Laboratoire de Physique des Interfaces et des Couches Minces

-doped garnet phosphors. It will summarize previous research on the structural design and optical properties of garnet phosphors and also discuss future research opportunities in this field.

Large-area, few-layer graphene is grown on a poly-nickel substrate using optimized CVD conditions. High temperature, short growth time, and an optimal gas mixing ratio (C2H2/H2 = 2/45) are found to be necessary to synthesize highly crystalline few-layer grapheme, which may find applications in electronic devices. The wrinkles that are observed under all growth conditions are proposed to be formed by two processes.

Hybrid organic–inorganic perovskites emerged as a new generation of absorber materials for high-efficiency low-cost solar cells in 2009. Very recently, fully inorganic perovskite quantum dots also led to promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins. Currently, the record efficiency is obtained with CsPbI3, whose crystallographical characterization is still limited. Here, we show through high-resolution in situ synchrotron XRD measurements that CsPbI3 can be undercooled below its transition temperature and temporarily maintained in its perovskite structure down to room temperature, stabilizing a metastable perovskite polytype (black γ-phase) crucial for photovoltaic applications. Our analysis of the structural phase transitions reveals a highly anisotropic evolution of the individual lattice parameters versus temperature. Structural, vibrational, and electronic properties of all the experimentally observed black phases are further inspected based on several theoretical approaches. Whereas the black γ-phase is shown to behave harmonically around equilibrium, for the tetragonal phase, density functional theory reveals the same anharmonic behavior, with a Brillouin zone-centered double-well instability, as for the cubic phase. Using total energy and vibrational entropy calculations, we highlight the competition between all the low-temperature phases of CsPbI3 (γ, δ, β) and show that avoiding the order–disorder entropy term arising from double-well instabilities is key to preventing the formation of the yellow perovskitoid phase. A symmetry-based tight-binding model, validated by self-consistent GW calculations including spin–orbit coupling, affords further insight into their electronic properties, with evidence of Rashba effect for both cubic and tetragonal phases when using the symmetry-breaking structures obtained through frozen phonon calculations.

Semi-transparent perovskite solar cells with silver nanowires are stacked on CIGS and Si to achieve solid-state polycrystalline tandems with efficiency improvement.

Coexistence of both edge plane and basal plane in graphite often hinders the understanding of lithium ion diffusion mechanism. In this report, two types of graphene samples were prepared by chemical vapor deposition (CVD): (i) well-defined basal plane graphene grown on Cu foil and (ii) edge plane-enriched graphene layers grown on Ni film. Electrochemical performance of the graphene electrode can be split into two regimes depending on the number of graphene layers: (i) the corrosion-dominant regime and (ii) the lithiation-dominant regime. Li ion diffusion perpendicular to the basal plane of graphene is facilitated by defects, whereas diffusion parallel to the plane is limited by the steric hindrance that originates from aggregated Li ions adsorbed on the abundant defect sites. The critical layer thickness (l(c)) to effectively prohibit substrate reaction using CVD-grown graphene layers was predicted to be ∼6 layers, independent of defect population. Our density functional theory calculations demonstrate that divacancies and higher order defects have reasonable diffusion barrier heights allowing lithium diffusion through the basal plane but neither monovacancies nor Stone-Wales defect.

In this study, we use time-resolved Kelvin probe force microscopy to investigate current–voltage hysteresis in a hybrid lead-halide perovskite solar cell.

This work describes the first thermally activated delayed fluorescence material enabling circularly polarized light emission through chiral perturbation. These new molecular architectures obtained through a scalable one-pot sequential synthetic procedure at room temperature (83% yield) display high quantum yield (up to 74%) and circularly polarized luminescence with an absolute luminescence dissymmetry factor, |glum|, of 1.3 × 10(-3). These chiral molecules have been used as an emissive dopant in an organic light emitting diode exhibiting external quantum efficiency as high as 9.1%.

