Low-Temperature Synthesis of GeTe Nanoparticles.

Nanoparticles can offer an alternative approach to fabricate phase-change materials. The chemical synthesis of GeTe nanoparticles using organometallic precursors exploits high-boiling solvents and relatively high temperatures (close or even above crystallization temperatures), as reported in the available literature. The aim of this work is the preparation of GeTe nanoparticles by a low-temperature synthetic method exploiting new organometallic precursors and common organic solvents. Indeed, different preparation methods and characterization of GeTe nanoparticles is discussed. The characterization of the prepared nanomaterial was performed on the basis of X-ray diffraction, transmission electron microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, laser ablation time-of-flight mass spectrometry, Raman scattering spectroscopy, and dynamic light scattering. The results show that the low-temperature synthetic route leads to amorphous GeTe nanoparticles. Exploited organometallic precursor is stabilised by neutral ligand which can be isolated after the reaction and repeatedly used for further reactions. Furthermore, GeTe nanoparticle size can be tuned by the conditions of the synthesis.

Surface functionalization of a chalcogenide IR photonic sensor by means of a polymer membrane for water pollution remediation.

Rapid, simultaneous detection of organic chemical pollutants in water is an important issue to solve for protecting human health. This study investigated the possibility of developing an in situ reusable optical sensor capable of selective measurements utilizing a chalcogenide transducer supplemented by a hydrophobic polymer membrane with detection based on evanescent waves in the mid-infrared spectrum. In order to optimise a polyisobutylene hydrophobic film deposited on a chalcogenide waveguide, a zinc selenide prism was utilized as a testbed for performing attenuated total reflection with Fourier-transform infrared spectroscopy. To comply with the levels mentioned in health guidelines, the target detection range in this study was kept rather low, with the concentration range extended from 50 ppb to 100 ppm to cover accidental pollution problems, while targeted hydrocarbons (benzene, toluene, and xylene) were still detected at a concentration of 100 ppb. Infrared measurements in the selected range showed a linear behaviour, with the exception of two constantly reproducible plateau phases around 25 and 80 ppm, which were observable for two polymer film thicknesses of 5 and 10 µm. The polymer was also found to be reusable by regenerating it with water between individual measurements by increasing the water temperature and flow to facilitate reverse exchange kinetics. Given the good conformability of the hydrophobic polymer when coated on chalcogenide photonic circuits and its demonstrated ability to detect organic pollutants in water and to be regenerated afterwards, a microfluidic channel utilising water flow over an evanescent wave optical transducer based on a chalcogenide waveguide and a polyisobutylene (PIB) hydrophobic layer deposited on its surface was successfully fabricated from polydimethylsiloxane by filling a mold prepared via CAD and 3D printing techniques.

Linear and nonlinear optical properties of co-sputtered Ge-Sb-Se amorphous thin films.

Amorphous Ge-Sb-Se thin films were co-sputtered from ${{\rm GeSe}_4}$GeSe4 and ${{\rm Sb}_2}{{\rm Se}_3}$Sb2Se3 targets. Depending on the film composition, linear optical properties were studied by ellipsometry. The Kerr coefficient and two-photon absorption coefficient were estimated using Sheik-Bahae's formalism for co-sputtered films of ${{\rm GeSe}_4} {\text -} {\rm Sb}_2{{\rm Se}_3}$GeSe4-Sb2Se3 compared to ${{\rm GeSe}_2}{\text -}{\rm Sb}_2{{\rm Se}_3}$GeSe2-Sb2Se3 pseudo-binary system and ${{\rm As}_2}{{\rm Se}_3}$As2Se3 as reference. The Kerr coefficient was found within the range of $4.9 {\unicode {x2013}}- 21 \times {10^{ - 18}}$4.9--21×10-18. Quantitatively by means of a figure of merit at 1.55 µm, thin films with compositions of ${{\rm Ge}_7}{\rm Sb}_{25}{\rm Se}_{68}$Ge7Sb25Se68 and ${{\rm Ge}_9}{\rm Sb}_{20}{\rm Se}_{71}$Ge9Sb20Se71 having an estimated Kerr coefficient of about ${10.1} \times {10^{ - 18}}\;{{\rm m}^2}{{\rm W}^{ - 1}}$10.1×10-18m2W-1 and ${13.4} \times {10^{ - 18}}\;{{\rm m}^2}{{\rm W}^{ - 1}}$13.4×10-18m2W-1 should be considered for the future nonlinear optical integrated platforms. Such compositions being close to ${({{\rm GeSe}_4})_{50}}{({{\rm Sb}_2}{{\rm Se}_3})_{50}}$(GeSe4)50(Sb2Se3)50 pseudo-binary (i.e., ${\rm Ge}_{7.5}{\rm Sb}_{25.0}{\rm Se}_{67.5}$Ge7.5Sb25.0Se67.5) provides just the trade-off between a high Kerr coefficient and low optical losses related to two-photon absorption.

