Showing papers on "Raman spectroscopy published in 2008"
TL;DR: The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction and establishes graphene as an excellent material for thermal management.
Abstract: We report the measurement of the thermal conductivity of a suspended single-layer graphene. The room temperature values of the thermal conductivity in the range ∼(4.84 ± 0.44) × 103 to (5.30 ± 0.48) × 103 W/mK were extracted for a single-layer graphene from the dependence of the Raman G peak frequency on the excitation laser power and independently measured G peak temperature coefficient. The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction. The superb thermal conduction property of graphene is beneficial for the proposed electronic applications and establishes graphene as an excellent material for thermal management.
11,878 citations
TL;DR: Graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone are demonstrated.
Abstract: Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of approximately 1 wt%, which could potentially be improved to 7-12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry.
5,600 citations
TL;DR: Only the alternating pattern of single-double carbon bonds within the sp2 carbon ribbons provides a satisfactory explanation for the experimentally observed blue shift of the G band of the Raman spectra relative to graphite.
Abstract: We investigate Raman spectra of graphite oxide and functionalized graphene sheets with epoxy and hydroxyl groups and Stone−Wales and 5−8−5 defects by first-principles calculations to interpret our experimental results. Only the alternating pattern of single−double carbon bonds within the sp2 carbon ribbons provides a satisfactory explanation for the experimentally observed blue shift of the G band of the Raman spectra relative to graphite. To obtain these single−double bonds, it is necessary to have sp3 carbons on the edges of a zigzag carbon ribbon.
4,000 citations
TL;DR: This work demonstrates a top-gated graphene transistor that is able to reach doping levels of up to 5x1013 cm-2, which is much higher than those previously reported.
Abstract: The recent discovery of graphene has led to many advances in two-dimensional physics and devices. The graphene devices fabricated so far have relied on $SiO_2$ back gating. Electrochemical top gating is widely used for polymer transistors, and has also been successfully applied to carbon nanotubes. Here we demonstrate a top-gated graphene transistor that is able to reach doping levels of up to $5\times 10^{13} cm^{-2}$, which is much higher than those previously reported. Such high doping levels are possible because the nanometre-thick Debye layer in the solid polymer electrolyte gate provides a much higher gate capacitance than the commonly used $SiO_2$ back gate, which is usually about 300 nm thick. In situ Raman measurements monitor the doping. The G peak stiffens and sharpens for both electron and hole doping, but the 2D peak shows a different response to holes and electrons. The ratio of the intensities of the G and 2D peaks shows a strong dependence on doping, making it a sensitive parameter to monitor the doping.
3,254 citations
TL;DR: In this article, the authors described the nanostructures, methods of preparing nanostructure, methods for detecting targets in subjects, and methods of treating diseases in subjects. An embodiment, among others, includes a metallic gold surface-enhanced Raman scattering nanoparticle, a Raman reporter and a protection structure.
Abstract: Nanostructures, methods of preparing nanostructures, methods of detecting targets in subjects, and methods of treating diseases in subjects, are disclosed An embodiment, among others, of the nanostructure includes a metallic gold surface- enhanced Raman scattering nanoparticle, a Raman reporter and a protection structure The protection structure may include a thiol-polyethylene glycol to which may be attached a target-specific probe
1,938 citations
TL;DR: Graphene nanosheets were produced in large quantity via a soft chemistry synthetic route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction in this paper.
Abstract: Graphene nanosheets were produced in large quantity via a soft chemistry synthetic route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction. X-ray diffraction and transmission electron microscopy (TEM) observations show that graphene nanosheets were produced with sizes in the range of tens to hundreds of square nanometers and ripple-like corrugations. High resolution TEM (HRTEM) and selected area electron diffraction (SAED) analysis confirmed the ordered graphite crystal structure of graphene nanosheets. The optical properties of graphene nanosheets were characterized by Raman spectroscopy.
1,916 citations
TL;DR: Three-dimensional multiphoton vibrational imaging technique based on stimulated Raman scattering (SRS) is reported, which offers background-free and readily interpretable chemical contrast in biomedical imaging and shows a variety of biomedical applications.
