Topography Of Films Research Articles

Tunable Infrared Emissivity Using Laser‐Sintered Liquid Metal Nanoparticle Films

AbstractThis paper describes laser exposure to tune the infrared (IR) emissivity of a film of eutectic gallium indium (EGaIn) particles. EGaIn – a liquid metal at room temperature – forms a native oxide that keeps particles of the metal from spontaneously percolating. Photothermal energy from a CO2 laser percolates the particles into a conductive network. Here, it also causes a decrease in the IR emissivity of the film of particles from 0.4 to 0.24 over the range of 7.5–13 µm wavelength (measured by an IR camera) with the increase of laser fluence from 1.4 to 1.9 J cm−2. The particles percolate most prominently at the bottom of the film, and thus, the apparent surface roughness does not change with laser exposure. This finding suggests the decrease in emissivity is not due to changes in the film's topography. Instead, the change in IR emissivity is attributed to a loss of the surface plasmonic resonance effect of EGaIn particles in the IR range after the sintering, which is confirmed by optical simulations. As a demonstration, it is shown that the ability to change the emissivity makes it possible to encrypt messages and camouflage laser‐processed patterns.

Investigation of Topography and Electrical Properties of K0.3MoO3 Thin Films

Abstract In this article we investigate topography and electrical properties of potassium blue bronze thin films by the means of atomic force microscopy. Thin films were prepared by pulsed laser depositions on two types of substrates (Al2O3 and SrTiO3) at different substrate temperatures and partial oxygen pressures. On the basis of topography measurements, granular nature of the films was revealed. Surface roughness, as well as the size and the orientation of grains was determined. Films deposited on SrTiO3 substrates are quite homogeneous and the grains display ordering in preferential directions. Films on Al2O3 contain randomly oriented grains. Roughness of the films increases with the increase of the deposition temperature. Electrical measurements provided qualitative information regarding the electrical properties of the films.

Optical Studies of Silver Oxide Deposited Thin Films Using the RF Sputtering Technique

Background/Objectives: Silver Oxide is an efficient material because it is used in batteries. Apart from this, it is a moderate oxidizing agent in a variety of processes including the oxidation of aldehydes to carboxylic acids. The objective of the study is to synthesize silver oxide films by RF sputtering technique so that synthesized films can be inserted in the spectrophotometer for optical study. Methods: Silver Oxide films were deposited on Fluorine-doped Tin Oxide (FTO) glass using Radio Frequency (RF) sputtering method and annealed at 200 °C, for two hours, and then it was used in DK2 Ratio recording Spectrophotometer to analyze absorption and transmission data. Findings: The thickness of the films was measured using a non-contact optical Profilometer, in the range of (42– 660) nm. The films were subsequently exposed to optical characterization, revealing exceptionally low transmittance and high absorbance. The band gap is estimated to be 2.2 eV. The X-ray diffraction (XRD) studies reveal that the material is crystalline and Miller indices have also been determined. The morphology and topography of the thin films were analyzed using Field Emission Scanning Electron Microscope (FESEM) and the chemical composition was estimated using EDS. Novelty: The present work reveals that the optical properties are highly dependent on the thickness and the material distribution. The direct band gap energy is evaluated from the absorption spectrum which comes out to be 2.2 eV. The XRD spectra synthesized Silver Oxide films are crystalline in nature. Keywords: Silver Oxide, Band gap, XRD, FESEM

Atomistic insight into structure and properties of oxide films formed upon oxidation of Al–Mg alloys – reactive molecular dynamics study

Oxidation phenomena on metal surfaces can be advanced using atomistic modeling for the study of the structure and properties of the growing oxide films. Molecular dynamics investigations were performed to study thermal oxidation of single-crystal and polycrystalline Al–Mg alloys with low Mg content of up to 2.5 at. %. Structure, topological atom network and surface topography of the oxide films grown on Al–Mg surfaces at 300, 475 and 663 K are determined. Mg-content and temperature dependent oxide films developed on Al-Mg alloy substrates with two-phase oxide film formation as also confirmed experimentally. It is related with a gradual long-range order formation above 475 K for (Al,Mg)-oxide films, for which solid amorphous phase predominates over crystalline phase. The 1.12-nm-thick oxide films grown at 300 K are fully amorphous and build up from (Al, Mg)-oxide which the Al2O3 dominates. Increase of Mg coefficient confirms faster Mg diffusion to oxide/alloy interface at high oxidation temperature and the formation of MgO-like network. The presence of planar crystal defect (grain boundary, GB) into Al-Mg alloy substrate governs the kinetics of oxide film growth and its structure evolution. GB also compensate internal stresses during oxide film growth. Obtained results are in good agreement with experimental observations.

