Dual-heterodyne Kelvin probe force microscopy.

We present a new open-loop implementation of Kelvin probe force microscopy (KPFM) that provides access to the Fourier spectrum of the time-periodic surface electrostatic potential generated under optical (or electrical) pumping with an atomic force microscope. The modulus and phase coefficients are probed by exploiting a double heterodyne frequency mixing effect between the mechanical oscillation of the cantilever, modulated components of the time-periodic electrostatic potential at harmonic frequencies of the pump, and an ac bias modulation signal. Each harmonic can be selectively transferred to the second cantilever eigenmode. We show how phase coherent sideband generation and signal demodulation at the second eigenmode can be achieved by using two numerical lock-in amplifiers configured in cascade. Dual-heterodyne KPFM (DHe-KPFM) can be used to map any harmonic (amplitude/phase) of the time-periodic surface potential at a standard scanning speed. The Fourier spectrum (series of harmonics) can also be recorded in spectroscopic mode (DHe-KPFM spectroscopy), and 2D dynamic images can be acquired in data cube mode. The capabilities of DHe-KPFM in terms of time-resolved measurements, surface photovoltage (SPV) imaging, and detection of weak SPV signals are demonstrated through a series of experiments on difference surfaces: a reference substrate, a bulk organic photovoltaic heterojunction thin film, and an optoelectronic interface obtained by depositing caesium lead bromide perovskite nanosheets on a graphite surface. The conclusion provides perspectives for future improvements and applications.

Star-shape non-fullerene acceptor featuring an aza-triangulene core for organic solar cells.

We present the simple synthesis of a star-shape non-fullerene acceptor (NFA) for application in organic solar cells. This NFA possesses a D(A)3 structure in which the electron-donating core is an aza-triangulene unit and we report the first crystal structure for a star shape NFA based on this motive. We fully characterized this molecule's optoelectronic properties in solution and thin films, investigating its photovoltaic properties when blended with PTB7-Th as the electron donor component. We demonstrate that the aza-triangulene core leads to a strong absorption in the visible range with an absorption edge going from 700 nm in solution to above 850 nm in the solid state. The transport properties of the pristine molecule were investigated in field effect transistors (OFETs) and in blends with PTB7-Th following a Space-Charge-Limited Current (SCLC) protocol. We found that the mobility of electrons measured in films deposited from o-xylene and chlorobenzene are quite similar (up to 2.70 × 10-4 cm2 V-1 s-1) and that the values are not significantly modified by thermal annealing. The new NFA combined with PTB7-Th in the active layer of inverted solar cells leads to a power conversion efficiency of around 6.3% (active area 0.16 cm2) when processed from non-chlorinated solvents without thermal annealing. Thanks to impedance spectroscopy measurements performed on the solar cells, we show that the charge collection efficiency of the devices is limited by the transport properties rather than by recombination kinetics. Finally, we investigated the stability of this new NFA in various conditions and show that the star-shape molecule is more resistant against photolysis in the presence and absence of oxygen than ITIC.

A simple KPFM-based approach for electrostatic- free topographic measurements: the case of MoS2on SiO2.

A simple implementation of Kelvin probe force microscopy (KPFM) is reported that enables recording topographic images in the absence of any component of the electrostatic force (including the static term). Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum (nc-AFM), the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that certain kind of defects can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to other sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxides.

Hidden surface photovoltages revealed by pump probe KPFM.