Abstract: Label-free chemical contrast is highly desirable in biomedical imaging. Spontaneous Raman microscopy provides specific vibrational signatures of chemical bonds, but is often hindered by low sensitivity. Here we report a three-dimensional multiphoton vibrational imaging technique based on stimulated Raman scattering (SRS). The sensitivity of SRS imaging is significantly greater than that of spontaneous Raman microscopy, which is achieved by implementing high-frequency (megahertz) phase-sensitive detection. SRS microscopy has a major advantage over previous coherent Raman techniques in that it offers background-free and readily interpretable chemical contrast. We show a variety of biomedical applications, such as differentiating distributions of omega-3 fatty acids and saturated lipids in living cells, imaging of brain and skin tissues based on intrinsic lipid contrast, and monitoring drug delivery through the epidermis.
1,862 citations
TL;DR: In this article, Zhao et al. used uniaxial tensile strain to tune the 2D and G bands of graphene and obtained a band gap opening of ∼300 meV under 1% tensile tensile stress.
Abstract: Graphene was deposited on a transparent and flexible substrate, and tensile strain up to ∼0.8% was loaded by stretching the substrate in one direction. Raman spectra of strained graphene show significant red shifts of 2D and G band (−27.8 and −14.2 cm−1 per 1% strain, respectively) because of the elongation of the carbon−carbon bonds. This indicates that uniaxial strain has been successfully applied on graphene. We also proposed that, by applying uniaxial strain on graphene, tunable band gap at K point can be realized. First-principle calculations predicted a band-gap opening of ∼300 meV for graphene under 1% uniaxial tensile strain. The strained graphene provides an alternative way to experimentally tune the band gap of graphene, which would be more efficient and more controllable than other methods that are used to open the band gap in graphene. Moreover, our results suggest that the flexible substrate is ready for such a strain process, and Raman spectroscopy can be used as an ultrasensitive method to ...
1,367 citations
TL;DR: In this paper, surface segregation and substrate transfer were used to synthesize high quality graphene by dissolving carbon in Ni at high temperatures followed by cooling down with various rates, which led to different segregation behaviors, strongly affecting the thickness and quality of the graphene films.
Abstract: We report an approach to synthesize high quality graphene by surface segregation and substrate transfer. Graphene was segregated from Ni surface under the ambient pressure by dissolving carbon in Ni at high temperatures followed by cooling down with various rates. Different cooling rates led to different segregation behaviors, strongly affecting the thickness and quality of the graphene films. Electron microscopy and Raman spectroscopy indicated that the graphene films synthesized with medium cooling rates have high quality crystalline structure and well-controlled thicknesses. The graphene films were transferred to insulating substrates by wet etching and found to maintain their high quality.
1,285 citations
01 Jan 2008
TL;DR: In this paper, the authors used the Raman spectra of strained graphene to estimate the band gap opening under 1% uniaxial tensile strain on a transparent and flexible substrate.
Abstract: Graphene was deposited on a transparent andflexible substrate, and tensile strain up to0.8% was loaded by stretching the substrate in one direction. Raman spectra of strained graphene show significant red shifts of 2D and G band (27.8 and14.2 cm 1 per 1% strain, respectively) because of the elongation of the carboncarbon bonds. This indicates that uniaxial strain has been successfully applied on graphene. We also proposedthat,byapplyinguniaxialstrainongraphene,tunablebandgapatKpointcanberealized.First-principle calculations predicted a band-gap opening of300 meV for graphene under 1% uniaxial tensile strain. The strained graphene provides an alternative way to experimentally tune the band gap of graphene, which would be more efficient and more controllable than other methods that are used to open the band gap in graphene. Moreover,ourresultssuggestthattheflexiblesubstrateisreadyforsuchastrainprocess,andRamanspectroscopy can be used as an ultrasensitive method to determine the strain.
1,171 citations
TL;DR: In this article, Raman spectroscopy and imaging can be used as a quick and unambiguous method to determine the number of layers of a single-layer graphite compared to graphite.