Engineering Thermoresponsive Poly(N-isopropylacrylamide)-Based Films with Enhanced Stability and Reusability for Efficient Bone Marrow Mesenchymal Stem Cell Culture and Harvesting.

Poly(N-isopropylacrylamide) (PNIPAM) offers a promising platform for non-invasive and gentle cell detachment. However, conventional PNIPAM-based substrates often suffer from limitations including limited stability and reduced reusability, which hinder their widespread adoption in biomedical applications. In this study, PNIPAM copolymer films were formed on the surfaces of glass slides or silicon wafers using a two-step film-forming method involving coating and grafting. Subsequently, a comprehensive analysis of the films' surface wettability, topography, and thickness was conducted using a variety of techniques, including contact angle analysis, atomic force microscopy (AFM), and ellipsometric measurements. Bone marrow mesenchymal stem cells (BMMSCs) were then seeded onto PNIPAM copolymer films prepared from different copolymer solution concentrations, ranging from 0.2 to 10 mg·mL-1, to select the optimal culture substrate that allowed for good cell growth at 37 °C and effective cell detachment through temperature reduction. Furthermore, the stability and reusability of the optimal copolymer films were assessed. Finally, AFM and X-ray photoelectron spectroscopy (XPS) were employed to examine the surface morphology and elemental composition of the copolymer films after two rounds of BMMSC adhesion and detachment. The findings revealed that the surface properties and overall characteristics of PNIPAM copolymer films varied significantly with the solution concentration. Based on the selection criteria, the copolymer films derived from 1 mg·mL-1 solution were identified as the optimal culture substrates for BMMSCs. After two rounds of cellular adhesion and detachment, some proteins remained on the film surfaces, acting as a foundation for subsequent cellular re-adhesion and growth, thereby implicitly corroborating the practicability and reusability of the copolymer films. This study not only introduces a stable and efficient platform for stem cell culture and harvesting but also represents a significant advance in the fabrication of smart materials tailored for biomedical applications.

PH-dependent self-assembly of an acid derivative of cholesterol at interfaces

Understanding and control over the self-assembly of molecules is desirable in many physico-chemical processes. Functional groups responsive to a pH change offer immense scope in driving selective molecular self-assembly. pH-dependent self-assembly of an aromatic acid derivative of cholesterol, 4-(6-(cholest-5-ene-3-yloxy)-5-(oxopentyloxy)) benzoic acid, ChBA, is investigated at the air-aqueous interface and characterized using different interface-sensitive techniques. Evidence for the presence of unstable films of ChBA at the air-water interface or for pH < 10 emerges from the surface pressure – area per molecule isotherm, surface pressure relaxation, and Brewster angle microscopy studies. In contrast, for pH > 10.6, ChBA forms a relatively stable film with a higher magnitude of the collapse pressure (45 mN/m). The compressional moduli and the textures obtained using Brewster angle microscopy reveal the presence of two phases (L1 and L2), which are also highly stable with temperature. The surface topography of ChBA films transferred from the air-water interface reveals the presence of multilayers of different thicknesses, for film transferred at pH 11 reveals primarily a uniform and homogenous monolayer. Based on the dependence of the collapse pressure with pH, the surface pKa of ChBA is estimated to be about 10.6. Our studies show that the undissociated ChBA spontaneously forms multilayers, whereas partially or fully dissociated ChBA forms distinct and ordered monolayer phases, highlighting the role of electrostatic interactions.

