Influence of the Template Layer on the Structure and Ferroelectric Properties of PbZr0.52Ti0.48O3 Films.

The microstructure of the PbZr0.52Ti0.48O3 (PZT) films is known to influence the ferroelectric properties, but so far mainly the effect of the deposition conditions of the PZT has been investigated. To our knowledge, the influence of the underlying electrode layer and the mechanisms leading to changes in the PZT microstructure have not been explored. Using LaNiO3 (LNO) as the bottom electrode material, we investigated the evolution of the PZT microstructure and ferroelectric properties for changing LNO pulsed-laser deposition conditions. The explored deposition conditions were the O2 pressure, total pressure, and thickness of the electrode layer. Increasing both the O2 pressure and the thickness of the electrode layer changes the growth of PZT from a smooth, dense film to a rough, columnar film. We explain the origin of the change in PZT microstructure as the increased roughness of the electrode layer in relaxing the misfit strain. The strain relaxation mechanism is evidenced by the increase in the crystal phase with bulk LNO unit cell dimensions in comparison to the crystal phase with substrate-clamped unit cell dimensions. We explain the change from a dense to a columnar microstructure as a result of the change in the growth mode from Frank-van der Merwe to Stranski-Krastanov. The ferroelectric properties of the columnar films are improved compared to those of the smooth, dense films. The ability to tune the ferroelectric properties with the microstructure is primarily relevant for ferroelectric applications such as actuators and systems for energy harvesting and storage.

Bifunctional catalytic effect of Mo2C/oxide interface on multi-layer graphene growth.

The role of the Mo2C/oxide interface on multi-layer graphene (MLG) nucleation during a chemical vapor deposition (CVD) process is investigated. During the CVD process, MLG growth is only observed in the presence of a Mo2C/SiO2 interface, indicating that the chemical reactions occurring at this interface trigger the nucleation of MLG. The chemical reaction pathway is explained in four steps as (1) creation of H radicals, (2) reduction of the oxide surface, (3) formation of C-C bonds at O-H sites, and (4) expansion of graphitic domains on the Mo2C catalyst. Different Mo2C/oxide interfaces are investigated, with varying affinity for reduction in a hydrogen environment. The results demonstrate a catalyst/oxide bifunctionality on MLG nucleation, comprising of CH4 dehydrogenation by Mo2C and initial C-C bond formation at the oxide interface.

Nb Texture Evolution and Interdiffusion in Nb/Si-Layered Systems.

In this paper, we present a detailed study on the microstructure evolution and interdiffusion in Nb/Si-layered systems. Interlayer formation during the early stages of growth in sputter-deposited Nb-on-Si and Si-on-Nb bilayer systems is studied in vacuo using a high-sensitivity low-energy ion-scattering technique. An asymmetric intermixing behavior is observed, where the Si-on-Nb interface is ∼2× thinner than the Nb-on-Si interface, and it is explained by the surface-energy difference between Nb and Si. During Nb-on-Si growth, the crystallization of the Nb layer occurs around 2.1 nm as-deposited Nb thickness with a strong Nb(110)-preferred orientation, which is maintained up to 3.3 nm as-deposited Nb thickness. A further increase in the Nb layer thickness above 3.3 nm results in a polycrystalline microstructure with a reduced degree of texture. High-resolution cross-sectional transmission electron microscopy imaging is performed on Nb/Si multilayers to study the effect of the Nb layer texture on interdiffusion during low-temperature annealing. Nb/Si multilayers with amorphous 2 nm Nb layers and strongly textured 3 nm thick Nb layers, with limited grain-boundary pathways for diffusion, show no observable interdiffusion during annealing at 200 °C for 8 h, whereas in a Nb/Si multilayer with polycrystalline 4 nm thick Nb layers, a ∼1 nm amorphous Nb/Si interlayer is formed at the Si-on-Nb interface during annealing.

Planar refractive lenses made of SiC for high intensity nanofocusing.

We report on the manufacturing and testing of the first nanofocusing refractive lenses made of single-crystal silicon carbide. We introduce the fabrication process based on lithography, followed by deep isotropic etching. The lenses were characterized at the energy of 12 keV at the beamline P06 of the synchrotron radiation source PETRA III. A focal spot of 186 nm×275 nm has been achieved with a lens working distance of 29 mm.