GaTe-Sb2Te3 thin-films phase change characteristics.

A radio frequency magnetron co-sputtering technique exploiting GaTe and ${\rm Sb}_2 {\rm Te}_3$Sb2Te3 targets was used for the fabrication of Ga-Sb-Te thin films. Prepared layers cover broad region of chemical composition (${\sim}{10.0 {-} 26.3}\,\, {\rm at.}$∼10.0-26.3at. % of Ga, ${\sim}{19.9 {-} 34.4}\,\, {\rm at.}$∼19.9-34.4at. % of Sb) while keeping Te content fairly constant (53.8-55.6 at. % of Te). Upon crystallization induced by annealing, large variations in electrical contrast were found, reaching a sheet resistance ratio of ${{R}_{\rm annealed}}/{{R}_{\rm as - deposited}}\;\sim{2.2} \times {{10}^{ - 8}}$Rannealed/Ras-deposited∼2.2×10-8 for the ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 layer. Phase transition from the amorphous to crystalline state further leads to huge changes of optical functions demonstrated by optical contrast values up to $|\Delta n| + |\Delta k| = {4.20}$|Δn|+|Δk|=4.20 for ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 composition.

Synthesis, Structure and Application of Intramolecularly-Coordinated Gallium Chalcogenides: Suitable Single-Source precursors for Gax Sey Materials.

Studies have been focused on the synthesis of N→Ga-coordinated organogallium selenides and tellurides [L1 Ga(µ-Se)]2 (1), [L2 Ga(µ-Se)]2 (2) and [L1 Ga(µ-Te)]2 (3), respectively, containing either N,C,N- or C,N-chelating ligands L1, 2 (L1 is {2,6-(Me2 NCH2 )2 C6 H3 }- and L2 is {2-(Et2 NCH2 )-4,6-tBu2 -C6 H2 }- ) having Ga/E (E=Se or Te) atoms in 1/1 ratio. To change the Ga/E ratio, an unusual N→Ga-coordinated organogallium tetraselenide L1 Ga(κ2 -Se4 ) (4) was prepared. An unprecedented complex (L1 Ga)2 (µ-Te2 )(µ-Te) (5), as the result of the non-stability of 3, was also isolated. Compound 2 is a suitable single-source precursor for the preparation of amorphous GaSe thin films by the spin coating. Moreover, simple heating of an octadecylamine solution of 2 provided, after work up, monoclinic Ga2 Se3 crystals with different crystallinity according to conditions used. Therefore, compound 2 may be also used as a source of Ga2 Se3 in the low-temperature doping process of Bi2 Se3 .

Photostability of pulsed-laser-deposited AsxTe100-x (x=40, 50, 60) amorphous thin films.

AsxTe100-x amorphous thin films were fabricated by a pulsed laser deposition technique with the aim of finding photostable layers in as-deposited but preferably in relaxed (annealed) state. Photostability was studied in terms of the films' stability of refractive index and bandgap under near-bandgap light irradiation. As40Te60 and As50Te50 layers were found to be photostable in both as-deposited as well as relaxed states. Moreover, As50Te50 layers present the lowest surface roughness. These characteristics make pulsed-laser-deposited As50Te50 thin films promising for applications in nonlinear optics.

Intramolecularly Coordinated Gallium Sulfides: Suitable Single Source Precursors for GaS Thin Films.

