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Sergei V. Kalinin

Publications and source records attributed to Sergei V. Kalinin.

At least 19 recordsLinked to original sources

Physics-Informed Sequential Reconstruction of Scanning Probe Microscopy Images with Calibrated Uncertainty

Scanning probe microscopy (SPM) has become a mainstay of materials science, condensed matter physics, nanotechnology, biology, and semiconductor metrology. An SPM image, however, is acquired sequentially as the probe traverses the surface under closed-loop feedback while thermal drift, feedback dynamics, tip state, mechanical disturbances, and electronic noise evolve during the experiment. Image correction has therefore become an intrinsic part of SPM data analysis. Classical approaches rely on line leveling, filtering, registration, interpolation, and explicit models of tip or scanner distortions, whereas recent work increasingly uses neural networks trained to map corrupted images to corrected ones. Here, we explore a different formulation in which SPM reconstruction is treated as a Bayesian sequential state-estimation problem. The hidden state represents surface height and its low-order evolution along the slow-scan direction; an artifact-dependent quality score continuously modifies the observation likelihood; a forward Kalman pass provides the causal estimate and innovation diagnostics; and a Rauch-Tung-Striebel (RTS) backward pass incorporates information from the complete acquisition. The result is a reconstructed surface, a relative posterior uncertainty map, and line-resolved diagnostic signals. The recursion is computationally lightweight and scales linearly with the number of image pixels, while the physical parameters can in principle be initialized from instrument characterization or from priors learned during previous operation, an extension not exercised here. We organize the method as a multi-axis family of models so that the contributions of state representation, artifact recognition, lateral coupling, and acquisition redundancy can be evaluated independently.

eess.IV

Human-agent discovery of reconfigurable in-plane ferroelectric superdomain control

Automated experimentation is most effective when the observables, available actions, and objective are defined before the experiment starts, as is the case for Bayesian optimization. However, in many exploratory experiments, the variables that describe the sample must be extracted from the data, new operations emerge during the experiments, and the instrument budget is too small to learn the problem by trials. Here we introduce the Scanning Probe Agentic Research Cycle (SPARC) framework, in which a coding agent and a human operator share one microscope, one notebook, and two persistent memory files. FINDINGS.md stores graded conclusions about the experiment, whereas PITFALLS.md records learned failure modes of analysis and instrument. We apply SPARC to reconfigure the in-plane superdomain direction of a (111)-oriented PbZr0.2Ti0.8O3 film. In an operator-supervised campaign, the agent reanalyzed earlier manual measurements and developed an oriented lattice of stationary bias pulses with alternating polarity to reconfigure the superdomain direction. In a subsequent agent-controlled campaign, PITFALLS.md entries were compiled into checks that validate a design before any write. The experiments showed that spatial polarity alternation, instead of the exact matching between the lattice and lamellar periods, determines directional selection. Combining a raster scan with a masked pulse lattice printed the letters UTK into the superdomain orientation. The campaign also identified practical requirements for agentic experimentation where physical verification of instrument execution, the conditions under which stored findings remain valid, validation of new observables on instrument data, and robust control protocols.

cond-mat.mtrl-sci

Hierarchical automation of scanning probe microscopy through agentic orchestration and algorithmic control

Rapid advances in agentic artificial intelligence enable scientific systems to interpret open-ended objectives, combine heterogeneous information, invoke specialized tools, and revise experimental strategies as evidence accumulates. However, physical experimentation also contains many tasks for which agentic reasoning provides little advantage and can reduce reliability. Quantitative analysis, optimization, spatial targeting, validation, and instrument execution are often better posed as deterministic or algorithmic operations with explicit objectives and verifiable outputs. Here, we introduce a hierarchical architecture for autonomous experimentation that separates these roles. Agentic components interpret scientific intent, construct task-dependent experimental representations, evaluate accumulated evidence, and select high-level actions, whereas deterministic algorithms perform numerical analysis, coordinate selection, validation, and physical execution. We implement this architecture in piezoresponse force microscopy. Starting from a broad scientific question concerning the relation between local domain structure and polarization switching, the system constructs spatial descriptors from multichannel imaging, selects and analyzes local hysteresis measurements, adapts the spectroscopy waveform, and terminates the experiment when additional measurements cease to provide new evidence. The autonomous trajectory also identifies a confounding relationship between polarization state and domain-wall proximity and recognizes that the requested contrast is not independently represented within the available field of view. These results demonstrate a route toward scientific autonomy in which agents determine what evidence is required while algorithms determine how that evidence is acquired reproducibly and within validated physical constraints.