In this work, we use pump-probe Kelvin probe force microscopy (pp-KPFM) in combination with non-contact atomic force microscopy (nc-AFM) under ultrahigh vacuum, to investigate the nature of the light-induced surface potential dynamics in alumina-passivated crystalline silicon, and in an organic bulk heterojunction thin film based on the PTB7-PC71BM tandem. In both cases, we demonstrate that it is possible to identify and separate the contributions of two different kinds of photo-induced charge distributions that give rise to potential shifts with opposite polarities, each characterized by different dynamics. The data acquired on the passivated crystalline silicon are shown to be fully consistent with the band-bending at the silicon-oxide interface, and with electron trapping processes in acceptors states and in the passivation layer. The full sequence of events that follow the electron-hole generation can be observed on the pp-KPFM curves, i.e. the carriers spatial separation and hole accumulation in the space charge area, the electron trapping, the electron-hole recombination, and finally the electron trap-release. Two dimensional dynamical maps of the organic blend photo-response are obtained by recording the pump-probe KPFM curves in data cube mode, and by implementing a specific batch processing protocol. Sample areas displaying an extra positive SPV component characterized by decay time-constants of a few tens of microseconds are thus revealed, and are tentatively attributed to specific interfaces formed between a polymer-enriched skin layer and recessed acceptor aggregates. Decay time constant images of the negative SPV component confirm that the acceptor clusters act as electron-trapping centres. Whatever the photovoltaic technology, our results exemplify how some of the SPV components may remain completely hidden to conventional SPV imaging by KPFM, with possible consequences in terms of photo-response misinterpretation. This work furthermore highlights the need of implementing time-resolved techniques that can provide a quantitative measurement of the time-resolved potential.

Implementation of data-cube pump-probe KPFM on organic solar cells.

An implementation of pump-probe Kelvin probe force microscopy (pp-KPFM) is reported that enables recording the time-resolved surface potential in single-point mode or over a 2D grid. The spectroscopic data are acquired in open z-loop configuration, which simplifies the pp-KPFM operation. The validity of the implementation is probed by measurements using electrical pumping. The dynamical photoresponse of a bulk heterojunction solar cell based on PTB7 and PC71BM is subsequently investigated by recording point-spectroscopy curves as a function of the optical power at the cathode and by mapping 2D time-resolved images of the surface photovoltage of the bare organic active layer.

New approach for the molecular beam epitaxy growth of scalable WSe2 monolayers.

The search for high-quality transition metal dichalcogenides mono- and multi-layers grown on large areas is still a very active field of investigation. Here, we use molecular beam epitaxy to grow WSe2 on 15 × 15 mm large mica in the van der Waals regime. By screening one-step growth conditions, we find that very high temperature (>900 °C) and very low deposition rate (<0.15 Å min-1) are necessary to obtain high quality WSe2 films. The domain size can be as large as 1 µm and the in-plane rotational misorientation of 1.25°. The WSe2 monolayer is also robust against air exposure, can be easily transferred over 1 cm2 on SiN/SiO2 and exhibits strong photoluminescence signal. Moreover, by combining grazing incidence x-ray diffraction and transmission electron microscopy, we could detect the presence of few misoriented grains. A two-dimensional model based on atomic coincidences between the WSe2 and mica crystals allows us to explain the formation of these misoriented grains and gives insight to achieve highly crystalline WSe2.

The valley Nernst effect in WSe2.

The Hall effect can be extended by inducing a temperature gradient in lieu of electric field that is known as the Nernst (-Ettingshausen) effect. The recently discovered spin Nernst effect in heavy metals continues to enrich the picture of Nernst effect-related phenomena. However, the collection would not be complete without mentioning the valley degree of freedom benchmarked by the valley Hall effect. Here we show the experimental evidence of its missing counterpart, the valley Nernst effect. Using millimeter-sized WSe[Formula: see text] mono-multi-layers and the ferromagnetic resonance-spin pumping technique, we are able to apply a temperature gradient by off-centering the sample in the radio frequency cavity and address a single valley through spin-valley coupling. The combination of a temperature gradient and the valley polarization leads to the valley Nernst effect in WSe[Formula: see text] that we detect electrically at room temperature. The valley Nernst coefficient is in good agreement with the predicted value.

A scanning probe microscopy study of nanostructured TiO2/poly(3-hexylthiophene) hybrid heterojunctions for photovoltaic applications.

