Interlayer Coupling of a Two-Dimensional Kondo Lattice with a Ferromagnetic Surface in the Antiferromagnet CeCo2P2.

The f-driven temperature scales at the surfaces of strongly correlated materials have increasingly come into the focus of research efforts. Here, we unveil the emergence of a two-dimensional Ce Kondo lattice, which couples ferromagnetically to the ordered Co lattice below the P-terminated surface of the antiferromagnet CeCo2P2. In its bulk, Ce is passive and behaves tetravalently. However, because of symmetry breaking and an effective magnetic field caused by an uncompensated ferromagnetic Co layer, the Ce 4f states become partially occupied and spin-polarized near the surface. The momentum-resolved photoemission measurements indicate a strong admixture of the Ce 4f states to the itinerant bands near the Fermi level including surface states that are split by exchange interaction with Co. The temperature-dependent measurements reveal strong changes of the 4f intensity at the Fermi level in accordance with the Kondo scenario. Our findings show how rich and diverse the f-driven properties can be at the surface of materials without f-physics in the bulk.

Isoselective Polymerization of rac-Lactide by Aluminum Complexes of N-Heterocyclic Carbene-Phosphinidene Adducts.

The N-heterocyclic carbene-phosphinidene adducts (NHC)PH were reacted with AlMe3 in toluene to afford the monoaluminum complexes [{(IDipp)PH}AlMe3 ] and [{(IMes)PH}AlMe3 ] (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene). In contrast, the dialuminum complex [{(Me IMes)PH}(AlMe3 )2 ] was obtained for Me IMes=1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazolin-2-ylidene. These complexes served as initiators for the efficient ring-opening polymerization of rac-lactide in toluene at 60 °C. High degrees of isoselectivity were found for the poly(rac-lactide) obtained in the presence of the monoaluminum complexes (Pm up to 0.92, Tm up to 191 °C), whereas almost atactic polymers were produced by the dialuminum complex. Detailed mechanistic studies reveal that the polymerization proceeds via a coordination-insertion mechanism with the carbene-phosphinidene ligands acting as stereodirecting groups.

Pogo-Stick Iron and Cobalt Complexes: Synthesis, Structures, and Magnetic Properties.

The synthesis, structures, and magnetic properties of monomeric half-sandwich iron and cobalt imidazolin-2-iminato complexes have been comprehensively investigated. Salt metathesis reactions of [Cp'M(µ-I)]2 (1-M, M = Fe, Co; Cp' = η5-1,2,4-tri-tert-butylcyclopentadienyl) with [ImDippNLi]2 (ImDippN = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) furnishes the terminal half-sandwich compounds [Cp'M(NImDipp)] (2-M, M = Fe, Co), which can be regarded as models for elusive half-sandwich iron and cobalt imido complexes. X-ray diffraction analysis confirmed the structure motif of a one-legged piano stool. Complex 2-Co can also be prepared by an acid-base reaction between [Cp'Co{N(SiMe3)2}] (3-Co) and ImDippNH. The electronic and magnetic properties of 2-M and 3-Co were probed by 57Fe Mössbauer spectroscopy (M = Fe), X-band EPR spectroscopy (M = Co), and solid-state magnetic susceptibility measurements. In particular, the central metal atom adopts a high-spin (S = 2) state in 2-Fe, while the cobalt complex 2-Co represents a rare example of a Co(II) species with a coordination number different from six displaying a low-spin to high-spin spin-crossover (SCO) behavior. The experimental observations are complemented by DFT calculations.

N-Heterocyclic Carbene Adducts of Main Group Elements and Their Use as Ligands in Transition Metal Chemistry.

N-Heterocyclic carbenes (NHC) are nowadays ubiquitous and indispensable in many research fields, and it is not possible to imagine modern transition metal and main group element chemistry without the plethora of available NHCs with tailor-made electronic and steric properties. While their suitability to act as strong ligands toward transition metals has led to numerous applications of NHC complexes in homogeneous catalysis, their strong σ-donating and adaptable π-accepting abilities have also contributed to an impressive vitalization of main group chemistry with the isolation and characterization of NHC adducts of almost any element. Formally, NHC coordination to Lewis acids affords a transfer of nucleophilicity from the carbene carbon atom to the attached exocyclic moiety, and low-valent and low-coordinate adducts of the p-block elements with available lone pairs and/or polarized carbon-element π-bonds are able to act themselves as Lewis basic donor ligands toward transition metals. Accordingly, the availability of a large number of novel NHC adducts has not only produced new varieties of already existing ligand classes but has also allowed establishment of numerous complexes with unusual and often unprecedented element-metal bonds. This review aims at summarizing this development comprehensively and covers the usage of N-heterocyclic carbene adducts of the p-block elements as ligands in transition metal chemistry.