Anisotropic weak antilocalization in thin films of the Weyl semimetal TaAs

Device applications of topological semimetals await the development of epitaxial films in the ultrathin limit. Weak antilocalization (WAL) has been extensively utilized in the understanding of surface states in topological insulators and shows promise for use in elucidating the properties of thin film topological semimetals. Here, we report insights from WAL in the surface state and interface transport properties of our recently synthesized single-crystal-like thin films of the Weyl semimetal TaAs(001) grown on GaAs(001). We observe robust, anisotropic WAL in the magnetoconductance from 2 to 20 K in films from 10 to 200 nm thick. We link the anisotropic WAL magnetoconductance to anisotropic mobility stemming from film topography. We conclude that WAL in the films likely originates from the antilocalization of topological surface states. The WAL magnetoconductance is impacted by the film thickness and topography, solidifying the useful role of WAL in the study of topological semimetal/semiconductor heterointerfaces. Published by the American Physical Society 2024

Solvent-Activated Transformation of Polymer Configurations for Advancing the Interfacial Reliability of Perovskite Photovoltaics.

Organic materials have been widely used as the charge transport layers in perovskite solar cells due to their structural versatility and solution processability. However, their low surface energy usually causes unsatisfactory thin-film wettability in contact with the perovskite solution, which limits the interfacial performance of the photovoltaic devices. Although solvent post-treatment could occasionally regulate the wetting behavior of organic films, the mechanism of the solid-liquid interaction is still unclear. Here, we present evidence of a possible correlation between the solvent and the wettability of a conventional polymer, poly[bis(4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), and reveal the critical roles of Hansen solubility parameters (HSPs) of solvents in wetting mechanisms. Our results suggest that the conventional solvent N,N-dimethylformamide (DMF) improves the wettability of PTAA by the morphological disruption mechanism but negatively impacts interfacial charge collection and stability. In contrast, 2-methoxyethanol (2-Me) with an appropriate HSP value induces the transformation of the PTAA configuration in an orderly manner, which simultaneously improves the wetting property and maintains the film topography. After careful optimization of the surface conformation of the PTAA film, both perovskite crystallization and interfacial compatibility have been enhanced. Benefiting from superior interfacial properties, the perovskite solar cells based on 2-Me deliver a champion efficiency of 24.15% compared to 21.4% for DMF-based ones. More encouragingly, the use of 2-Me minimizes the perovskite buried interfacial defects, enabling the unencapsulated devices to maintain about 95% of their initial efficiencies after light illumination for 1100 h. The present study demonstrates the high effectiveness of solvent-polymer interaction for adjusting interfacial properties and strengthening the robustness of perovskite solar cells.

Kraft lignin-based polyurethanes: Bulk properties, stability and adhesion to native aluminum surfaces

Lignin as a byproduct from pulp and paper manufacturing has been extensively investigated as raw material for polymer developments. Although, fundamental topics related to the adhesion mechanisms of lignin-based reactive polyurethanes (LPU) still remain unclear. In this work, LPU thin films on native aluminum surface were prepared and characterized. Diluted in THF, employed as the solvent, reactive mixtures of 4,4′-methylene diphenyl isocyanate (4,4′-MDI) and the soluble fraction of three lignins (liquid hydroxypropylated Kraft lignin and two powder Kraft lignins with different pH) were used for LPU thin film deposition via spin coating on aluminum (PVD layer on silicon wafer). The resulting film thickness ranged from 8 nm to several micrometers. The chemical state of the three LPU compositions was assessed in bulk by infrared attenuated total reflectance (IR-ATR) and in the thin films by infrared external reflection absorption spectroscopy (IR-ERAS). Binding energies of 4,4′-methylene diphenyl diisocyanate with aliphatic and aromatic hydroxyl groups were estimated using Density Functional Theory (DFT) simulations. Thus, besides the elucidation of the bulk chemical state of LPUs, the relation to adhesion and stability of LPUs to a native aluminum surface was evaluated. In addition, film topography and homogeneity were monitored by SFM. All lignin types form uniform and homogeneous films. Results revealed a higher consumption of isocyanate groups (NCO) in the formulation with the alkaline Kraft lignin than with the acid one, despite its lower hydroxyl content. A gradient of unreacted NCO was observed in LPU thin films obtained with the powder Kraft lignin types. Residual NCO is also found in thicker films, while the thinnest films did not contain unreacted NCO anymore, indicating the activating effect of the native aluminum surface on LPU formation.

