arXiv subjects

Christian Klinke

Publications and source records attributed to Christian Klinke.

At least 37 records · Page 2Linked to original sources

arXiv2020

Single Crystalline Colloidal Quasi-Two-Dimensional Tin Telluride

Tin telluride is a narrow gap semiconductor with promising properties for IR optical applications and topological insulators. We report a convenient colloidal synthesis of quasi-two-dimensional SnTe nanocrystals through the hot-injection method in a non-polar solvent. By introducing the halide alkane 1-bromotetradecane as well as oleic acid and trioctylphosphine, the thickness of two dimensional SnTe nanostripes can be tuned down to 30 nm, while the lateral dimensional can reach 6 microns. The obtained SnTe nanostripes are single-crystalline with a rock-salt crystal structure. The absorption spectra demonstrate pronounced absorption features in the IR range revealing the effect of quantum confinement in such structures.

cond-mat.mtrl-sci↗

arXiv2020

Function follows form: From semiconducting to metallic towards superconducting PbS nanowires by faceting the crystal

In the realm of colloidal nanostructures, with its immense capacity for shape and dimensionality control, the form is undoubtedly a driving factor for the tunability of optical and electrical properties in semiconducting or metallic materials. However, influencing the fundamental properties is still challenging and requires sophisticated surface or dimensionality manipulation. In this work, we present such a modification for the example of colloidal lead sulphide nanowires. We show that the electrical properties of lead sulphide nanostructures can be altered from semiconducting to metallic with indications of superconductivity, by exploiting the flexibility of the colloidal synthesis to sculpt the crystal and to form different surface facets. A particular morphology of lead sulphide nanowires has been synthesized through the formation of {111} surface facets, which shows metallic and superconducting properties in contrast to other forms of this semiconducting crystal, which contain other surface facets ({100} and {110}). This effect, which has been investigated with several experimental and theoretical approaches, is attributed to the presence of lead rich {111} facets. The insights promote new strategies for tuning the properties of crystals as well as new applications for lead sulphide nanostructures.

cond-mat.mtrl-sci↗

arXiv2020

Anisotropic circular photogalvanic effect in colloidal tin sulfide nanosheets

Tin sulfide promises very interesting properties such as a high optical absorption coefficient and a small band gap, while being less toxic compared to other metal chalcogenides. However, the limitations in growing atomically thin structures of tin sulfide hinder the experimental realization of these properties. Due to the flexibility of the colloidal synthesis, it is possible to synthesize very thin and at the same time large nanosheets. Electrical transport measurements show that these nanosheets can function as field-effect transistors with high on/off ratio and p-type behavior. The temperature dependency of the charge transport reveals that defects in the crystal are responsible for the formation of holes as majority carriers. During illumination with circularly polarized light, these crystals generate a helicity dependent photocurrent at zero-volt bias, since their symmetry is broken by asymmetric interfaces (substrate and vacuum). Further, the observed circular photogalvanic effect shows a pronounced in-plane anisotropy, with a higher photocurrent along the armchair direction, originating from the higher absorption coefficient in this direction. Our new insights show the potential of tin sulfide for new functionalities in electronics and optoelectronics, for instance as polarization sensors.

cond-mat.mtrl-sci↗

arXiv2019

Photoexcitation of PbS Nanosheets Leads to Highly Mobile Charge Carriers and Stable Excitons

Solution-processable two-dimensional (2D) semiconductors with chemically tunable thickness and associated tunable band gaps are highly promising materials for ultrathin optoelectronics. Here, the properties of free charge carriers and excitons in 2D PbS nanosheets of different thickness are investigated by means of optical pump-terahertz probe spectroscopy. By analyzing the frequency-dependent THz response, a large quantum yield of excitons is found. The scattering time of free charge carriers increases with nanosheet thickness, which is ascribed to reduced effects of surface defects and ligands in thicker nanosheets. The data discussed provide values for the DC mobility in the range 550 - 1000 cm2/Vs for PbS nanosheets with thicknesses ranging from 4 to 16 nm. Results underpin the suitability of colloidal 2D PbS nanosheets for optoelectronic applications.

physics.chem-ph↗

arXiv2019

Synthesis of single-crystalline lead sulfide nanoframes and nanorings

We present a colloidal synthesis strategy to obtain single-crystalline PbS nanorings. By controlling the ripening process in the presence of halide ions, a transformation of initial PbS nanosheets to frame-like structures and finally to nanorings was achieved. We found that the competing ligands oleic acid, oleate and halide ions play an important role in the formation of these nanostructures. Therefore, we propose a formation mechanism based on a thermally induced ripening of crystal facets dependent on the surface passivation. With this method, it became possible to synthesize colloidal nanorings of cubic crystal phase galena PbS. The synthesis was followed via TEM and the products are characterized by XRD, AFM and STEM tomography. Control of the initial nanoframe morphology allows adjusting the later nanoring dimensions.

