The TiO2 films are prepared by atomic layer deposition (ALD) method using titanium
isopropoxide precursors at 250 °C and analyzed using resonant photoemission spectroscopy (resPES). We report on the Ti2p and O1s core levels, on the valence band (VB) spectra and
x-ray absorption spectroscopy (XAS) data, and on the resonant photoelectron spectroscopy (resPES) profiles at the O1s and the Ti3p absorption edges. We determine the elemental
abundance, the position of the VB maxima, the partial density of states (PDOS) in the VB and in the conduction band (CB) and collect these data in a band scheme. In addition, we analyze the band-gap states as well as the intrinsic states due to polarons and charge-transfer
excitations. These states are found to cause multiple Auger decay processes upon resonant
excitation. We identify several of these processes and determine their relative contribution to the Auger signal quantitatively. As our resPES data allow a quantitative analysis of these defect states, we determine the relative abundance of the PDOS in the VB and in CB and also the charge neutrality level.
The anatase and rutile polymorphs of TiO2 are analyzed in the same way as the TiO2 ALD layer. The electronic properties of the TiO2ALD layer are compared with the anatase and rutile polymorphs of TiO2. In our comparative study, we find that ALD has its own
characteristic electronic structure that is distinct from that of anatase and rutile. However, many details of the electronic structure are comparable and we benefit from our spectroscopic
data and our careful analysis to find these differences. These can be attributed to a stronger hybridization of the O2p and Ti3d4s states for the ALD films when compared to the anatase and rutile polymorphs.
We study the electronic structure of ultrathin Al₂O₃, HfO₂, and TiO₂ ALD films by resonant photoelectron spectroscopy. We identify intrinsic defects which are responsible for the active sites in interface reactions, for the incorporation of intrinsic charges, and for the formation of local dipole momenta. All of these features determine the surface potentials and the reactivity of the surface of the atomic layer deposition coated systems. We give examples of charges and dipoles in Al₂O₃, on a study of the surface potentials in HfO₂, and relate the intrinsic defects in TiO₂ to their electrochemical relevance.
Atomic Layer-Deposited Aluminum Oxide Hinders Iodide Migration and Stabilizes Perovskite Solar Cells
(2020)
Iodide migration causes degradation of the perovskite solar cells. Here,we observe the direct migration of iodide into the hole-transport
layer in a device. We demonstrate that ultrathin room temperature
atomic layer-deposited Al2O3 on the perovskite surface very effectively hinders the migration. The perovskite-Al2O3 interface enables charge transfer across the Al2O3 layer in the solar cells, without causing any drastic changes in the properties of the perovskite absorber. Furthermore, it helps to preserve the initial properties of the perovskite film during exposure to light and air under real operating conditions, and thus, improves the stability of the solar cells. The ultrathin Al2O3 layer deposited at room temperature significantly increases the lifetime of the perovskite solar cells, and we hope this may be a step toward the mass production of stable devices.
Band Bending at Hole Transporting Layer-Perovskite Interfaces in n-i-p and in p-i-n Architecture
(2022)
Interfaces between hybrid perovskite absorber and its adjacent charge-transporting layers are of high importance for solar cells performance. Understanding their chemical and electronic properties is a key step in designing efficient and stable perovskite solar cells. In this work, the tapered cross-section photoemission spectroscopy (TCS-PES) method is used to study the methylammonium lead iodide (CH3NH3PbI3) (MAPI)-based solar cells in two configurations, that is, in an inverted p–i–n and in a classical n–i–p architecture. It is revealed in the results that the MAPI film deposited once on the n-type TiO2 and once on the p-type NiOx substrates is neither an intrinsic semiconductor nor adapts to the dopant nature of the substrate underneath, but it is heavily n-type doped on both substrates. In addition to that, the TCS-PES results identify that the band bending between the MAPI film and the hole transporting layer (HTL) layer depends on the perovskite solar cells architecture. In particular, a band bending on the HTL side in the n–i–p and at the MAPI in the p–i–n architecture is found. The flat band of NiOx at the NiOx/MAPI interface can be explained by the Fermi level pinning of the NiOx at the interface.
In this work we have utilized near-ambient pressure and ultra-high vacuum X-ray photoelectron spectroscopy as well as atomic layer deposition to investigate perovskite solar cells (PSCs). We have demonstrated that ultrathin room temperature atomic layer-deposited aluminium oxide on the perovskite surface very effectively suppresses iodine migration[1] and improves the long term stability and efficiency of PSCs [2,3]. Furthermore, exposure to light proves more detrimental to the perovskite film than exposure to water vapor.[2] Absorbed photons create Frenkel defects in the perovskite crystal and their number strongly depends on the used illumination. The higher the photon flux, the higher the concentration of Frenkel defects, and thus the stronger the degradation of power conversion efficiency and the stronger the hysteresis in the J-V characteristics. [1] C. Das, M. Kot et al., Cell Reports Physical Science 2020, 1, 100112. [2] M. Kot et al., ChemSusChem 2020, 13, 5722. [3] M. Kot et al., ChemSusChem 2018, 11, 3640.
