 to 18 months plus complementary feeding counselling; 53 clusters), WASH (construction of a ventilated improved pit latrine, provision of two handwashing stations, liquid soap, chlorine, and play space plus hygiene counselling; 53 clusters), or IYCF plus WASH (53 clusters). A constrained randomisation technique was used to achieve balance across the groups for 14 variables related to geography, demography, water access, and community-level sanitation coverage. Masking of participants and fieldworkers was not possible. The primary outcomes were infant length-for-age Z score and haemoglobin concentrations at 18 months of age among children born to mothers who were HIV negative during pregnancy. These outcomes were analysed in the intention-to-treat population. We estimated the effects of the interventions by comparing the two IYCF groups with the two non-IYCF groups and the two WASH groups with the two non-WASH groups, except for outcomes that had an important statistical interaction between the interventions. This trial is registered with ClinicalTrials.gov, number NCT01824940. FINDINGS: Between Nov 22, 2012, and March 27, 2015, 5280 pregnant women were enrolled from 211 clusters. 3686 children born to HIV-negative mothers were assessed at age 18 months (884 in the standard of care group from 52 clusters, 893 in the IYCF group from 53 clusters, 918 in the WASH group from 53 clusters, and 991 in the IYCF plus WASH group from 51 clusters). In the IYCF intervention groups, the mean length-for-age Z score was 0·16 (95% CI 0·08-0·23) higher and the mean haemoglobin concentration was 2·03 g/L (1·28-2·79) higher than those in the non-IYCF intervention groups. The IYCF intervention reduced the number of stunted children from 620 (35%) of 1792 to 514 (27%) of 1879, and the number of children with anaemia from 245 (13·9%) of 1759 to 193 (10·5%) of 1845. The WASH intervention had no effect on either primary outcome. Neither intervention reduced the prevalence of diarrhoea at 12 or 18 months. No trial-related serious adverse events, and only three trial-related adverse events, were reported. INTERPRETATION: Household-level elementary WASH interventions implemented in rural areas in low-income countries are unlikely to reduce stunting or anaemia and might not reduce diarrhoea. Implementation of these WASH interventions in combination with IYCF interventions is unlikely to reduce stunting or anaemia more than implementation of IYCF alone. FUNDING: Bill & Melinda Gates Foundation, UK Department for International Development, Wellcome Trust, Swiss Development Cooperation, UNICEF, and US National Institutes of Health.The SHINE trial is funded by the Bill & Melinda Gates Foundation (OPP1021542 and OPP113707); UK Department for International Development; Wellcome Trust, UK (093768/Z/10/Z, 108065/Z/15/Z and 203905/Z/16/Z); Swiss Agency for Development and Cooperation; US National Institutes of Health (2R01HD060338-06); and UNICEF (PCA-2017-0002)

Chemical vapor growth of nitrogen doped carbon nanotube and graphene materials for application in organic photovoltaic devices.

Application of carbon nanomaterials like fullerene, carbon nanotubes, and graphene in solar cells using solution processable methods presents a great potential to reduce the cost of producing electricity from solar energy. However, carbon nanotubes and graphene materials are predominantly metallic and this limits their function in organic photovoltaic devices (OPVs) where semiconducting behavior is required. Doping of carbon nanomaterials is a well-known method for making them semiconducting. Doping of carbon nanomaterials with nitrogen and boron can tune their properties to suit the requirements for use in photovoltaic applications as n-type and p-type semiconducting materials, respectively. Indeed, the use of nitrogen doped and boron doped carbon nanotubes in organic solar cells together with fullerene acceptors can improve the current density of the OPV devices. Nitrogen doping of carbon nanotubes can be achieved by using nitrogen-containing precursor materials during chemical vapor deposition. However the doping of carbon nanotubes with nitrogen does not automatically make them n-type materials; they remain metallic unless a large amount of quaternary type nitrogen is incorporated in the carbon nanotubes. In this work we have developed a method to control the type of nitrogen that is incorporated in CNTs by using an appropriate synthesis temperature and use of oxygen-containing carbon precursors during the chemical deposition of carbon nanotubes. Quaternary N was incorporated in a CVD process when high temperatures and a high concentration of O in the precursor materials were used. We also showed that the type and amount of N can be changed from pyrrolic and pyridinic-N-oxide to pyridinic N and quaternary N by annealing N doped carbon nanotubes at temperatures above 400°C. At temperatures above 800°C most of the nitrogen is converted to quaternary nitrogen. N-CNT thin films were used in OPVs so as to modify the ITO electrode and transform it into a 3D electrode. The resulting effect was an improved short circuit current density in the devices containing an N-CNT thin film that was placed on top of the ITO electrode. A reduction in efficiency losses in OPVs at increasing light intensity was observed in the NCNT ITO modified electrode OPVs. This is a remarkable finding when considering that one of the main problems hindering commercialization of OPVs is the loss of efficiency at high light intensities. We related these effects to the efficient charge collection by the modified ITO electrode. Incorporation of N-CNTs in the bulk heterojunction layer of the OPV device resulted in poor performance when compared to an OPV device made without N-CNTs. This effect is caused by shorting of the OPVs. We used a method of incorporating N-CNTs whilst minimizing shorting and this showed potential for better performance. A study on the attempted doping of graphene with B to make it a p-type material showed that in the presence of a nitrogen carrier gas, BN instead of B was incorporated in graphene. This remarkable finding enabled us to grow a p-type graphene with a possible a band gap opening. This was corroborated by XPS and Raman spectroscopy studies of the material. This BN doped graphene material showed potential as a possible replacement of PEDOT:PSS as a hole transport material in OPVs. The BN doped graphene material can match the performance of PEDOT:PSS when the level of BN doping in graphene is increased