cond-mat.mtrl-sci↗

arXiv2019

From wurtzite nanoplatelets to zinc blende nanorods: Simultaneous control of shape and phase in ultrathin ZnS nanocrystals

Ultrathin semiconductor nanocrystals (NCs) with at least one dimension below their exciton Bohr radius receive a rapidly increasing attention due to their unique physicochemical properties such as strong quantum confinement, large surface-to-volume ratio, and giant oscillator strength. These superior properties highly depend on the shape and crystal phase of semiconductor NCs. Slight changes in the shape and phase of NCs can cause significant changes in their properties. Therefore, it is crucial to controllably synthesize semiconductor NCs. Here, we demonstrate not only the synthesis of robust well-defined ultrathin ZnS nanoplatelets (NPLs) with excitonic absorption and emission, but also the precise shape and phase control of ZnS NCs based on a soft template strategy. The key feature of our approach is the tuning of the sulfur precursor amount, resulting in a simultaneous shape/phase transformation between wurtzite (WZ) ZnS NPLs and zinc blende (ZB) ZnS nanorods (NRs) at moderate temperatures (150 degree). UV-vis absorption and photoluminescence (PL) spectra reveal very distinct optical properties between WZ-ZnS NPLs and ZB-ZnS NRs. UV-vis absorption spectra of WZ-ZnS NPLs clearly exhibit a sharp excitonic peak that is not observed in ZB-ZnS NRs. Besides, the PL characterization shows that WZ-ZnS NPLs have a narrow excitonic emission peak (292 nm), while the ZB-ZnS NRs exhibit a broad collective emission band consisting of four emission peaks (335, 359, 395, and 468 nm). The appearance of excitonic features in the absorption spectra of ZnS NPLs is explained by interband electronic transitions, which is simulated in the framework of density functional theory (DFT). The presented simple and effective synthetic strategy opens a new path to synthesize further NCs with shape and phase control for advanced applications in electronics and photonics.

cond-mat.mtrl-sci↗

arXiv2019

Micron-size two-dimensional methylammonium lead halide perovskites

Hybrid lead halide perovskites with 2D stacking structures have recently emerged as promising materials for optoelectronic applications. We report a method for growing 2D nanosheets of hybrid lead halide perovskites (I, Br and Cl), with tunable lateral sizes ranging from 0.05 to 8 microns, and a structure consisting of n stacked monolayers separated by long alkylamines, tunable from bulk down to n=1. The key to obtaining such a wide range of perovskite properties hinged on utilizing the respective lead halide nanosheets as precursors in a hot-injection synthesis that afforded careful control over all process parameters. The layered, quantum confined (n small than 4) nanosheets were comprised of major and minor fractions with differing n. Energy funneling from low to high n (high to low energy) regions within a single sheet, mediated by the length of the ligands between stacks, produced photoluminescent quantum yields as high as 49 percent. These large, tunable 2D nanosheets could serve as convenient platforms for future high efficiency optoelectronic devices.

physics.app-ph↗

arXiv2019

Field effect and photoconduction in Au25 Nanoclusters Films

Quantum confined Au nanoclusters exhibit molecule-like properties, including atomic precision and discrete energy levels. The electrical conductivity of Au nanocluster films can vary by several orders of magnitude, and is determined by the strength of the electronic coupling between the individual nanoclusters in the film. Similar to quantum confined, semiconducting quantum dots, the electrical coupling in films is dependent on the size and structure of the Au core and the length and conjugation of the organic ligands surrounding it. Unlike quantum dots, however, semiconducting transport has not been reported in Au nanocluster films. We demonstrate that through a simple yet careful choice of cluster size and organic ligands, stable Au nanocluster films can electronically couple and become semiconducting, exhibiting electric field effect and photoconductivity. The molecule-like nature of the Au nanoclusters is evidenced by a hopping transport mechanism reminiscent of doped, disordered organic semiconductor films. These results demonstrate the potential of metal nanoclusters as a solution processed material for semiconducting devices.

physics.app-ph↗

arXiv2019

In-plane anisotropic faceting of ultralarge and thin single-crystalline colloidal SnS nanosheets

The colloidal synthesis of large thin two-dimensional (2D) nanosheets is fascinating but challenging, since the growth along the lateral and vertical dimensions need to be controlled independently. In-plane anisotropy in 2D nanosheets is attracting more attention as well. We present a new synthesis for large colloidal single-crystalline SnS nanosheets with the thicknesses down to 7 nm and lateral sizes up to 8 um. The synthesis uses trioctylphosphine-S (TOP-S) as sulfur source and oleic acid (with or without TOP) as ligands. Upon adjusting the capping ligand amount, the growth direction can be switched between anisotropic directions (armchair and zigzag) and isotropic directions ("ladder" directions), leading to an edge-morphology anisotropy. This is the first report on solution-phase synthesis of large thin SnS NSs with tunable edge faceting. Furthermore, electronic transport measurements show strong dependency on the crystallographic directions confirming structural anisotropy.