Interface engineering is a common strategy for passivating surface defects to attain open circuit voltages (Voc) in perovskite solar cells (PSCs). In this work, we introduce the concept of polishing a perovskite thin-film surface using a nanosecond (ns) pulsed ultraviolet laser to reduce surface defects, such as dangling bonds, undesirable phases, and suboptimal stoichiometry. A careful control of laser energy and scanning speed improves the photophysical properties of the surface without compromising the thickness. Using laser polishing, a Voc of 1.21 V is achieved for planar PSCs with a triple cation composition, showing an improved perovskite/hole transport interface by mitigating surface recombination losses. We measure an efficiency boost from 18.0% to 19.3% with improved stability of up to 1000 h. The results open the door to a new class of surface modification using lasers for interface passivation in well-controllable, automated, scalable, and solvent-free surface treatments.
Interfaces in perovskite solar cells play a crucial role in their overall performance, and therefore, detailed fundamental studies are needed for a better understanding. In the case of the classical n–i–p architecture, TiO2 is one of the most used electron-selective layers and can induce chemical reactions that influence the performance of the overall device stack. The interfacial properties at the TiO2/perovskite interface are often neglected, owing to the difficulty in accessing this interface. Here, we use X-rays of variable energies to study the interface of (compact and mesoporous) TiO2/perovskite in such a n–i–p architecture. The X-ray photoelectron spectroscopy and X-ray absorption spectroscopy methods show that the defect states present in the TiO2 layer are passivated by a chemical interaction of the perovskite precursor solution during the formation of the perovskite layer and form an organic layer at the interface. Such passivation of intrinsic defects in TiO2 removes charge recombination centers and shifts the bands upward. Therefore, interface defect passivation by oxidation of Ti3+ states, the organic cation layer, and an upward band bending at the TiO2/perovskite interface explain the origin of an improved electron extraction and hole-blocking nature of TiO2 in the n–i–p perovskite solar cells.
A study of the chemical and electronic properties of various layers across perovskite solar cell (PSC) stacks is challenging. Depth-profiling photoemission spectroscopy can be used to study the surface, interface, and bulk properties of different layers in PSCs, which influence the overall performance of these devices. Herein, sputter depth profiling (SDP) and tapered cross-sectional (TCS) photoelectron spectroscopies (PESs) are used to study highly efficient mixed halide PSCs. It is found that the most used SDP-PES technique degrades the organic and deforms the inorganic materials during sputtering of the PSCs while the TCS-PES method is less destructive and can determine the chemical and electronic properties of all layers precisely. The SDP-PES dissociates the chemical bonding in the spiro-MeOTAD and perovskite layer and reduces the TiO2, which causes the chemical analysis to be unreliable. The TCS-PES revealed a band bending only at the spiro-MeOTAD/perovskite interface of about 0.7 eV. Both the TCS and SDP-PES show that the perovskite layer is inhomogeneous and has a higher amount of bromine at the perovskite/TiO2 interface.
Room temperature atomic layer deposited Al₂O₃ improves perovskite solar cells efficiency over time
(2018)
Electrical characterisation of perovskite solar cells consisting of room-temperature atomic-layer-deposited aluminium oxide (RT-ALD-Al₂O₃) film on top of a methyl ammonium lead triiodide (CH₃NH₃PbI₃) absorber showed excellent stability of the power conversion efficiency (PCE) over along time. Under the same environmental conditions (for 355 d), the average PCE of solar cells without the ALD layer decreased from 13.6 to 9.6 %, whereas that of solar cells containing 9 ALD cycles of depositing RT-ALD-Al₂O₃on top of CH₃NH₃PbI₃ increased from 9.4 to 10.8 %. Spectromicroscopic investigations of the ALD/perovskite interface revealed that the maximum PCE with the ALD layer is obtained when the so-called perovskite cleaning process induced by ALD precursors is complete. The PCE enhancement over time is probably related to a self-healing process induced by the RT-ALD-Al₂O₃ film. This work may provide a new direction for further improving the long-term stability and performance of perovskite solar cells.
