The effect of post-deposition annealing conditions on structural and thermoelectric properties of sputtered copper oxide films.

The development of thin-film thermoelectric applications in sensing and energy harvesting can benefit largely from suitable deposition methods for earth-abundant materials. In this study, p-type copper oxide thin films have been prepared on soda lime silicate glass by direct current (DC) magnetron sputtering at room temperature from a pure copper metallic target in an argon atmosphere, followed by subsequent annealing steps at 300 °C under various atmospheres, namely air (CuO:air), nitrogen (CuO:N) and oxygen (CuO:O). The resultant films have been studied to understand the influence of various annealing atmospheres on the structural, spectroscopic and thermoelectric properties. X-ray diffraction (XRD) patterns of the films showed reflexes that could be assigned to those of crystalline CuO with a thin mixed Cu(I)Cu(II) oxide, which was also observed by near edge X-ray absorption fine structure spectroscopy (NEXAFS). The positive Seebeck coefficient (S) reached values of up to 204 µV K-1, confirming the p-type behavior of the films. Annealing under oxygen provided a significant improvement in the electrical conductivity up to 50 S m-1, resulting in a power factor of 2 µW m-1 K-2. The results reveal the interplay between the intrinsic composition and the thermoelectric performance of mixed copper oxide thin films, which can be finely adjusted by simply varying the annealing atmosphere.

In Situ Investigations of Mechanochemical One-Pot Syntheses.

We present an in situ triple coupling of synchrotron X-ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C-C bond formation (Knoevenagel condensation), and the formation of a manganese-phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a by-product. Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction.

In Situ Complementary Doping, Thermoelectric Improvements, and Strain-Induced Structure within Alternating PEDOT:PSS/PANI Layers.

Although the deposition of alternating layers from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and polyaniline (PANI) salts has recently provided a breakthrough in the field of conductive polymers, the cause for the conductivity improvement has remained unclear. In this work, we report a cooperative doping effect between alternating PANI base and PEDOT:PSS layers, resulting in electrical conductivities of 50-100 S cm-1 and power factors of up to 3.0 ± 0.5 µW m-1 K-2, which surpass some of the recent values obtained for protonated PANI/PEDOT:PSS multilayers by a factor of 20. In this case, the simultaneous improvement in the electrical conductivity of both types of layers is caused by the in situ protonation of PANI, which corresponds to the removal of the excess acidic PSS chains from the PEDOT:PSS grains. The interplay between the functional groups' reactivity and the supramolecular chain reorganization leads to an array of preparation-dependent phenomena, including a stepwise increase in the film thickness, an alternation in the electrical conductivity, and the formation of a diverse surface landscape. The latter effect can be traced to a buildup of strain within the layers, which results in either the formation of folds or the shrinkage of the film. These results open new paths for designing nanostructured thin-film thermoelectrics.

Fabrication and Characterization of Surfaces Modified with Carboxymethylthio Ligands for Chelate-Assisted Trapping of Copper.

The metal ion chelating property was conferred onto silicon (Si) and gold (Au) surfaces by direct electrografting of the 4-[(carboxymethyl)thio]benzenediazonium cation (4-CMTBD). Infrared spectroscopic ellipsometry showed the presence of characteristic phenyl and carbonyl vibrational bands on the functionalized surfaces as a proof of existence of surface-bound organic units of 4-[(carboxymethyl)thio]benzene, (4-CMTB). The loss of diazonium group (N≡N+) upon electrografting of 4-CMTBD was investigated using IR spectroscopy. A Faradaic efficiency of about 18.8-20.0% was realized in mass deposition experiments for grafting 4-CMTB on the Au surface using an electrochemical quartz crystal microbalance technique. Raman spectroscopy performed on the Si-(4-CMTB) surface after treatment with copper (Cu) ion solution provided evidence of metal ion chelation based on an observed v(Cu-O) peak at about 487 cm-1 and a v(Cu-S) signal at about 267 cm-1. The binding of Cu ions by the chelating ligands also caused a red shift of about 10 cm-1 in the Raman spectrum of the Si-(4-CMTB)-Cu surface within the spectral region, characteristic of the v(C-O) signal. X-ray photoelectron spectroscopy investigations showed indications of the Cu(II) ion species chelated by the surface-bound carboxymethylthio ligands. The functionalized surface, Si-(4-CMTB), constitutes an alternative metal ion chelating surface that may potentially be developed for applications in trace-level trapping of Cu ions.

Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding.

Benzamide has been known for its polymorphism for almost 200 years. Three polymorphic forms are described. To date, it was only possible to crystallize a metastable form in a mixture together with the thermodynamically most stable form I. A complete transformation of form I into the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X-ray diffraction.

The crystallisation of copper(ii) phenylphosphonates.

The crystal structures and syntheses of four different copper(ii) phenylphosphonates, the monophenylphosphonates α-, ß-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) ß-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of ß-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder of the crystal structure was elucidated by electron diffraction. The relationship between the compounds and their reaction pathways were investigated by in situ synchrotron measurements.

Quantitative determination of activation energies in mechanochemical reactions.

Mechanochemical reactions often result in 100% yields of single products, making purifying procedures obsolete. Mechanochemistry is also a sustainable and eco-friendly method. The ever increasing interest in this method is contrasted by a lack in mechanistic understanding of the mechanochemical reactivity and selectivity. Recent in situ investigations provided direct insight into formation pathways. However, the currently available theories do not predict temperature T as an influential factor. Here, we report the first determination of an apparent activation energy for a mechanochemical reaction. In a temperature-dependent in situ study the cocrystallisation of ibuprofen and nicotinamide was investigated as a model system. These experiments provide a pivotal step towards a comprehensive understanding of milling reaction mechanisms.

In Situ Investigation of a Self-Accelerated Cocrystal Formation by Grinding Pyrazinamide with Oxalic Acid.

A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.

The structure and in situ synthesis investigation of isomorphic mononuclear molecular metal phenylphosphonates.

We describe a fast and effective synthesis for molecular metal phosphonates. Isomorphic compounds [M(ii)(HO3PPh)2(H2O3PPh)2(H2O)2] (M = Mn (1), Co (2), Ni (3); Ph = C6H5) were obtained by grinding. The complexes are mononuclear compounds containing neutral and monodeprotonated phenylphosphonic acid and water as ligands. The crystal structures were determined using powder X-ray diffraction (PXRD) data and validated by extended X-ray absorption fine structure (EXAFS) data. Combined synchrotron XRD measurements and Raman spectroscopy were conducted for investigating the reactions in situ. Based on these data, the intermediates were characterized and the formation mechanism was derived.

Adjusting the thermoelectric properties of copper(I) oxide-graphite-polymer pastes and the applications of such flexible composites.

We present a facile alternative to other well known strategies for synthesizing flexible thermoelectric materials. Instead of printing thin active layers on flexible substrates or doping conductive polymers, we produce thermoelectric pastes, using a mixture of graphite, copper(I) oxide and polychlorotrifluoroethene. The Seebeck coefficient of the investigated pastes varies between 10 and 600 µV K(-1), while the electrical conductivity spans over an even wider range of 10(-4) to 10(2) S m(-1). Here, the influence of phenomena such as percolation on the electrical transport is revealed. The resulting power factor reaches 5.69 × 10(-4) ± 0.70 × 10(-4) µW m(-1) K(-2) for the graphite-polymer paste, with an unexpected minimum at a graphite molar fraction of approximately 0.4. The values are comparable to those of the powder mixtures, which are slightly higher, but less precisely tunable. Such compounds are further evaluated for practical applications. The graphite-polymer paste is used to exemplify, how a flexible thermoelectric sensor can be easily manufactured, step by step. Our results represent a proof of principle, that thermoelectric pastes are viable alternatives to current solutions. A further expansion of the scope for the composites can be achieved by using high performance thermoelectric materials and conductive polymers.

Decreasing the Effective Thermal Conductivity in Glass Supported Thermoelectric Layers.