Influence of calcination temperature on the 3D nanoscale topography of LaMnO3 thin films: A comprehensive surface analysis

In this paper, we present a comprehensive study on the 3D nanoscale topography of LaMnO3 thin films, focusing on the influence of calcination temperature on surface morphology. The study reveals significant structural, chemical, and morphological changes as a function of the calcination temperature. XRD analysis confirmed the formation of the orthorhombic LaMnO3 structure at 700 °C, 750 °C, and 800 °C, with increasing unit cell volume and crystallite size observed at higher temperatures. FTIR spectra identified characteristic functional groups associated with molecular vibrations, indicating the perovskite structure. SEM imaging showed grain growth with temperature, while EDS analysis confirmed compound formation and substrate interactions. AFM analysis revealed increased surface roughness with temperature, attributed to nucleation and crystal growth. Morphological and microtextural analyses further detailed changes in surface features, peaks, valleys, and voids. Fractal characterization highlighted variations in surface texture with temperature, with a decrease in dominant wavelength indicating changes in microtexture complexity. Overall, the findings provide insights into the temperature-dependent properties of LaMnO3 thin films, essential for optimizing growth conditions and understanding their potential applications in various fields.

Influence of topography on nano-mechanical properties of cylindrical magnetron sputtered TiN films

Numerous studies on Nano-mechanical behavior of the thin films explained primarily in terms of their film morphology and particle size rather than film topography. Therefore, the current study investigates the effect of film topography on the nano-mechanical characteristics of the film. Ti/TiN multilayer thin films were deposited at varying deposition pressures by using an indigenously developed Cylindrical Magnetron Sputtering (CMS) unit. Surface crystallographic information is characterized by synchrotron-based Grazing Incidence XRD analysis. Film growth follows self-assembled nano hill architecture as revealed by AFM and in situ Scanning Probe Microscopy images. The tribo-mechanical properties of the film is dependent on the height and spacing of its self-assembled structure, which experiences either crushing or buckling under the indenter load, thereby affecting film characteristics. Film deposited at moderate pressure exhibits superior wear behavior, attributed to the interplay between Plasticity Index (PI) and Depth Recovery Ratio (DRR). The study primarily focused on film growth phenomena by using cylindrical targets and their influence on nanomechanical properties of the film.

Copper doped hydroxyapatite nanocomposite thin films: synthesis, physico–chemical and biological evaluation

Cu-doped hydroxyapatite (CuHAp) thin films were obtained using spin coating method. To make these thin films, CuHAp suspensions obtained by sol–gel method were used. The coatings obtained were thermally treated at 500 °C. After the thermal treatment, the thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). Moreover, the stability of the suspensions before being used to obtain the thin films was certified by dynamic light scattering (DLS), zeta potential methods and ultrasound measurements. In the XRD patterns, the peaks associated with hexagonal hydroxyapatite were identified in accordance with JCPDS no. 09-0432. EDS and XPS results confirmed the presence of Cu ions in the samples. Data about the morphological features and chemical composition of CuHAp thin films were obtained by performing scanning electron microscopy (SEM) measurements. Our results suggest that the CuHAp thin films surface is continuous and homogenous. The presence of the functional groups in the CuHAp thin films was confirmed by Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy studies. Information about the surface topography of the CuHAp thin films has been obtained using atomic force microscopy (AFM). The AFM images determined that the surface topography of the CuHAp thin layer is homogenous and continuous without presenting any unevenness or fissures. The cytotoxicity of CuHAp thin films was assessed using human gingival fibroblasts (HGF-1) cells. The results of the cell viability assays demonstrated that the thin films presented good biocompatible properties towards the HGF-1 cells. Additionally, the adherence and development of HGF-1 cells on the surface of CuHAp thin films were determined using AFM. The AFM surface topographies highlighted that the CuHAp thin film’s surface favored the attachment and proliferation of HGF-1 cells on their surface.