Valence band (VB) spectra of titanium dioxide (TiO2) and oxynitride (TiOxNy) films prepared by different atomic layer deposition (ALD) processes are compared and related to electrical characterization [current–voltage (JV) and capacitance–voltage (CV)] results. By increasing the nitrogen amount in the TiO2 film, band-gap narrowing is observed. The band-gap decrease is related to the contribution of the nitrogen density of states, which induces defects within the band-gap and thus reduces its optical band-gap. In-gap states are found in the VB spectra at 1 eV below the Fermi energy in all investigated ALD samples, i.e., in TiO2 as well as in TiOxNy films. An exponential correlation between leakage current density and in-gap state intensity is derived
by the combination of JV measurements and VB spectra, whereas the in-gap states seem to have no influence on hysteresis and fixed oxide charges found in the CV data. It is argued that the in-gap states in TiO2 and TiOxNy have an excitonic or polaronic origin. Both, band-gap narrowing and in-gap state intensity can be tuned by the ALD process selection and the variation of its parameters.
A systematic structural elucidation of the near-surface active species of the two remarkably active nickel phosphides Ni12P5 and Ni2P on the basis of extensive analytical, microscopic, and spectroscopic investigations is reported. The latter can serve as complementary efficient electrocatalysts in the hydrogen (HER) versus oxygen evolution reaction (OER) in alkaline media. In
the OER Ni12P5 shows enhanced performance over Ni2P due to the higher concentration of nickel in this phase, which enables the formation of an amorphous NiOOH/Ni(OH)2 shell on a modified multiphase with a disordered phosphide/phosphite core. The situation is completely reversed in the HER, where Ni2P displayed a significant improvement in electrocatalytic activity over Ni12P5 owing to
a larger concentration of phosphide/phosphate species in the shell. Moreover, the efficiently combined use of the two nickel phosphide phases deposited on nickel foam in overall electrocatalytic water splitting is demonstrated by a strikingly low cell voltage and high stability with pronounced current density, and these catalysts could be an apt choice for applications in commercial alkaline water electrolysis.
Ultra-small rock salt cobalt monoxide (CoO) nanoparticles were synthesized and subjected to partial oxidation (‘corrosion’) with ceric ammonium nitrate (CAN) to form mixed-valence CoOx(1 < x< 2) water oxidation catalysts. Spectroscopic, microscopic and analytical methods evidenced a structural reformation of cubic CoO to active CoOx with a spinel structure. The superior water oxidation activity of CoOx has been established in electrochemical water oxidation under alkaline conditions.
Electrochemical water oxidation with CoOx was recorded at a considerably low overpotential of merely 325 mV at a current density of 10 mA cm-2 in comparison to 370 mV for CoO. Transformation of both octahedral CoII and CoIII sites into amorphous Co(OH)2–CoOOH is the key to high electrochemical activity while the presence of a higher amount of octahedral CoIII sites in CoOx is imperative for an efficient oxygen evolution process.
A comparative study of thin titanium oxynitride (TiOxNy) films prepared by plasma enhanced atomic layer deposition using tetrakis(dimethylamino)titanium (TDMAT) and N2 plasma as well as titanium(IV)isopropoxide and NH3 plasma is reported. The comparison is based on the combination of Ti2p core level and valence band spectroscopy and current-voltage measurements. The TDMAT/N2 process delivers generally higher fractions of TiN and TiON within the Ti2p spectra of the films and stronger photoemissions within the bandgap as resolved in detail by high energy resolution synchrotron-based spectroscopy. In particular, it is shown that higher TiN contributions and in-gap emission intensities correlate strongly with increased leakage currents within the films and might be modified by the process parameters and precursor selection.
Platinum, being the most efficient and stable catalyst, is used in photoelectrochemical (PEC) devices. However, a minimal amount of Pt with maximum catalytic activity is required to be used to minimize the cost of production. In this work, we use an environmentally friendly, ost-effective, and less Pt-consuming method to prepare PEC devices for the hydrogen evolution reaction (HER). The Pt monolayer catalyst is selectively deposited on a Au-nanoisland-supported boron-doped p-type Si (100) photocathode. The PEC device based on the Si photocathode with an ultralow loading of the Pt catalyst exhibits a comparable performance for the HER to that of devices with a thick Pt layer. In addition, we demonstrate that by using a thin TiO2 layer deposited by atomic layer deposition photo-oxidation of the Si photocathode can be blocked resulting in a stable PEC performance.
An ultrathin Al₂O₃ film deposited on methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite has the capability to suppress the carrier recombination process and improve the perovskite solar cells efficiency
and stability. However, annealing at temperatures higher than 85°C degrades the CH₃NH₃PbI₃ perovskite film. The X-ray photoelectron spectroscopy study performed in this work indicates that it is possible to grow Al₂O₃ by atomic layer deposition on the perovskite at room temperature, however, besides pure Al₂O₃ some OH groups are found and the creation of lead and iodine oxides at the Al₂O₃/CH₃NH₃PbI₃ interface takes place.
