Photothermal Deflection Spectroscopy Measurements Research Articles

Rapid Microwave Annealing for Improved Crystallinity and Morphology of Perovskite Materials

Perovskite solar cells are gaining significant attention for their remarkable power conversion efficiency, cost‐effective processing, and material abundance. This study investigates the impact of rapid microwave annealing on the crystallinity and morphology of MAPbI3 films on FTO glass substrates. Multifaceted characterization techniques, including field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), UV–Vis spectroscopy, photothermal deflection spectroscopy (PDS), and steady‐state photoluminescence (PL) measurements are used to compare microwave‐annealed samples with traditional hotplate‐annealed samples. Microwave annealing yields significantly larger crystals in shorter processing times, suggesting enhanced crystallinity, as evidenced by SEM analysis and XRD data. UV‐Vis and PDS measurements indicate improved optical properties and reduced sub‐bandgap states, while PL results suggest diminished nonradiative recombination in microwave‐annealed samples. However, a partial film detachment has been observed at higher microwave powers, a phenomenon explained by COMSOL simulations. These findings demonstrate rapid microwave annealing as an energy‐efficient and cost‐effective alternative while highlighting the need for further optimization to address film degradation issues, which remain a significant challenge. This research supports the potential for scalable, high‐quality perovskite material production, facilitating large‐scale production and commercialization of next‐generation solar cells.

Refining Photothermal Deflection Spectroscopy: Incorporating Reflectance for Enhanced Accuracy in Light‐Absorption Measurements

A method for measuring light absorption using photothermal deflection spectroscopy (PDS) is investigated. Typical reflectance and transmittance (R & T) absorption measurements have low spectral resolution (SR) with standard setups. It is believed that absorption measurements using PDS solve this problem because of its high sensitivity, even at a high SR. However, accurate absorption measurements have not been obtained using conventional PDS. The reflectance of the sample must be considered in the absorptance calculations. Various absorption measurement methods are compared and a novel calculation method for accurate PDS absorption measurements is proposed. A sample with quantum structures is fabricated and PDS measurements are performed. Exciton absorption peaks are also observed. The high SR of PDS is demonstrated and the measured exciton absorption peaks are confirmed using piezoelectric photothermal measurements. Furthermore, it is confirmed that the absolute values of absorptance derived from the R & T and PDS measurements agree well. The new PDS absorption measurement technique enables to obtain accurate absorption characteristics, which are indispensable for designing and optimizing optoelectronic devices.

Structural properties of graded In x GaAs metamorphic buffer layers for quantum dots emitting in the telecom bands

In recent years, there has been a significant increase in interest in tuning the emission wavelength of InAs quantum dots (QDs) to wavelengths compatible with the already existing silica fiber networks. In this work, we develop and explore compositionally graded In x GaAs metamorphic buffer layers (MBLs), with lattice constant carefully tailored to tune the emission wavelengths of InAs QDs towards the telecom O-band. The designed heterostructure is grown by molecular beam epitaxy (MBE), where a single layer of InAs QDs is grown on top of the MBL and is capped with a layer having a fixed indium (In) content. We investigate the structural properties of the grown MBLs by reciprocal space mapping, as well as transmission electron microscopy, and verify the dependence of the absorption edge of the MBL on the In-content by photothermal deflection spectroscopy measurements. This allows us to identify a growth temperature range for which the MBLs achieve a near-equilibrium strain relaxation for In-content up to ∼30. Furthermore, we explore the emission wavelength tunability of QDs grown on top of a residual strained layer with a low density of dislocations. Specifically, we demonstrate a characteristic red-shift of the QD photoluminescence towards the telecom O-band (1300 nm) at low temperature. This study provides insights into the relaxation profiles and dislocation propagation in compositionally graded MBLs grown via MBE thus paving the way for realizing MBE-grown heterostructures containing InAs QDs for advanced nanophotonic devices emitting in the telecom bands.

KSEMAW: an open source software for the analysis of spectrophotometric, ellipsometric and photothermal deflection spectroscopy measurements.

The optical behavior of devices based on thin films is determined by complex refractive index and thickness of each slab composing the stack; these important parameters are usually evaluated from photometric and/or ellipsometric spectral measurements, given a model of the stack, by means of dedicated software. In the case of complex multilayer devices, generally a number of simpler specimens (like single-film on substrate) must be preliminarily characterized. This paper introduces the reader to a new open source software for thin film characterization finally released after about 30 years of development. The software has already been used in various fields of physics, such as thin film optical filters, architectural glazing, detectors for high energy physics, solar energy, and, last but not least, photovoltaic devices. Code source files, MS Windows executable, user manual as well as a sample of working directories populated with assorted files can be freely downloaded from the kSEMAW GitHub repository.

