Covalent

X-ray Photoelectron Spectroscopy (XPS)

XPS measures surface elemental composition and chemical states within ~7–10 nm, enabling angle-resolved and depth profiling.

What Is X-ray Photoelectron Spectroscopy?

X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for Chemical Analysis (ESCA), is a surface-sensitive analytical technique that probes the top 70–100 Å of a sample. The technique is based on photoelectrons emitted from atoms on the sample surface after excitation by x-rays, usually Al K-alpha (1487 eV).

The key strength of XPS is its surface sensitivity. The mean free path of the emitted photoelectrons limits the depth from which they can escape and be detected to the top 70 – 100Å of the surface using the typical Take-off-Angle (TOA, measured between the detector and the surface) of 90° and depending on the element from which the electron originated. Changing this TOA to a more grazing angle can reduce the analytical depth. This makes XPS the ideal technique for the analysis of thin films, surface contaminants, and oxidation/corrosion.

Depth and Angle Profiling

Offers depth profiling and
angle-resolved measurements to examine layered materials and surface composition variations.

Surface-Specific Analysis

Provides detailed chemical and elemental information from the top 7-10nm of a sample, ideal for thin films, coatings, and contamination studies.

Chemical Bonding Insight

Determines the bonding states of elemwnts, enabling identification of oxidation, corrosion, and functional groups.

Why Use XPS?

X-ray Photoelectron Spectroscopy (XPS) is a highly surface-specific technique that provides detailed chemical and elemental information from the top 7–10 nm of a material. It is ideal for analyzing thin films, surface contamination, oxidation, corrosion, and chemical bonding states. XPS enables both depth profiling and angle-resolved analysis, making it indispensable for understanding surface chemistry in industrial and research applications.

High-Resolution Detection

Adjustable spot sizes (10–400 µm) and high spectral resolution for accurate surface characterization.

Advanced Sample Handling

Supports vacuum transfer, angle-tilt mounts, and work function measurements for versatile experiments.

Layered Material Analysis

Argon ion etching enables depth profiling to study composition changes across layers without losing chemical information.

How XPS Works

  • Elemental Composition:
    • XPS collects a survey spectrum over a wide energy range (-10eV to 1350eV) with high signal strength.
    • Elements are identified by the detected peaks.
    • Peaks are integrated to give the relative atomic percent of each element, normalized to 100%.
  • Chemical Bonding Information:
    • XPS takes high-resolution spectra focused on specific elements.
    • These spectra use settings that enhance spectral resolution.
    • Special models are used to fit each peak and determine their exact positions.
    • The positions (binding energies) help identify what types of chemical bonds are present, using reference data.
  • Depth Profiles:
    • XPS can combine measurements with argon ion etching, which slowly removes material from the surface.
    • This allows you to see how the composition changes with depth, useful for analyzing layered materials and estimating layer thickness.
  • Angle-Resolved Analysis:
    • By changing the angle of measurement, XPS can collect information from different depths without removing material.
    • This helps estimate the thickness of layers in your sample.

Equipment Used for XPS

ThermoFisher Nexsa

  • Spot Size: 10µm to 400µm.
  • Sensitivity: 0.01 atomic % to 0.5 atomic % depending on the element.
  • X-ray Source: Monochromated, micro-focused, high-efficiency Al Kα X-ray Anode.
Specifications

Key differentiators

Strengths

  • Provides chemical bonding information from the top 7-10nm not obtainable with any other technique.
  • Capable of analyzing conductors and insulators.
  • Compatible with a wide variety of sample types.
  • Excellent detection limits (part per thousand for some elements) and spectral resolution.

Limitations

  • Does not have ppm detection limits.
  • Some sample degradation can occur due to heating from x-ray or flood guns.
  • Chemical bonding information is not always possible in depth profiles due to reduction of sensitive species by argon ion sputtering.
  • Not suited to very rough samples.

Example Outputs

High resolution Al2p spectrum acquired from aluminum foil, peak deconvoluted to separate metal versus oxide. Data can be used to calculate oxide thickness, or 57Â.
High resolution Ta4f spectrum showing different oxidation states; peak deconvoluted to separate metal versus oxides and suboxides.
High-resolution C1s spectra showing different forms of carbon: HOPG, diamond, and organic carbon tape
Peak deconvolution of carbon tape C1s high-resolution spectrum showing binding energies and quantitation of different carbon bonding present; indicative of a polyester adhesive
Survey spectrum of carbon tape showing carbon, oxygen and silicon for quantitation of elements detected and to identify contaminants, such as silicon
Depth profile of SiO2 on Si used to determine argon ion etch rate based on known thickness and etch time

Sample Requirements

XPS can analyze any sample compatible with an Ultra-High Vacuum (10-9 mbar) including polymerspowders, cured adhesives, liquid residues, fibers, viscous oil and gels, and any other solid sample. 