cond-mat.mtrl-sci↗

arXiv2019

Preparation of high-yield and ultra-pure Au25 nanoclusters: towards their implementation in real-world applications

Colloidal approaches allow for the synthesis of Au nanoclusters (NCs) with atomic precision and sizes ranging from a few to hundreds of atoms. In most of the cases, these processes involve a common strategy of thiol etching of initially polydisperse Au nanoparticles into atomically precise NCs, resulting in the release of Au-thiolate complexes as byproducts. To the best of our knowledge, neither the removal of these byproducts nor the mass spectra in the relevant mass region were shown in previous studies. A thorough analysis of inorganic byproducts in the synthesis of Au25 NCs reveals that published protocols lead to Au25 NCs in vanishingly small quantities compared to their byproducts. Three purification methods are presented to separate byproducts from the desired Au25 NCs which are proposed to be applicable to other promising Au NC systems. Additionally, critical factors for a successful synthesis of Au25 NCs are identified and discussed including the role of residual water. An important finding is that the etching duration is very critical and must be monitored by UV-Vis spectroscopy resulting in synthetic yields as high as 40%.

cond-mat.mtrl-sci↗

arXiv2018

Molecular Doping of Electrochemically Prepared Triazine-based Carbon Nitride by 2,4,6-Triaminopyrimidine for Improved Photocatalytic Properties

The copolymerization of melamine with 2,4,6-triaminopyrimidine (TAP) in an electrochemical induced polymerization process leads to the formation of molecular doped poly (triazine imide) (PTI). The polymerization is based on the electrolysis of water and evolving radicals during this process. The incorporation of TAP is shown by techniques such as elemental analysis, FTIR and NMR spectroscopy and powder x-ray diffraction (XRD), and it is shown that the carbon content can be tuned by the variation of the molar ratio of the two precursors. This incorporation of TAP directly influences the electronic structure of PTI and as a result a red-shift can be observed in UV-Vis spectroscopy. The smaller bandgap and the increased absorption in the visible range lead to improved photocatalytic properties. In dye degradation experiments it was possible to observe an increase of the rate of the degradation of methylene blue (MB) by a factor of 4 in comparison to undoped PTI or 7 if compared to melon.

cond-mat.mtrl-sci↗

arXiv2018

Colloidal Lead Iodide Nanorings

Colloidal chemistry of nanomaterials experienced a tremendous development in the last decades. In the course of the journey 0D nanoparticles, 1D nanowires, and 2D nanosheets have been synthesized. They have in common to possess a simple topology. We present a colloidal synthesis strategy for lead iodide nanorings, with a non-trivial topology. First, two-dimensional structures were synthesized in nonanoic acid as the sole solvent. Subsequently, they underwent an etching process in the presence of trioctylphosphine, which determines the size of the hole in the ring structure. We propose a mechanism for the formation of lead iodide nanosheets which also explains the etching of the two-dimensional structures starting from the inside, leading to nanorings. In addition, we demonstrate a possible application of the as-prepared nanorings in photodetectors. These devices are characterized by a fast response, high gain values, and a linear relation between photocurrent and incident light power intensity over a large range. The synthesis approach allows for inexpensive large-scale production of nanorings with tunable properties.

cond-mat.mtrl-sci↗

arXiv2018

Copper sulfide nanosheets with shape-tunable plasmonic properties in the NIR

2D copper sulfide nanocrystals are promising building blocks for plasmonic materials in the near-infrared (NIR) spectral region. We demonstrate precise shape and size control (hexagonal/triangle) of colloidal plasmonic copper sulfide (covellite) nano-prisms simply by tuning the precursors concentration without introduction of additional ligands. The ultra-thin 2D nanocrystals possess sizes between 13 and 100 nm and triangular or hexangular shapes. We also demonstrate CuS nanosheets (NSs) with lateral sizes up to 2 microns using a syringe pump. Based on the experimental findings and DFT simulations we propose a qualitative and quantitative mechanism for the formation of different shapes. The analysis of the spectral features in the NIR of synthesized CuS nanocrystals has been performed in respect to the shape and the size of particles by the discrete dipole approximation method and the Drude-Sommerfeld theory.

cond-mat.mtrl-sci↗

arXiv2018

Colloidal Tin Sulfide Nanosheets: Formation Mechanism, Ligand-mediated Shape Tuning and Photo-detection