Calibration of polarization-state generators (PSG's), polarimeters, and Mueller-matrix ellipsometers (MME's) is an important factor in the practical use of these instruments. A new general procedure, the eigenvalue calibration method (ECM), is presented. It can calibrate any complete MME consisting of a PSG and a polarimeter that generate and measure, respectively, all the states of polarization of light. In the ECM, the PSG and the polarimeter are described by two 4 x 4 matrices W and A, and their 32 coefficients are determined from three or four measurements performed on reference samples. Those references are smooth isotropic samples and perfect linear polarizers. Their optical characteristics are unambiguously determined during the calibration from the eigenvalues of the measured matrices. The ECM does not require accurate alignment of the various optical elements and does not involve any first-order approximation. The ECM also displays an efficient error control capability that can be used to improve the MME behavior. The ECM is illustrated by an experimental calibration, at two wavelengths (458 and 633 nm), of a MME consisting of a coupled phase modulator associated with a prism division-of-amplitude polarimeter.

Electronic transitions in luminescent molecules or centers in crystals couple to vibrations. This results in broadening of absorption and emission bands, as well as in the occurence of a Stokes shift EStokes. In principle, one can derive from EStokes the Huang-Rhys parameter S, which describes the microscopic details of the vibrational coupling and can be related to the equilibrium position offset ΔQe between the ground state and excited state. The commonly used textbook relations EStokes = (2S - 1)ℏω and EStokes = 2Sℏω are only approximately valid. In this paper we investigate how EStokes is related to S, taking into account the effects of a finite temperature. We show that in different ranges of temperature, different approximate relations between EStokes and S are appropriate. Moreover, we demonstrate that the difference between the barycenters of absorption and emission bands can be used to determine S in an unambiguous way. The position of the barycenter is, contrary to the Stokes shift, unaffected by temperature.

Abstract This paper presents the background for the calculation of various numbers that can be used to characterize crystal-preferred orientation (CPO), also known as texture in materials science, for large datasets using the combined scripting possibilities of MTEX and MatLab®. The paper is focused on three aspects in particular: the strength of CPO represented by orientation and misorientation distribution functions (ODFs, MDFs) or pole figures (PFs); symmetry of PFs and components of ODFs; and elastic tensors. The traditional measurements of texture strength of ODFs, MDFs and PFs are integral measurements of the distribution squared. The M-index is a partial measure of the MDF as the difference between uniform and measured misorientation angles. In addition there other parameters based on eigen analysis, but there are restrictions on their use. Eigen analysis does provide some shape factors for the distributions. The maxima of an ODF provides information on the modes. MTEX provides an estimate of the lower bound uniform fraction of an ODF. Finally, we illustrate the decomposition of arbitrary elastic tensor into symmetry components as an example of components in anisotropic physical properties. Ten examples scripts and their output are provided in the appendix.

We present a study of the charge state conversion of single nitrogen-vacancy (NV) defects hosted in nanodiamonds (NDs). We first show that the proportion of negatively charged ${\text{NV}}^{\ensuremath{-}}$ defects, with respect to its neutral counterpart ${\text{NV}}^{0}$, decreases with the size of the ND. We then propose a simple model based on a layer of electron traps located at the ND surface which is in good agreement with the recorded statistics. By using thermal oxidation to remove the shell of amorphous carbon around the NDs, we demonstrate a significant increase in the proportion of ${\text{NV}}^{\ensuremath{-}}$ defects in 10 nm NDs. These results are invaluable for further understanding, control, and use of the unique properties of negatively charged NV defects in diamond.