Exploration of sub-bandgap states in 2D halide perovskite single-crystal photodetector

Greater stability of low-dimensional halide perovskites as opposed to their three-dimensional counterparts, alongside their high extinction coefficient and thus excellent emission properties, have made them popular candidates for optoelectronic applications. Topological edges are found in two-dimensional perovskites that show distinct electronic properties. In this work, using Kelvin Probe Force Microscopy, performed on butylammonium lead bromide (BA2PbBr4) single crystals with optical bandgap of ~413 nm, we elucidate the electronic response of the edges and their potential impact on photodetector devices. We show that the charge-carriers are accumulated at the edges, increasing with the edge height. Wavelength-dependent surface photovoltage (SPV) measurements reveal that multiple sub-bandgap states exist in BA2PbBr4. As the edge height increases, the SPV amplitude at the edges reduces slightly more as compared to the adjacent regions, known as terraces, indicating relatively less reduction in band-bending at the surface due possibly to increased de-population of electrons from sub-bandgap states in the upper bandgap half. The existence of sub-bandgap states is further confirmed by the observation of below-bandgap emission (absorption) peaks characterised by spectral photoluminescence and photothermal deflection spectroscopy measurements. Finally, we fabricated a photodetector using a millimetre size BA2PbBr4 single crystal. Noticeable broadband photodetection response was observed in the sub-bandgap regions under green and red illumination, which is attributed to the existence of sub-bandgap states. Our observations suggest edge-height dependence of charge-carrier behaviour in BA2PbBr4 single crystals, a potential pathway that can be exploited for efficient broadband photodetector fabrication.

Single-Crystalline Germanium Nanocrystals via a Two-Step Microwave-Assisted Colloidal Synthesis from GeI4.

Colloidal germanium (Ge) nanocrystals (NCs) are of great interest with possible applications for photovoltaics and near-IR detectors. In many examples of colloidal reactions, Ge(II) precursors are employed, and NCs of diameter ∼3-10 nm have been prepared. Herein, we employed a two-step microwave-assisted reduction of GeI4 in oleylamine (OAm) to prepare monodispersed Ge NCs with a size of 18.9 ± 1.84 nm. More importantly, the as-synthesized Ge NCs showed high crystallinity with single-crystal nature as indicated by powder X-ray diffraction, selected area electron diffraction, and high-resolution transmission electron microscopy. The Tauc plot derived from photothermal deflection spectroscopy measurement on Ge NCs thin films shows a decreased bandgap of the Ge NCs obtained from GeI4 compared with that of the Ge NCs from GeI2 with a similar particle size, indicating a higher crystallinity of the samples prepared with the two-step reaction from GeI4. The calculated Urbach energy indicates less disorder in the larger NCs. This disorder might correlate with the fraction of surface states associated with decreased particle size or with the increased molar ratio of ligands to germanium. Solutions involved in this two-step reaction were investigated with 1H NMR spectroscopy and high-resolution mass spectrometry (MS). One possible reaction pathway is proposed to unveil the details of the reaction involving GeI4 and OAm. Overall, this two-step synthesis produces high-quality Ge NCs and provides new insight on nanoparticle synthesis of covalently bonding semiconductors.

Thick‐Film Low Driving‐Force Indoor Light Harvesters

Organic indoor light harvesters require large‐area active layers for power‐greedy internet of thing (IoT) things due to much weaker light emissions from indoor sources than the standard 1‐Sun case. This presents new challenges for the thick‐film indoor photovoltaic (IPV) device fabrication to meet the requirements of current leading roll‐to‐roll (R2R) techniques. Herein, a concept of low driving‐force bulk heterojunction (BHJ) into the IPV field is introduced, and a P3TEA:FTTB‐PDI4 solar cell is demonstrated with negligible energy offset between donor and acceptor materials for the electron transport that can achieve high efficiencies over 20% in the thick‐film region, which is comparable with their optimized thin‐film counterpart. In the low driving‐force P3TEA:FTTB‐PDI4 BHJ film, negative Poole–Frenkel (PF) effect of the electron transport can be observed. Such an effect originates from alternative electron pathways opened up by the donor polymer P3TEA. The negative PF effect results in improved electron extraction in the thick‐film BHJs, leading to comparable fill factors (FFs) and efficiencies of thick‐film and thin‐film devices. From the photothermal deflection spectroscopy measurement, similar but low Urbach energy values of the low driving‐force BHJ and the neat acceptor film are observed, indicating reduced defect states for the electron transport in such low driving‐force devices.

