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1.
Opt Express ; 30(8): 12326-12336, 2022 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-35472870

RESUMO

The field of ultraviolet (UV)-laser applications is currently experiencing rapid growth in the semiconductor processing, laser micromachining and biomedical markets. Key enablers for these technologies are optical coatings used to manipulate and guide laser beams in a targeted manner. As laser power, laser fluence and pulse frequencies increase, the demands on the physical properties of the coating materials become more stringent. Ion beam sputtering is a technique that allows producing optical coatings with the low losses required in these applications. In this study, we investigate the influence of ion beam sputtering (IBS) parameters on the optical properties of HfO2 and SiO2 single layers as well as the impact of annealing duration at 475 °C for anti-reflective (AR) and highly reflective (HR) optical coatings at 355 nm. For HfO2 sputtered from a metal target the O2 flow during the coating process is a key parameter to reduce absorption. SiO2 single layers exhibit improved transmission in the UV-range as the ion beam energy for the sputtering process is reduced. Furthermore, a complex behavior for film stress, absorption, surface roughness and coating structure was unraveled as a function of annealing duration for AR- and HR-coatings at 355 nm. The reflectance of the HR-mirror after optimized annealing exceeded 99.94% at 355 nm and a high laser induced damage threshold (LIDT) of 6.9 J/cm2 was measured after 2 hours of annealing. For the AR-coating a LIDT-value of 15.7 J/cm2 was observed after 12 hours of annealing.

2.
Nanoscale ; 11(2): 622-630, 2019 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-30560967

RESUMO

We report on the high temperature thin film growth of BaTiO3 on Ti3C2Tx MXene flakes using van der Waals epitaxy on a degradable template layer. MXene was deposited on amorphous and crystalline substrates by spray- and dip-coating techniques, while the growth of BaTiO3 at 700 °C was accomplished using pulsed laser deposition in an oxygen rich environment. We demonstrate that the MXene flakes act as a temporary seed layer, which promotes highly oriented BaTiO3 growth along the (111) direction independent of the underlying substrate. The lattice parameters of the BaTiO3 films are close to the bulk value suggesting that the BaTiO3 films remains unstrained, as expected for van der Waals epitaxy. The initial size of the MXene flakes has an impact on the orientation of the BaTiO3 films with larger flake sizes promoting a higher fraction of the polycrystalline film to grow along the (111) direction. The deposited BaTiO3 film adopts the same morphology as the original flakes and piezoresponse force microscopy shows a robust ferroelectric behavior for individual grains. Transmission electron microscopy results indicate that the Ti3C2Tx MXene fully decomposes during the BaTiO3 deposition and the surplus Ti atoms are readily incorporated into the BaTiO3 film. Electrical measurements show a similar dielectric constant as a BaTiO3 film grown without the MXene seed layer. The demonstrated process has the potential to overcome the longstanding issue of integrating highly oriented complex oxide thin films directly on any desired substrate.

3.
Nanoscale ; 10(46): 21798-21808, 2018 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-30452041

RESUMO

Traditionally, the ferroelectric Curie temperature can be manipulated by chemical substitution, e.g., in Ba1-xSrxTiO3 as one of the archetypical representatives. Here, we show a novel approach to tune the ferroelectric phase transition applicable for nanostructured thin films. We demonstrate this effect in nano-grained BaTiO3 films. Based on an enhanced metastable cation solubility with Ba/Ti-ratios of 0.8 to 1.06, a significant shift of the phase transition temperature is discovered. The transition temperature increases linearly from 212 K to 350 K with increasing Ba/Ti ratio. For all Ba/Ti ratios, a completely diffused phase transition is present resulting in a negligible temperature sensitivity of the dielectric constant. Schottky defects are identified as the driving force behind the off-stoichiometry and the shift of the phase transition temperature as they locally induce lattice strain. Complementary temperature dependent Raman experiments reveal the presence of the hexagonal polymorph in addition to the perovskite phase in all cases. Interestingly, the hexagonal BaTiO3 influences the structural transformation on the Ba-rich side, while on the Ti-rich side no changes for the hexagonal polymorph at the ferroelectric transition temperature are observed. This concerted structural change of both polymorphs on the Ba-rich side causes a broad phase transition region spanning over a wide range up to 420 K including the transition temperature of 350 K obtained from dielectric measurements. These findings are promising for fine adjustment of the phase transition temperature and low temperature coefficient of permittivity.