Nanoscale Transition Metal Thin Films: Growth Characteristics and Scaling Law for Interlayer Formation.

A comprehensive study on the growth of nanoscale transition metal-on-transition metal (TM-on-TM) systems is presented. The near room-temperature intermixing and segregation phenomena during growth are studied in vacuo using high-sensitivity low-energy ion scattering. The investigated TM-on-TM systems are classified into four types according to the observed intermixing and segregation behavior. Empirical rules are suggested to qualitatively predict the growth characteristics of any TM-on-TM system based on the atomic size difference, surface-energy difference, and enthalpy of mixing between the film and substrate atoms. An exponential trend is observed in the effective interface width as a function of the surface-energy difference between the film and substrate layers, with a subtrend based on the crystal structure of the TM layers. A semiempirical model that accurately describes the experimental data is presented. It serves as a scaling law to predict the effective interface width and the minimum film thickness required for full film coverage in TM-on-TM systems in general. The ability to predict the growth characteristics as well as the interface width for any TM-on-TM system significantly contributes to the process of finding the best material combination for a specific application, where layer growth characteristics are implicitly considered when selecting materials based on their functional properties.

Nanoscale piezoelectric surface modulation for adaptive extreme ultraviolet and soft x-ray optics.

Extreme ultraviolet and soft x-ray wavelengths have ever-increasing applications in photolithography, imaging, and spectroscopy. Adaptive schemes for wavefront correction at such a short wavelength range have recently gained much attention. In this Letter we report, to the best of our knowledge, the first demonstration of a functional actuator based on piezoelectric thin films. We introduce a new approach that allows producing a gradually varying surface deformation. White light interferometery is used to show the level of control in generating arbitrary surface profiles at the nanoscale.

Mechanism of single-shot damage of Ru thin films irradiated by femtosecond extreme UV free-electron laser.

Ruthenium is a perspective material to be used for XUV mirrors at free-electron laser facilities. Yet, it is still poorly studied in the context of ultrafast laser-matter interaction. In this work, we present single-shot damage studies of thin Ru films irradiated by femtosecond XUV free-electron laser pulses at FLASH. Ex-situ analysis of the damaged spots, performed by different types of microscopy, shows that the weakest detected damage is surface roughening. For higher fluences we observe ablation of Ru. Combined simulations using Monte-Carlo code XCASCADE(3D) and the two-temperature model reveal that the damage mechanism is photomechanical spallation, similar to the case of irradiating the target with optical lasers. The analogy with the optical damage studies enables us to explain the observed damage morphologies.

In situ and real-time monitoring of structure formation during non-reactive sputter deposition of lanthanum and reactive sputter deposition of lanthanum nitride.

Lanthanum and lanthanum nitride thin films were deposited by magnetron sputtering onto silicon wafers covered by natural oxide. In situ and real-time synchrotron radiation experiments during deposition reveal that lanthanum crystallizes in the face-centred cubic bulk phase. Lanthanum nitride, however, does not form the expected NaCl structure but crystallizes in the theoretically predicted metastable wurtzite and zincblende phases, whereas post-growth nitridation results in zincblende LaN. During deposition of the initial 2-3 nm, amorphous or disordered films with very small crystallites form, while the surface becomes smoother. At larger thicknesses, the La and LaN crystallites are preferentially oriented with the close-packed lattice planes parallel to the substrate surface. For LaN, the onset of texture formation coincides with a sudden increase in roughness. For La, the smoothing process continues even during crystal formation, up to a thickness of about 6 nm. This different growth behaviour is probably related to the lower mobility of the nitride compared with the metal. It is likely that the characteristic void structure of nitride thin films, and the similarity between the crystal structures of wurtzite LaN and La2O3, evoke the different degradation behaviours of La/B and LaN/B multilayer mirrors for off-normal incidence at 6.x nm wavelength.

High Reflectance Nanoscale V/Sc Multilayer for Soft X-ray Water Window Region.

