arXiv subjects

Guido Schmitz

Publications and source records attributed to Guido Schmitz.

11 recordsLinked to original sources

arXiv2026

MicroCup: A Cryogenic Specimen Preparation Strategy for Atom Probe Tomography of Organic Molecular Liquids

Atom probe tomography (APT) of organic molecular liquids is limited by poorly reproducible specimen geometry, reduced milling rates, and beam sensitivity during cryo-FIB preparation. Here we introduce a MicroCup strategy that confines liquids in a FIB-prepared nanoscale cavity prior to phase separation, reduces deposited volume to increase preparation throughput, enables reproducible specimen geometry, and minimizes beam exposure in the region of interest. Using the liquid crystals 4'-octyl-4-cyanobiphenyl (8CB) and 4'-octyloxy-4-cyanobiphenyl (8OCB) as model systems, we establish stable and reproducible field evaporation conditions, enabling the detected intact ion molecular preservation above 70% in smectic-like phases with interpretable fragmentation behavior. Comparative analysis further shows that the oxygen atom in 8OCB promotes preferential cleavage pathways associated with bond polarization under high electric fields. By inducing partial crystallization within the MicroCup cavity, distinct regions could be resolved: 8CB shows broadly similar evaporation behavior across crystalline and amorphous regions, whereas 8OCB exhibits clearer regional contrast, with smectic-like regions dominated by intact molecular or large fragments and crystalline domains producing small alkyl fragments and ether-type species. These results provide spatially resolved evidence of a solid-liquid interface in a freeze-prepared organic liquid by APT and establish a reproducible workflow for probing local phase behavior in soft materials.

cond-mat.mtrl-sci↗

arXiv2025

Revealing Nanoscale Molecular Organization in Liquid Crystals via Cryogenic Atom Probe Tomography

While liquid crystals (LCs) have been extensively studied, obtaining a comprehensive nanoscale picture of their molecular organization remains challenging, as conventional techniques face an intrinsic trade-off between spatial and chemical resolution. Here, cryogenic atom probe tomography (cryo-APT) is introduced as a new analytical approach for LC materials, using 4'-Pentyl-4-cyanobiphenyl (5CB) and 4'-Octyl-4-cyanobiphenyl (8CB) as representative model compounds. This was enabled by a tailored cryogenic focused ion beam (cryo-FIB) protocol optimized for small organic molecules. The method enables controlled field evaporation of both intact molecules and diagnostic fragments, achieving over 90% molecular retention while preserving four characteristic dissociation patterns. By spatially correlating these fragmentation profiles with the local electric field derived from the tip geometry, we reveal field-directed dissociation pathways of CB molecules. In parallel, the distribution of intact molecular ions enables nanoscale visualization of material structure: we resolve homogeneous mixing of 5CB and 8CB in the nematic phase and directly observe the sub-nanometer crystalline layering in a supercooled 8CB sample, with contrast to the surrounding amorphous matrix suggesting the presence of a solid-liquid interface. This work establishes cryo-APT as a new powerful analytical platform for LC research and reveals its broad potential for application in soft matter systems.

cond-mat.mtrl-sci↗

arXiv2025

Surface oxidation of Pt and PtPd alloys during NO conversion investigated by Atom Probe Tomography

In this study, the dynamic oxidation state changes of pure Pt and 50at% PtPd alloy catalysts were investigated during a temperature ramp from 80 to 450 C under a reactive gas mixture of 500 ppm NO and 3 % Oxygen in Nitrogen atmosphere. These changes are closely correlated with variations in NO conversion efficiency. Sharp tip specimens were prepared from Pt and PtPd alloy wires by electrochemical polishing and Focused Ion Beam annular milling, with the hemispherical apex serving as a model for nanoscale catalyst surfaces. The samples were exposed to the reactive atmosphere in a dedicated reaction chamber and subsequently analyzed using atom probe tomography. Effective oxide thicknesses and three-dimensional surface morphology were quantitatively evaluated. A pronounced decrease in oxide thickness was observed during the first cooling and second heating cycles, particularly below 200 C, indicating reversible redox behavior on both Pt and PtPd alloy surfaces. This behavior correlates with the inverse hysteresis of NO conversion measured for both systems, suggesting that the redox reversibility is driven primarily by reaction kinetics rather than thermodynamic stability.

cond-mat.mtrl-sci↗

arXiv2021

The modular Atom Probe Concept

Atomic probe tomography (APT), based on the work of Erwin Mueller, is able to generate three-dimensional chemical maps in atomic resolution. The required instruments for APT have evolved over the last 20 years from an experimental to an established method of materials analysis. Here, we describe the realization of a new instrument concept that allows the direct attachment of APT to a dual beam SEM microscope with the main achievement of fast and direct sample transfer. New operational modes are enabled regarding sample geometry, alignment of tips and microelectrode. The instrument is optimized to handle cryo-samples at all stages of preparation and storage. The instrument comes with its own software for evaluation and reconstruction. The performance in terms of mass resolution, aperture angle, and detection efficiency is demonstrated with a few application examples.