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States.

We report quantum chemical calculations using multireference perturbation theory (MRPT) with the density matrix renormalization group (DMRG) plus photothermal deflection spectroscopy measurements to investigate the manifold of carotenoid excited states and establish their energies relative to the bright state (S2) as a function of nuclear reorganization. We conclude that the primary photophysics and function of carotenoids are determined by interplay of only the bright (S2) and lowest-energy dark (S1) states. The lowest-lying dark state, far from being energetically distinguishable from the lowest-lying bright state along the entire excited-state nuclear reorganization pathway, is instead computed to be either the second or first excited state depending on what equilibrium geometry is considered. This result suggests that, rather than there being a dark intermediate excited state bridging a non-negligible energy gap from the lowest-lying dark state to the lowest-lying bright state, there is in fact no appreciable energy gap to bridge following photoexcitation. Instead, excited-state nuclear reorganization constitutes the bridge from S2 to S1, in the sense that these two states attain energetic degeneracy along this pathway.

Key signal contributions in photothermal deflection spectroscopy

We report on key signal contributions in photothermal deflection spectroscopy (PDS) of semiconductors at photon energies below the bandgap energy and show how to extract the actual absorption properties from the measurement data. To this end, we establish a rigorous computation scheme for the deflection signal including semianalytic ray tracing to analyze the underlying physical effects. The computation takes into account linear and nonlinear absorption processes affecting the refractive index, thus leading to a deflection of the probe beam. We find that besides the linear mirage effect, nonlinear absorption mechanisms make a substantial contribution to the signal for strongly focused pump beams and sample materials with high two-photon absorption coefficients. For example, the measured quadratic absorption contribution exceeds 5% at a pump beam intensity of about 1.3×105W/cm2 in Si and at 5×104W/cm2 in GaAs. In addition, our method also includes thermal expansion effects as well as spatial gradients of the attenuation properties. We demonstrate that these effects result in an additional deflection contribution that substantially depends on the distance of the photodetector from the readout point. This distance dependent contribution enhances the surface related PDS signal up to two orders of magnitude and may be misinterpreted as surface absorption if not corrected in the analysis of the measurement data. We verify these findings by PDS measurements on crystalline silicon at a wavelength of 1550 nm and provide guidelines on how to extract the actual attenuation coefficient from the PDS signal.

Impact of surface dipole in NiOx on the crystallization and photovoltaic performance of organometal halide perovskite solar cells

Despite the success of solution processed nickel oxide (s-NiOx) as the hole transporting layer (HTL) in organic solar cells, applying s-NiOx in perovskite solar cells (PVSCs) is not that straight forward. The reported power conversion efficiencies (PCEs) of the s-NiOx based PVSCs span a wide range from 8% to over 20% even with a similar recipe. Here, we report that one of the causes for the performance discrepancy might be the large surface dipole on the s-NiOx surface. We find that the perovskite deposited on the as-prepared sol-gel derived s-NiOx has large number of defects at the s-NiOx/perovskite interface. Based on the in-depth mechanism study with various spectroscopy techniques, we propose that the strong surface dipole of the s-NiOx composite film induces adhesion of perovskite precursor ions on the surface of s-NiOx during the perovskite film formation and creates defects in the perovskite crystals at the interface. Such interfacial dipole-ion attachment has been demonstrated can be dissociated by ultraviolet (UV) light soaking experiment. The high energy of the UV light helps to dissociate the physical dipole-ion attachment and mobilize the ions to accommodate the perovskite defect sites. The defect density of the perovskite film on s-NiOx has been significantly reduced by an amount of 4.1 × 1017 cm−3 after the UV light soaking as evidenced by photothermal deflection spectroscopy (PDS) measurement. By treating the s-NiOx surface with a dipolar molecule n-Butylamine, the surface dipole of the s-NiOx film is efficiently reduced and it significantly reduces the defect density in the perovskite film. As a result, the PVSCs based on the n-Butylamine treated s-NiOx layer have achieved a dramatical enhancement in PCE to 18.9% with decent stability at the maximum power point tracking. It is believed that this work provides insight and strategy to develop highly reproducible PVSCs with solution derived metal oxide as interlayers.