V/Sc multilayer is experimentally demonstrated for the first time as a high reflectance mirror for the soft X-ray water window region. It primarily works at above the Sc-L edge (λ = 3.11 nm) under near normal incidence while a second peak appears at above the V-L edge (λ = 2.42 nm) under grazing incidence. The V/Sc multilayer fabricated with a d-spacing of 1.59 nm and 30 bilayers has a smaller interface width (σ = 0.27 and 0.32 nm) than the conventional used Cr/Sc (σ = 0.28 and 0.47 nm). For V/Sc multilayer with 30 bilayers, the introduction of B4C barrier layers has little improvement on the interface structure. As the number of bilayers increasing to 400, the growth morphology and microstructure of the V/Sc layers evolves with slightly increased crystallization. Nevertheless, the surface roughness remains to be 0.25 nm. A maximum soft X-ray reflectance of 18.4% is measured at λ = 3.129 nm at 9° off-normal incidence using the 400-bilayers V/Sc multilayer. According to the fitted model, an s-polarization reflectance of 5.2% can also be expected at λ = 2.425 nm under 40° incidence. Based on the promising experimental results, further improvement of the reflectance can be achieved by using a more stable deposition system, exploring different interface engineering methods and so on.

Tuning of large piezoelectric response in nanosheet-buffered lead zirconate titanate films on glass substrates.

Renewed interest has been witnessed in utilizing the piezoelectric response of PbZr0.52Ti0.48O3 (PZT) films on glass substrates for applications such as adaptive optics. Accordingly, new methodologies are being explored to grow well-oriented PZT thin films to harvest a large piezoelectric response. However, thin film piezoelectric response is significantly reduced compared to intrinsic response due to substrate induced clamping, even when films are well-oriented. Here, a novel method is presented to grow preferentially (100)-oriented PZT films on glass substrates by utilizing crystalline nanosheets as seed layers. Furthermore, increasing the repetition frequency up to 20 Hz during pulsed laser deposition helps to tune the film microstructure to hierarchically ordered columns that leads to reduced clamping and enhanced piezoelectric response evidenced by transmission electron microscopy and analytical calculations. A large piezoelectric coefficient of 250 pm/V is observed in optimally tuned structure which is more than two times the highest reported piezoelectric response on glass. To confirm that the clamping compromises the piezoelectric response, denser films are deposited using a lower repetition frequency and a BiFeO3 buffer layer resulting in significantly reduced piezoelectric responses. This paper demonstrates a novel method for PZT integration on glass substrates without compromising the large piezoelectric response.

Coexistence of ice clusters and liquid-like water clusters on the Ru(0001) surface.

The RAIRS spectra of water adsorbed on Ru(0001) at 85 K are recorded from 600 cm-1 to 4000 cm-1. Measured at water coverages from 0.13 ML to 2.0 ML, the RAIRS spectra suggest that chemisorption of water on Ru(0001) depends on coverage. Water adsorbs on a clean Ru surface as chemisorbed ice-like clusters (likely through an O-Ru bond) up to 0.33 ML. Above this coverage, the chemisorbed layer saturates. Upon more exposure, water adsorbs as a liquid-like H-bonded layer without bonding to the Ru substrate. The chemisorbed water absorbs 7 times less IR per molecule than the liquid-like structure, which indicates that the orientation of the chemisorbed water is more parallel to the surface. Additionally, the influence of water-Ru bonding on H-bonding is reflected in the OH symmetric stretching mode. Under perturbation from water-Ru bonding, a large red shift (40 cm-1) in the free OH stretching frequency is observed in the chemisorbed clusters. By deconvoluting the main H-bonded OH stretching peak into five Gaussian sub-bands at 2945 ± 5 cm-1, 3210 ± 5 cm-1, 3300 ± 15 cm-1, 3430 ± 5 cm-1 and 3570 ± 10 cm-1, changes in the H-bonding network are rationalized in terms of H-bonding motifs. The donor-acceptor-acceptor motif is significant only in the chemisorbed clusters. On the other hand, the donor-acceptor motif dominates in the liquid-like structure, which increases the disorder present in the adlayer. Although chemisorption is suppressed above 0.33 ML, no structural changes in the ice-like clusters are observed up to multilayer coverage. Therefore, ice-like and liquid-like water coexist in a meta-stable state at 85 K.

High efficiency structured EUV multilayer mirror for spectral filtering of long wavelengths.