physics.ins-det↗

arXiv2021

Status and direction of atom probe analysis of frozen liquids

Imaging of liquids and cryogenic biological materials by electron microscopy has been recently enabled by innovative approaches for specimen preparation and the fast development of optimised instruments for cryo-enabled electron microscopy (cryo-EM). Yet, Cryo-EM typically lacks advanced analytical capabilities, in particular for light elements. With the development of protocols for frozen wet specimen preparation, atom probe tomography (APT) could advantageously complement insights gained by cryo-EM. Here, we report on different approaches that have been recently proposed to enable the analysis of relatively large volumes of frozen liquids from either a flat substrate or the fractured surface of a wire. Both allowed for analysing water ice layers which are several microns thick consisting of pure water, pure heavy-water and aqueous solutions. We discuss the merits of both approaches, and prospects for further developments in this area. Preliminary results raise numerous questions, in part concerning the physics underpinning field evaporation. We discuss these aspects and lay out some of the challenges regarding the APT analysis of frozen liquids.

cond-mat.mtrl-sci↗

arXiv2017

The Web SSO Standard OpenID Connect: In-Depth Formal Security Analysis and Security Guidelines

Web-based single sign-on (SSO) services such as Google Sign-In and Log In with Paypal are based on the OpenID Connect protocol. This protocol enables so-called relying parties to delegate user authentication to so-called identity providers. OpenID Connect is one of the newest and most widely deployed single sign-on protocols on the web. Despite its importance, it has not received much attention from security researchers so far, and in particular, has not undergone any rigorous security analysis. In this paper, we carry out the first in-depth security analysis of OpenID Connect. To this end, we use a comprehensive generic model of the web to develop a detailed formal model of OpenID Connect. Based on this model, we then precisely formalize and prove central security properties for OpenID Connect, including authentication, authorization, and session integrity properties. In our modeling of OpenID Connect, we employ security measures in order to avoid attacks on OpenID Connect that have been discovered previously and new attack variants that we document for the first time in this paper. Based on these security measures, we propose security guidelines for implementors of OpenID Connect. Our formal analysis demonstrates that these guidelines are in fact effective and sufficient.

cs.CR↗

arXiv2016

A Comprehensive Formal Security Analysis of OAuth 2.0

The OAuth 2.0 protocol is one of the most widely deployed authorization/single sign-on (SSO) protocols and also serves as the foundation for the new SSO standard OpenID Connect. Despite the popularity of OAuth, so far analysis efforts were mostly targeted at finding bugs in specific implementations and were based on formal models which abstract from many web features or did not provide a formal treatment at all. In this paper, we carry out the first extensive formal analysis of the OAuth 2.0 standard in an expressive web model. Our analysis aims at establishing strong authorization, authentication, and session integrity guarantees, for which we provide formal definitions. In our formal analysis, all four OAuth grant types (authorization code grant, implicit grant, resource owner password credentials grant, and the client credentials grant) are covered. They may even run simultaneously in the same and different relying parties and identity providers, where malicious relying parties, identity providers, and browsers are considered as well. Our modeling and analysis of the OAuth 2.0 standard assumes that security recommendations and best practices are followed, in order to avoid obvious and known attacks. When proving the security of OAuth in our model, we discovered four attacks which break the security of OAuth. The vulnerabilities can be exploited in practice and are present also in OpenID Connect. We propose fixes for the identified vulnerabilities, and then, for the first time, actually prove the security of OAuth in an expressive web model. In particular, we show that the fixed version of OAuth (with security recommendations and best practices in place) provides the authorization, authentication, and session integrity properties we specify.

cs.CR↗

arXiv2015

SPRESSO: A Secure, Privacy-Respecting Single Sign-On System for the Web

Single sign-on (SSO) systems, such as OpenID and OAuth, allow web sites, so-called relying parties (RPs), to delegate user authentication to identity providers (IdPs), such as Facebook or Google. These systems are very popular, as they provide a convenient means for users to log in at RPs and move much of the burden of user authentication from RPs to IdPs. There is, however, a downside to current systems, as they do not respect users' privacy: IdPs learn at which RP a user logs in. With one exception, namely Mozilla's BrowserID system (a.k.a. Mozilla Persona), current SSO systems were not even designed with user privacy in mind. Unfortunately, recently discovered attacks, which exploit design flaws of BrowserID, show that BrowserID does not provide user privacy either. In this paper, we therefore propose the first privacy-respecting SSO system for the web, called SPRESSO (for Secure Privacy-REspecting Single Sign-On). The system is easy to use, decentralized, and platform independent. It is based solely on standard HTML5 and web features and uses no browser extensions, plug-ins, or other executables. Existing SSO systems and the numerous attacks on such systems illustrate that the design of secure SSO systems is highly non-trivial. We therefore also carry out a formal analysis of SPRESSO based on an expressive model of the web in order to formally prove that SPRESSO enjoys strong authentication and privacy properties.