cond-mat.mtrl-sci

Beyond FAIR Data: Instrument Traces for Active and Autonomous Scientific Experimentation

Artificial intelligence is turning scientific instruments into active systems in which observations can determine what is measured next. We argue that this creates an additional scientific record, the experimental trajectory, complementing sample provenance, acquired data and metadata, and analysis workflows. Instrument Traces should ultimately be synchronized with Sample Traces describing specimen evolution and Decision Traces recording human or algorithmic choices. We reconstruct an Instrument Trace retrospectively from a longitudinal AFM/PFM archive containing 118,000 timestamped events from 2023-2026. Conventional saved files reveal material campaigns, latent probe and calibration states, session-level complexity, experimental decision grammar, and composite tuning actions. They also expose what is missing, including unsaved tuning and failures, explicit sample/probe identities, complete timing, exogenous state, and decision rationale. We therefore propose a prospective trace architecture that records synchronized sample, instrument, and decision histories, enabling reproducible autonomy, predictive maintenance, counterfactual analysis, operator training, and transfer across facilities.

cs.DL

Composition-Driven Phase Evolution in Sm-Doped BiFeO3 via Latent-Field Reconstruction of Atomically Resolved STEM Data

Functionalities of ferroelectric materials are governed by the spatial organization and coupling of polarization, strain, lattice rotation, and structural order accessible via atomically resolved scanning transmission electron microscopy (STEM) images. Quantitative interpretation of atomic-resolution STEM data has conventionally relied on locating atomic columns and converting their fitted coordinates into local structural descriptors. Here, we develop a field-based approach in which atomic-resolution images are represented by spatially varying latent Bragg fields, whose amplitudes and phases provide continuous maps of crystalline order, lattice displacement, strain, rotation, and mode-specific residual structure. The observed atomically resolved images are decoded from the latent fields. We apply this framework to image series of Sm-substituted BiFeO3 spanning 0-20% Sm and crossing the composition-driven boundary between the R3c ferroelectric phase and the orthorhombic, nonpolar Pnma phase. Conventional atom-resolved parameterization is used as an independent validation, showing that reconstructed Bragg amplitude tracks local atomic-column intensity and that field-derived shear reproduces unit-cell angular distortions obtained from atom fitting. The combined analysis reveals a systematic evolution from extended ferroelectric domains at low Sm concentration, through the appearance and growth of localized regions with period-doubled Pnma order at intermediate compositions, to a connected Pnma-dominated state at high Sm content. The period-doubled order is accompanied by enhanced shear and lattice rotation and by progressive reorganization of the ferroelectric domain structure. These results establish latent-field reconstruction as a physically interpretable complement to atom finding and provide a unified framework for resolving composition-driven phase evolution in ferroic materials.

cond-mat.mtrl-sci

Beyond Directed Acyclic Graphs: Causal Zeros and Causal Differential Equations

Pearl's structural causal model (SCM) framework, built on directed acyclic graphs (DAGs) and the do-calculus, is the dominant formal language for causal reasoning. Yet it carries two structural restrictions: every relationship must be pre-specified as a directed causal edge, and feedback cycles are forbidden. This paper examines two classes of phenomena that strain these restrictions. First, symmetric physical and economic constraints, the ideal gas law being the canonical case, carry no intrinsic causal direction. Direction emerges only under intervention, and which variable is solved for must be specified as part of the intervention. We formalize such constraints as causal zeros within an Extended Causal Model by adding an activation operator, subject to local solvability and graph-admissibility conditions. Second, for the class of finite-propagation state-space systems considered here, we treat apparent instantaneous cycles as artifacts of suppressed time and ground both causal zeros and feedback in Causal Differential Equations (CDEs). In these, the transient regime is a time-unrolled acyclic causal process, and causal zeros arise as the defining functions of attracting equilibrium manifolds; periodic and chaotic attractors define further regimes of the same dynamics, treated through attractor-relative intervention. We give the extended do-calculus, identifiability conditions, counterfactual semantics, and open problems.