High spectral purity at longer wavelength side is demanded in many extreme ultraviolet (EUV) and soft X-ray (together also referred to as XUV) optical systems. It is usually obtained at the expense of a high loss of XUV efficiency. We proposed and developed a new method based on a periodic, tapered structure integrated with an EUV multilayer. The longer wavelength radiation is scattered/diffracted away by the tapered multilayer structure while the EUV light is reflected. The first proof-of-principle showed a broadband suppression from λ = 100-400 nm with an average factor of 14. Moreover, a high EUV reflectance of 64.7% was achieved, which corresponds to 94% of the efficiency of a regular EUV multilayer mirror.

Spectral purification and infrared light recycling in extreme ultraviolet lithography sources.

We present the design of a novel collector mirror for laser produced plasma (LPP) light sources to be used in extreme ultraviolet (EUV) lithography. The design prevents undesired infrared (IR) drive laser light, reflected from the plasma, from reaching the exit of the light source. This results in a strong purification of the EUV light, while the reflected IR light becomes refocused into the plasma for enhancing the IR-to-EUV conversion. The dual advantage of EUV purification and conversion enhancement is achieved by incorporating an IR Fresnel zone plate pattern into the EUV reflective multilayer coating of the collector mirror. Calculations using Fresnel-Kirchhoff's diffraction theory for a typical collector design show that the IR light at the EUV exit is suppressed by four orders of magnitude. Simultaneously, 37% of the reflected IR light is refocused back the plasma.

UV spectral filtering by surface structured multilayer mirrors.

A surface structured extreme ultraviolet multilayer mirror was developed showing full band suppression of UV (λ=100-400 nm) and simultaneously a high reflectance of EUV light (λ=13.5 nm). The surface structure consists of Si pyramids, which are substantially transparent for EUV but reflective for UV light. The reflected UV is filtered out by blazed diffraction, interference, and absorption. A first demonstration pyramid structure was fabricated on a multilayer by using a straightforward deposition technique. It shows an average suppression of 14 times over the whole UV range and an EUV reflectance of 56.2% at 13.5 nm. This robust scheme can be used as a spectral purity solution for all XUV sources that emit longer wavelength radiation as well.

Wavefront correction in the extreme ultraviolet wavelength range using piezoelectric thin films.

A new scheme for wavefront correction in the extreme ultraviolet wavelength range is presented. The central feature of the scheme is the successful growth of crystalline piezoelectric thin films with the desired orientation on an amorphous glass substrate. The piezoelectric films show a high piezoelectric coefficient of 250 pm/V. Using wavefront calculations we show that the grown films would enable high-quality wavefront correction, based on a stroke of 25 nm, with voltages that are well below the electrical breakdown limit of the piezoelectric film.

Mo/Si multilayer-coated amplitude-division beam splitters for XUV radiation sources.

Amplitude-division beam splitters for XUV radiation sources have been developed and extensively characterized. Mo/Si multilayer coatings were deposited on 50 nm-thick SiN membranes. By changing the multilayer structure (periodicity, number of bilayers, etc.) the intensity of the reflected and transmitted beams were optimized for selected incident radiation parameters (wavelength, incident angle). The developed optical elements were characterized by means of XUV reflectometry and transmission measurements, atomic force microscopy and optical interferometry. Special attention was paid to the spatial homogeneity of the optical response and reflected beam wavefront distortions. Here the results of the characterization are presented and improvements required for advanced applications at XUV free-electron lasers are identified. A flatness as low as 4 nm r.m.s. on 3 × 3 mm beam splitters and 22 nm r.m.s. on 10 × 10 mm beam splitters has been obtained. The high-spatial-frequency surface roughness was about 0.7-1 nm r.m.s. The middle-spatial-frequency roughness was in the range 0.2-0.8 nm r.m.s. The reflection and transmission of the beam splitters were found to be very homogeneous, with a deviation of less than 2% across the full optical element.

Short period La/B and LaN/B multilayer mirrors for ~6.8 nm wavelength.