The nanoscale morphology of photoactive hybrid heterojunctions plays a key role in the performances of hybrid solar cells. In this work, the heterojunctions consist of a nanocolumnar TiO2 surface covalently grafted with a monolayer of poly(3-hexylthiophene) (P3HT) functionalized with carboxylic groups (-COOH). Through a joint analysis of the photovoltaic properties at the nanoscale by photoconductive-AFM (PC-AFM) and surface photovoltage imaging, we investigated the physical mechanisms taking place locally during the photovoltaic process and the correlation to the nanoscale morphology. A down-shift of the vacuum level of the TiO2 surface upon grafting was measured by Kelvin probe force microscopy (KPFM), evidencing the formation of a dipole at the TiO2/P3HT-COOH interface. Upon in situ illumination, a positive photovoltage was observed as a result of the accumulation of photogenerated holes in the P3HT layer. A positive photocurrent was recorded in PC-AFM measurements, whose spatial mapping was interpreted consistently with the corresponding KPFM analysis, offering a correlated analysis of interest from both a theoretical and material design perspective.

Numerical analysis of single-point spectroscopy curves used in photo-carrier dynamics measurements by Kelvin probe force microscopy under frequency-modulated excitation.

In recent years, the investigation of the complex interplay between the nanostructure and photo-transport mechanisms has become of crucial importance for the development of many emerging photovoltaic technologies. In this context, Kelvin probe force microscopy under frequency-modulated excitation has emerged as a useful technique for probing photo-carrier dynamics and gaining access to carrier lifetime at the nanoscale in a wide range of photovoltaic materials. However, some aspects about the data interpretation of techniques based on this approach are still the subject of debate, for example, the plausible presence of capacitance artifacts. Special attention shall also be given to the mathematical model used in the data-fitting process as it constitutes a determining aspect in the calculation of time constants. Here, we propose and demonstrate an automatic numerical simulation routine that enables to predict the behavior of spectroscopy curves of the average surface photovoltage as a function of a frequency-modulated excitation source in photovoltaic materials, enabling to compare simulations and experimental results. We describe the general aspects of this simulation routine and we compare it against experimental results previously obtained using single-point Kelvin probe force microscopy under frequency-modulated excitation over a silicon nanocrystal solar cell, as well as against results obtained by intensity-modulated scanning Kelvin probe microscopy over a polymer/fullerene bulk heterojunction device. Moreover, we show how this simulation routine can complement experimental results as additional information about the photo-carrier dynamics of the sample can be gained via the numerical analysis.

Multimodal noncontact atomic force microscopy and Kelvin probe force microscopy investigations of organolead tribromide perovskite single crystals.

In this work, methylammonium lead tribromide (MAPbBr3) single crystals are studied by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). We demonstrate that the surface photovoltage and crystal photostriction can be simultaneously investigated by implementing a specific protocol based on the acquisition of the tip height and surface potential during illumination sequences. The obtained data confirm the existence of lattice expansion under illumination in MAPbBr3 and that negative photocarriers accumulate near the crystal surface due to band bending effects. Time-dependent changes of the surface potential occurring under illumination on the scale of a few seconds reveal the existence of slow ion-migration mechanisms. Lastly, photopotential decay at the sub-millisecond time scale related to the photocarrier lifetime is quantified by performing KPFM measurements under frequency-modulated illumination. Our multimodal approach provides a unique way to investigate the interplay between the charges and ionic species, the photocarrier-lattice coupling and the photocarrier dynamics in hybrid perovskites.

Calibrated work function mapping by Kelvin probe force microscopy.

We propose and demonstrate the implementation of an alternative work function tip calibration procedure for Kelvin probe force microscopy under ultrahigh vacuum, using monocrystalline metallic materials with known crystallographic orientation as reference samples, instead of the often used highly oriented pyrolytic graphite calibration sample. The implementation of this protocol allows the acquisition of absolute and reproducible work function values, with an improved uncertainty with respect to unprepared highly oriented pyrolytic graphite-based protocols. The developed protocol allows the local investigation of absolute work function values over nanostructured samples and can be implemented in electronic structures and devices characterization as demonstrated over a nanostructured semiconductor sample presenting Al0.7Ga0.3As and GaAs layers with variable thickness. Additionally, using our protocol we find that the work function of annealed highly oriented pyrolytic graphite is equal to 4.6 ± 0.03 eV.