Colloidal materials of tin(II) sulfide (SnS), as a layered semiconductor with a narrow band gap, are emerging as a potential alternative to the more toxic metal chalcogenides (PbS, PbSe, CdS, CdSe) for various applications such as electronic and optoelectronic devices. We describe a new and simple pathway to produce colloidal SnS nanosheets with large lateral sizes and controllable thickness, as well as single-crystallinity. The synthesis of the nanosheets is achieved by employing tin(II) acetate as tin precursor instead of harmful precursors such as bis[bis(trimethylsilyl)amino] tin(II) and halogen-involved precursors like tin chloride, which limits the large-scale production. We successfully tuned the morphology between squared nanosheets with lateral dimensions from 150 to about 500 nm and a thickness from 24 to 29 nm, and hexagonal nanosheets with lateral sizes from 230 to 1680 nm and heights ranging from 16 to 50 nm by varying the ligands oleic acid and trioctylphosphine. The formation mechanism of both shapes has been investigated in depth, which is also supported by DFT simulations. The optoelectronic measurements show their relatively high conductivity with a pronounced sensitivity to light, which is promising in terms of photo-switching, photo-sensing, and photovoltaic applications also due to their reduced toxicity.

cond-mat.mtrl-sci↗

arXiv2018

High Performance n- and p-Type Field-Effect Transistors Based on Hybridly Surface-Passivated Colloidal PbS Nanosheets

Colloidally synthesized nanomaterials are among the promising candidates for future electronic devices due to their simplicity and the inexpensiveness of their production. Specifically, colloidal nanosheets are of great interest since they are conveniently producible through the colloidal approach while having the advantages of two-dimensionality. In order to employ these materials, according transistor behavior should be adjustable and of high performance. We show that the transistor performance of colloidal lead sulfide nanosheets is tunable by altering the surface passivation, the contact metal, or by exposing them to air. We found that adding halide ions to the synthesis leads to an improvement of the conductivity, the field-effect mobility, and the on/off ratio of these transistors by passivating their surface defects. Superior n-type behavior with a field-effect mobility of 248 cm^2V^-1s^-1 and an on/off ratio of 4x10^6 is achieved. The conductivity of these stripes can be changed from n-type to p-type by altering the contact metal and by adding oxygen to the working environment. As a possible solution for the post-Moore era, realizing new high quality semiconductors such as colloidal materials is crucial. In this respect, our results can provide new insights which helps to accelerate their optimization for potential applications.

cond-mat.mtrl-sci↗

arXiv2018

A New Synthesis Approach for Carbon Nitrides: Poly (Triazine Imide) and Its Photocatalytic Properties

Poly (triazine imide) (PTI) is a material belonging to the group of carbon nitrides and has shown to have competitive properties compared to melon or g-C3N4, especially in photocatalysis. As most of the carbon nitrides PTI is usually synthesized by thermal or hydrothermal approaches. We present and discuss an alternative synthesis for PTI which exhibits a pH dependent solubility in aqueous solutions. This synthesis is based on the formation of radicals during electrolysis of an aqueous melamine solution, coupling of resulting melamine radicals and the final formation of PTI. We applied different characterization techniques to identify PTI as the product of this reaction and report the first liquid state NMR experiments on a triazine-based carbon nitride. We show that PTI has a relatively high specific surface area and a pH dependent adsorption of charged molecules. This tunable adsorption has a significant influence on the photocatalytic properties of PTI which we investigated in dye degradation experiments.

cond-mat.mtrl-sci↗

arXiv2018

Insights into the formation mechanism of two-dimensional lead halide nanostructures

We present a colloidal synthesis strategy for lead halide nanosheets with a thickness of far below 100 nm. Due to the layered structure and the synthesis parameters the crystals of PbI2 are initially composed of many polytypes. We propose a mechanism which gives insight into the chemical process of the PbI2 formation. Further, we found that the crystal structure changes with increasing reaction temperature or by performing the synthesis for longer time periods changing for the final 2H structure. In addition, we demonstrate a route to prepare nanosheets of lead bromide as well as lead chloride in a similar way. Lead halides can be used as a detector material for high-energy photons including gamma and X-rays.

cond-mat.mtrl-sci↗

arXiv2018

Halogens in the synthesis of colloidal semiconductor nanocrystals

In this review, we highlight the role of halogenated compounds in the colloidal synthesis of nanostructured semiconductors. Halogen-containing metallic salts used as precursors and halogenated hydrocarbons used as ligands allow stabilizing different shapes and crystal phases, and enable the formation of colloidal systems with different dimensionality. We summarize recent reports on the tremendous influence of these compounds on the physical properties of nanocrystals, like field-effect mobility and solar cell performance and outline main analytical methods for the nanocrystal surface control.

cond-mat.mtrl-sci↗