It has been recently demonstrated that the photoactivity toward oxygen evolution of a number of n-type metal oxides can be substantially improved by a reductive electrochemical pretreatment. Such an enhancement has been primarily linked to the formation of low valent metal species that increase electrode conductivity. In this work, we report new insights into the electrochemical doping using highly ordered (110)-oriented hematite nanorods directly grown on FTO. The reductive pretreatment consists in applying negative potentials for a controlled period of time. Such a pretreatment was optimized in both potentiostatic and potentiodynamic regimes. We show that the optimized pretreatment enhances electrode conductivity due to an increase in charge carrier density. However, it additionally triggers changes in the morphologic, catalytic and electronic properties that facilitate the separation and collection of the photogenerated charge carriers causing an up to 8-fold enhancement in the photocurrent for water oxidation. The reductive pretreatment can be considered as a highly controllable electrochemical n-type doping with the amount of generated Fe2+/polaron species and the change in film morphology as the main factors determining the final efficiency for water photooxidation of the resulting electrodes.
Alkaline electrochemical water oxidation with multi-shelled cobalt manganese oxide hollow spheres
(2017)
Multi-shelled hollow spheres of cobalt manganese oxides (CMOs) deposited on Ni foam exhibited superior alkaline electrochemical water oxidation activity and surpassed those of bulk CMO and commercial noble metal-based catalysts. A higher amount of cobalt in the spinel structure resulted in the transformation of the tetragonal to the cubic phase with a decrease in the overpotential of oxygen evolution.
Titanium oxynitride films are prepared by plasma enhanced atomic layer deposition method using two different precursors and nitrogen sources. Synchrotron radiation-based X-ray photoelectron spectroscopy and X-ray absorption spectroscopy are used to characterize the nitrogen species incorporated
within these films depending on the deposition parameters.
It is found that nitrogen atoms in these films are differently bonded. In particular, it can be distinguished between Ti-ON and Ti-N bonding configurations and molecular nitrogen species caused by precursor fragments.
Organic-inorganic lead halide perovskites have emerged as very attractive absorber materials for the fabrication of low cost and high efficiency solar cells, but a delicate nature of these films is one of the main challenges for a successful commercialization. Typically, when exposed to air or moisture, perovskite films degrade within a couple of hours or days. Moreover, the methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite cannot sustain a prolonged annealing at temperatures around 85∘C. In this work, we are investigating stability (upon air and thermal exposure) of a CH₃NH₃PbI₃ perovskite film coated with a thin layer of Al₂O₃ deposited by atomic layer deposition
(ALD). In particular, the chemical and electronic changes occurred at the Al₂O₃/CH₃NH₃PbI₃ interface during the first 50 ALD cycles were monitored ex-situ by high-resolution and surface-sensitive synchrotron-based X-ray photoelectron spectroscopy (SR-XPS). The advantage of the ALD as a deposition method is that it can produce extremely dense layers with a very precise thickness control at room temperature. Detailed SR-XPS data analysis and a stability test of the perovskite film with alumina will be presented.
The photoelectrochemical (PEC) water splitting is one of the most efficient ways to obtain hydrogen from water using solar power which can be used as carbon free fuel. The PEC device can bedesigned using semiconducting material that will convert solar radiation to H2. Silicon can be one of the best choices for PEC due to its success in solar cells technology. There are certain issues with Si such as stability in electrochemical medium [1] and higher surface reflectance (25%) which limits the Si as an ideal candidate for PEC technique [2]. In the present work we addressed these issues by surface structuring and laminating the surface with metal oxide. The microstructuring of Si was done by electrochemical method. The Si microstructure photocathode was stabilized by thin layer of ALD grown TiO2 film. The microstructuring and lamination of Si photocathode by ALD layer of TiO2 decreased the reflectance ofthe surface and shift the onset potential towards anodic direction by 350 mV with a prolonged stability over 60 hours[3]. [1] C. Levy-Clement, J. Electrochem. Soc 1991, 12, 69 [2] J. Oh, et al. Energy Environ. Sci., 2011, 4, 1690 [3] C. Das, et al. Nanoscale
2015,7, 7726
Atomic layer deposition of Al2O3 on CH3NH3PbI3 for enhancement of perovskite solar cells stability
(2016)
Engineering of Sub-Nanometer SiOₓ Thickness in Si Photocathodes for Optimized Open Circuit Potential
(2016)
Silicon is one of the most promising materials to be used for tandem-cell water-splitting devices. However, the electrochemical instability of bare Si makes it difficult to be used for stable devices. Besides that, the photovoltage loss in Si, caused by several factors (e.g., metal oxide protection layer and/or SiO₂/Si or catalyst/Si interface), limits its use in these devices. In this work, we present that an optimized open circuit potential (OCP) of Si can be obtained by controlling the SiOₓ thickness in sub-nanometer range. It can be done by means of a simple and cost-effective way using the combination of a wet chemical etching and the low temperature atomic layer deposition (ALD) of TiO₂. We have found that a certain thickness of the native SiOₓ is necessary to prevent further oxidation of the Si photocathode during the ALD growth of TiO₂. Moreover, covering the Si photocathode with an ALD TiO₂ layer enhances its stability.