As thermoelectric devices begin to make their way into commercial applications, the emphasis is put on decreasing the thermal conductivity. In this purely theoretical study, finite element analysis is used to determine the effect of a supporting material on the thermal conductivity of a thermoelectric module. The simulations illustrate the heat transfer along a sample, consisting from Cu, Cu2O and PbTe thermoelectric layers on a 1 mm thick Pyrex glass substrate. The influence of two different types of heating, at a constant temperature and at a constant heat flux, is also investigated. It is revealed that the presence of a supporting material plays an important role on lowering the effective thermal conductivity of the layer-substrate ensemble. By using thinner thermoelectric layers the effective thermal conductivity is further reduced, almost down to the value of the glass substrate. As a result, the temperature gradient becomes steeper for a fixed heating temperature, which allows the production of devices with improved performance under certain conditions. Based on the simulation results, we also propose a model for a robust thin film thermoelectric device. With this suggestion, we invite the thermoelectric community to prove the applicability of the presented concept for practical purposes.

Survival of the Fittest: Competitive Co-crystal Reactions in the Ball Mill.

The driving forces triggering the formation of co-crystals under milling conditions were investigated by using a set of multicomponent competitive milling reactions. In these reactions, different active pharmaceutical ingredients were ground together with a further compound acting as coformer. The study was based on new co-crystals including the coformer anthranilic acid. The results of the competitive milling reactions indicate that the formation of co-crystals driven by intermolecular recognition are influenced and inhibited by kinetic aspects including the formation of intermediates and the stability of the reactants.

Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis.

This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.

Fragmentation mechanism of the generation of colloidal copper(i) iodide nanoparticles by pulsed laser irradiation in liquids.

Pulsed laser ablation in liquids (PLAL) is a versatile route to stable colloids without the need for stabilizing agents. The use of suspensions instead of bulk targets further simplifies the experimental set-up and even improves the productivity. However, the utilization of this approach is hindered by limited knowledge about the underlying mechanisms of the nanoparticle formation. We present the synthesis of copper(i) iodide nanoparticles via ns-pulsed laser irradiation of CuI powder suspended in water or ethyl acetate. A thorough study of the nanoparticle size by transmission electron microscopy reveals a log-normal distribution with a mean diameter of 31 nm (±11 nm) in water and 18 nm (±7 nm) in ethyl acetate. The duration of the laser irradiation appears to have only a minor influence on the size distribution. Selected area diffraction and electron energy-loss spectroscopy verify the chemical composition of the generated CuI nanoparticles. While comparable precursors like CuO and Cu3N follow a reductive ablation mechanism, a fragmentation mechanism is found for CuI. With a productivity of 1.7 µg J(-1) this pulsed laser fragmentation in liquids (PLFL) proves to be an efficient route to colloidal CuI nanoparticles.

In situ determination of colloidal gold concentrations with UV-vis spectroscopy: limitations and perspectives.

This paper studies the UV-vis absorbance of colloidal gold nanoparticles at 400 nm and validates it as a method to determine Au(0) concentrations in colloidal gold solutions. The method is shown to be valid with restrictions depending on the investigated system. The uncertainty of the determined Au(0) concentration can be up to 30%. This deviation is the result of the combined influence of parameters such as particle size, surface modification, or oxidation state. However, quantifying the influence of these parameters enables a much more precise Au(0) determination for specific systems. As an example, the reduction process of the well-known Turkevich method was monitored and the Au(0) concentration was determined with a deviation of less than 5%. Hence, a simple, fast, easy, and cheap in situ method for Au(0) determination is demonstrated that has in the presence of other gold species such as Au(III) an unprecedented accuracy.

Metallic copper colloids by reductive laser ablation of nonmetallic copper precursor suspensions.

Pulsed laser ablation in liquids (PLAL) has developed to a convenient and efficient method for the synthesis of colloidal solutions. So far, in most cases, the laser pulse is focused on bulk targets like metal plates. An interesting alternative is the use of suspended µm-sized precursors. This leads to higher production rates and simpler setups. A thorough understanding of the mechanism is essential in order to gain control over the characteristics of the synthesized nanoparticles. Therefore, we investigated the formation of copper colloids by PLAL of CuO, Cu3N, Cu(N3)2, and Cu2C2 powders in organic liquids. Thus, we can compare copper precursors based on elements of the 4th, 5th, and 6th main group. The chemical composition of the resulting nanoparticles is revealed by electron energy loss spectroscopy (EELS). The presented investigations point to a reductive ablation process followed by laser-driven aggregation and coalescence steps instead of a simple fragmentation mechanism.