Abstract: Graphene has many unique properties that make it an ideal material for fundamental studies as well as for potential applications. Here we review recent results on the Raman spectroscopy and imaging of graphene. We show that Raman spectroscopy and imaging can be used as a quick and unambiguous method to determine the number of graphene layers. The strong Raman signal of single layer graphene compared to graphite is explained by an interference enhancement model. We have also studied the effect of substrates, the top layer deposition, the annealing process, as well as folding (stacking order) on the physical and electronic properties of graphene. Finally, Raman spectroscopy of epitaxial graphene grown on a SiC substrate is presented and strong compressive strain on epitaxial graphene is observed. The results presented here are highly relevant to the application of graphene in nano-electronic devices and help in developing a better understanding of the physical and electronic properties of graphene.
TL;DR: Surfactant-wrapped chemically converted graphene sheets obtained from reduction of graphene oxide with hydrazine were functionalized by treatment with aryl diazonium salts, allowing alternative avenues for simple incorporation into different polymer matrices.
Abstract: Surfactant-wrapped chemically converted graphene sheets obtained from reduction of graphene oxide with hydrazine were functionalized by treatment with aryl diazonium salts. The nanosheets are characterized by X-ray photoelectron spectroscopy, attenuated total reflectance infrared spectroscopy, Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. The resulting functionalized nanosheets disperse readily in polar aprotic solvents, allowing alternative avenues for simple incorporation into different polymer matrices.
TL;DR: In this article, the position, width and intensity of G and D peaks at the edges are studied as a function of the incident light polarization, and the D-band is strongest for light polarized parallel to the edge and minimum for perpendicular orientation.
Abstract: Graphene edges are of particular interest, since their chirality determines the electronic properties. Here we present a detailed Raman investigation of graphene flakes with well defined edges oriented at different crystallographic directions. The position, width and intensity of G and D peaks at the edges are studied as a function of the incident light polarization. The D-band is strongest for light polarized parallel to the edge and minimum for perpendicular orientation. Raman mapping shows that the D peak is localized in proximity of the edge. The D to G ratio does not always show a significant dependence on edge orientation. Thus, even though edges can appear macroscopically smooth and oriented at well defined angles, they are not necessarily microscopically ordered.
TL;DR: This tutorial review focuses on recent progress in the design and fabrication of substrates for surface-enhanced Raman spectroscopy, with an emphasis on the influence of nanotechnology.
Abstract: Research on surface-enhanced Raman spectroscopy (SERS) is an area of intense interest because the technique allows one to probe small collections of, and in certain cases, individual molecules using relatively straightforward spectroscopic techniques and nanostructured substrates. Researchers in this area have attempted to develop many new technological innovations including high sensitivity chemical and biological detection systems, labeling schemes for authentication and tracking purposes, and dual scanning-probe/spectroscopic techniques that simultaneously provide topographical and spectroscopic information about an underlying surface or nanostructure. However, progress has been hampered by the inability of researchers to fabricate substrates with the high sensitivity, tunability, robustness, and reproducibility necessary for truly practical and successful SERS-based systems. These limitations have been due in part to a relative lack of control over the nanoscale features of Raman substrates that are responsible for the enhancement. With the advent of nanotechnology, new approaches are being developed to overcome these issues and produce substrates with higher sensitivity, stability, and reproducibility. This tutorial review focuses on recent progress in the design and fabrication of substrates for surface-enhanced Raman spectroscopy, with an emphasis on the influence of nanotechnology.
TL;DR: Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.
Abstract: Metallic nanostructures attract much interest as an efficient media for surface-enhanced Raman scattering (SERS). Significant progress has been made on the synthesis of metal nanoparticles with various shapes, composition, and controlled plasmonic properties, all critical for an efficient SERS response. For practical applications, efficient strategies of assembling metal nanoparticles into organized nanostructures are paramount for the fabrication of reproducible, stable, and highly active SERS substrates. Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.
Patent•
02 Apr 2008
TL;DR: In this paper, the authors described the nanostructures, methods of preparing nanostructure, methods for detecting targets in subjects, and methods of treating diseases in subjects. An embodiment, among others, includes a metallic gold surface-enhanced Raman scattering nanoparticle, a Raman reporter and a protection structure.