Our studies have been focused on the synthesis of N→Ga coordinated organogallium sulfides [L1 Ga(µ-S)]3 (1) and [L2 Ga(µ-S)]2 (2) containing either N,C,N- or C,N-chelating ligands L1 or L2 (L1 is {2,6-(Me2 NCH2 )2 C6 H3 }- and L2 is {2-(Et2 NCH2 )-4,6-tBu2 -C6 H2 }- ). As the result of the different ligands, compounds 1 and 2 differ mutually in their structure. To change the Ga/S ratio, unusually N→Ga coordinated organogallium tetrasulfide L1 Ga(κ2 -S4 ) (3) was prepared and the unprecedented complex [{2-[CH{(CH2 )3 CH3 }(µ-OH)]-6-CH2 NMe2 }C6 H3 ]GaS (4) was also isolated as the minor by-product of the reaction. Compounds 1-3 were further studied as potential single-source precursors for amorphous GaS thin film deposition by spin-coating.

Less is more: three-coordinate c,n-chelated distannynes and digermynes.

We report here the synthesis of new C,N-chelated chlorostannylenes and germylenes L(3) MCl (M=Sn(1), Ge (2)) and L(4) MCl (M=Sn(3), Ge (4)) containing sterically demanding C,N-chelating ligands L(3, 4) (L(3) =[2,4-di-tBu-6-(Et2 NCH2 )C6 H2 ](-) ; L(4) =[2,4-di-tBu-6-{(C6 H3 -2',6'-iPr2 )N=CH}C6 H2 ](-) ). Reductions of 1-4 yielded three-coordinate C,N-chelated distannynes and digermynes [L(3, 4) M]2 for the first time (5: L(3) , M=Sn, 6: L(3) , M=Ge, 7: L(4) , M=Sn, 8: L(4) , M=Ge). For comparison, the four-coordinate distannyne [L(5) Sn]2 (10) stabilized by N,C,N-chelate L(5) (L(5) =[2,6-{(C6 H3 -2',6'-Me2 )NCH}2 C6 H3 ](-) ) was prepared by the reduction of chlorostannylene L(5) SnCl (9). Hence, we highlight the role of donor-driven stabilization of tetrynes. Compounds 1-10 were characterized by means of elemental analysis, NMR spectroscopy, and in the case of 1, 2, 5-7, and 10, also by single-crystal X-ray diffraction analysis. The bonding situation in either three- or four-coordinate distannynes 5, 7, and 10 was evaluated by DFT calculations. DFT calculations were also used to compare the nature of the metal-metal bond in three-coordinate C,N-chelating distannyne [L(3) Sn]2 (5) and related digermyme [L(3) Ge]2 (6).

N-Coordinated Tin(II) Trifluoromethanesulfonates and Their Reactions with Transition Metal Carbonyls.

The syntheses of the compounds [L(1)SnCl][M(CO)5(SnCl3)] (3, M = W; 4, M = Cr), [L(1)SnCl]OTf (5), [L(1)SnCl][W(CO)5(SnCl2OTf)] (6), [L(1)SnOTf][OTf] (7), and [L(2)Sn(OTf)2] (8) with L(1) = {2,6-[(CH3)C═N(C6H3-2,6-(i)Pr2)2]C5H3N} (DIMPY) and L(2) = {2-[(CH3)C═N(C6H3-2,6-(i)Pr2)]-6-(CH3O)}C5H3N) is reported. The compounds were characterized by elemental analyses, (1)H, (13)C, (19)F, and (119)Sn NMR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analyses (3·1.5C7H8, 5·CH2Cl2, 7·C7H8, 8). For compounds 7 and 8, the experimental work is accompanied by density functional theory calculations.

Synthesis of star-shaped poly(lactide)s, poly(valerolactone)s and poly(caprolactone)s via ROP catalyzed by N-donor tin(ii) cations and comparison of their wetting properties with linear analogues.

In this study, we report the use of N-coordinated tin(ii) cations [L1→Sn(H2O)][OTf]2·THF (1) and [L1→SnCl][SnCl3] (2) (L1 = 1,2-(C5H4N-2-CH = N)2CH2CH2) as efficient ROP catalysts, which, in combination with benzyl alcohol, afford well-defined linear poly(ε-caprolactone) (PCL) and poly(δ-valerolactones) (PVL) via an activated monomer mechanism (AMM). Thanks to the versatility of complexes 1 and 2 as catalysts, star-shaped PCL, PVL and PLA were also prepared using three-, four-, five- and six-functional alcohols. The number of arms was determined by SEC-MALS-Visco analysis. Spin-coated thin layers of linear and selected six-armed polymers were further studied in terms of their wettability to water. Attention was focused on the influence of the composition and structure of the polymers. Finally, to increase the hydrophobic properties of the studied polymers, stannaboroxines L2(Ph)Sn[(OB-(C6H4-4-CF3))2O] and L2(Ph)Sn[(OB-(C6H4-3,5-CF3)2)2O] (L2 = C6H3-2,6-(Me2NCH2)2) were applied.