4.
Nanoscale ; 10(26): 12515-12525, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29931017

RESUMO

Thin films of ≈50 nm thickness with Ba/Ti-ratios ranging from 0.8 to 1.06 were prepared by depositing alternating layers of Ba(OH)2 and TiO2. Annealing at 750 °C promoted the solid-solid transformation into polycrystalline BaTiO3 films containing a mixture of the perovskite and the hexagonal polymorphs with average crystallite sizes smaller than 14 nm and without impurity phases. This, together with an increase of the cubic lattice parameters for Ba-rich films, suggests an extended metastable solubility range for the perovskite-phase in these nanocrystalline thin films on both sides of the stoichiometric composition. Mapping of the cation distribution utilizing energy-filtered transmission electron microscopy corroborates defect accommodation within the BaTiO3 grains. While the cation off-stoichiometry in thermodynamic equilibrium is negligible for BaTiO3, the metastable extended solubility range in the thin films can be directly correlated to the low annealing temperature and nanocrystalline nature. The leakage current behavior can be explained by the formation of Schottky defects for nonstoichiometric films, and the cation ratio has a distinct impact on the dielectric properties: while excess-BaO has a marginal detrimental effect on the permittivity, the dielectric constant declines rapidly by more than 50% towards the Ti-rich side. The present findings highlight the importance of compositional control for the synthesis of nanocrystalline BaTiO3 thin films, in particular for low annealing and/or deposition temperatures. Our synthesis approach using alternating layers of Ba(OH)2 and TiO2 provides a route to precisely control the cation stoichiometry.

5.
Chemphyschem ; 18(15): 1966-1970, 2017 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-28631872

RESUMO

We report on the growth of polycrystalline BiFeO3 thin films on SiO2 /Si(001) and Pt(111) substrates by atomic layer deposition using the precursors ferrocene, triphenyl-bismuth, and ozone. By growing alternating layers of Fe2 O3 and Bi2 O3 , we employ a superlattice approach and demonstrate an efficient control of the cation stoichiometry. The superlattice decay and the resulting formation of polycrystalline BiFeO3 films are studied by in situ X-ray diffraction, in situ X-ray photoelectron spectroscopy, and transmission electron microscopy. No intermediate ternary phases are formed and BiFeO3 crystallization is initiated in the Bi2 O3 layers at 450 °C following the diffusion-driven intermixing of the cations. Our study of the BiFeO3 formation provides an insight into the complex interplay between microstructural evolution, grain growth, and bismuth oxide evaporation, with implications for optimization of ferroelectric properties.

6.
Phys Rev Lett ; 118(9): 096601, 2017 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-28306282

RESUMO

We show how finite-size scaling of a bulk photovoltaic effect-generated electric field in epitaxial ferroelectric insulating BaTiO_{3}(001) films and a photo-Hall response involving the bulk photovoltaic current reveal a large room-temperature mean free path of photogenerated nonthermalized electrons. Experimental determination of mesoscopic ballistic optically generated carrier transport opens a new paradigm for hot electron-based solar energy conversion, and for facile control of ballistic transport distinct from existing low-dimensional semiconductor interfaces, surfaces, layers, or other structures.

7.
Sci Rep ; 6: 33457, 2016 09 16.
Artigo em Inglês | MEDLINE | ID: mdl-27634465

RESUMO

Hybrid electronic heterostructure films of semi- and superconducting layers possess very different properties from their bulk counterparts. Here, we demonstrate superconductivity in ferecrystals: turbostratically disordered atomic-scale layered structures of single-, bi- and trilayers of NbSe2 separated by PbSe layers. The turbostratic (orientation) disorder between individual layers does not destroy superconductivity. Our method of fabricating artificial sequences of atomic-scale 2D layers, structurally independent of their neighbours in the growth direction, opens up new possibilities of stacking arbitrary numbers of hybrid layers which are not available otherwise, because epitaxial strain is avoided. The observation of superconductivity and systematic Tc changes with nanostructure make this synthesis approach of particular interest for realizing hybrid systems in the search of 2D superconductivity and the design of novel electronic heterostructures.