cs.LG

From Closed-Loop Optimization to Open Decision Making: Coupled Digital Twins for Predictive and Autonomous Microscopy

Automated experimentation is moving from closed-loop optimization toward open decision-making, where human or AI planners must forecast the consequences of candidate actions before executing them. Such forecasts require a model of both sides of the experiment: how the sample is likely to respond and what the instrument is likely to detect. We therefore introduce a coupled digital-twin framework that separates these roles and then links them. In this framework, the sample twin encodes material state inferred from prior knowledge and measurements till the moment. The instrument twin captures signal formation, feedback dynamics, and operating constraints based on prior knowledge. When coupled, the two twins estimate expected outcomes, uncertainty, and risk for candidate microscope operations. For amplitude-modulation scanning probe microscopy, we realize this framework with a physics-informed encoder of force-distance curves, a deterministic scanner model of cantilever and feedback dynamics, and sparse learned residual corrections. The encoder first recovers scanner-driving descriptors with sub-nanometer accuracy. The calibrated scanner then reproduces typical traces within a few nanometers and identifies operating-point noise amplification as the main source of mismatch. Supplementary phase analysis localizes residual error to the phase channel, which clarifies where added physics is needed. Together, these results establish coupled sample and instrument twins as a practical foundation for predictive microscope operation and autonomous experimental planning.

cond-mat.mtrl-sci

Closed-loop discovery of out-of-distribution processing protocols by evolutionary search and uncertainty-aware learning

Many materials and chemical systems exhibit history-dependent responses, where functional outcomes are governed not only by final-state variables but by the time-dependent sequence of fields, temperatures, or chemical potentials applied during operation. Discovering new processing protocols is therefore a high-dimensional search problem in which the control variable is an entire waveform or sample history, and conventional strategies either remain confined to conservative interpolative families or become prohibitively measurement intensive. Here, a closed-loop workflow is introduced that couples evolutionary search over a compact waveform representation with uncertainty-aware deep kernel learning to generate, rank, and experimentally validate candidate protocols. Applied to ferroelectric thin films, with the scanning-probe tip-bias waveform as the protocol and the nonlinear electromechanical response as the reward, the workflow discovers waveform families that enhance nonlinearity by de-aging the film. Spatially resolved before/after measurements show that the best-performing waveforms selectively activate pre-existing, weakly pinned domain-wall segments, whereas the worst drive long-range irreversible switching. This framework reframes protocol tuning as out-of-distribution discovery, generalizable to synthesis and annealing trajectories, battery formation protocols, and other high-dimensional control problems.

cond-mat.mtrl-sci

Born-Qualified: An Autonomous Framework for Deploying Advanced Energy and Electronic Materials

Autonomous science is transforming how we discover materials and chemical systems for advanced energy technologies. However, many initially promising systems never reach deployment. This "valley of death" stems from optimization that prioritizes laboratory metrics over industrial viability. We propose a new strategy: "born-qualified" autonomous development, which embeds manufacturability, cost, and durability constraints from the outset. This approach is enabled by four pillars, including the development of multi-objective metrics, causal models, a modular infrastructure, and embedding manufacturing in the discovery loop. Realizing this vision will require sustained, community-wide commitment, but the potential return on that investment is commensurate with the scale of the challenge.