Pentamethylcyclopentadienyl ruthenium "pogo stick" complexes with nitrogen donor ligands.

The half-sandwich 1,3-bis(trimethylsilyl)allyl and bis(trimethylsilyl)amido ruthenium complexes [(η5-C5Me5)RuX] (X = η3-C3H3(SiMe3)2, 1; X = N(SiMe3)2, 2) were prepared by reaction of tetranuclear [(η5-C5Me5)RuCl]4 with four equivalents of K[C3H3(SiMe3)2] or Na[N(SiMe3)2]. Complexes 1 and 2 are formally 16- and 14-electron complexes, respectively, and exhibit γ-agostic C-HRu interactions in the solid state, which were further investigated by density functional theory (DFT) calculations and quantum theory of atoms in molecules (QTAIM) analysis. The acid-base reaction of the amido complex 2 with 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (ImDippNH) afforded the imidazolin-2-iminato complex [(η5-C5Me5)Ru(NImDipp)] (4); 4 was also obtained from the reaction of [(η5-C5Me5)RuCl]4 with the lithium reagent [(ImDippN)Li]2. 4 represents the first terminal imidazolin-2-iminato complex with a late transition metal and shows a rare one-legged piano stool ("pogo stick") geometry with a short Ru-N bond of 1.8607(15) Å. The reaction of 4 with tert-butyl isocyanate (tBuNCO) gave the ureato complex [(η5-C5Me5)Ru{ImDippN(C[double bond, length as m-dash]O)NtBu}] (5) by [2 + 2] cycloaddition. This reactivity together with a DFT study on the bonding situation in 4 suggest a close similarity with related half-sandwich imido complexes [(arene)M(NR)] (M = Ru, Os) and [CpM(NR)] (M = Rh, Ir).

N-Heterocyclic Carbene-Phosphinidene and Carbene-Phosphinidenide Transition Metal Complexes.

Half-sandwich complexes of the N-heterocyclic carbene-phosphinidene adduct [(IPr)PH] (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by its reaction with dimeric complexes of the type [LMCl2]2, which afforded the three-legged piano-stool complexes [LMCl2{HP(IPr)}] (9a/9b: M = Ru/Os, L = η6-p-cymene; 10a/10b: M = Rh/Ir, L = η5-C5Me5). Their conversion into the corresponding carbene-phosphinidenide complexes [LMCl{P(IPr)}] (11a/11b: M = Ru/Os; 12a/12b: M = Rh/Ir) with a two-legged piano stool geometry was studied by NMR spectroscopy in the presence of the strong base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively, the complexes 11 and 12 were isolated in high yields from the reactions of the carbene-phosphinidene adduct [(IPr)PTMS] (2) with [LMCl2]2, whereby formation of the metal-phosphorus bonds was accompanied by elimination of trimethylsilyl chloride (Me3SiCl). Theoretical calculations reveal a strong polarization of the phosphorus ligands upon metal complexation, which can be ascribed to the ability of the imidazole moiety to effectively stabilize a positive charge. Dehydrohalogenation of complexes 9/10 to 11/12 affords a significant increase of the metal-phosphorus bond order, with the carbene-phosphinidenide ligand acting as a strong 2σ,2π-electron donor.

3D optical simulation formalism OPTOS for textured silicon solar cells.

In this paper we introduce the three-dimensional formulation of the OPTOS formalism, a matrix-based method that allows for the efficient simulation of non-coherent light propagation and absorption in thick textured sheets. As application examples, we calculate the absorptance of solar cells featuring textures on front and rear side with different feature sizes operating in different optical regimes. A discretization of polar and azimuth angle enables a three-dimensional description of systems with arbitrary surface textures. We present redistribution matrices for 3D surface textures, including pyramidal textures, binary crossed gratings and a Lambertian scatterer. The results of the OPTOS simulations for silicon sheets with different combinations of these surfaces are in accordance with both optical measurements and results based on established simulation methods like ray tracing. Using OPTOS, we show that the integration of a diffractive grating at the rear side of a silicon solar cell featuring a pyramidal front side results in absorption close to the Yablonovitch Limit enhancing the photocurrent density by 0.6 mA/cm2 for a 200 µm thick cell.

