Nothing could be more coupled than Growth and Characterization. When two dimensional (2D) materials appeared on the radar of the scientific community (with the amazing properties of graphene), it was immediately obvious that large area samples would be needed. Exfoliating flakes was insufficient for the demands of scientific studies, in addition to not being viable should a commercial application be developed. Thus, the search began for growth methods to produce large-area 2D materials for large scale testing and development.

The Naval Research Laboratory has, over the past 15 years, pursued research programs in producing large areas of graphene, transition metal dichalcogenides (TMDs), boron nitride (BN), and other 2D materials. In every one of those programs, they began with surface analysis of composition, chemistry, and morphology of the grown films. The uniquely sensitive nature of x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and scanning tunneling and atomic force microscopy (STM and AFM) to 2D materials was necessary to measure the electrical, chemical, and physical properties obtained in the large area films and to understand what was observed in the exfoliated flakes. The production of large areas allowed “mass-scale” optical and electrical characterization, which then became a feedback loop in the search for new and interesting properties and relevant applications. In this presentation, I will show how we developed large-area graphene, by both epitaxial growth and chemical vapor deposition methods, TMDs, and other 2D materials for characterization and device utilization.

Over the past years, the field of surface and interface analysis has been greatly expanded by new developments made possible by lab-scale instruments enabling higher excitation energies. These new developments are directly serving technological advances especially in the area of technologies in renewable energies and nanoelectronics, which are adressing more and more complex system requiring to go beyond traditional ways of characterizing surfaces and interfaces. Different dimensions are to be explored in multi-modal surface analysis : the depth dimension, the lateral dimension, and the dynamic dimension.

After a short review of some of the achievements towards enhancing the depth dimension by lab-scale hard X-ray photoelectron spectroscopy (HAXPES) and the lateral dimension using X-ray PEEM, we will present different application cases of operando HAXPES. Here, the material is analyzed as being part of a device operated in situ during the experiment, in conditions that are as close as possible to the final applications and where the interfaces can be studied in dynamic conditions. We will first review some results of operando HAXPES on resistive memories obtained with synchrotron radiation [1, 2] before presenting various lab-scale experiments [3, 4] and the current limitations to such approaches.

[1]B. Meunier, E. Martinez, O. Renault et al. J. Appl. Phys. 126, 225302 (2019).

[2]B. Meunier, E. Martinez, O. Renault et al., ACS Appl. Electron. Mater. 3 (12), 5555–5562 (2021).

[3]O. Renault et al., Faraday Disc. 236, 288-310 (2022).

[4]A. Benayad et al., J. Phys. Chem. A 2021, 125, 4, 1069-81.

Bathocuproine (BCP) is a small organic molecule that is typically used as an ultrathin hole blocking interlayer (< 10 nm thickness) in organic solar cells and perovskite solar cells. The film is typically deposited via low-throughput vacuum thermal evaporation with an in-situ Quartz Crystal Monitor to measure film thickness. Open-air ultrasonic spray deposition for low-cost and large-scale deposition is an attractive alternative method for solution processing of BCP films, but the process lacks a comparable in-situ metrology. Given that the BCP film is transparent to visible light and ultrathin, it is important to utilize a multi-modal approach to evaluate optoelectronic and physical properties of the sprayed film.

A suite of characterization techniques that span a range of equipment complexity, measurement time, and measurement sensitivity are used to analyze the BCP films. We begin by demonstrating the limitations of the singular ellipsometry model¹ for BCP found in literature and motivate a need to rely on other techniques. Multi-modal analyses including X-Ray Reflectivity, Angle-Resolved X-ray Photon Spectroscopy (AR-XPS), Auger Spectroscopy, Scanning Electron Microscopy, and Transmission Electron Microscopy with EELS are then performed on the sprayed BCP film. The advantages and disadvantages of each characterization technique are compared and discussed. We conclude that AR-XPS provides the most distinctive determination of individual layer thicknesses for a sample architecture consisting of silicon substrate/native SiO_x/BCP across the applicable range of AR-XPS from ~ 1-10 nm.

^[1]Liu, Z.T., et al. The characterization of the optical functions of BCP and CBP thin films by spectroscopic ellipsometry. Synthetic Materials. 150(2):159-163. (2005)

A few binary metal alloys are predicted to form thermally stable, compositionally segregated structures owing to the thermodynamic preference for minority species to collect and remain at grain boundaries established within the solid.(J.R. Trelewicz et al., PRB, 2009) When produced as a nanocrystalline thin film, these stable structures afford the potential to maintain excellent mechanical properties (e.g., high hardness) even after annealing to elevated temperature. Indeed, several systems, including Pt_.9Au_.1 thin films, are reported to develop thermally-stabilized, hard, nanocrystalline structures attributed to solute segregation at grain boundaries.(P. Lu et al., Materialia, 2019)