Over the past few years, a wide range of device architectures employing organic-inorganic metal halide perovskite absorbers has been reported, with efficiencies exceeding 20%. Despite the tremendous progress, a number of key issues must be resolved before the wide-spread com-
mercialization will be possible. Some of the primary challenges include lead toxicity, long-term stability, and fast degradation upon exposure to humid atmosphere. Recent computational and experimental studies suggest that hybrid metal-halide perovskites act as an ionic-electronic conductor. The study of vacancy-mediated migration of I−, Pb2+ and CH3NH3− ions and their relative activation energies suggests that migration of halide vacancies, to and from the interfaces in the solar cell during its operation, is the main conduction mechanism. In this work, we are presenting high resolution synchrotron-based spectroscopic study, which indicates that the contribution of nitrogen into the conduction mechanism of methyl ammonium lead iodide-based (CH3NH3PbI3) perovskite films should not be neglected. The N1s core level and resonant X-ray photoelectron spectroscopy at the N1s-egde of the CH3NH3PbI3 films are discussed in detail.
Ytterbium (Yb3+) assisted porous poly(vinylidene fluoride) (PVDF) composite film comprising flexible ferroelectretic nanogenerator (FTNG) is highlighted where traditional poling treatment is completely avoided. The piezoelectric output of FTNG is realized by the co-operative activity of self-polarized -CH2/-CF2 dipoles with porous electret-like structure in the composite film. Owing to extraordinary ferroelectric and dielectric properties, FTNG is acting as a highly efficient mechanical energy harvester. It is capable to capture several forms of abundant mechanical energy arising from humanfinger movements, machine vibrations and sound waves. As a proof of concept, under compressive deformation, FTNG is enable to instantly powers up several consumer electronics and thus provides a promising strategy for achieving self-powered electronic devices.
In this work, solar cells with a freshly made CH₃NH₃PbI₃ perovskite film showed a power conversion efficiency (PCE) of 15.4 % whereas the one with 50 days aged perovskite film only 6.1 %. However, when the aged perovskite was covered with a layer of Al₂O₃ deposited by atomic layer deposition (ALD) at room temperature (RT), the PCE value was clearly enhanced. X-ray photoelectron spectroscopy study showed that the ALD precursors are chemically active only at the perovskite surface and passivate it. Moreover, the RT-ALD-Al2O3-covered perovskite films showed enhanced ambient air stability.
Titanium oxide (TiO2) deposited by atomic layer deposition (ALD) is used as a protective layer in
photocatalytic water splitting system as well as a dielectric in resistive memory switching. The way
ALD is performed (thermally or plasma-assisted) may change the growth rate as well as the electronic properties of the deposited films. In the present work, the authors verify the influence of the ALD mode on functional parameters, by comparing the growth rate and electronic properties of
TiO2 films deposited by thermal (T-) and plasma-enhanced (PE-) ALD. The authors complete the
study with the electrical characterization of selected samples by means of capacitance–voltage and
current–voltage measurements. In all samples, the authors found a significant presence of Ti3+ states, with the lowest content in the PE-ALD grown TiO2 films. The observation of Ti3+ states
was accompanied by the presence of in-gap states above the valence band maximum. For films thinner than 10 nm, the authors found also a strong leakage current. Also in this case, the PE-ALD films showed the weakest leakage currents, showing a correlation between the presence of Ti3+ states and leakage current density.
Photoelectrochemical (PEC) water splitting is one of the most emerging fields for green energy generation and storage. Here we show a study of microstructured Si covered by a TiO2 nano-layer. The microstructures are prepared by galvanostatic selective etching of Si. The TiO2 nano-layer was deposited by atomic layer deposition (ALD) to protect the microstructured photocathode against corrosion. The obtained microstructured photocathode showed a shift in the onset potential of 400 mV towards the anodic direction compared to bare Si. The Si microstructures laminated with a nano-layer of TiO2 show stability over 60 hours of measurement.
