Life on the Urbach Edge.

The Urbach energy is an expression of the static and dynamic disorder in a semiconductor and is directly accessible via optical characterization techniques. The strength of this metric is that it elegantly captures the optoelectronic performance potential of a semiconductor in a single number. For solar cells, the Urbach energy is found to be predictive of a material's minimal open-circuit-voltage deficit. Performance calculations considering the Urbach energy give more realistic power conversion efficiency limits than from classical Shockley-Queisser considerations. The Urbach energy is often also found to correlate well with the Stokes shift and (inversely) with the carrier mobility of a semiconductor. Here, we discuss key features, underlying physics, measurement techniques, and implications for device fabrication, underlining the utility of this metric.

Temperature Dependence of the Urbach Energy in Lead Iodide Perovskites.

To gain insight into the properties of photovoltaic and light-emitting materials, detailed information about their optical absorption spectra is essential. Here, we elucidate the temperature dependence of such spectra for methylammonium lead iodide (CH3NH3PbI3), with specific attention to its sub-band gap absorption edge (often termed Urbach energy). On the basis of these data, we first find clear further evidence for the universality of the correlation between the Urbach energy and open-circuit voltage losses of solar cells. Second, we find that for CH3NH3PbI3 the static, temperature-independent, contribution of the Urbach energy is 3.8 ± 0.7 meV, which is smaller than that of crystalline silicon (Si), gallium arsenide (GaAs), indium phosphide (InP), or gallium nitride (GaN), underlining the remarkable optoelectronic properties of perovskites.

Measurement of doping profiles by a contactless method of IR reflectance under grazing incidence.

An improved contactless method of the measurement and evaluation of charge carrier profiles in polished wafers by infrared reflectance was developed. The sensitivity of optical reflectance to the incidence angle was theoretically analyzed. A grazing incident angle enhances sensitivity to doping profile parameters. At the same time, the sensitivity to experimental errors sharply increases around the Brewster angle. Therefore, the optimal angle of 65° was chosen. Experimental errors such as unintentional polarization of the measurement beam were minimized by division by reference spectra taken on an undoped sample and further by normalization to a fixed value in the region of 4000 cm-1 to 7000 cm-1. The carrier profile in boron-doped samples was parametrized by 3 parameters and that in phosphorous-doped samples was parametrized by 4 parameters, using additional empirically determined assumptions. As a physical model, the Drude equation is used with two parameters assumed to be concentration-dependent: relaxation time and contribution from band-to-band excitations. The model parameters were calibrated independently by infrared ellipsometry. The presented method gives results in satisfactory agreement with the profiles measured by the electrochemical capacitance-voltage method.

Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation.

Optical absorptance spectroscopy of polycrystalline CH3NH3PbI3 films usually indicates the presence of a PbI2 phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI2 phase restricts charge-carrier transport, suggesting that PbI2 encapsulates CH3NH3PbI3 grains. We also find that PbI2 injects holes into the CH3NH3PbI3 grains, increasing the apparent photosensitivity of PbI2. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

Comparison of Silicon Nanocrystals Prepared by Two Fundamentally Different Methods.

This work compares structural and optical properties of silicon nanocrystals prepared by two fundamentally different methods, namely, electrochemical etching of Si wafers and low-pressure plasma synthesis, completed with a mechano-photo-chemical treatment. This treatment leads to surface passivation of the nanoparticles by methyl groups. Plasma synthesis unlike electrochemical etching allows selecting of the particle sizes. Measured sizes of the nanoparticles by dynamic light scattering show 3 and 20 nm for electrochemically etched and plasma-synthetized samples, respectively. Plasma-synthetized 20-nm particles do not exhibit photoluminescence due to absence of quantum confinement effect, and freshly appeared photoluminescence after surface passivation could indicate presence of organic molecules on the nanoparticle surface, luminescing instead of nanocrystal core. Electrochemically etched sample exhibits dramatic changes in photoluminescence during the mechano-photo-chemical treatment while no photoluminescence is observed for the plasma-synthetized one. We also used the Fourier transform infrared spectroscopy for comparison of the chemical changes happened during the treatment.

Experimental quantification of useful and parasitic absorption of light in plasmon-enhanced thin silicon films for solar cells application.