Mixed organotin(IV) chalcogenides: from molecules to Sn-S-Se semiconducting thin films deposited by spin-coating.

Put the right spin on it: Mixed monomeric organotin(IV) chalcogenides of the general formula L(2)Sn(2)EX(2) containing two terminal Sn-X (X = Se, Te) bonds were prepared and were tested as potential single-source precursors for the deposition of semiconducting thin films. Spin-coating deposition of [{2,6-(Me(2)NCH(2))(2)C(6)H(3)}SnSe](2)(µ-S), as the useful single-source precursor, provided amorphous Sn-S-Se semiconducting thin films.

Intramolecularly coordinated organotin tellurides: stable or unstable?

The step-wise oxidation of an organotin(I) compound with elemental tellurium gave a variety of unprecedented organotin tellurides containing tin atoms in the oxidation states +II and +IV.

Synthesis and optical properties of N→Ga coordinated gallium boroxines.

Reactions of the N,C,N-chelated organogallium amide LGa(NEt2)2 (1), where L is {2,6-(Me2NCH2)2C6H3}-, with organoboronic acids RB(OH)2 yielded molecular gallium boroxines LGa(O3B2R2) (2: R = OH, 3: R = Ph, 4: R = 4-MeO-C6H4, 5: R = 4-CHO-C6H4, 6: R = Fc), neutral analogues of gallaborates. The molecular structures revealed the presence of a six-membered central GaB2O3 ring. The film forming properties of 5 allowed the deposition of transparent thin films by a spin coating method. The thicknesses, refractive index, energy of the optical gap (Eoptg), activation energy of surface electrical conductivity (Esa) and pre-exponential factor (σ0) of the thin layers of 5 were measured and they are close to those found for related oxygen glass. Finally, GBO 5 was also used as an additive to printing ink and a thin film of 5 was prepared by the gravure printing technique.

Spectroscopic Ellipsometry Characterization of As-Deposited and Annealed Non-Stoichiometric Indium Zinc Tin Oxide Thin Film.

A spectroscopic ellipsometry study on as-deposited and annealed non-stoichiometric indium zinc tin oxide thin films of four different compositions prepared by RF magnetron sputtering was conducted. Multi-sample analysis with two sets of samples sputtered onto glass slides and silicon wafers, together with the analysis of the samples onto each substrate separately, was utilized for as-deposited samples. Annealed samples onto the glass slides were also analyzed. Spectroscopic ellipsometry in a wide spectral range (0.2-6 eV) was used to determine optical constants (refractive index n and extinction coefficient k) of these films. Parameterized semiconductor oscillator function, together with Drude oscillator, was used as a model dielectric function. Geometrical parameters (layer thickness and surface roughness) and physical parameters (direct optical bandgap, free carrier concentration, mobility, and specific electrical resistivity) were determined from spectroscopic ellipsometry data modeling. Specific electrical resistivity determined from the Drude oscillator corresponds well with the results from electrical measurements. Change in the optical bandgap, visible especially for annealed samples, corresponds with the change of free carrier concentration (Moss-Burstein effect). Scanning electron microscope did not reveal any noticeable annealing-induced change in surface morphology.

Comparative study of Er3+-doped Ga-Ge-Sb-S thin films fabricated by sputtering and pulsed laser deposition.

Despite the renewed interest in rare earth-doped chalcogenide glasses lying mainly in mid-infrared applications, a few comprehensive studies so far have presented the photoluminescence of amorphous chalcogenide films from visible to mid-infrared. This work reports the fabrication of luminescent quaternary sulfide thin films using radio-frequency sputtering and pulsed laser deposition, and the characterization of their chemical composition, morphology, structure, refractive index and Er3+ photoluminescence. The study of Er3+ 4I13/2 level lifetimes enables developing suitable deposition parameters; the dependency of composition, structural and spectroscopic properties on deposition parameters provides a way to tailor the RE-doped thin film properties. The surface roughness is very low for both deposition methods, ensuring reasonable propagation optical losses. The effects of annealing on the sulfide films spectroscopy and lifetimes were assessed. PLD appears consistent composition-wise, and largely independent of the deposition conditions, but radiofrequency magnetron sputtering seems to be more versatile, as one may tailor the film properties through deposition parameters manipulation. The luminescence via rare earth-doped chalcogenide waveguiding micro-structures might find easy-to-use applications concerning telecommunications or on-chip optical sensors for which luminescent sources or amplifiers operating at different wavelengths are required.