8.
Nanoscale ; 8(28): 13646-51, 2016 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-27363315

RESUMO

Targeted heterostructures containing intergrown two dimensional (2D) layers of 3 different constituent layers, SnSe2, PbSe and TiSe2, were prepared by controlling the composition and sequence of elemental bilayers within a designed precursor. Varying the structure of the precursor enabled the number of structural units of each constituent and the sequence of crystalline 2D layers to be precisely controlled. The stacking of the 2D layers, their structures, and the segregation of the elements between them were determined using X-ray diffraction and electron microscopy techniques, with the observed sequence of the 2D layers consistent with the targeted intergrowth. This ability to prepare targeted heterostructures is critical, since the number of possible configurations in the final compound increases rapidly as the number of constituents increases, from almost 60 000 with two constituents to over 130 million with three constituents and to over 35 billion with four constituents for 20 or fewer distinct layers in the unit cell. This general route for synthesizing specific multiple component heterostructures will accelerate the feedback loop in this growing research area, permitting theorists to assume specific structures in the search for enhanced properties and providing experimentalists with crystallographically aligned samples to test these predictions.

9.
Angew Chem Int Ed Engl ; 54(51): 15468-72, 2015 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-26545566

RESUMO

Selecting specific 2D building blocks and specific layering sequences of van der Waals heterostructures should allow the formation of new materials with designed properties for specific applications. Unfortunately, the synthetic ability to prepare such structures at will, especially in a manner that can be manufactured, does not exist. Herein, we report the targeted synthesis of new metal-semiconductor heterostructures using the modulated elemental-reactant technique to nucleate specific 2D building blocks, control their thickness, and avoid epitaxial structures with long-range order. The building blocks, VSe2 and GeSe2 , have different crystal structures, which inhibits cation intermixing. The precise control of this approach enabled us to synthesize heterostructures containing GeSe2 monolayers alternating with VSe2 structural units with specific sequences. The transport properties systematically change with nanoarchitecture and a charge-density wave-like transition is observed.

10.
Inorg Chem ; 54(21): 10309-15, 2015 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-26465820

RESUMO

(BiSe)(1+δ)NbSe2 ferecrystals were synthesized in order to determine whether structural modulation in BiSe layers, characterized by periodic antiphase boundaries and Bi-Bi bonding, occurs. Specular X-ray diffraction revealed the formation of the desired compound with a c-axis lattice parameter of 1.21 nm from precursors with a range of initial compositions and initial periodicities. In-plane X-ray diffraction scans could be indexed as hk0 reflections of the constituents, with a rectangular basal BiSe lattice and a trigonal basal NbSe2 lattice. Electron micrographs showed extensive turbostratic disorder in the samples and the presence of periodic antiphase boundaries (approximately 1.5 nm periodicity) in BiSe layers oriented with the [110] direction parallel to the zone axis of the microscope. This indicates that the structural modulation in the BiSe layers is not due to coherency strain resulting from commensurate in-plane lattices. Electrical transport measurements indicate that holes are the dominant charge carrying species, that there is a weak decrease in resistivity as temperature decreases, and that minimal charge transfer occurs from the BiSe to NbSe2 layers. This is consistent with the lack of charge transfer from the BiX to the TX2 layers reported in misfit layer compounds where antiphase boundaries were observed. This suggests that electronic considerations, i.e., localization of electrons in the Bi-Bi pairs at the antiphase boundaries, play a dominant role in stabilizing the structural modulation.

11.
ACS Nano ; 9(8): 8440-8, 2015 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-26172638

RESUMO

A series of ferecrystalline compounds ([SnSe]1+δ)1(VSe2)1 with varying Sn/V ratios were synthesized using the modulated elemental reactant technique. Temperature-dependent specific heat data reveal a phase transition at 102 K, where the heat capacity changes abruptly. An abrupt increase in electrical resistivity occurs at the same temperature, correlated with an abrupt increase in the Hall coefficient. Combined with the magnitude and nature of the specific heat discontinuity, this suggests that the transition is similar to the charge density wave transitions in transition metal dichalcogenides. An ordered intergrowth was formed over a surprisingly wide compositional range of Sn/V ratios of 0.89 ≤ 1 + δ ≤ 1.37. X-ray diffraction and transmission electron microscopy reveal the formation of various volume defects in the compounds in response to the nonstoichiometry. The electrical resistivity and Hall coefficient data of samples with different Sn/V ratios show systematic variation in the carrier concentration with the Sn/V ratio. There is no significant change in the onset temperature of the charge density wave transition, only a variation in the carrier densities before and after the transition. Given the sensitivity of the charge density wave transitions of transition metal dichalcogenides to variations in composition, it is very surprising that the charge density wave transition observed at 102 K for ([SnSe]1.15)1(VSe2)1 is barely influenced by the nonstoichiometry and structural defects. This might be a consequence of the two-dimensional nature of the structurally independent VSe2 layers.