Charakterisierung von TiO2-ALD-Schichten und deren Nutzung für die Passivierung von Si-Photokathoden
(2015)
Wir berichten zunächst über den Einfluss der Methode der Atomlagenabscheidung auf die TiO2-Schichteigenschaften. Insbesondere wird der Zusammenhang zwischen Ti3+- sowie Interbandzuständen mit elektrischen Kennlinien und deren Einfluss auf funktionale Schichteigenschaften diskutiert. Anschließend werden Mikrostrukturierung, Grenzflächen-Engineering und konforme Abscheidung einer TiO2-ALD-Schutzschicht effektiv zur Performance-Steigerung von p-Si-Photokathoden angewendet.
This thesis focuses on the deposition of thin TiO2 films on p-type Si using atomic layer deposition (ALD) technique, on the study of the electronic proprieties of the grown films and on the electrochemical characterization of TiO2/Si photoelectrodes. The deposition parameters, electronic properties and electrochemical performance and stability of the TiO2/Si samples are correlated.
The ALD technique is used to deposit TiO2 with two different precursors namely Titanium isopropoxide and Titanium methoxide onto Si substrates. Laboratory as well as synchrotron based X-ray spectroscopy techniques are used to characterize these films. The growth quality of the TiO2 ALD films is determined by analyzing X-Ray photoelectron spectroscopy (XPS) data in terms of stoichiometry, defect states and Ti3+:Ti4+ ratios. The ALD technique was modified with different heating arrangements to obtain various polymorphs of TiO2.
The ALD and anatase TiO2 films are characterized using synchrotron radiation to study their electronic properties and these films are compared with single crystal rutile TiO2. X-ray absorption spectroscopy (XAS) and resonant photoelectron spectroscopy (res-PES) measurements are performed with synchrotron radiation. XAS measurements are used to determine the polymorphs as well as the electronic structure of TiO2. Res-PES measurements are conducted at the O1s and Ti2p edges to study multiple hole Auger decay processes and polaronic and charge transfer states as well as to determine the electronic band gap of the TiO2 layers. One of the main findings of this thesis is the determination of the partial density of states (pDOS) of O and Ti in the conduction and valence band. The combination of the pDOS and the band edge positions obtained from res-PES measurements are used to calculate the charge neutrality level of the TiO2 polymorphs.
The photoelectrochemical measurements are conducted on bare-Si and TiO2/Si photoelectrodes. The electrochemical performance of these photoelectrodes is studied in electrolytes having pH values ranging from 1 to 13. The deposition of TiO2 on Si enhances the photoelectrochemical performance of the Si photoelectrode. The TiO2 increases the stability of the photoelectrode in all electrochemical media over 12 hours of experimental condition. Moreover, it is also observed that the TiO2/Si photoelectrode is less responsive to the pH value of the electrolyte. The electrochemical findings are explained on the basis of the electronic properties of the TiO2 layer. The electronic band gap obtained from spectroscopic measurement and the photoelectrochemical measurements are used to explain the performance and stability of the TiO2/Si photoelectrodes. The thesis also addresses the stability of Si microstructured photoelectrodes (SiMPs) prepared by an electrochemical method. The stability of the SiMPs deteriorates more rapidly than that one of the planar Si photoelectrode. However, using a protective ALD TiO2 layer on these SiMPs the overall performance is even more enhanced than on the TiO2/planar Si system.
Titanium dioxide is one of the metal oxides which have versatile application in different fields. The applications of TiO2 are in the field of cosmetics, electronics (memory resistive switching), dye, photonics and photocatalysis. In the present paper we study the resPES data of TiO2 films prepared by atomic layer deposition. The measurements are done in in-situ system at beam line U49/2-PGM2 in BESSY-II. The density of state in valence band and conduction band is obtained from the resonance photo electron spectroscopy (res-PES) of the O1s and the Ti2p edge. The data allow to determine the position of the VBM and CBM with respect to the Fermi energy. Also the existence of localized O2p and Ti2p derived states is deduced which appear in the gap. In addition we determine the charge neutrality level (CNL).The CNL is the position where the weight of the density of state from valence band and conduction band are equal. This is an important quantity for the discussion of interface properties.
We study the atomic layer deposition of TiO2 by means of X-ray absorption spectroscopy. The Ti precursor, titanium isopropoxide, was used in combination with H2O on Si/SiO2 substrates that were heated at 200 °C. The low growth rate (0.15 Å/cycle) and the in situ characterization permitted to follow changes in the electronic structure of TiO2 in the sub-nanometer range, which are influenced by quantum size effects. The modified electronic properties may play an important role in charge carrier transport and separation, and increase the efficiency of energy conversion systems.