Cancerous and healthy human colon samples have been analyzed ex-vivo using a multispectral imaging Mueller polarimeter operated in the visible (from 500 to 700 nm) in a backscattering configuration with diffuse light illumination. Three samples of Liberkühn colon adenocarcinomas have been studied: common, mucinous and treated by radiochemotherapy. For each sample, several specific zones have been chosen, based on their visual staging and polarimetric responses, which have been correlated to the histology of the corresponding cuts. The most relevant polarimetric images are those quantifying the depolarization for incident linearly polarized light. The measured depolarization depends on several factors, namely the presence or absence of tumor, its exophytic (budding) or endophytic (penetrating) nature, its thickness (its degree of ulceration) and its level of penetration in deeper layers (submucosa, muscularis externa and serosa). The cellular density, the concentration of stroma, the presence or absence of mucus and the light penetration depth, which increases with wavelength, are also relevant parameters. Our data indicate that the tissues with the lowest and highest depolarizing powers are respectively mucus-free tumoral tissue with high cellular density and healthy serosa, while healthy submucosa, muscularis externa as well as mucinous tumor probably feature intermediate values. Moreover, the specimen coming from a patient treated successfully with radiochemotherapy exhibited a uniform polarimetric response typical of healthy tissue even in the initially pathological zone. These results demonstrate that multi-spectral Mueller imaging can provide useful contrasts to quickly stage human colon cancer ex-vivo and to distinguish between different histological variants of tumor.

A four-grid electrostatic energy analyzer for measurements of the ion velocity distribution and the emission of secondary electrons on the electrodes of low-pressure radio frequency glow-discharge systems has been conceived. Problems arising from poor analyzer design are discussed and the performance of the presented analyzer is shown for measurements of the ion velocity distribution in pure hydrogen, helium, and argon discharges. Moreover, the secondary electron yields on aluminium, stainless steel, copper, and amorphous silicon exposed to radio frequency argon, helium, and hydrogen plasmas are determined in situ, for the first time to our knowledge. In parallel-plate radio frequency discharges secondary electron emission involves the contributions of ions, fast neutrals, metastables, and photons impinging on the electrode surfaces. Therefore, secondary electron emission must be considered as a global phenomenon. Global secondary electron emission can be up to ten times larger than only ion-induced secondary electron emission. Typically, the global emission coefficient is of the order of 0.1 (secondary electrons per ion) but can exceed 1 when the contribution of metastables is important. This is a noteworthy result since secondary electron emission is often neglected or underestimated in modeling of electrical discharges.

Azzam's differential matrix formalism [J. Opt. Soc. Am. 68, 1756 (1978)], originally developed for longitudinally inhomogeneous anisotropic nondepolarizing media, is extended to include depolarizing media. The generalization is physically interpreted in terms of means and uncertainties of the elementary optical properties of the medium, as well as of three anisotropy absorption parameters introduced to describe the depolarization. The formalism results in a particularly simple mathematical procedure for the retrieval of the elementary properties of a generally depolarizing anisotropic medium, assumed to be globally homogeneous, from its experimental Mueller matrix. The approach is illustrated on literature data and the conditions of its validity are identified and discussed.

We demonstrate a Mueller polarimeter in which the polarization-state generator and analyzer are both composed of a linear polarizer and two liquid-crystal variable retarders. The polarimeter is designed to optimize the accuracy of the final results by minimization of the condition numbers of the modulation and analysis matrices. The polarimeter calibration, a difficult task by conventional procedures, is achieved easily by use of the eigenvalue method of Compain et al. [Appl. Opt. 38, 3490 (1999)]. The overall polarimeter performance is tested with a linear polarizer at various angles and a compensator at various retardations.

We present a preliminary investigation of macroscopic polarimetric imaging of uterine cervix. Orthogonal state contrast (OSC) images of healthy and anomalous cervices have been taken in vivo at 550 nm. Four ex vivo cervix samples have been studied in full Muller polarimetry, at 550 nm and 700 nm, and characterized in detail by standard pathology. One sample was totally healthy, another one carried CIN lesions at very early stage (CIN1) in its visible exocervical region, while for the other two samples more advanced (CIN3) lesions were present, together with visible glandular epithelium (ectropion). Significant birefringence has been observed in the healthy regions of all six samples, both in vivo and ex vivo. Standard treatments of the Mueller images of the ex vivo samples allowed to quantify both retardation and depolarization. Retardation reached 60° in healthy regions, and disappeared in the anomalous regions of the other three ex vivo samples. The depolarization power was largest in healthy regions, and lower in CINs and ectropion. Possible origins of the observed effects are briefly discussed.