Future studies that seek optimal stoichiometry and/or preferred synthesis processes require access to a wide range of composition as well as an ability to vary key deposition parameters. Toward this end, our team reports on the challenges and the benefits of combinatorial synthesis for expediting the discovery of improved binary metal thin films. Our study utilized confocal sputter deposition wherein Pt and Au targets were individually sputtered via pulsed DC magnetron methods. Substrates (150 mm diameter wafers) were fixed in order to gain access to a wide compositional range for each deposition. The sputter power and cathode tilt orientation were then varied in subsequent depositions to access the nearly full binary metal compositional range. The binary collision Monte Carlo program SiMTra (D. Depla et al., Thin Solid Films 2012), which simulates the transport of sputtered atoms within the process gas, helped guide the selection of these process parameters in order to achieve compositional goals in relatively few depositions. Notably, the binary compositions predicted by SiMTra closely matched (within a few molar %) the measured compositions determined by Wavelength Dispersive Spectroscopy completed in 112 different areas across each wafer. The various combinatorial Pt-Au films were further characterized by high-throughput Atomic Force Microscopy, automated X-ray Diffraction, fast X-ray Reflectivity, mapping four-point probe sheet resistance, and automated nanoindentation. These studies reveal how hardness, modulus, film density, crystal texture, and resistivity of combinatorial films varied with composition as well the atomistics of film deposition. Attempts to correlate key film characteristics with the kinetic energies and incident angles of arriving metal species (estimated by SiMTra) are discussed with a goal of improving fabrication processes.

Sandia National Laboratories is managed and operated by NTESS under DOE NNSA contract DE-NA0003525.

As traditional scaling of transistors comes to end, transistor channels and capacitors are being stacked to form new 3D transistor and memory devices.Many of these devices are fabricated using films stacks consisting of multiple Si/Si(1-x)Gex layers known as superlattices which must be fabricated with near atomic precision.In this talk, we discuss how Optical and X-Ray methods are used to measure the feature shape and dimensions of these structures.The use of X-Ray methods such as ω-2θscans and reciprocal space maps provide layer thickness and stress characterization. We will use simulations to show how a buried layer with a different thickness or Ge concentration alters the data. Recent electron microscopy studies have quantified the stress at the interfaces of these superlattices.We will also discuss how Mueller Matrix spectroscopic ellipsometry (MMSE) based scatterometry is used to measure feature shape and dimension for the nanowire/nanosheet structures used to fabricate nanosheet transistors and eventually 3D DRAM.The starting point for optical scatterometry is determining the optical properties of stressed pseudomorphic Si(1-x)Gex.MMSE can be extended into the infra-red and into the EUV.In addition, small angle X-Ray scattering has been adapted into a method knows as CDSAXS which can be used to characterize these structures.This talk will be an overview of these methods.

An OrbiSIMS [1] instrument features a dual analyser configuration with a time-of-flight (ToF) mass spectrometer (MS) and an Orbitrap^TM MS, which confer advantages of speed and high-performance mass spectrometry, respectively. The ability to combine the MS performance usually found in a state-of-the-art proteomics and metabolomics MS with 3D imaging at the microscale and from nanolayers of <10 nm of material has proved popular in a broad field of application from organic electronics to drug discovery. For secondary ions to be efficiently transferred to the Orbitrap analyser, the sample is biased by a target voltage V_T necessary to match the acceptance window of the Orbitrap. Furthermore, the ions kinetic energy from the SIMS collision process must be reduced. Therefore, in the OrbiSIMS, a transfer system with helium gas at a pressure P_He slows the ions and reduces their kinetic energy distribution through inelastic collisions with gas atoms. Usually, an Orbitrap is used with an ambient pressure ion source and so here an extra gas flow of nitrogen is introduced that leads to an increase of pressure P_N2 to compensate.

We conducted a systematic assessment of V_T and P_He and P_N2 on the transmitted secondary ion intensities [2] and revealed a complex behaviour, indicating the possibility for additional separation of ions based on their shape, stability, and kinetics of formation. We showed that the V_T for maximum transmission of secondary ions will not be the same for all molecules of the same material and that sometimes multiple maxima exist. Here, we present recent progress towards the understanding of these phenomena and how we are leveraging it to measure molecular shape by using reference trisaccharides raffinose, maltrosiose and melozitose [3].

[1] M. K. Passarelli et al., “The 3D OrbiSIMS—label-free metabolic imaging with subcellular lateral resolution and high mass-resolving power,” Nat. Methods, no. november, p. nmeth.4504, 2017, doi: 10.1038/nmeth.4504.

[2] L. Matjacic et al., “OrbiSIMS metrology part I: Optimisation of the target potential and collision cell pressure,” Surf. Interface Anal., no. November 2021, pp. 1–10, 2021, doi: 10.1002/sia.7058.

[3] G.F. Trindade et al., In preparation.