cond-mat.mtrl-sci

PATHFINDER: Multi-objective discovery in structural and spectral spaces

Automated decision-making is becoming key for automated characterization including electron and scanning probe microscopies and nano indentation. Most machine learning driven workflows optimize a single predefined objective and tend to converge prematurely on familiar responses, overlooking rare but scientifically important states. More broadly, the challenge is not only where to measure next, but how to coordinate exploration across structural, spectral, and measurement spaces under finite experimental budgets while balancing target-driven optimization with novelty discovery. Here we introduce PATHFINDER, a framework for autonomous microscopy that combines novelty driven exploration with optimization, helping the system discover more diverse and useful representations across structural, spectral, and measurement spaces. By combining latent space representations of local structure, surrogate modeling of functional response, and Pareto-based acquisition, the framework selects measurements that balance novelty discovery in feature and object space and are informative and experimentally actionable. Benchmarked on pre acquired STEM EELS data and realized experimentally in scanning probe microscopy of ferroelectric materials, this approach expands the accessible structure property landscape and avoids collapse onto a single apparent optimum. These results point to a new mode of autonomous microscopy that is not only optimization-driven, but also discovery-oriented, broad in its search, and responsive to human guidance.

cond-mat.mtrl-sci

Novelty-Driven Target-Space Discovery in Automated Electron and Scanning Probe Microscopy

Modern automated microscopy faces a fundamental discovery challenge: in many systems, the most important scientific information does not reside in the immediately visible image features, but in the target space of sequentially acquired spectra or functional responses, making it essential to develop strategies that can actively search for new behaviors rather than simply optimize known objectives. Here, we developed a deep-kernel-learning BEACON framework that is explicitly designed to guide discovery in the target space by learning structure-property relationships during the experiment and using that evolving model to seek diverse response regimes. We first established the method through demonstration workflows built on pre-acquired ground-truth datasets, which enabled direct benchmarking against classical acquisition strategies and allowed us to define a set of monitoring functions for comparing exploration quality, target-space coverage, and surrogate-model behavior in a transparent and reproducible manner. This benchmarking framework provides a practical basis for evaluating discovery-driven algorithms, not just optimization performance. We then operationalized and deployed the workflow on STEM, showing that the approach can transition from offline validation to real experimental implementation. To support adoption and extension by the broader community, the associated notebooks are available, allowing users to reproduce the workflows, test the benchmarks, and adapt the method to their own instruments and datasets.

cs.LG

Mechanism-Resolved PFM of Ferroionic and Ferroelectric Responses in Thickness-Gradient Hf0.5Zr0.5O2 Libraries

Resolving growth mechanisms and thickness evolution of functional properties is one of the key tasks in materials discovery and optimization involving thin-film materials, traditionally requiring significant experimental budgets. Here we introduce the combination of thickness-gradient libraries and automated scanning probe microscopy as a systematic pathway to elucidate growth modes and disentangle ferroelectric and electrochemical contributions in ferroelectric thin films. As a model system, we explore the Hf0.5Zr0.5O2 (HZO) gradient thin films grown on LaxSr1-xMnO3 (LSMO) bottom electrode thin films. Automated piezoresponse force microscopy, spectroscopy, and lithography reveals that irreversible topographic deformation arises from electrochemical activity at the LSMO surface, whereas reversible phase inversion in HZO reflects ferroelectric switching. Automated topography height-map scans are used to further quantify nucleation density, particle-size evolution, and roughness correlations across the thickness-gradient, demonstrating that improved plume stabilization during growth suppresses interfacial reactions and promotes dense, fine-grained HZO conducive to ferroelectric phase formation. This combined materials-engineering and automated-SPM framework establishes a platform for high-throughput, mechanism-resolved characterization of ferroionic and ferroelectric responses in complex oxide films.