The electronic properties of hematite were investigated by means of synchrotron radiation photoemission (SR-PES) and X-ray absorption spectroscopy (XAS). Hematite samples were exposed to trimethyl aluminum (TMA) pulses, a widely used Al-precursor for the atomic layer deposition (ALD) of Al2O3. SR-PES and XAS showed that the electronic properties of hematite were modified by the interaction with TMA. In particular, the hybridization of O 2p states with Fe 3d and Fe 4s4p changed upon TMA pulses due to electron inclusion as polarons. The change of hybridization correlates with an enhancement of the photocurrent density due to water oxidation for the hematite electrodes. Such an enhancement has been associated with an improvement in charge carrier transport. Our findings open new perspectives for the understanding and utilization of electrode modifications by very thin ALD films and show that the interactions between metal precursors and substrates seem to be important factors in defining their electronic and photoelectrocatalytic properties.
Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.
Among the various metal oxides TiO2 has been investigated because of its wide range of applications in various fields such as self-cleaning, photocatalysis, solar cell, water splitting, bio-implants. In order to increase its efficiency in water splitting and solar cell energy conversion, it is necessary to understand the crystal structure and electronic properties of thin films. Generally the process of synthesis may modify the electronic properties of TiO2. In the present work we show X-ray linear dichroism (XLD) measurements of TiO2 thin films of different polymorphs. Titania thin films were produced by atomic layer deposition (ALD) and were characterized in-situ with X-ray photoelectron and absorption spectroscopy at synchrotron radiation center BESSY-II. We found that that all titania phases show XLD at Ti-L and O-K edges, but the intensity of XLD is different for different phases. We discuss our data in terms of the partial density of states.
Silicon with a band gap of 1.1eV is an excellent candidate for visible photocatalytic water splitting. But p-type Si has a low quantum yield and are less efficient for water splitting [1]. It has been shown that preventing oxidation of Si surface can shift the onset potential for water reduction by about 300mV towards more positive [2]. We investigated in detail the influence of the SiO2 layer thickness on the onset potential for water splitting on Si photocathodes: we used p-type Si substrates covered with SiO2 layers of varying thickness. Then, we deposited a thin TiO2 film on using atomic layer deposition (ALD) to inhibit Si oxidation during the electrochemical experiment. In this way we could shift the onset potential up to 200mV, depending on the SiO2 thickness.
[1]E. L. Warren, S. W. Boettcher, M. G. Walter, H. A. Atwater, and N. S. Lewis: J. Phys. Chem. C 115 (2011) 594. [2]B. Seger, Anders B. Laursen, P. C. K. Vesborg, T. Pedersen, O. Hansen, S. Dahl, I. Chorkendorff, Angew. Chem. Int. Ed. 2012, 51, 9128
Nanostructured iron(III) oxide deposits are grown by chemical vapor deposition (CVD) at 400−500 °C on Si(100) substrates from
Fe(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA =
N,N,N′N′-tetramethylethylenediamine), yielding the selective formation of α-Fe2O3or the scarcely studiedε-Fe2O3 polymorphs under suitably optimized preparative conditions. By using Ti(OPr
i)4(OPri= iso-propoxy) and water asatomic layer deposition (ALD) precursors, we subsequently functionalized
the obtained materials at moderate temperatures (<300°C) by an ultrathin
titanomagnetite (Fe3−xTixO4) overlayer. An extensive multitechnique character-ization, aimed at elucidating the system structure, morphology, composition and
optical properties, evidenced that the photoactivated hydrophilic and photocatalytic behavior of the synthesized materials is dependent both on iron oxide phase composition and ALD surface modification. The proposed CVD/ALD hybrid synthetic approach candidates itself as a powerful tool for a variety of applications where semiconductor-based nanoarchitectures can benefit from the coupling with an ad hoc surface layer.
We prepare TiO₂film by ALD and study their electronic properties by soft X-ray absorption spectroscopy (XAS) and photoelectron spectroscopy. We focus on XAS and X-ray linear dichroism to indentify band onset and learn about local distortion of the Ti–O octahedral atomic and about defects which cause Ti-based electronic states within the band gap.
Considering numerous applications such as transparent conducting oxides, gas sensors, photovoltaic applications, deep UV photo detectors, field effect transistors and spintronics gallium oxide (Ga2O3) has earned quite a lot of focus recently. Various techniques have already been demonstrated to produce Ga2O3 naming evaporation, sputtering, pulsed laser deposition, chemical vapor deposition and atomic layer deposition (ALD). Among them, ALD gives the possibility of controlling the thickness at the atomic level, good step coverage and delivers dense and homogeneous films. In this contribution, we report on the growth of ALD Ga2O3 using trimethylgallium (TMG) and H2O as metal and oxygen precursors, respectively. We deposited thin Ga2O3 films on Si, TiO2, Al2O3 and RuO2 over a temperature range of 150-300°C and characterized them by X-ray photo emission spectroscopy and atomic force microscopy. From this study, we are able to discuss the influence of the temperature on the growth dynamics of Ga2O3 and its chemical composition.