Multimodal Kelvin Probe Force Microscopy Investigations of a Photovoltaic WSe2/MoS2 Type-II Interface.

Atomically thin transition-metal dichalcogenides (TMDC) have become a new platform for the development of next-generation optoelectronic and light-harvesting devices. Here, we report a Kelvin probe force microscopy (KPFM) investigation carried out on a type-II photovoltaic heterojunction based on WSe2 monolayer flakes and a bilayer MoS2 film stacked in vertical configuration on a Si/SiO2 substrate. Band offset characterized by a significant interfacial dipole is pointed out at the WSe2/MoS2 vertical junction. The photocarrier generation process and phototransport are studied by applying a differential technique allowing to map directly two-dimensional images of the surface photovoltage (SPV) over the vertical heterojunctions (vHJ) and in its immediate vicinity. Differential SPV reveals the impact of chemical defects on the photocarrier generation and that negative charges diffuse in the MoS2 a few hundreds of nanometers away from the vHJ. The analysis of the SPV data confirms unambiguously that light absorption results in the generation of free charge carriers that do not remain coulomb-bound at the type-II interface. A truly quantitative determination of the electron-hole (e-h) quasi-Fermi levels splitting (i.e., the open-circuit voltage) is achieved by measuring the differential vacuum-level shift over the WSe2 flakes and the MoS2 layer. The dependence of the energy-level splitting as a function of the optical power reveals that Shockley-Read-Hall processes significantly contribute to the interlayer recombination dynamics. Finally, a newly developed time-resolved mode of the KPFM is applied to map the SPV decay time constants. The time-resolved SPV images reveal the dynamics of delayed recombination processes originating from photocarriers trapping at the SiO2/TMDC interfaces.

Photo-Carrier Multi-Dynamical Imaging at the Nanometer Scale in Organic and Inorganic Solar Cells.

Investigating the photocarrier dynamics in nanostructured and heterogeneous energy materials is of crucial importance from both fundamental and technological points of view. Here, we demonstrate how noncontact atomic force microscopy combined with Kelvin probe force microscopy under frequency-modulated illumination can be used to simultaneously image the surface photopotential dynamics at different time scales with a sub-10 nm lateral resolution. The basic principle of the method consists in the acquisition of spectroscopic curves of the surface potential as a function of the illumination frequency modulation on a two-dimensional grid. We show how this frequency-spectroscopy can be used to probe simultaneously the charging rate and several decay processes involving short-lived and long-lived carriers. With this approach, dynamical images of the trap-filling, trap-delayed recombination and nongeminate recombination processes have been acquired in nanophase segregated organic donor-acceptor bulk heterojunction thin films. Furthermore, the spatial variation of the minority carrier lifetime has been imaged in polycrystalline silicon thin films. These results establish two-dimensional multidynamical photovoltage imaging as a universal tool for local investigations of the photocarrier dynamics in photoactive materials and devices.

Equal variations of the Fermi level and work function in graphene at the nanoscale.

If surface effects are neglected, any change of the Fermi level in a semiconductor is expected to result in an equal and opposite change of the work function. However, this is in general not observed in three-dimensional semiconductors, because of Fermi level pinning at the surface. By combining Kelvin probe force microscopy and scanning tunneling spectroscopy on single layer graphene, we measure both the local work function and the charge carrier density. The one-to-one equivalence of changes in the Fermi level and the work function is demonstrated to accurately hold in single layer graphene down to the nanometer scale.

High-resolution noncontact AFM and Kelvin probe force microscopy investigations of self-assembled photovoltaic donor-acceptor dyads.