  • Solid phase.
  • Stable under ultra-high vacuum conditions.
  • Max dimensions: 60 mm (L) x 60 mm (W) x 20 mm (T).
  • Flatter topographies improve signal detection.
  • For Powder Samples: 5-10 mg is sufficient (as long as it can cover 0.5 cm x 0.5 cm of foil or Cu tape).

XPS Applications by Industry

Semiconductor & Microelectronics

XPS detects surface contamination, and checks oxidation states that could affect device yield. XPS can measure material work functions, critical for semiconductor performance. Depth profiling verifies thin-film chemistry and reveals interlayer diffusion in multilayer stacks.

Aerospace & Defense

XPS identifies oxidation, corrosion, and contaminants on metals and coatings. It validates surface treatments and supports failure analysis of mission-critical parts, such as delaminations.

Energy & Battery Technology

XPS analyzes electrode surfaces, SEI layers, and catalyst coatings for surface contamination and oxidation states, especially effective when paired with inert gas/vacuum transfer directly into instrument.

Polymers / Coatings / Adhesives

XPS detects contamination, chemical variations, and surface treatments on polymer and coating surfaces. It supports adhesion studies and failure analysis, such as delaminations and discolorations.

Medical Devices & Biotech

XPS verifies surface cleanliness, functionalization, and bioactive coatings and surface treatments. It helps detect residues and ensure material compatibility for regulated applications.

Automotive & Industrial Manufacturing

XPS identifies corrosion products, contaminants, and wear-related chemistry. It verifies pre-coat surface quality and supports root-cause investigations.

Environmental & Catalysis Research

XPS determines oxidation states and surface species on catalysts and environmental samples. It aids in evaluating reaction mechanisms and material degradation.

Techniques That Complement XPS

Similar to XPS but making use of the Auger electron transition, initiated by electrons and not x-rays, capable of smaller (~1µm) spot sizes; best applied to depth profiling experiments. Provides limited chemical information. Similar detection limits. Not able to analyze non-conductive samples.

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Uses different metal ion guns to etch the sample surface, generating ions which are passed to a mass spectrometer to determine mass of ions, which are then used to identify molecular fragments. Species and molecular structures can be identified from the molecular fragments. Data can be very complicated but can provide detailed chemical information. Part per million detection limits.
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Why Choose Covalent for Your XPS Needs?

Covalent’s Thermo Scientific Nexsa G2 provides advanced analytical capabilities, excellent signal to noise, accessories for all types of XPS experiments, and a team of XPS scientists with over 20 years of combined experience in XPS and materials science and engineering.

Frequently Asked Questions

How do the accessories help me do different XPS experiments?

The different XPS accessories allow for a more varied array of XPS experiments, such as air-free transfer (vacuum transfer vessel), angle-resolved analysis, and work function measurements.

Why is having experienced XPS scientists important for understanding my results?

An experienced XPS scientist has knowledge beyond what is available in literature searches, and can quickly distinguish a real peak for an element of interest from an overlap with a secondary peak of another element. An experienced XPS scientist is also skilled in designing specialized experiments to obtain the required information.

What types of information can XPS provide about my sample?

XPS provides elemental composition, chemical bonding and oxidation state information for the near-surface region of a sample, with sensitivity ranging from a few nanometers at the surface to several tens of nanometers using depth profiling or angle-resolved measurements.

How should I prepare my sample for XPS to ensure reliable results?

The recommended method for sample preparation is:
  • Avoid contact of any kind with the region of interest.
  • Loosely wrap the sample in aluminum foil and secure using double sided tape to the bottom of a rigid container.
  • Secure the sample to the bottom of a rigid container with the surface of interest facing up.

What is the analysis depth and spatial resolution of XPS?

  • XPS analyzes the top 7-10nm of a surface.
  • Spot sizes range from 10 to 400µm (elliptical) and can be adjusted in increments of 5µm.

What is the maximum sample size?

The maximum sample size is 60mm x 60mm x 20mm with a height difference of less than 10mm.