Atmospherically induced defects in (FASnI3)0.6(MAPbI3−3xCl3x)0.4 perovskites

The effects of brief atmospheric exposure are assessed for mixed composition perovskites comprised of a combination of formamidinium tin iodide (FASnI3) and methylammonium lead iodide + chloride (MAPbI3−3xCl3x) as well as MA0.7FA0.3PbI3 perovskite for use as absorber layers in high-efficiency thin film solar cells. Photothermal deflection spectroscopy (PDS) is employed to probe the relative defect density of all films by way of extracting the Urbach energy characterizing the width of the sub-bandgap absorption tail. Exposure to atmosphere for ~3 min prior to PDS measurement is found to degrade mixed composition films such that exposed films had an average increase of 36% in Urbach energies compared to those that are fully kept out of atmosphere through immersion in inert C6F14 liquid. By contrast, the same exposure to atmosphere induced no change in Urbach energy for MA0.7FA0.3PbI3. These results demonstrate the influence of ambient exposure on perovskites, particularly those containing Sn, and highlight the fact that handling procedure itself throughout all fabrication and subsequent characterization steps influences the measured results.

Charge transfer-induced photoluminescence in ZnO nanoparticles.

The quality of solution-processed zinc oxide (ZnO) nanoparticles (NPs) is often correlated with their photoluminescence (PL) spectral characteristics. However, the reported PL spectral characteristics lack consistency and remain controversial. Here we report that "defect-emission free" PL spectra can even be obtained in thin films composed of as-synthesized ZnO NPs. It is found that both the PL spectral line-shape and intensity are extremely sensitive to nitrogen and oxygen. By conducting time-dependent PL (t-PL) and photothermal deflection spectroscopy (PDS) measurements under vacuum and different gases, it is proposed that both inert (N2) and reactive (O2) molecules can be absorbed on the ZnO NP surface and induce charge transfer (CT). The CT states induced by N2 are non-radiative which significantly reduces the band emission. Whereas the CT states induced by O2 are radiative at the visible region, and the exciton transfer is efficient which increases the overall PL quantum yield. Owing to such effects, the previously reported correlation between defects and PL emission becomes questionable and needs to be revisited. Particularly, the visible emission from the ZnO NPs is proved to be facilitated by external effects, instead of direct recombination from defect states.

A simple method to measure intermolecular charge-transfer absorption of organic films

Abstract Intermolecular charge transfer (CT) complexes of organic molecules are actively researched due to their wide use and strong influence on organic optoelectronic device performance. In previous studies, exciplexes, excited-state intermolecular CT complexes, failed to show absorption in ultraviolet-visible-near-infrared absorption spectroscopy measurements. Recently, however, direct exciplex CT absorption from the ground state of donor-acceptor mixed films was detected in the sub-bandgap region by Fourier transform photocurrent spectroscopy (FTPS) and photothermal deflection spectroscopy (PDS) measurements. Here, we report a simple method to measure intermolecular CT absorption that combines simple reflection–transmission and ellipsometry measurements of thick films to determine the extinction coefficient for the small-molecular CT state. The extinction coefficients extracted from different film thicknesses were consistent, up to 10−4 in the sub-bandgap wavelength region, comparable to that obtained with PDS executed on thin films.

Radiative Efficiency Limit with Band Tailing Exceeds 30% for Quantum Dot Solar Cells

Thin films of colloidal quantum dots (QDs) are promising solar photovoltaic (PV) absorbers in spite of their disordered nature. Disordered PV materials face a power conversion efficiency limit lower than the ideal Shockley–Queisser bound because of increased radiative recombination through band-tail states. However, investigations of band tailing in QD solar cells have been largely restricted to indirect measurements, leaving their ultimate efficiency in question. Here we use photothermal deflection spectroscopy (PDS) to robustly characterize the absorption edge of lead sulfide (PbS) QD films for different bandgaps, ligands, and processing conditions used in leading devices. We also present a comprehensive overview of band tailing in many commercial and emerging PV technologies—including c-Si, GaAs, a-Si:H, CdTe, CIGS, and perovskites—then calculate detailed-balance efficiency limits incorporating Urbach band tailing for each technology. Our PDS measurements on PbS QDs show sharp exponential band tails, w...

On the way to enhance the optical absorption of a-Si in NIR by embedding Mg2Si thin film

Mg2Si thin film was embedded in amorphous silicon matrix by solid phase epitaxy. The structure and optical properties were investigated by electron energy loss, X-ray photoelectron, Raman, and photo thermal deflection spectroscopy measurements. It was found that in the photon energy range of 0.8–1.7 eV, the light absorption of the structure with magnesium silicide (Mg2Si) film embedded in a-Si(i) matrix is 1.5 times higher than that for the same structure without Mg2Si.