cond-mat.mtrl-sci

Stress-Induced Ferroelectricity in Hafnium Oxide Core-Shell Nanoparticles

In contrast to hafnia (HfO2) thin films, where the appearance of switchable ferroelectric polarization can be induced by strain or defect engineering, reliable methods for controlling ferroelectricity are absent in HfO2 nanoparticles. Direct experimental observations of ferroelectric hysteresis and ferroelectric domains in these nanoparticles are also absent. To the best of our knowledge, stress-induced ferroelectric states in the HfO2 nanoparticles have not been explored. In this work, we study the influence of chemical stress on phase diagrams, dielectric and polar properties of spherical HfO2 core-shell nanoparticles using a Landau-Ginzburg-Devonshire free energy functional that includes trilinear and biquadratic couplings involving polar, antipolar, and nonpolar order parameters. The ferroelectric phase exhibits reentrant behavior as a function of nanoparticle size, such that the spontaneous polarization exists only within a limited range of core radii R_c, namely R_cr^min<R_c<R_cr^max. The minimal critical radius R_cr^min is primarily determined by the size dependence of the depolarization field and correlation effects; the maximal critical radius R_cr^max is primarily determined by the size dependence of chemical stresses induced by the elastic defects in the shell. Thus, this work identifies a stress-driven mechanism for reentrant ferroelectricity stabilization in nanoscale HfO2 systems, arising from the competition between depolarization field-induced suppression of ferroelectricity and its stabilization by shell-induced chemical stress. We revealed that relatively large compressive chemical strains are necessary to induce the ferroelectric phase in the HfO2 nanoparticles. Successful chemical strain engineering opens the way for significant enhancement of nanoscale HfO2 polar properties for applications in advanced memory cells and logic devices.

cond-mat.mtrl-sci

Embedded Ferroelectric Nanoclusters can drive Polarization Reversal in a Non-Ferroelectric Polar Film via the Proximity Effect

Heterogeneous nucleation from defects dominates the electric field required for polarization switching of ferroelectrics. Here, we consider the switching of a nominally non-switchable polar thin film of AlN due to the proximity effect arising from embedded ferroelectric nanoclusters of Al1-xScxN. Using a Landau-Ginzburg-Devonshire thermodynamic approach and finite element modeling, we study the influence of nanocluster shape on polarization switching and domain nucleation emerging in AlN. The ferroelectric nanocluster boundary is modeled as a thin layer transitioning from Al1-xScxN to AlN. We analyze the conditions under which polarization switching in the AlN film occurs at coercive fields significantly lower than its dielectric breakdown field. In the presence of spike-like Al1-xScxN nanoclusters, the proximity effect enables switching of the spontaneous polarization in AlN and significantly reduces the corresponding coercive field. The internal field, which is depolarizing inside the AlN (due to its larger spontaneous polarization) and polarizing within the ferroelectric Al1-xScxN nanoclusters (due to its smaller spontaneous polarization), lowers the potential barrier in the clusters and nucleates nanodomains at the Al1-xScxN-AlN interface, forming localized regions of reversed polarization. Proximity effect can thus provide a pathway towards "thawing" previously "frozen" ferroelectrics through engineered nucleation for memory, actuation and optical technologies.

cond-mat.mtrl-sci

Dynamic Multiband Microscopy: A Universal Paradigm for Quantitative Nanoscale Metrology

Scanning Probe Microscopy (SPM) is the primary tool for exploring nanoscale functionality, yet standard single-frequency operation is fundamentally limited, because the dynamic tip-sample interaction is mathematically underdetermined. While advanced methods such as Dual Amplitude Resonance Tracking (DART) and Band Excitation (BE) address this by tracking resonance, they face critical limitations: DART suffers from feedback instability on complex topographies, while Band Excitation is constrained by severe trade-offs between spectral resolution and acquisition speed. Here, we introduce Dynamic Multiband Microscopy (DMM), a general framework that bridges these gaps by combining multifrequency excitation with continuous frequency sweeping. We implement this within an automated experimental workflow that autonomously identifies and targets measurement points of interest. In combination with quantitative interferometric detection, this approach brings SPM to the fundamental limits of noise and spectral sensitivity. Validated on ferroelectric nanofibers, this platform enables simultaneous, crosstalk-free 3D polarization mapping, establishing a universal framework for autonomous, high-fidelity nanoscale metrology.

cond-mat.mtrl-sci

Autonomous Probe Microscopy with Robust Bag-of-Features Multi-Objective Bayesian Optimization: Pareto-Front Mapping of Nanoscale Structure-Property Trade-Offs