Self-assembled donor-acceptor dyads are used as model nanostructured heterojunctions for local investigations by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). With the aim to probe the photo-induced charge carrier generation, thin films deposited on transparent indium tin oxide substrates are investigated in dark conditions and upon illumination. The topographic and contact potential difference (CPD) images taken under dark conditions are analysed in view of the results of complementary transmission electron microscopy (TEM) experiments. After in situ annealing, it is shown that the dyads with longer donor blocks essentially lead to standing acceptor-donor lamellae, where the acceptor and donor groups are π-stacked in an edge-on configuration. The existence of strong CPD and surface photo-voltage (SPV) contrasts shows that structural variations occur within the bulk of the edge-on stacks. SPV images with a very high lateral resolution are achieved, which allows for the resolution of local photo-charging contrasts at the scale of single edge-on lamella. This work paves the way for local investigations of the optoelectronic properties of donor-acceptor supramolecular architectures down to the elementary building block level.

High-Resolution Kelvin Probe Force Microscopy Imaging of Interface Dipoles and Photogenerated Charges in Organic Donor-Acceptor Photovoltaic Blends.

We present noncontact atomic force microscopy and Kelvin probe force microscopy studies of nanophase segregated photovoltaic blends based on an oligothiophene-fluorenone oligomer and [6,6]-phenyl C70 butyric acid methyl ester. We carried out a complete analysis of the influence of the tip-surface interaction regime on the topographic, in-dark contact potential and surface photovoltage contrasts. It is demonstrated that an optimal lateral resolution is achieved for all channels below the onset of a contrast in the damping images. With the support of electrostatic simulations, it is shown that in-dark contact potential difference contrasts above subsurface acceptor clusters are consistent with an uneven distribution of permanent charges at the donor-acceptor interfaces. A remarkable dependence of the surface photovoltage magnitude with respect to the tip-surface distance is evidenced and attributed to a local enhancement of the electromagnetic field at the tip apex.

On the photo-induced charge-carrier generation within monolayers of self-assembled organic donor-acceptor dyads.

By means of STM and nc-AFM the self-assembly of a new donor-acceptor (DA) dyad molecule on highly oriented pyrolytic graphite is identified and compared to molecular simulations. Kelvin probe force microscopy (KPFM) measurements clearly show the photovoltaic activity of this model system under illumination. The optoelectronic properties and the local morphology of the DA dyad assembly are simultaneously probed by KPFM down to the level of one molecular monolayers.

Fast responding exhaled-breath sensors using WO3 hemitubes functionalized by graphene-based electronic sensitizers for diagnosis of diseases.

Diagnostic sensing device using exhaled breath of human have critical advantages due to the noninvasive diagnosis and high potential for portable device with simple analysis process. Here, we report ultrafast as well as highly sensitive bumpy WO3 hemitube nanostructure assisted by O2 plasma surface modification with functionalization of graphene-based material for the detection of acetone (CH3COCH3) and hydrogen sulfide (H2S) which are biomarkers for the diagnosis of diabetes and halitosis, respectively. 0.1 wt % graphene oxide (GO)- and 0.1 wt % thin layered graphite (GR)- WO3 hemitube composites showed response times of 11.5 ± 2.5 s and 13.5 ± 3.4 s to 1 ppm acetone as well as 12.5 ± 1.9 s and 10.0 ± 1.6 s to 1 ppm of H2S, respectively. In addition, low limits of detection (LOD) of 100 ppb (Rair/Rgas = 1.7 for acetone and Rair/Rgas = 3.3 for H2S at 300 °C) were achieved. The superior sensing properties were ascribed to the electronic sensitization of graphene based materials by modulating space charged layers at the interfaces between n-type WO3 hemitubes and p-type graphene based materials, as identified by Kelvin Probe Force Microscopy (KPFM). Rapid response and superior sensitivity of the proposed sensing materials following cyclic thermal aging demonstrates good potential for real-time exhaled breath diagnosis of diseases.

On the transfer of cooperative self-assembled π-conjugated fibrils to a gold substrate.

The transfer of the cooperative self-assembled fibrils to a gold substrate has been studied by means of scanning probe microscopy techniques revealing the crucial role of the early formation of a monolayer.