Optical spectroscopic studies of aqueous suspensions and composites of SWNT

We discuss the intrinsic optical spectroscopy (UV-vis-NIR absorption, Raman and photoluminescence)signatures of single layer graphene (SLG) and single wall carbon nanotubes (SWNT) dispersed indegassed water without additives, so called "eau de graphene" (EdN) [1-3] and ‘‘eau de nanotubes”(EdN) [4].The most characteristic signature of SLG in EdG is a narrow and symmetric 2D band with a widthdepending on processing conditions [2,3]. The position of the G and 2D bands indicate moderate biaxialcompressive strain and weak n doping. The intensity of the D band and the width of the G band arediscussed in terms of point-defect density and flake size. We show that point defects can be easily curedby preparing thin films from EdG and annealing at 800°C.The signatures of SWNT in EdN are found to be very close to those of SWNT dispersed in aqueoussuspensions stabilized with surfactants [4]. Absorption peaks appear to be even slightly better resolvedfor EdN, suggesting sharper excitonic resonances, which is also supported by the Raman data. Thesesignatures support that SWNT are dispersed as individuals in EdN, in a similar way SLG aredispersable in EdG [1-3].[1] G. Bepete et al, Nat. Chem. 2016, DOI 10.1038/NCHEM2669[2] G. Bepete et al, J. Phys. Chem. C 2016, 120 (49), 28204–28214.[3] G. Bepte et al, Phys. Stat. Solidi 2016, 10 (12), 895-899.[4] G. Bepete et al, to be publishe

Raman signatures of SLG dispersed in degassed water (‘‘eau de graphene’’)

We study the intrinsic Raman signatures of single layer graphene (SLG) dispersed in degassed water without additives, so called ‘‘eau de graphene” (EdG) and compare them to those of suspended SLG. The Raman signatures of SLG superimpose to those of water. The most characteristic signature of SLG in EdG is a narrow and symmetric 2D band with a width depending on processing conditions. The position of the G and 2D bands indicate moderate biaxial compressive strain and weak n doping. The intensity of the D band and the width of the G band are discussed in terms of point-defect density and flake size. We show that point defects can be easily cured by preparing thin films from EdG and annealing at 800°C

Raman signatures of bulk aqueous dispersions of single-layer graphene, "eau de graphene"

We have recently described how metastable aqueous dispersions of single layer graphene (SLG) can beprepared simply by transferring SLG, prepared by oxidation of fully exfoliated graphenide, into water, with nosurfactant.1 The aqueous graphene dispersions are named eau de Graphene (EdG) to convey the idea of waterwith only graphene inside.Here, we report the intrinsic Raman signatures of graphene dispersed in EdG and we show that theycorrespond to all the expected characteristics of SLG. We stress the difference in these signatures with respect tothose of the natural graphite precursor and to those of some aqueous dispersions of few-layers graphene (FLG)stabilized by surfactants. We discuss the Raman shifts of the G and 2D band in terms of doping and strain of thegraphene flakes2,3. Finally, by comparing the second order Raman signatures (D and D’ bands)3 of EdG and thoseof corresponding thin films, we discuss the nature and amount of defects on the graphene sheets.4,5 All togetherthis provides a full description of the structure and properties of graphene flakes dispersed in water without anyadditive

Spectroscopic studies of dispersion and orientation of carbon nanotubes and graphene in aqueous inks and related nanomaterials