12.
ACS Nano ; 9(4): 4427-34, 2015 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-25853288

RESUMO

Inorganic isomers ([SnSe]1+δ)m(NbSe2)n([SnSe]1+δ)p(NbSe2)q([SnSe]1+δ)r(NbSe2)s where m, n, p, q, r, and s are integers and m + p + r = n + q + s = 4 were prepared using the modulated elemental reactant technique. This series of all six possible isomers provides an opportunity to study the influence of interface density on properties while maintaining the same unit cell size and composition. As expected, all six compounds were observed to have the same atomic compositions and an almost constant c-axis lattice parameter of ≈4.90(5) nm, with a slight trend in the c-axis lattice parameter correlated with the different number of interfaces in the isomers: two, four and six. The structures of the constituents in the ab-plane were independent of one another, confirming the nonepitaxial relationship between them. The temperature dependent electrical resistivities revealed metallic behavior for all the six compounds. Surprisingly, the electrical resistivity at room temperature decreases with increasing number of interfaces. Hall measurements suggest this results from changes in carrier concentration, which increases with increasing thickness of the thickest SnSe block in the isomer. Carrier mobility scales with the thickness of the thickest NbSe2 block due to increased interfacial scattering as the NbSe2 blocks become thinner. The observed behavior suggests that the two constituents serve different purposes with respect to electrical transport. SnSe acts as a charge donor and NbSe2 acts as the charge transport layer. This separation of function suggests that such heterostructures can be designed to optimize performance through choice of constituent, layer thickness, and layer sequence. A simplistic model, which predicts the properties of the complex isomers from a weighted sum of the properties of building blocks, was developed. A theoretical model is needed to predict the optimal compound for specific properties among the many potential compounds that can be prepared.

13.
Nanoscale ; 7(16): 7378-85, 2015 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-25826023

RESUMO

A series of ([SnSe]1+δ)m(NbSe2)2 compounds with two layers of NbSe2 separated by m bilayers of SnSe, where 1 ≤ m ≤ 20, were prepared from modulated precursors by systematically changing the number of SnSe layers in the repeating unit. A change in the c-lattice parameter of 0.579(3) nm per SnSe bilayer was observed. The thickness of the NbSe2 layer was determined to be 1.281(4) nm: twice the value of a single NbSe2 layer. HAADF-STEM images revealed the presence of extensive rotational disorder and the lack of any epitaxial relationship among the constituent layers. Two different coordination environments for the Nb in NbSe2 (trigonal prismatic and octahedral) were observed. The electrical resistivity increases and the carrier concentration decreases in the ([SnSe]1+δ)m(NbSe2)2 compounds with increasing number of SnSe bilayers. The temperature dependence of the resistivity suggests localization of carriers for higher m values. The decline in carrier concentration as a function of m implies the presence of charge transfer from SnSe to NbSe2. The transport properties of the ([SnSe]1+δ)m(NbSe2)2 compounds and the previously reported ([SnSe]1+δ)m(NbSe2)1 compounds both have unusually temperature independent resistivity compared to bulk NbSe2. Compounds with similar m/n ratios exhibit similar transport properties. Consequently, the dominant effect on the transport properties of ([SnSe]1+δ)m(NbSe2)2 is charge transfer, and there are only subtle differences between a monolayer and a bilayer of NbSe2.

14.
J Am Chem Soc ; 137(14): 4831-9, 2015 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-25807217

RESUMO

Intergrowth compounds of ([SnSe]1+δ)m(NbSe2)n, where 1 ≤ m = n ≤ 20, with the same atomic composition but different c-axis lattice parameters and number of interfaces per volume were synthesized using the modulated elemental reactant technique. A c-axis lattice parameter change of 1.217(6) nm as a function of one unit of m = n was observed. In-plane X-ray diffraction shows an increase in distortion of the rock salt layer as a function of m and a broadening of the NbSe2 reflections as n increases, indicating the presence of different coordination environments for Nb (trigonal prismatic and octahedral) and smaller crystallite size, which were confirmed via scanning transmission electron microscopy investigations. The electrical resistivities of all 12 compounds exhibit metallic temperature dependence and are similar in magnitude as would be expected for isocompositional compounds. Carrier concentration and mobility of the compounds vary within a narrow range of 2-6 × 10(21) cm(-3) and 2-6 cm(2) V(-1) s(-1), respectively. Even at a thickness of 12 nm for the SnSe and NbSe2 blocks, the properties of the intergrowth compounds cannot be explained as composite behavior, due to significant charge transfer between them. Upon being annealed at 500 °C, the higher order m = n compounds were found to convert to the thermodynamically stable phase, the (1,1) compound. This suggests that the capacitive energy of the interfaces stabilizes these intergrowth compounds.