We present a study on the development and the evaluation of a fully automated radio-frequency glow discharge system devoted to the deposition of amorphous thin film semiconductors and insulators. The following aspects were carefully addressed in the design of the reactor: (1) cross contamination by dopants and unstable gases, (2) capability of a fully automated operation, (3) precise control of the discharge parameters, particularly the substrate temperature, and (4) high chemical purity. The new reactor, named ARCAM, is a multiplasma-monochamber system consisting of three separated plasma chambers located inside the same isothermal vacuum vessel. Thus, the system benefits from the advantages of multichamber systems but keeps the simplicity and low cost of monochamber systems. The evaluation of the reactor performances showed that the oven-like structure combined with a differential dynamic pumping provides a high chemical purity in the deposition chamber. Moreover, the studies of the effects associated with the plasma recycling of material from the walls and of the thermal decomposition of diborane showed that the multiplasma-monochamber design is efficient for the production of abrupt interfaces in hydrogenated amorphous silicon (a-Si:H) based devices. Also, special attention was paid to the optimization of plasma conditions for the deposition of low density of states a-Si:H. Hence, we also present the results concerning the effects of the geometry, the substrate temperature, the radio frequency power and the silane pressure on the properties of the a-Si:H films. In particular, we found that a low density of states a-Si:H can be deposited at a wide range of substrate temperatures (100 °C≤Ts≤300 °C).

This paper discusses the fundamentals, applications, potential, limitations, and future perspectives of polarized light reflection techniques for the characterization of materials and related systems and devices at the nanoscale. These techniques include spectroscopic ellipsometry, polarimetry, and reflectance anisotropy. We give an overview of the various ellipsometry strategies for the measurement and analysis of nanometric films, metal nanoparticles and nanowires, semiconductor nanocrystals, and submicron periodic structures. We show that ellipsometry is capable of more than the determination of thickness and optical properties, and it can be exploited to gain information about process control, geometry factors, anisotropy, defects, and quantum confinement effects of nanostructures.

Covalent surface modification of conductive, semiconductive, and insulating substrates with thin organic polymers films induced by redox activation of aryl diazonium salts in the presence of vinyl monomers has been investigated in acidic aqueous media. This new process, called diazonium-induced anchoring process (DIAP), is an efficient technique to impart covalent adhesion of polyvinyl coatings onto raw inorganic or organic surfaces without any conductivity requirement. Typically, aryl diazonium salts are reduced with iron powder to give surface-active aryl radicals leading (i) to the formation of a grafted polyphenylene-like film on the substrate surface and (ii) to the initiation of the radical polymerization of the vinylic monomer in solution. The resulting radical-terminated macromolecular chains formed in solution are then able to react with the polyphenylene primer layer to form a very homogeneous thin organic film on the surface. The final organic thin coating is strongly grafted on materials surfaces, as evidenced by its persistence after a long ultrasonic treatment in a good solvent of the polymer. We speculate this process is supported by the large concentration of aryl and hydrogen radicals formed when iron powder is added in the acidic aqueous solution. The thickness of the polymer film can be controlled as a function of time, typically a few minutes, and was measured between 10 and several hundred nanometers. Infrared reflection–absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and contact angle measurements were used to characterize the surface modification of metals, glass, carbon nanotubes, or polytetrafluoroethylene (PTFE). This very simple and efficient grafting method provides a powerful tool for the covalent coating of organic or inorganic surfaces possessing complex geometrical shapes.

The response of PEDOT:PSS planar electrochemical transistors to H2O2 can be tuned by varying the ratio between the areas of the channel and the gate electrode. Devices with small gates show lower background signal and higher sensitivity. The detection range, on the other hand, is found to be rather independent of the gate/channel area ratio.