Hydrogen fuel cells, being environmental friendly to produce energy, are a technology of future. One of the efficient ways to produce hydrogen is solar driven photocatalysis using semiconducting materials as photo electrodes. The choice of electrodes is a crucial factor and is done on the basis of photo corrosion stability, light absorption efficiency, and photocarrier lifetime. P-type Si can be used as photo cathode to produce H2 by direct photocatalysis. Si cathodes can be used in acidic electrolytes to have efficient photo catalytic activity but they are unstable in alkaline electrolytes. Therefore, to use both Si electrodes in the same electrolyte, their chemical stability should be extended over a wide range of pH. To this purpose we modified the surface of a p-type Si photocathode with very thin films of TiO2 grown by atomic layer deposition (ALD). We found that the modified Si cathode shows an increased photoresponse and a lower onset potential with respect to the pristine surface and an increased stability at various pH values.
Titanium dioxide is on the most studied material due to its wide range of applications in various fields such as self cleaning, photocatalysis, solar cell, water splitting, bio-implants, etc. In order to increase its efficiency in water splitting and solar cell, it is necessary to understand the crystal structure and electronic properties in thin films. In our approach we are investigating the X-ray linear dichroism (XLD) of thin layers of TiO2. XLD studies have been done in multiferroics, antiferromagnetic, and ferromagnetic materials, but a very less amount of work have been done in studying XLD effect of TiO2 thin films. These layers are grown by in-situ atomic layer deposition (ALD) system and are investigated with X-ray absorption spectroscopy (XAS) at BESSY II, Berlin. ALD is a promising technique to grow thin films on different substrates conveniently due to its uniform deposition property. XAS study will also help us to better understand the interfacial electronic properties of thin films of TiO2.
We show recent results of our in-situ investigations where the role of substrate chemistry in ALD is outlined. While the usual strategy to develop new properties of ALD films is to find new precursors or new procedures, the influence of substrate chemistry on the growth properties of ALD films has been often underestimated. This has principally a technical reason, as the usual characterization methods (QMS, FTIR, ellipsometry) are only weakly sensitive to the substrate, and a characterization of substrates before ALD is often not possible. Thanks to the use of in-situ characterization methods, including photoemission and X-ray absorption spectroscopy with synchrotron radiation, we are able to determine chemical properties of substrates before ALD and after either half or complete ALD cycles. The substrate chemistry influences the standard Al2O3 ALD with TMA and water [1,2], as well as the TiO2 ALD with TTIP and either water, O2 or O2-plasma.
[1] M. Tallarida, K. Kukli, M. Michling, M. Ritala, M. Leskelä and D. Schmeisser, Chem. Mater. 23, 3159 (2011);
[2] M. Tallarida, C. Adelmann, A. Delabie, S. van Elshocht, M. Caymax, and D. Schmeisser, Appl. Phys. Lett. 92, 042906 (2011).
The most efficient and stable perovskite solar cells (PSCs) are made from a complex mixture of precursors. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g., by vacuum, an airstream, or a so-called antisolvent. Unfortunately, most oversaturation triggers do not expel the lingering (and highly coordinating) dimethyl sulfoxide (DMSO), which is used as a precursor solvent, from the thin films; this detrimentally affects long-term stability. In this work, (the green) dimethyl sulfide (DMS) is introduced as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, MAPbI3 PSCs are processed, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of the strategy, DMS is tested for FAPbI3 as another composition, which shows higher efficiency of 23.5% compared to 20.9% for a device fabricated with chlorobenzene. This work provides a universal strategy to control perovskite crystallization using coordination chemistry, heralding the revival of perovskite compositions with pure DMSO.
Perovskite solar cells (PSCs) excel in achieving high open-circuit voltages (VOC) for narrow bandgaps (∼1.6 eV) but face challenges with wide-bandgap perovskites, like methylammonium lead trichloride (MAPbCl3) with a 3.03 eV bandgap. These materials are transparent in visible absorbing ultraviolet (UV) light. However, achieving uniform film crystallization remains a hurdle. Here, we enhance MAPbCl3 crystallization by manipulating annealing atmospheres (nitrogen, air, and MACl vapor). Excess MACl vapor improves surface coverage, which is crucial for film stability. We demonstrate that the microstructure of the perovskite film, including surface morphology, grain boundaries, and interfaces, can affect the photovoltaic properties. The subsequently obtained VOC of 1.78 V is the highest recorded for single-junction PSCs to the best of our knowledge. Surprisingly, the conventional hole-transport layer spiro-OMeTAD, optimized for narrow bandgaps, sustains such high voltages. Photoluminescence measurements reveal a trap-assisted recombination peak at 1.65 eV, indicating deep traps as significant to voltage loss in MAPbCl3.