Abstract: Nanostructures, methods of preparing nanostructures, methods of detecting targets in subjects, and methods of treating diseases in subjects, are disclosed An embodiment, among others, of the nanostructure includes a metallic gold surface- enhanced Raman scattering nanoparticle, a Raman reporter and a protection structure The protection structure may include a thiol-polyethylene glycol to which may be attached a target-specific probe
TL;DR: The as-prepared cobalt oxide (assigned as CoO x ) was fabricated by precipitation-oxidation from aqueous cobalt nitrate solution using sodium hydroxide and oxidation with hydrogen peroxide as mentioned in this paper.
TL;DR: In this article, the effect of substrate on the atomic/electronic structures of monolayer graphene is investigated and it is shown that the Raman features are independent of the substrate used.
Abstract: Graphene has attracted a lot of interest for fundamental studies as well as for potential applications. Till now, micromechanical cleavage (MC) of graphite has been used to produce high-quality graphene sheets on different substrates. Clear understanding of the substrate effect is important for the potential device fabrication of graphene. Here we report the results of the Raman studies of micromechanically cleaved monolayer graphene on standard SiO2 (300 nm)/Si, single crystal quartz, Si, glass, polydimethylsiloxane (PDMS), and NiFe. Our data suggests that the Raman features of monolayer graphene are independent of the substrate used; in other words, the effect of substrate on the atomic/electronic structures of graphene is negligible for graphene made by MC. On the other hand, epitaxial monolayer graphene (EMG) on SiC substrate is also investigated. Significant blueshift of Raman bands is observed, which is attributed to the interaction of the graphene sheet with the substrate, resulting in the change o...
TL;DR: In this paper, the authors measured carrier relaxation times in epitaxial graphene layers grown on SiC wafers and found that an initial fast relaxation transient in the 70-120fs range is followed by a slower relaxation process in the 0.4-1.7ps range.
Abstract: Using ultrafast optical pump-probe spectroscopy, we have measured carrier relaxation times in epitaxial graphene layers grown on SiC wafers. We find two distinct time scales associated with the relaxation of nonequilibrium photogenerated carriers. An initial fast relaxation transient in the 70–120fs range is followed by a slower relaxation process in the 0.4–1.7ps range. The slower relaxation time is found to be inversely proportional to the degree of crystalline disorder in the graphene layers as measured by Raman spectroscopy. We relate the measured fast and slow time constants to carrier-carrier and carrier-phonon intraband and interband scattering processes in graphene.
TL;DR: Noninvasive deep-tissue molecular images in a living subject with the use of Raman spectroscopy are presented and the imaging modality reported here holds significant potential as a strategy for biomedical imaging of living subjects.
Abstract: Molecular imaging of living subjects continues to rapidly evolve with bioluminescence and fluorescence strategies, in particular being frequently used for small-animal models. This article presents noninvasive deep-tissue molecular images in a living subject with the use of Raman spectroscopy. We describe a strategy for small-animal optical imaging based on Raman spectroscopy and Raman nanoparticles. Surface-enhanced Raman scattering nanoparticles and single-wall carbon nanotubes were used to demonstrate whole-body Raman imaging, nanoparticle pharmacokinetics, multiplexing, and in vivo tumor targeting, using an imaging system adapted for small-animal Raman imaging. The imaging modality reported here holds significant potential as a strategy for biomedical imaging of living subjects.
TL;DR: In this paper, the transfer and identification of single and few-layer graphene sheets from SiO2/Si substrates to other types of substrates is presented, which enables the fast localization of graphene sheets on substrates on which optical microscopy does not allow direct and fast visualization of the thin graphene sheets.
Abstract: The transferring and identification of single- and few- layer graphene sheets from SiO2/Si substrates to other types of substrates is presented. Features across large areas (∼cm2) having single and few-layer graphene flakes, obtained by the microcleaving of highly oriented pyrolytic graphite (HOPG), can be transferred reliably. This method enables the fast localization of graphene sheets on substrates on which optical microscopy does not allow direct and fast visualization of the thin graphene sheets. No major morphological deformations, corrugations, or defects are induced on the graphene films when transferred to the target surface. Moreover, the differentiation between single and bilayer graphene via the G′ (∼2700 cm−1) Raman peak is demonstrated on various substrates. This approach opens up possibilities for the fabrication of graphene devices on a substrate material other than SiO2/Si.