Thermal characterization of Li-ion cell electrodes by photothermal deflection spectroscopy

Contactless and temperature-dependent evaluation of thermal diffusivities of Li-ion cell electrodes based on photothermal deflection spectroscopy (PDS) measurements is introduced and applied to electrodes from three prismatic hardcase Li-ion cells. The accuracy of the method is validated using reference materials, which cover a wide range of thermal diffusivity. The effective thermal diffusivities of the three anode and cathode coatings and of the current collectors are determined in the temperature range of 5–45 °C.Furthermore, the temperature-dependent specific heat capacity of the electrodes is evaluated by differential scanning calorimetry (DSC) measurements in the same temperature range. Based on the experimental results the through-plane and in-plane thermal conductivity of the electrodes is calculated and compared to previously reported values. The results indicate significant influence of the porosity and manufacturing process on the effective thermal conductivity of the electrodes. The three mayor impact factors on thermal conductivity of electrodes are (i) composition, (ii) morphology of the coating and (iii) the thickness ratio of coating to current collector.

Photothermal deflection investigation of thermally oxidized mesoporous silicon

In this paper we investigate the thermal oxidation effect on optical and thermal properties of meso-porous silicon (meso-PS) layers using photoluminescence (PL) and photothermal deflection techniques (PDS, PTD). Samples have been successfully prepared by electrochemical anodization process. After a pre-oxidation for 1h 30min at 300°C, layers are thermally oxidized in dry oxygen at different temperatures (800, 1000°C) and durations. PL measurements show that the annealed layers have comparable spectra with a peak position focused on 2.1eV. This behavior indicates the formation of luminescent silicon (Si) nanocrystallites with comparable average sizes. From the effective mass theory, the diameter of those nanocrystallites is estimated to be around 2.2nm. Another estimation of the mean size of the silicon nanocrystallites obtained from the evolution of the thermal conductivity of the meso-PS layers based on photothermal deflection technique (PTD) data was close to the values obtained from the PL results. Photothermal deflection spectroscopy (PDS) measurements show that the thermal oxidation affects the absorption edge of the Si substrate. The optical band gap energy of the started substrates determined from the Tauc's relation is observed to increase with the thermal temperature and duration. The possible origins of this shift are discussed.

Separation of semiconducting and ferromagnetic FeSi2-nanoparticles by magnetic filtering

We have investigated the potential of solution-processed β-phase iron disilicide (FeSi2) nanoparticles as a novel semiconducting material for photovoltaic applications. Combined ultraviolet-visible absorption and photothermal deflection spectroscopy measurements have revealed a direct band gap of 0.85 eV and, therefore, a particularly high absorption in the near infrared. With the help of Fourier-transform infrared and X-ray photoelectron spectroscopy, we have observed that exposure to air primarily leads to the formation of a silicon oxide rather than iron oxide. Mössbauer measurements have confirmed that the nanoparticles possess a phase purity of more than 99%. To diminish the small fraction of metallic iron impurities, which were detected by superconducting quantum interference device magnetometry and which would act as unwanted Auger recombination centers, we present a novel concept to magnetically separate the FeSi2 nanoparticles (NPs). This process leads to a reduction of more than 95% of the iron impurities.

CZTS stoichiometry effects on the band gap energy

Abstract The considerable spread of Cu2ZnSnS4 (CZTS) optical properties reported in the literature is discussed in terms of material stoichiometry. To this purpose, kesterite thin films were prepared by sulfurization of multilayered precursors of ZnS, Cu and Sn, changing the relative amounts to obtain CZTS layers with different compositions. X-Ray Diffraction (XRD), Energy Dispersive X-Ray (EDX) spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Raman spectroscopy were used for structural and compositional analysis. XRD quantitative phase analysis provides the amount of spurious phases and information on Sn-site occupancy. The optical properties were investigated by spectrophotometric and Photothermal Deflection Spectroscopy (PDS) measurements to assess the absorption coefficient of samples with different compositions. The PDS data show an increase of the sub-band absorption as the Sn content decreases. The results are interpreted assuming the formation of additional defects as the tin content is reduced. Those defects can also be responsible for the decrease of the band gap energy value as the Sn/Cu ratio is decreased.

Optical detection of deep electron traps in poly(p-phenylene vinylene) light-emitting diodes

The trap-limited electron currents in poly(p-phenylene vinylene) (PPV) derivatives can be modeled using a Gaussian trap distribution that is positioned approximately 0.75 eV below the lowest unoccupied molecular orbital (LUMO) of PPV. Photothermal deflection spectroscopy measurements and internal photo-emission spectroscopy measurements confirm the claim of a Gaussian shaped trap distribution centered at 0.75 eV below the LUMO of PPV. Additionally, two PPV derivatives that differ in the number of conformational defects incorporated during synthesis exhibit identical electron trapping behavior, showing that the traps do not originate from extrinsic impurities of the synthesis or defects in the polymer chains.