In the first part of this article we experimentally show that contrast between the very thin layers of La and B enables close to theoretical reflectance. The reflectivity at 6.8 nm wavelength was measured from La/B multilayer mirrors with period thicknesses ranging from 3.5 to 7.2 nm at the appropriate angle for constructive interference. The difference between the measured reflectance and the reflectance calculated for a perfect multilayer structure decreases with increasing multilayer period. The reflectance of the multilayer with the largest period approaches the theoretical value, showing that the optical contrast between the very thin layers of these structures allows to experimentally access close to theoretical reflectance. In the second part of the article we discuss the structure of La/B and LaN/B multilayers. This set of multilayers is probed by hard X-rays (λ = 0.154 nm) and EUV radiation (λ = 6.8 nm). The structure is reconstructed based on a simultaneous fit of the grazing incidence hard X-ray reflectivity and the EUV reflectivity curves. The reflectivity analysis of the La/B and LaN/B multilayer mirrors shows that the lower reflectance of La/B mirrors compared to LaN/B mirrors can be explained by the presence of 5% of La atoms in the B layer and 63% of B in La layer. After multi-parametrical optimization of the LaN/B system, including the nitridation of La, the highest near normal incidence reflectivity of 57.3% at 6.6 nm wavelength has been measured from a multilayer mirror, containing 175 bi-layers. This is the highest value reported so far.

Structural properties of subnanometer thick Y layers in extreme ultraviolet multilayer mirrors.

We studied the structure and optical properties of B(4)C/Mo/Y/Si multilayer systems. Using extended x-ray absorption fine structure measurements at the Y and Mo K-edge, the structure of the subnanometer thick Y layer and the underlying Mo layer were analyzed. It was found that even a 0.2 nm thick Y layer significantly reduced silicon diffusion toward Mo, thus reducing Mo silicide formation. Hard x-ray reflectometry showed that the difference in average interface roughness of the B(4)C/Mo/Y/Si multilayer structure compared to Mo/Si and B(4)C/Mo/B(4)C/Si multilayer structures was negligible. Soft x-ray reflectometry showed optical improvement of B(4)C/Mo/Y/Si with respect to Mo/Si and B(4)C/Mo/B(4)C/Si multilayer structures.

Spectral properties of La/B--based multilayer mirrors near the boron K absorption edge.

The spectral properties of La/B, La/B(4)C, and LaN/B, LaN/B(4)C multilayer mirrors have been investigated in the 6.5-6.9 nm wavelength range based on measured B and B(4)C optical constants. Experimentally it is verified to what extent measured and tabulated optical constants are applicable for simulations of the reflectivity of these short period multilayer mirrors. The measured maximum reflectance at various wavelength values around the boron-K absorption edge is compared to calculated values from model systems. The measured reflectance profiles of La/B and La/B(4)C show a maximum at a slightly larger wavelength than calculations would predict based on the measured B and B(4)C optical constants. This is explained by the influence of a formed boron-lanthanum compound on the wavelength where the multilayer shows maximum reflectance. The maximum reflectance profiles of LaN/B and LaN/B(4)C multilayers can be described accurately by using the same boron atomic scattering factors, indicating boron in the LaN/B(4)C multilayer to be in a similar chemical state as boron in the LaN/B multilayer. It also indicates that nitridation of the La layer in the multilayer prevents the formation of La-B compounds. We show that the optimal wavelength for boron based optics is about 6.65 nm and depends on the B chemical state. Finally, using the measured B optical constants we are able to calculate the spectral response of the multilayers, enabling the prediction of the optimal parameters for the above mentioned multilayers.

Ellipsometry with randomly varying polarization states.

We show that, under the right conditions, one can make highly accurate polarization-based measurements without knowing the absolute polarization state of the probing light field. It is shown that light, passed through a randomly varying birefringent material has a well-defined orbit on the Poincar sphere, which we term a generalized polarization state, that is preserved. Changes to the generalized polarization state can then be used in place of the absolute polarization states that make up the generalized state, to measure the change in polarization due to a sample under investigation. We illustrate the usefulness of this analysis approach by demonstrating fiber-based ellipsometry, where the polarization state of the probe light is unknown, and, yet, the ellipsometric angles of the investigated sample (Ψ and Δ) are obtained with an accuracy comparable to that of conventional ellipsometry instruments by measuring changes to the generalized polarization state.