Enhancing the Range and Reliability of the Spacer Layer Imaging Method

The spacer layer imaging method (SLIM) is widely used to measure the thickness of additive and lubricant films, in lubricant development and evaluation, and for fundamental research into elastohydrodynamic lubrication and tribofilm formation mechanisms. The film thickness measurement, as implemented on several popular tribometers, provides powerful, non-destructive in-situ mapping of film topography with nanometre-scale height sensitivity. However, the results can be highly sensitive to experimental procedure, machine condition, and image analysis, in some cases reporting unphysical film thickness trends. The prevailing image analysis techniques make it challenging to interrogate these errors, often hiding their multivariate nonlinear behaviour from the user by spatial averaging. Herein, several common ‘silent errors’ in the SLIM measurement, including colour matching to incorrect fringe orders, and colour drift due to the optical properties of the system or film itself, are discussed, with examples. A robust suite of novel a priori and a posteriori methods to address these issues, and to improve the accuracy and reliability of the measurement, are also presented, including a novel, computationally inexpensive circle-finding algorithm for automated image processing. In combination, these methods allow reliable mapping of films up to at least 800 nm in thickness, representing a significant milestone for the utility of SLIM applied to elastohydrodynamic contact.Graphical abstract

Tailoring the surface topography and crystallinity of EuMnO3 films: A study on sintering effects

We obtained EuMnO3 films through a sol-gel process at varying temperatures, aiming to investigate spatial layout variations influenced by different sintering temperatures. Our results indicate that films adopt an orthorhombic structure when sintered between 800 °C and 850 °C, accompanied by a reduction in nanocrystal size during annealing. Surface analysis reveals that films processed at higher temperatures exhibit increased roughness, negative asymmetry, heightened kurtosis, elevated peak densities, and more distinct peak forms. Furthermore, these films display surfaces with greater anisotropy and lower spatial frequencies compared to those sintered at lower temperatures. Nevertheless, fractal analysis uncovers that both the EuMnO800 and EuMnO850 samples showcase heightened spatial complexity, a more uniform nanotexture, optimal surface porosity, and improved topographic consistency. The findings suggest that films sintered at 800 °C display a spatial arrangement with superior topographic qualities, rendering them potentially valuable for the advancement of semiconductor films derived from perovskite rare-earth oxides for various technological applications.

Physical Properties of CaTiO3-Modified NaNbO3 Thin Films.

NaNbO3(NN)-based lead-free materials are attracting widespread attention due to their environment-friendly and complex phase transitions, which can satisfy the miniaturization and integration for future electronic components. However, NN materials usually have large remanent polarization and obvious hysteresis, which are not conducive to energy storage. In this work, we investigated the effect of introducing CaTiO3((1-x)NaNbO3-xCaTiO3) on the physical properties of NN. The results indicated that as x increased, the surface topography, oxygen vacancy and dielectric loss of the thin films were significantly improved when optimal value was achieved at x = 0.1. Moreover, the 0.9NN-0.1CT thin film shows reversible polarization domain structures and well-established piezoresponse hysteresis loops. These results indicate that our thin films have potential application in future advanced pulsed power electronics.

Microstructures and tribological properties of MoS2/Mo2N multilayer gradient films deposited by reactive magnetron sputtering

In order to compare the microstructures and tribological properties of films, pure Mo2N, pure MoS2, 3-layer and 13-layer MoS2/Mo2N gradient films were deposited by reactive magnetron sputtering. The crystalline structure, surface and cross-section morphologies, 3D surface topography, binding energy, hardness and tribological properties of films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), nanoindenter, and wear tester, respectively. The results indicate that the preferred orientation of MoS2 in gradient films has changed. The surface and cross-section structures of gradient films become denser with increasing the number of gradient layers. Average surface roughness (Ra) of pure MoS2 film is the highest, and Ra of 13-layer film is the lowest. The binding energy of MoS2 in the composite layer of gradient film has changed. The hardness of gradient film is higher than that of MoS2 and lower than that of Mo2N. The wear resistance of gradient films is much better than that of pure MoS2, and this phenomenon is more obvious under high load conditions. The improvement in the wear resistance of gradient films is attributed to the increase of dense, hardness, H/E and H3/E2. In the initial stage of friction, the 3-layer gradient film can maintain low friction coefficient (≤0.15), which is attributed to the thick MoS2 surface layer. The wear resistance of 13-layer is much better than that of 3-layer gradient film, because it has higher hardness, higher H/E and H3/E2 than 3-layer gradient film.

Evaluation of the Surface Topography of Microfinishing Abrasive Films in Relation to Their Machining Capability of Nimonic 80A Superalloy.