Combinatorial materials libraries are an efficient route to generate large families of candidate compositions, but their impact is often limited by the speed and depth of characterization and by the difficulty of extracting actionable structure-property relations from complex characterization data. Here we develop an autonomous scanning probe microscopy (SPM) framework that integrates automated atomic force and magnetic force microscopy (AFM/MFM) to rapidly explore magnetic and structural properties across combinatorial spread libraries. To enable automated exploration of systems without a clear optimization target, we introduce a combination of a static physics-informed bag-of-features (BoF) representation of measured surface morphology and magnetic structure with multi-objective Bayesian optimization (MOBO) to discover the relative significance and robustness of features. The resulting closed-loop workflow selectively samples the compositional gradient and reconstructs feature landscapes consistent with dense grid "ground truth" measurements. The resulting Pareto structure reveals where multiple nanoscale objectives are simultaneously optimized, where trade-offs between roughness, coherence, and magnetic contrast are unavoidable, and how families of compositions cluster into distinct functional regimes, thereby turning multi-feature imaging data into interpretable maps of competing structure-property trends. While demonstrated for Au-Co-Ni and AFM/MFM, the approach is general and can be extended to other combinatorial systems, imaging modalities, and feature sets, illustrating how feature-based MOBO and autonomous SPM can transform microscopy images from static data products into active feedback for real-time, multi-objective materials discovery.

cond-mat.mtrl-sci

Sizes of Ferroelectricity Appearance and Disappearence in Nanosized Hafnia-Zirconia:Landau-type Theory

Nanosized hafnia-zirconia HfxZr1-xO2 in the form of thin films, multilayers and heterostructures are indispensable silicon-compatible ferroelectric materials for advanced electronic memories and logic devices. The distinctive feature of nanoscale hafnia-zirconia are the critical sizes of ferroelectricity appearance, whereas the critical sizes of ferroelectricity disappearance exist in other ferroelectrics. Using the Landau-Ginzburg-Devonshire free energy functional with higher powers, trilinear and biquadratic couplings of polar, nonpolar and antipolar order parameters, we calculated analytically the strain-dependent critical sizes of the ferroelectricity appearance and disappearance, analyzed how the size effect and mismatch strains influence the phase diagrams and polarization switching barrier in epitaxial HfO2 thin films and nano-islands with the out-of-plane spontaneous polarization. We have shown that the critical thickness/height of out-of-plane spontaneous polarization disappearance is determined by the size dependence of the depolarization field and correlation effects. The critical thickness/height of the ferroelectricity appearance is determined by the size dependence of the effective mismatch strain considering possible appearance of misfit dislocations and lateral relaxion of strains. Derived analytical expressions can be generalized for HfxZr1-xO2 solid solutions, providing that corresponding parameters of the free energy are known from the first principles calculations.

cond-mat.mtrl-sci

Bayesian Co-Navigation of a Computational Physical Model and AFM Experiment to Autonomously Survey a Combinatorial Materials Library

Building autonomous experiment workflows requires transcending beyond the data-driven surrogate models to incorporate and dynamically refine physical theory during exploration. Here we demonstrate the first fully automated experimental realization of Bayesian co-navigation - a framework in which an autonomous agent simultaneously runs a physical experiment and a computationally expensive physical model. Using an automated AFM platform coupled to a kinetic Monte Carlo (kMC) model of thin-film growth, the system infers a set of effective bond energies for the (CrTaWV)x-Mo(1-x) pseudo-binary combinatorial library, progressively adjusting the kMC parameters to decrease the epistemic disparity between simulation and experiment. This real-time theoretical refinement enables the kMC model to capture the behavior of the specific materials system and reveals the mechanistic role of hetero-bonding in governing surface diffusion. Together, these results establish co-navigation as a general strategy for tightly integrating physical models with autonomous experimental platforms to produce interpretable and continually self-correcting theoretical modelling of complex materials systems.

cond-mat.mtrl-sci