cs.CR↗

arXiv2015

Analyzing the BrowserID SSO System with Primary Identity Providers Using an Expressive Model of the Web

BrowserID is a complex, real-world Single Sign-On (SSO) System for web applications recently developed by Mozilla. It employs new HTML5 features (such as web messaging and web storage) and cryptographic assertions to provide decentralized login, with the intent to respect users' privacy. It can operate in a primary and a secondary identity provider mode. While in the primary mode BrowserID runs with arbitrary identity providers (IdPs), in the secondary mode there is one IdP only, namely Mozilla's default IdP. We recently proposed an expressive general model for the web infrastructure and, based on this web model, analyzed the security of the secondary IdP mode of BrowserID. The analysis revealed several severe vulnerabilities. In this paper, we complement our prior work by analyzing the even more complex primary IdP mode of BrowserID. We do not only study authentication properties as before, but also privacy properties. During our analysis we discovered new and practical attacks that do not apply to the secondary mode: an identity injection attack, which violates a central authentication property of SSO systems, and attacks that break an important privacy promise of BrowserID and which do not seem to be fixable without a major redesign of the system. Some of our attacks on privacy make use of a browser side channel that has not gained a lot of attention so far. For the authentication bug, we propose a fix and formally prove in a slight extension of our general web model that the fixed system satisfies all the requirements we consider. This constitutes the most complex formal analysis of a web application based on an expressive model of the web infrastructure so far. As another contribution, we identify and prove important security properties of generic web features in the extended web model to facilitate future analysis efforts of web standards and web applications.

cs.CR↗

arXiv2014

An Expressive Model for the Web Infrastructure: Definition and Application to the BrowserID SSO System

The web constitutes a complex infrastructure and as demonstrated by numerous attacks, rigorous analysis of standards and web applications is indispensable. Inspired by successful prior work, in particular the work by Akhawe et al. as well as Bansal et al., in this work we propose a formal model for the web infrastructure. While unlike prior works, which aim at automatic analysis, our model so far is not directly amenable to automation, it is much more comprehensive and accurate with respect to the standards and specifications. As such, it can serve as a solid basis for the analysis of a broad range of standards and applications. As a case study and another important contribution of our work, we use our model to carry out the first rigorous analysis of the BrowserID system (a.k.a. Mozilla Persona), a recently developed complex real-world single sign-on system that employs technologies such as AJAX, cross-document messaging, and HTML5 web storage. Our analysis revealed a number of very critical flaws that could not have been captured in prior models. We propose fixes for the flaws, formally state relevant security properties, and prove that the fixed system in a setting with a so-called secondary identity provider satisfies these security properties in our model. The fixes for the most critical flaws have already been adopted by Mozilla and our findings have been rewarded by the Mozilla Security Bug Bounty Program.

cs.CR↗

arXiv2011

Hillock formation of Pt thin films on Yttria stabilized Zirconia single crystals

The stability of a metal thin films on a dielectric substrate is conditioned by the magnitude of the interactive forces at the interface. In the case of a non-reactive interface and weak adhesion, the minimization of free surface energy gives rise to an instability of the thin film. In order to study these effects, Pt thin films with a thickness of 50 nm were deposited via ion-beam sputtering on yttria stabilized zirconia single crystals. All Pt films were subjected to heat treatments up to 973 K for 2 h. The morphological evolution of Pt thin films has been investigated by means of scanning electron microscopy (SEM), atomic force microscopy (AFM) and standard image analysis techniques. Three main observations have been made: i) the deposition method has a direct impact on the morphological evolution of the film during annealing. Instead of hole formation, that is typically observed as response to a thermal treatment, anisotropic pyramidal shaped hillocks are formed on top of the film. ii) It is shown by comparing the hillocks' aspect ratio with finite element method (FEM) simulations that the hillock formation can be assigned to a stress relaxation process inside the thin film. iii) By measuring the equilibrium shapes and the shape fluctuations of the formed Pt hillocks the anisotropy of the step free energy and its stiffness have been derived in addition to the anisotropic kink energy of the hillock's edges.

cond-mat.mtrl-sci↗