Matrix formalism for light propagation and absorption in thick textured optical sheets.

In this paper, we introduce a simulation formalism for determining the Optical Properties of Textured Optical Sheets (OPTOS). Our matrix-based method allows for the computationally-efficient calculation of non-coherent light propagation and absorption in thick textured sheets, especially solar cells, featuring different textures on front and rear side that may operate in different optical regimes. Within the simulated system, the angular power distribution is represented by a vector. This light distribution is modified by interaction with the surfaces of the textured sheets, which are described by redistribution matrices. These matrices can be calculated for each individual surface texture with the most appropriate technique. Depending on the feature size of the texture, for example, either ray- or wave-optical methods can be used. The comparison of the simulated absorption in a sheet of silicon for a variety of surface textures, both with the results from other simulation techniques and experimentally measured data, shows very good agreement. To demonstrate the versatility of this newly-developed approach, the absorption in silicon sheets with a large-scale structure (V-grooves) at the front side and a small-scale structure (diffraction grating) at the rear side is calculated. Moreover, with minimal computational effort, a thickness parameter variation is performed.

Thin-film a-Si:H solar cells processed on aluminum-induced texture (AIT) glass superstrates: prediction of light absorption enhancement.

Light scattering superstrates are important for thin-film a-Si:H solar cells. In this work, aluminum-induced texture (AIT) glass, covered with nonetched Al-doped ZnO (AZO), is investigated as an alternative to the commonly used planar glass with texture-etched AZO superstrate. Four different AIT glasses with different surface roughnesses and different lateral feature sizes are investigated for their effects on light trapping in a-Si:H solar cells. For comparison, two reference superstrates are investigated as well: planar glass covered with nonetched AZO and planar glass covered with texture-etched AZO. Single-junction a-Si:H solar cells are deposited onto each superstrate, and the scattering properties (haze and angular resolved scattering) as well as the solar cell characteristics (current-voltage and external quantum efficiency) are measured and compared. The results indicate that AIT glass superstrates with nonetched AZO provide similar, or even superior, light trapping than the standard reference superstrate, which is demonstrated by a higher short-circuit current Jsc and a higher external quantum efficiency. Using the trapped light fraction δ, a quantity based on the integrated light scattering at the AZO/a-Si:H interface, we show that Jsc linearly increases with δ in the scattering regime of the samples, regardless of the type of superstrate used.

Hexagonal sphere gratings for enhanced light trapping in crystalline silicon solar cells.

Enhanced absorption of near infrared light in silicon solar cells is important for achieving high conversion efficiencies while reducing the solar cell's thickness. Hexagonal gratings on the rear side of solar cells can achieve such absorption enhancement. Our wave optical simulations show photocurrent density gains of up to 3 mA/cm2 for solar cells with a thickness of 40 µm and a planar front side. Hexagonal sphere gratings have been fabricated and optical measurements confirm the predicted absorption enhancement. The measured absorption enhancement corresponds to a photocurrent density gain of 1.04 mA/cm2 for planar wafers with a thickness of 250 µm and 1.49 mA/cm2 for 100 µm.

Analytical solution for haze values of aluminium-induced texture (AIT) glass superstrates for a-Si:H solar cells.

Light scattering at randomly textured interfaces is essential to improve the absorption of thin-film silicon solar cells. Aluminium-induced texture (AIT) glass provides suitable scattering for amorphous silicon (a-Si:H) solar cells. The scattering properties of textured surfaces are usually characterised by two properties: the angularly resolved intensity distribution and the haze. However, we find that the commonly used haze equations cannot accurately describe the experimentally observed spectral dependence of the haze of AIT glass. This is particularly the case for surface morphologies with a large rms roughness and small lateral feature sizes. In this paper we present an improved method for haze calculation, based on the power spectral density (PSD) function of the randomly textured surface. To better reproduce the measured haze characteristics, we suggest two improvements: i) inclusion of the average lateral feature size of the textured surface into the haze calculation, and ii) considering the opening angle of the haze measurement. We show that with these two improvements an accurate prediction of the haze of AIT glass is possible. Furthermore, we use the new equation to define optimum morphology parameters for AIT glass to be used for a-Si:H solar cell applications. The autocorrelation length is identified as the critical parameter. For the investigated a-Si:H solar cells, the optimum autocorrelation length is shown to be 320 nm.