We study the intrinsic optical spectroscopy (UV-vis-NIR absorption, Raman and photoluminescence) signatures of single wall carbon nanotubes (SWNT) dispersed in degassed water without additives, so called ‘‘eau de nanotubes” (EdN). They are found to be very close to those of SWNT dispersed in aqueous suspensions stabilized with surfactants. Absorption peaks appear to be even slightly better resolved for EdN, suggesting sharper excitonic resonances, which is also supported by the Raman data. On the other hand, the photoluminescence signal is significantly weaker. These signatures suggest that SWNT are dispersed as individuals in degassed water, in a similar way single layer graphene was recently shown to be readily dispersable in degassed water [1-3].References[1]G. Bepete et al, Nat. Chem. 2016, DOI 10.1038/NCHEM2669[2]G. Bepete et al, J. Phys. Chem. C 2016, 120 (49), 28204–28214.[3]G. Bepte et al, Phys. Stat. Solidi 2016, 10 (12), 895-899

Raman Signatures of Single Layer Graphene Dispersed in Degassed Water, “‘Eau de Graphene”’

We report a detailed Raman study of single layergraphene dispersed in degassed water without additives (SLGiw), so-called “‘eau de graphene”’ (EdG).23 The most characteristic signature of SLGiw is a narrow (28 ± 2 cm−1) and symmetric 2D band. The intensity of the D band is dominated by the contribution of sp3 defects due to slight functionalization of the basal-planes. The density of defects is estimated in the range 200-650 ppm by studying thin films prepared from EdG. These defects can be fully and easily cured by annealing the films at 800 °C. The position of the G and 2D bands, blue-shifted with respect to pristine SLG, are assigned to moderate biaxial compressive strain (≈0.09 ± 0.02%) and likely weak n doping (<4 × 1012 electrons/cm2) of SLGiw

Etudes Raman d’encres de nanotubeset de graphene monofeuillets

Nous discutons les signatures Raman de nanotubes de carbone monofeuillets (single-wall carbon nanotubes,SWNT) et de feuillets de graphène monofeuillets (single layer graphene, SLG) dispersés dans l’eau (fig. 1) et leurorigine physique. Les encres de SWNT sont stabilisées avec des tensio-actifs. Les études optiques dans le procheinfrarouge permettent de mesurer simultanément le signal Raman et le signal de photoluminescence caractéristiquedes nanotubes dispersés à l’échelle individuelle (fig. 2, gauche). Le signal de PL est sensible à l’environnementdiélectrique des nanotubes et permet d’étudier les interactions avec le tensio-actif [1]. A fortes concentrations, lesSWNT forment des phases cristal liquide et l’étude de la polarisation des signaux Raman/PL conduit à la mesure du paramètre d’ordre orientationnel [2]. Les encres de SWNT peuvent être déposées par jet d’encre, les textures des dépôts et leur conductivité électrique dépendent de la concentration des encres [3]. Des encres de graphène SLG, baptisées ‘‘eau de graphène’’ peuvent être préparées sans tensioactif en dispersant despolyélectrolytes de SLG dans de l’eau dégazée [4]. Les signatures Raman des SLG dispersées dans l’eau sontvoisines de celles des SLG suspendues dans l’air (fig. 2), avec des décalages modérés des bandes principales quisont discutées en terme de dopage et de contraintes mécaniques [5]. Les défauts ponctuels observés sur les SLG dispersées dans l’eau peuvent être facilement éliminés par un recuit des dépôts à 800°C. References [1] F. Torres-Cañas et al, J. Phys. Chem. C 119 (2015), pp. 703-709 [2] C. Zamora-Ledezma et al, J. Phys. Chem. C 115 (2011), pp. 3272-3278 [3] F. Torres-Cañas et al, Mat. Res. Exp. 4 (2016) [4] G. Bepete et al, Nature Chem. 9 (2016), pp. 347-352 [5] G. Bepete et al, J. Phys. Chem. C 120 (2016), pp. 28204-28214 <BR

Degradation of Single-Layer and Few-Layer Graphene by Neutrophil Myeloperoxidase

International audienceBiodegradability of graphene is one of the fundamental parameters determining the fate of this material in vivo. Two types of aqueous dispersible graphene, corresponding to single‐layer (SLG) and few‐layer graphene (FLG), devoid of either chemical functionalization or stabilizing surfactants, were subjected to biodegradation by human myeloperoxidase (hMPO) mediated catalysis. Graphene biodegradation was also studied in the presence of activated, degranulating human neutrophils. The degradation of both FLG and SLG sheets was confirmed by Raman spectroscopy and electron microscopy analyses, leading to the conclusion that highly dispersed pristine graphene is not biopersistent