Amorphous Ge-Bi-Se Thin Films: A Mass Spectrometric Study.

The Ge-Bi-Se thin films of varied compositions (Ge content 0-32.1 at. %, Bi content 0-45.7 at. %, Se content 54.3-67.9 at. %) have been prepared by rf magnetron (co)-sputtering technique. The present study was undertaken in order to investigate the clusters generated during the interaction of laser pulses with Ge-Bi-Se thin films using laser ablation time-of-flight mass spectrometry. The stoichiometry of the clusters was determined in order to understand the individual species present in the plasma plume. Laser ablation of Ge-Bi-Se thin films accompanied by ionization produces about 20 positively and/or negatively charged unary, binary and ternary (Gex+, Biy+, Sez+/-, GexSez+/-, BiySez+/- and GexBiySez-) clusters. Furthermore, we performed the laser ablation experiments of Ge:Bi:Se elemental mixtures and the results were compared with laser ablation time-of-flight mass spectrometry analysis of thin films. Moreover, to understand the geometry of the generated clusters, we calculated structures of some selected binary and ternary clusters using density functional theory. The generated clusters and their calculated possible geometries can give important structural information, as well as help to understand the processes present in the plasma processes exploited for thin films deposition.

Synthesis and Application of Monomeric Chalcogenolates of 13†Group Elements.

Utilization of the N,C,N-chelating ligand L (L={2,6-(Me2 NCH2 )2 C6 H3 }- ) in the chemistry of 13 group elements provided either N→In coordinated monomeric chalcogenides LIn(µ-E4 ) (E=S, Se) with unprecedented InE4 inorganic ring or monomeric chalcogenolates LM(EPh)2 (M=Ga, In). Complex LGa(SePh)2 was selected as the most suitable single source precursor (SSP) for the deposition of amorphous semiconducting GaSe thin films using spin coating method.

Mass spectrometric investigation of amorphous Ga-Sb-Se thin films.

Amorphous chalcogenide thin films are widely studied due to their enhanced properties and extensive applications. Here, we have studied amorphous Ga-Sb-Se chalcogenide thin films prepared by magnetron co-sputtering, via laser ablation quadrupole ion trap time-of-flight mass spectrometry. Furthermore, the stoichiometry of the generated clusters was determined which gives information about individual species present in the plasma plume originating from the interaction of amorphous chalcogenides with high energy laser pulses. Seven different compositions of thin films (Ga content 7.6-31.7 at. %, Sb content 5.2-31.2 at. %, Se content 61.2-63.3 at. %) were studied and in each case about ~50 different clusters were identified in positive and ~20-30 clusters in negative ion mode. Assuming that polymers can influence the laser desorption (laser ablation) process, we have used parafilm as a material to reduce the destruction of the amorphous network structure and/or promote the laser ablation synthesis of heavier species from those of lower mass. In this case, many new and higher mass clusters were identified. The maximum number of (40) new clusters was detected for the Ga-Sb-Se thin film containing the highest amount of antimony (31.2 at. %). This approach opens new possibilities for laser desorption ionization/laser ablation study of other materials. Finally, for selected binary and ternary clusters, their structure was calculated by using density functional theory optimization procedure.

Laser Desorption Ionization of As2Ch3 (Ch = S, Se, and Te) Chalcogenides Using Quadrupole Ion Trap Time-of-Flight Mass Spectrometry: A Comparative Study.

Laser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As2Ch3 (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (S p+/- and As m+/- ) and 34 binary (As m S p+/- ) species for As2S3 glass, 2 unary (Se q+/- ) and 26 binary (As m Se q+/- ) species for As2Se3 glass, 7 unary (Te r+/- ) and 23 binary (As m Te r+/- ) species for As2Te3 material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials. Graphical abstract ᅟ.