TL;DR: In this paper, the authors show the evolution of Raman spectra with a number of graphene layers on different substrates, $SiO_2/Si$ and conducting indium tin oxide (ITO) plate.
Abstract: We show the evolution of Raman spectra with a number of graphene layers on different substrates, $SiO_2/Si$ and conducting indium tin oxide (ITO) plate. The G mode peak position and the intensity ratio of G and 2D bands depend on the preparation of sample for the same number of graphene layers. The 2D Raman band has characteristic line shapes in single and bilayer graphene, capturing the differences in their electronic structure. The defects have a significant influence on the G band peak position for the single layer graphene: the frequency shows a blue shift up to $12 cm^{-1}$ depending on the intensity of the D Raman band, which is a marker of the defect density. Most surprisingly, Raman spectra of graphene on the conducting ITO plates show a lowering of the G mode frequency by $\sim 6cm^{-1}$ and the 2D band frequency by $\sim 20cm^{-1}$. This red-shift of the G and 2D bands is observed for the first time in single layer graphene.
TL;DR: Graphene has been prepared by different methods: pyrolysis of camphor under reducing conditions (CG), exfoliation of graphitic oxide (EG), conversion of nanodiamond (DG) and arc evaporation of SiC (SG) as mentioned in this paper.
Abstract: Graphene has been prepared by different methods: pyrolysis of camphor under reducing conditions (CG), exfoliation of graphitic oxide (EG), conversion of nanodiamond (DG) and arc evaporation of SiC (SG). The samples were examined by X-ray diffraction (XRD), transmission electron microscopy, atomic force microscopy, Raman spectroscopy and magnetic measurements. Raman spectroscopy shows EG and DG to exhibit smaller in-plane crystallite sizes, but in combination with XRD results EG comes out to be better. The CG, EG and DG samples prepared by us have BET surface areas of 46, 925 and 520 m2 g−1 respectively and exhibit significant hydrogen uptake up to 3 wt%. EG also exhibits a high CO2 uptake (34.7 wt%). Electrochemical redox properties of the graphene samples have been examined in addition to their use in electrochemical supercapacitors. Functionalization of EG and DG through amidation has been carried out with the purpose of solubilizing them in non-polar solvents. Water-soluble graphene has been produced by extensive acid treatment of EG or treatment with polyethylene glycol.
TL;DR: This Feature Article examines recent advances in chemical analyte detection and optical imaging applications using gold and silver nanoparticles, with a primary focus on the authors' own work.
TL;DR: In this article, the Raman spectroscopy was used to study the structure of epitaxial graphene (EG) and its interaction with SiC substrate, which was attributed to the compressive strain induced by the substrate.
Abstract: The fabrication of epitaxial graphene (EG) on SiC substrate by annealing has attracted a lot of interest as it may speed up the application of graphene for future electronic devices The interaction of EG and the SiC substrate is critical to its electronic and physical properties In this work, the Raman spectroscopy was used to study the structure of EG and its interaction with SiC substrate All the Raman bands of EG blueshift from that of bulk graphite and graphene made by micromechanical cleavage, which was attributed to the compressive strain induced by the substrate A model containing $13\ifmmode\times\else\texttimes\fi{}13$ honeycomb lattice cells of graphene on carbon nanomesh was constructed to explain the origin of strain The lattice mismatch between graphene layer and substrate causes the compressive stress of $227\phantom{\rule{03em}{0ex}}\mathrm{GPa}$ on graphene We also demonstrate that the electronic structures of EG grown on Si- and C-terminated SiC substrates are quite different Our experimental results shed light on the interaction between graphene and SiC substrate, which are critical to the future applications of EG
TL;DR: The excited electronic states of noble metal Au and Ag nanocrystals are very different than those of molecules as discussed by the authors, which makes them ideal nanoantennas, in that they focus incident light into the local neighborhood of subwavelength size.