Deep eutectic solvents for the self-assembly of gold nanoparticles: a SAXS, UV-Vis, and TEM investigation.

In this work, we report the formation and growth mechanisms of gold nanoparticles (AuNPs) in eco-friendly deep eutectic solvents (DES; choline chloride and urea). AuNPs are synthesized on the DES surface via a low-energy sputter deposition method. Detailed small angle X-ray scattering (SAXS), UV-Vis, and cryogenic transmission electron microscopy (cryo-TEM) investigations show the formation of AuNPs of 5 nm diameter. Data analysis reveals that for a prolonged gold-sputtering time there is no change in the size of the particles. Only the concentration of AuNPs increases linearly in time. More surprisingly, the self-assembly of AuNPs into a first and second shell ordered system is observed directly by in situ SAXS for prolonged gold-sputtering times. The self-assembly mechanism is explained by the templating nature of DES combined with the equilibrium between specific physical interaction forces between the AuNPs. A disulfide-based stabilizer, bis((2-mercaptoethyl)trimethylammonium) disulfide dichloride, was applied to suppress the self-assembly. Moreover, the stabilizer even reverses the self-assembled or agglomerated AuNPs back to stable 5 nm individual particles as directly evidenced by UV-Vis. The template behavior of DES is compared to that of nontemplating solvent castor oil. Our results will also pave the way to understand and control the self-assembly of metallic and bimetallic nanoparticles.

Graphene oxide/α-Bi(2)O(3) composites for visible-light photocatalysis, chemical catalysis, and solar energy conversion.

The growing challenges of environmental purification by solar photocatalysis, precious-metal-free catalysis, and photocurrent generation in photovoltaic cells receive the utmost global attention. Here we demonstrate a one-pot, green chemical synthesis of a new stable heterostructured, ecofriendly, multifunctional microcomposite that consists of α-Bi2 O3 microneedles intercalated with anchored graphene oxide (GO) microsheets (1.0 wt %) for the above-mentioned applications on a large economical scale. The bare α-Bi2 O3 microneedles display two times better photocatalytic activities than commercial TiO2 (Degussa-P25), whereas the GO-hybridized composite exhibits approximately four to six times enhanced photocatalytic activities than the neat TiO2 photocatalyst in the degradation of colored aromatic organic dyes (crystal violet and rhodamine 6G) under visible-light irradiation (300 W tungsten lamp). The highly efficient activity is associated with the strong surface adsorption ability of GO for aromatic dye molecules, the high carrier acceptability, and the efficient electron-hole pair separation in Bi2 O3 by individual adjoining GO sheets. The introduction of Ag nanoparticles (2.0 wt %) further enhances the photocatalytic performance of the composite over eightfold because of a plasmon-induced electron-transfer process from Ag nanoparticles through the GO sheets into the conduction band of Bi2 O3 . The new composites are also catalytically active and catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of borohydride ions. Photoanodes assembled from GO/α-Bi2 O3 and Ag/GO/α-Bi2 O3 composites display an improved photocurrent response (power conversion efficiency ∼20 % higher) over those prepared without GO in dye-sensitized solar cells.

Formation mechanism of silver nanoparticles stabilized in glassy matrices.

In any given matrix control over the final particle size distribution requires a constitutive understanding of the mechanisms and kinetics of the particle evolution. In this contribution we report on the formation mechanism of silver nanoparticles embedded in a soda-lime silicate glass matrix. For the silver ion-exchanged glass it is shown that at temperatures below 410 °C only molecular clusters (diameter <1 nm) are forming which are most likely silver dimers. These clusters grow to nanoparticles (diameter >1 nm) by annealing above this threshold temperature of 410 °C. It is evidenced that the growth and thus the final silver nanoparticle size are determined by matrix-assisted reduction mechanisms. As a consequence, particle growth proceeds after the initial formation of stable clusters by addition of silver monomers which diffuse from the glass matrix. This is in contrast to the widely accepted concept of particle growth in metal-glass systems, in which it is assumed that the nanoparticle formation is predominantly governed by Ostwald ripening processes.