This study investigates the surface topography of microfinishing abrasive films and their machining capability on the Nimonic 80A superalloy, a high-performance nickel-based alloy commonly used in aerospace and gas turbine engine applications. Surface analysis was conducted on three abrasive films with nominal grain sizes of 30, 15, and 9 μm, exploring wear patterns, contact frequency, and distribution. To assess the distribution of grain apexes, Voronoi cells were employed. Results revealed distinct wear mechanisms, including torn abrasive grains and cracked bond surfaces, highlighting the importance of efficient chip removal mechanisms in microfinishing processes. Larger grain sizes exhibited fewer contacts with the workpiece but provided more storage space for machining products, while smaller grain sizes facilitated smoother surface finishes. The research demonstrated the effectiveness of microfinishing abrasive films in reducing surface irregularities. Additionally, surface analysis of worn abrasive tools provided insights into wear mechanisms and chip formation, with the segmentation of microchips contributing to efficient chip removal. These findings underscore the significance of selecting appropriate abrasive films and implementing effective chip removal mechanisms to optimize microfinishing processes and improve surface finishing quality in advanced material machining applications. It is worth emphasizing that no prior research has investigated the microfinishing of components crafted from Nimonic 80A utilizing abrasive films, rendering this study truly unique in its contribution to the field.

Unveiling Texture and Topography of Fatty Acid Langmuir Films: Domain Stability and Isotherm Analysis.

3D texturing by self-assembly at the air-water interface has recently been proposed. The hypothesis of this work is that, if this is true, such domain formation should be inferable directly from pressure-area isotherms and be thermodynamically stable. Monolayers of branched fatty acid mixtures with straight chain analogues and their stability are thus studied using a combination of pressure-area isotherms, thermodynamic analysis, in situ Brewster angle microscopy, and atomic force microscopy of both LB-deposited and drop-cast films on silicon wafers. Isotherms reflecting the behavior of monodisperse 3D domains are shown to be independent of compression rate and display long-term stability. Gibbs analysis further confirms the thermodynamic rather than kinetic origin of such novel species by revealing that deviations from ideal mixing can be explained only a priori by differences in the topography of the water surface, thus also indirectly confirming the self-assembly deformation of the water interface. The intrinsic self-assembly curvature and miscibility of the two fatty acids is confirmed by drop-casting, which also provides a rapid, tunable thin-film preparation approach. Finally, the longevity of the nanostructured films is extraordinary, the long-range order of the deposited films increases with equilibration time at the water interface, and the integrity of the nanopatterns remains intact on the scale of years.

An Investigation of the Structural and Surface Topography of Aluminum Nitride Thin Films Deposited at Low Sputtering Power for Piezoelectric Applications

An Investigation of the Structural and Surface Topography of Aluminum Nitride Thin Films Deposited at Low Sputtering Power for Piezoelectric Applications

Adsorption and Structuration of PEG Thin Films: Influence of the Substrate Chemistry.

This study investigates polyethylene glycol (PEG) homopolymer thin film adsorption on gold surfaces of controlled surface chemistry. The conformational states of physisorbed PEG are analyzed through polarization modulation infrared reflection-absorption spectrometry (PM-IRRAS). The PM-IRRAS principle is based on specific optical selection rules allowing the detection of surface-specific FTIR response of thin polymer films on the basis of differential reflectivity at the polymer/substrate interface for p- and s-polarized light. The intensification of the electric field generated at the PEG/substrate interface for p-polarized IR light in comparison with s-polarized light permits the analysis of PEG chain anisotropy and conformational changes induced by the adsorption. Results showed that PEG adsorbs on model substrates having a rather hydrophilic character in a way that the PEG chains spread parallel to the surface. In the case of a very hydrophilic substrate, the adsorbed PEG chains are in a stable thermodynamic state which allows them to arrange and crystallize as stacked crystalline lamellae after adsorption. The surface topography and morphology of the PEG thin films were also investigated by atomic force microscopy (AFM). While in the bulk state, PEG crystallizes in the form of large spherulites; on substrates whose adsorption is favored by surface chemistry, PEG crystallizes in the form of stacked lamellae with a thickness equal to 20 nm. Conversely, on a hydrophobic substrate, the PEG chains do not crystallize and adsorption occurs in the statistical coil state.