Water- and heat-activated dynamic passivation for perovskite photovoltaics.

Further improvements in perovskite solar cells (PSCs) require better control of ionic defects in the perovskite photoactive layer during the manufacturing stage and their usage1-5. Here, we report a living passivation strategy using a hindered urea/thiocarbamate bond6-8 Lewis acid-base material (HUBLA), where dynamic covalent bonds with water and heat-activated characteristics can dynamically heal the perovskite to ensure device performance and stability. Upon exposure to moisture or heat, HUBLA generates new agents and further passivates defects in the perovskite. This passivation strategy achieved high-performance devices with a power conversion efficiency (PCE) of 25.1%. HUBLA devices retained 94% of their initial PCE for approximately 1500 hours of aging at 85 °C in N2 and maintained 88% of their initial PCE after 1000 hours of aging at 85 °C and 30% relative humidity (RH) in air.

Enhanced Carrier Diffusion Enables Efficient Back-Contact Perovskite Photovoltaics.

Back-contact architectures offer a promising route to improve the record efficiencies of perovskite solar cells (PSCs) by eliminating parasitic light absorption. However, the performance of back-contact PSCs is limited by inadequate carrier diffusion in perovskite. Here, we report that perovskite films with a preferred out-of-plane orientation show improved carrier dynamic properties. With the addition of guanidine thiocyanate, the films exhibit carrier lifetimes and mobilities increased by 3-5 times, leading to diffusion lengths exceeding 7 µm. The enhanced carrier diffusion results from substantial suppression of nonradiative recombination and improves charge collection. Devices using such films achieve reproducible efficiencies reaching 11.2 %, among the best performances for back-contact PSCs. Our findings demonstrate the impact of carrier dynamics on back-contact PSCs and provide the basis for a new route to high-performance back-contact perovskite optoelectronic devices at low cost.

Intensity Modulated Photocurrent Microspectrosopy for Next Generation Photovoltaics.

In this report, a large-area laser beam induced current microscope that has been adapted to perform intensity modulated photocurrent spectroscopy (IMPS) in an imaging mode is described. Microscopy-based IMPS method provides a spatial resolution of the frequency domain response of the solar cell, allowing correlation of the optoelectronic response with a particular interface, bulk material, specific transport layer, or transport parameter. The system is applied to study degradation effects in back-contact perovskite cells where it is found to readily differentiate areas based on their markedly different frequency response. Using the diffusion-recombination model, the IMPS response is modeled for a sandwich structure and extended for the special case of lateral diffusion in a back-contact cell. In the low-frequency limit, the model is used to calculate spatial maps of the carrier ambipolar diffusion length. The observed frequency response of IMPS images is then discussed.

How Transparent Oxides Gain Some Color: Discovery of a CeNiO3 Reduced Bandgap Phase As an Absorber for Photovoltaics.

In this work, we describe the formation of a reduced bandgap CeNiO3 phase, which, to our knowledge, has not been previously reported, and we show how it is utilized as an absorber layer in a photovoltaic cell. The CeNiO3 phase is prepared by a combinatorial materials science approach, where a library containing a continuous compositional spread of Ce xNi1- xO y is formed by pulsed laser deposition (PLD); a method that has not been used in the past to form Ce-Ni-O materials. The library displays a reduced bandgap throughout, calculated to be 1.48-1.77 eV, compared to the starting materials, CeO2 and NiO, which each have a bandgap of ∼3.3 eV. The materials library is further analyzed by X-ray diffraction to determine a new crystalline phase. By searching and comparing to the Materials Project database, the reduced bandgap CeNiO3 phase is realized. The CeNiO3 reduced bandgap phase is implemented as the absorber layer in a solar cell and photovoltages up to 550 mV are achieved. The solar cells are also measured by surface photovoltage spectroscopy, which shows that the source of the photovoltaic activity is the reduced bandgap CeNiO3 phase, making it a viable material for solar energy.

Process-Function Data Mining for the Discovery of Solid-State Iron-Oxide PV.

Data mining tools have been known to be useful for analyzing large material data sets generated by high-throughput methods. Typically, the descriptors used for the analysis are structural descriptors, which can be difficult to obtain and to tune according to the results of the analysis. In this Research Article, we show the use of deposition process parameters as descriptors for analysis of a photovoltaics data set. To create a data set, solar cell libraries were fabricated using iron oxide as the absorber layer deposited using different deposition parameters, and the photovoltaic performance was measured. The data was then used to build models using genetic programing and stepwise regression. These models showed which deposition parameters should be used to get photovoltaic cells with higher performance. The iron oxide library fabricated based on the model predictions showed a higher performance than any of the previous libraries, which demonstrates that deposition process parameters can be used to model photovoltaic performance and lead to higher performing cells. This is a promising technique toward using data mining tools for discovery and fabrication of high performance photovoltaic materials.

A graphene field-effect transistor as a molecule-specific probe of DNA nucleobases.

Fast and reliable DNA sequencing is a long-standing target in biomedical research. Recent advances in graphene-based electrical sensors have demonstrated their unprecedented sensitivity to adsorbed molecules, which holds great promise for label-free DNA sequencing technology. To date, the proposed sequencing approaches rely on the ability of graphene electric devices to probe molecular-specific interactions with a graphene surface. Here we experimentally demonstrate the use of graphene field-effect transistors (GFETs) as probes of the presence of a layer of individual DNA nucleobases adsorbed on the graphene surface. We show that GFETs are able to measure distinct coverage-dependent conductance signatures upon adsorption of the four different DNA nucleobases; a result that can be attributed to the formation of an interface dipole field. Comparison between experimental GFET results and synchrotron-based material analysis allowed prediction of the ultimate device sensitivity, and assessment of the feasibility of single nucleobase sensing with graphene.

Graphene field effect transistor as a probe of electronic structure and charge transfer at organic molecule-graphene interfaces.

The electronic structure of physisorbed molecules containing aromatic nitrogen heterocycles (triazine and melamine) on graphene is studied using a combination of electronic transport, X-ray photoemission spectroscopy and density functional theory calculations. The interfacial electronic structure and charge transfer of weakly coupled molecules on graphene is found to be governed by work function differences, molecular dipole moments and polarization effects. We demonstrate that molecular depolarization plays a significant role in these charge transfer mechanisms even at submonolayer coverage, particularly for molecules which possess strong dipoles. Electronic transport measurements show a reduction of graphene conductivity and charge carrier mobility upon the adsorption of the physisorbed molecules. This effect is attributed to the formation of additional electron scattering sites in graphene by the molecules and local molecular electric fields. Our results show that adsorbed molecules containing polar functional groups on graphene exhibit different coverage behaviour to nonpolar molecules. These effects open up a range of new opportunities for recognition of different molecules on graphene-based sensor devices.

Direct observation of phonon emission from hot electrons: spectral features in diamond secondary electron emission.

In this work we use high-resolution synchrotron-based photoelectron spectroscopy to investigate the low kinetic energy electron emission from two negative electron affinity surfaces of diamond, namely hydrogenated and lithiated diamond. For hydrogen-terminated diamond electron emission below the conduction band minimum (CBM) is clearly observed as a result of phonon emission subsequent to carrier thermalization at the CBM. In the case of lithiated diamond, we find the normal conduction band minimum emission peak is asymmetrically broadened to higher kinetic energies and argue the broadening is a result of ballistic emission from carriers thermalized to the CBM in the bulk well before the onset of band-bending. In both cases the spectra display intensity modulations that are the signature of optical phonon emission as the main mechanism for carrier relaxation. To our knowledge, these measurements represent the first direct observation of hot carrier energy loss via photoemission.