Abstract: The excited electronic states of noble metal Au and Ag nanocrystals are very different than those of molecules. Ag and Au nanocrystal optical transitions (plasmons) in the visible can be so intense that they significantly modify the local electromagnetic field. Also, coherent elastic Rayleigh light scattering is stronger than normal electronic absorption of photons for larger nanocrystals. These two facts make Au and Ag nanocrystals ideal nanoantennas, in that they focus incident light into the local neighborhood of subwavelength size. Surface-enhanced Raman scattering (SERS), in which the Raman scattering rate of nearby molecules increases by many orders of magnitude, is a consequence of this nanoantenna effect. Metallic nanocrystals also have no band gap; this makes them extraordinarily polarizable. Their electronic transitions sense the local environment. An extreme case is the interaction of two 30 nm Ag nanocrystals separated by a 1 nm gap. Their mutual polarization completely transforms the nature o...
TL;DR: This approach is used to monitor the interaction of DNA with cisplatin, a chemotherapy agent in widespread use and useful for assessing reproducibility and for quantifying the highly complex changes corresponding to modifications in molecular conformation of the adsorbate molecules.
Abstract: We report a method for obtaining highly reproducible surface-enhanced Raman spectroscopy (SERS) of single and double-stranded thiolated DNA oligomers. Following a protocol that relaxes the DNA into an extended conformation, SERS spectra of DNA oligonucleotides are found to be extremely similar, strongly dominated by the Stokes modes of adenine. A spectral correlation function analysis useful for assessing reproducibility and for quantifying the highly complex changes corresponding to modifications in molecular conformation of the adsorbate molecules is introduced. This approach is used to monitor the interaction of DNA with cisplatin, a chemotherapy agent in widespread use.
TL;DR: A way to extend the capabilities of plasma-enhanced chemical vapour deposition to the synthesis of freestanding few-layer graphene is presented and the resulting graphene flakes are aligned vertically to the substrate surface and grow according to a three-step process.
Abstract: If graphene is ever going to live up to the promises of future nanoelectronic devices, an easy and cheap route for mass production is an essential requirement. A way to extend the capabilities of plasma-enhanced chemical vapour deposition to the synthesis of freestanding few-layer graphene is presented. Micrometre-wide flakes consisting of four to six atomic layers of stacked graphene sheets have been synthesized by controlled recombination of carbon radicals in a microwave plasma. A simple and highly reproducible technique is essential, since the resulting flakes can be synthesized without the need for a catalyst on the surface of any substrate that withstands elevated temperatures up to 700 °C. A thorough structural analysis of the flakes is performed with electron microscopy, x-ray diffraction, Raman spectroscopy and scanning tunnelling microscopy. The resulting graphene flakes are aligned vertically to the substrate surface and grow according to a three-step process, as revealed by the combined analysis of electron microscopy and x-ray photoelectron spectroscopy.
TL;DR: In this review, recent developments in SERS spectroscopy are discussed and their impact on different research fields are discussed.
Abstract: Raman spectroscopy is a valuable tool in various research fields. The technique yields structural information from all kind of samples often without the need for extensive sample preparation. Since the Raman signals are inherently weak and therefore do not allow one to investigate substances in low concentrations, one possible approach is surface-enhanced (resonance) Raman spectroscopy. Here, rough coin metal surfaces enhance the Raman signal by a factor of 10(4)-10(15), depending on the applied method. In this review we discuss recent developments in SERS spectroscopy and their impact on different research fields.
TL;DR: Although structural distortions are robust to changes in particle size, what is affected is the coherency of the distortions, which is decreased in the smaller particles, in contrast to the sharp transition that is found for the bulk sample.
Abstract: We have investigated the paraelectric-to-ferroelectric phase transition of various sizes of nanocrystalline barium titanate (BaTiO3) by using temperature-dependent Raman spectroscopy and powder X-ray diffraction (XRD). Synchrotron X-ray scattering has been used to elucidate the room temperature structures of particles of different sizes by using both Rietveld refinement and pair distribution function (PDF) analysis. We observe the ferroelectric tetragonal phase even for the smallest particles at 26 nm. By using temperature-dependent Raman spectroscopy and XRD, we find that the phase transition is diffuse in temperature for the smaller particles, in contrast to the sharp transition that is found for the bulk sample. However, the actual transition temperature is almost unchanged. Rietveld and PDF analyses suggest increased distortions with decreasing particle size, albeit in conjunction with a tendency to a cubic average structure. These results suggest that although structural distortions are robust to cha...