A combination of photocurrent and photothermal spectroscopic techniques is applied to experimentally quantify the useful and parasitic absorption of light in thin hydrogenated microcrystalline silicon (µc-Si:H) films incorporating optimized metal nanoparticle arrays, located at the rear surface, for improved light trapping via resonant plasmonic scattering. The photothermal technique accounts for the total absorptance and the photocurrent signal accounts only for the photons absorbed in the µc-Si:H layer (useful absorptance); therefore, the method allows for independent quantification of the useful and parasitic absorptance of the plasmonic (or any other) light trapping structure. We demonstrate that with a 0.9 µm thick absorber layer the optical losses related to the plasmonic light trapping in the whole structure are insignificant below 730 nm, above which they increase rapidly with increasing illumination wavelength. An average useful absorption of 43% and an average parasitic absorption of 19% over 400-1100 nm wavelength range is measured for µc-Si:H films deposited on optimized self-assembled Ag nanoparticles coupled with a flat mirror (plasmonic back reflector). For this sample, we demonstrate a significant broadband enhancement of the useful absorption resulting in the achievement of 91% of the maximum theoretical Lambertian limit of absorption.

Effect of the thin-film limit on the measurable optical properties of graphene.

The fundamental sheet conductance of graphene can be directly related to the product of its absorption coefficient, thickness and refractive index. The same can be done for graphene's fundamental opacity if the so-called thin-film limit is considered. Here, we test mathematically and experimentally the validity of this limit on graphene, as well as on thin metal and semiconductor layers. Notably, within this limit, all measurable properties depend only on the product of the absorption coefficient, thickness, and refractive index. As a direct consequence, the absorptance of graphene depends on the refractive indices of the surrounding media. This explains the difficulty in determining separately the optical constants of graphene and their widely varying values found in literature so far. Finally, our results allow an accurate estimation of the potential optical losses or gains when graphene is used for various optoelectronic applications.

Raman Spectroscopy of Organic-Inorganic Halide Perovskites.

Micro-Raman spectroscopy provides laterally resolved microstructural information for a broad range of materials. In this Letter, we apply this technique to tri-iodide (CH3NH3PbI3), tribromide (CH3NH3PbBr3), and mixed iodide-bromide (CH3NH3PbI3-xBrx) organic-inorganic halide perovskite thin films and discuss necessary conditions to obtain reliable data. We explain how to measure Raman spectra of pristine CH3NH3PbI3 layers and discuss the distinct Raman bands that develop during moisture-induced degradation. We also prove unambiguously that the final degradation products contain pure PbI2. Moreover, we describe CH3NH3PbI3-xBrx Raman spectra and discuss how the perovskite crystallographic symmetries affect the Raman band intensities and spectral shapes. On the basis of the dependence of the Raman shift on the iodide-to-bromide ratio, we show that Raman spectroscopy is a fast and nondestructive method for the evaluation of the relative iodide-to-bromide ratio.

Attenuated total reflectance Fourier-transform infrared spectroscopic investigation of silicon heterojunction solar cells.

Silicon heterojunction solar cells critically depend on the detailed properties of their amorphous/crystalline silicon interfaces. We report here on the use of attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy to gain precise insight into the vibrational properties of the surfaces and ultrathin layers present in such solar cells. We fabricate ATR prisms from standard silicon wafers similar to those used for device fabrication. In this fashion, we acquire very-high sensitivity FTIR information on device-relevant structures. Our method has no requirement for minimum layer thickness, enabling the study of the impact of the different fabrication process steps on the film microstructure. We discuss the necessary requirements for the method implementation and give a comprehensive overview of all observed vibration modes. In particular, we study vibrational signatures of Si-H(X), Si-H(X)(Si(Y)O(Z)), B-H, hydroxyl groups, and hydrocarbons on the Si(111) surface. We observe subtle effects in the evolution of the chemical state of the surface during sample storage and process-related wafer handling and discuss their effect on the electronic properties of the involved interfaces.

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance.

Solar cells based on organometallic halide perovskite absorber layers are emerging as a high-performance photovoltaic technology. Using highly sensitive photothermal deflection and photocurrent spectroscopy, we measure the absorption spectrum of CH3NH3PbI3 perovskite thin films at room temperature. We find a high absorption coefficient with particularly sharp onset. Below the bandgap, the absorption is exponential over more than four decades with an Urbach energy as small as 15 meV, which suggests a well-ordered microstructure. No deep states are found down to the detection limit of ∼1 cm(-1). These results confirm the excellent electronic properties of perovskite thin films, enabling the very high open-circuit voltages reported for perovskite solar cells. Following intentional moisture ingress, we find that the absorption at photon energies below 2.4 eV is strongly reduced, pointing to a compositional change of the material.

Thin-film limit formalism applied to surface defect absorption.

The thin-film limit is derived by a nonconventional approach and equations for transmittance, reflectance and absorptance are presented in highly versatile and accurate form. In the thin-film limit the optical properties do not depend on the absorption coefficient, thickness and refractive index individually, but only on their product. We show that this formalism is applicable to the problem of ultrathin defective layer e.g. on a top of a layer of amorphous silicon. We develop a new method of direct evaluation of the surface defective layer and the bulk defects. Applying this method to amorphous silicon on glass, we show that the surface defective layer differs from bulk amorphous silicon in terms of light soaking.