15.
Materials (Basel) ; 8(4): 2000-2029, 2015 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-28788045

RESUMO

A basic summary of thermoelectric principles is presented in a historical context, following the evolution of the field from initial discovery to modern day high-zT materials. A specific focus is placed on nanocomposite materials as a means to solve the challenges presented by the contradictory material requirements necessary for efficient thermal energy harvest. Misfit layer compounds are highlighted as an example of a highly ordered anisotropic nanocomposite system. Their layered structure provides the opportunity to use multiple constituents for improved thermoelectric performance, through both enhanced phonon scattering at interfaces and through electronic interactions between the constituents. Recently, a class of metastable, turbostratically-disordered misfit layer compounds has been synthesized using a kinetically controlled approach with low reaction temperatures. The kinetically stabilized structures can be prepared with a variety of constituent ratios and layering schemes, providing an avenue to systematically understand structure-function relationships not possible in the thermodynamic compounds. We summarize the work that has been done to date on these materials. The observed turbostratic disorder has been shown to result in extremely low cross plane thermal conductivity and in plane thermal conductivities that are also very small, suggesting the structural motif could be attractive as thermoelectric materials if the power factor could be improved. The first 10 compounds in the [(PbSe)1+δ]m(TiSe2)n family (m, n ≤ 3) are reported as a case study. As n increases, the magnitude of the Seebeck coefficient is significantly increased without a simultaneous decrease in the in-plane electrical conductivity, resulting in an improved thermoelectric power factor.

16.
Nano Lett ; 15(2): 943-8, 2015 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-25546501

RESUMO

The compounds, ([SnSe]1.15)1(VSe2)n with n = 1, 2, 3, and 4, were prepared using designed precursors in order to investigate the influence of the thickness of the VSe2 constituent on the charge density wave transition. The structure of each of the compounds was determined using X-ray diffraction and scanning transmission electron microscopy. The charge density wave transition observed in the resistivity of ([SnSe]1.15)1(VSe2)1 was confirmed. The electrical properties of the n = 2 and 3 compounds are distinctly different. The magnitude of the resistivity change at the transition temperature is dramatically lowered and the temperature of the resistivity minimum systematically increases from 118 K (n = 1) to 172 K (n = 3). For n = 1, this temperature correlates with the onset of the charge density wave transition. The Hall-coefficient changes sign when n is greater than 1, and the temperature dependence of the Hall coefficient of the n = 2 and 3 compounds is very similar to the bulk, slowly decreasing as the temperature is decreased, while for the n = 1 compound the Hall coefficient increases dramatically starting at the onset of the charge density wave. The transport properties suggest an abrupt change in electronic properties on increasing the thickness of the VSe2 layer beyond a single layer.

17.
Dalton Trans ; 42(8): 2913-20, 2013 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-23243666

RESUMO

A systematic investigation is presented on the influence of Sn-substitution in the clathrate-I compound Ba(8)Zn(x)Ge(46-x-y)Sn(y), particularly for the crystal structure and thermoelectric properties including electrical resistivity, Seebeck coefficient, and thermal conductivity. Two series of samples were prepared to explore the changes for different Sn-contents, (y), and to define the optimum Zn-content, (x), for Ba(8)Zn(x)Ge(46-x-y)Sn(y). Sn-incorporation leads to a linear expansion of the unit cell parameters. Sn-atoms occupy the 6d and 24k positions of the clathrate type-I structure (SG Pm3n, standardized setting). Whereas the electrical resistivity and the Seebeck coefficient modify only slightly compared to Ba(8)Zn(x)Ge(46-x), the thermal conductivity is significantly decreased by the Sn-atoms incorporated into the clathrate-I framework. Furthermore the charge carrier mobility is larger and the effective mass (m* = 1.7 m(e)) is much smaller than those of the ternary compound Ba(8)Zn(x)Ge(46-x). The maximum thermoelectric figure of merit is improved by 80% and reaches ZT = 0.82 at 850 K for Ba(8)Zn(7.66)Ge(36.55)Sn(1.79).

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