Nanoimprinted diffraction gratings for crystalline silicon solar cells: implementation, characterization and simulation.

Light trapping is becoming of increasing importance in crystalline silicon solar cells as thinner wafers are used to reduce costs. In this work, we report on light trapping by rear-side diffraction gratings produced by nano-imprint lithography using interference lithography as the mastering technology. Gratings fabricated on crystalline silicon wafers are shown to provide significant absorption enhancements. Through a combination of optical measurement and simulation, it is shown that the crossed grating provides better absorption enhancement than the linear grating, and that the parasitic reflector absorption is reduced by planarizing the rear reflector, leading to an increase in the useful absorption in the silicon. Finally, electro-optical simulations are performed of solar cells employing the fabricated grating structures to estimate efficiency enhancement potential.

Cooperativity of H-bonding and anion-π interaction in the binding of anions with neutral π-acceptors.

A rare anion-π complex between bromide and a neutral receptor is reported and related receptor systems are studied with a series of anions. The interaction is observed in the solid state and in solution, and further evidence for it is obtained by a computational study.

Electromagnetic simulations of a photonic luminescent solar concentrator.

Luminescent solar concentrators (LSC) are used in photovoltaic applications to concentrate direct and diffuse sunlight without tracking. We employed 2D FDTD simulations to investigate the concept of a photonic LSC (PLSC), where the luminescent material is embedded in a photonic crystal to mitigate the primary losses in LSCs: the escape cone and reabsorption. We obtain suppressed emission inside the photonic band gap, which can be utilized to reduce reabsorption. Furthermore, the efficiency of light guiding is strongly enhanced in a broad spectral range, reaching up to 99.7%. Our optimization of design parameters suggests emitting layers of sub-wavelength thickness.

Directionally selective light trapping in a germanium solar cell.

Restricting the angular range in which a photovoltaic system emits light, is a promising but rather unexplored approach to enhance conversion efficiency. In this paper we analyze and discuss the effect of a directionally selective filter on the absorption of light and the generation of charge carriers in a germanium solar cell. A directionally selective filter transmits photons of perpendicular incidence and reflects photons under oblique incidence in a given spectral range. To investigate its effect on light trapping, we perform reflection and quantum efficiency measurements. The reflection measurements show that a wavelength dependent absorption enhancement is induced by the application of the directionally selective filter. We calculate a maximum absorption enhancement of 45% at λ ≈ 1900 nm. We show that the absorption enhancement is caused by light trapping of non-absorbed and scattered light and is not due to a suppression of radiative processes. A trapping of photons generated by radiative recombination could not be detected. Measurements of the quantum efficiency confirm the results of the reflection measurements. The generation of charge carriers is increased by up to 33% at λ ≈1900 nm. A comparison of path length enhancement factors calculated from reflection and quantum efficiency measurements indicates a low parasitic absorption in the solar cell device.

Electro--optical simulation of diffraction in solar cells.

A simulation method is presented and evaluated for simulating two- and three dimensional wave optical effects in crystalline silicon solar cells. Due to a thickness in the 100 µm range, optical properties of these solar cells typically are simulated, primarily through the use of ray-tracing. Recently, diffractive elements such as gratings or photonic crystals have been investigated for their application in crystalline silicon solar cells, making it necessary to consider two- and three dimensional wave optical effects. The presented approach couples a rigorous wave optical simulation to a semiconductor device simulation. In a first step, characteristic parameters, simulated for a reference setup using the electro-optical method and the standard procedure are compared. Occurring differences provide a measure to quantify the errors of the electro-optical method. These errors are below 0.4% relative. In a second step the electro-optical method is used to simulate a crystalline silicon solar cell with a back side diffractive grating. It is found that the grating enhances to short circuit current density jSC of the solar cell by more than 1 mA/cm².

Enhanced light trapping in thin-film solar cells by a directionally selective filter.

A directionally selective multilayer filter is applied to a hydrogenated amorphous silicon solar cell to improve the light trapping. The filter prevents non-absorbed long-wavelength photons from leaving the cell under oblique angles leading to an enhancement of the total optical path length for weakly absorbed light within the device by a factor of kappa(r) = 3.5. Parasitic absorption in the contact layers limits the effective path length improvement for the photovoltaic quantum efficiency to a factor of kappa(EQE) = 1.5. The total short-circuit current density increases by DeltaJ(sc) = 0.2 mAcm(-2) due to the directional selectivity of the Bragg-like filter.