# Spectroscopy of the Li K emission band

Philippe Jonnard

► To cite this version:

Philippe Jonnard. Spectroscopy of the Li K emission band. Workshop on Soft X-ray Spectroscopy Collection and Analysis, Feb 2026, Melbourne (AUS), Australia. hal-05508009

HAL Id: hal-05508009

https://hal.science/hal-05508009v1

Submitted on 12 Feb 2026

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
# Spectroscopy of the Li K emission band

**P. Jonnard**

Laboratoire de Chimie Physique – Matière et Rayonnement
Sorbonne Université – CNRS
Paris, France
## Collaboration

* **ANR "Spectroscopy and quantification of lithium by microanalysis"**

* **LCPMR**

* K. Le Guen

* K. Hassebi

* N. Temmar

* W. Aid

* R. Benbalagh

* R. Vacheresse

* A. Boucly

* **Sorbonne Université**

* N. Rividi

* M. Fialin

* A. Verlaguet

* G. Godard

* B. Dubacq

* O. Boudouma

* W. Bai

* **CEA Marcoule**

* E. Brackx

* P. Schweizer

* **CEA Saclay**

* M.-C. Lépy

* Y. Ménesguen

* **McGill University, Canada**

* R. Gauvin

* N. Brodusch

* **Nano Optics Berlin**

* **Greateyes**
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
* Attenuation length (CXRO) related to absorption

Important parameters

* Acceleration energy generation of Li 1s ionizations Monte Carlo (McXRay)

<figure><img src="image_2.png" /></figure>
# Spectrometer

* Variable line spacing grating or **reflection Fresnel zone plate**

* Flat field spectrometer, **no scanning**

* Detection with a linear detector or **CCD camera**

* Grating law **nλ = d (sinα – sinβ)** d is the period of the grating
α and β are the incident and detection angles

<figure><img src="image_3.png" /></figure>

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /></figure>
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
Lithium metal

<figure><img src="image_6.png" /><figcaption>Sample holder prepared in glove box
Transfer in inert atmosphere (N₂)</figcaption></figure>

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>

Experiment

* corrected spectrometer efficiency

* divided by E³

DFT

* Li *p* valence states

* Lorentz 0.03 eV – Gauss 0.35 eV

<figure><img src="image_9.png" /></figure>
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
# MgLi alloy (6% wt. Li)

Mg L2,3 emission band: 3sd – 2p transition

Li Kα emission band: 2p – 1s transition
5 kV 100 nA 2000 s 5 µm

<figure><img src="image_10.png" /></figure>

<figure><img src="image_11.png" /></figure>

CXRO

Li K strongly absorbed by Mg
# MgLi alloy (6% wt. Li, 18% at. Li) – Mg metal

Mg L emission band: 3sd – 2p transition

Li K emission band: 2p – 1s transition

<figure><img src="image_12.png" /></figure>

Estimation
MgLi (15% at. Li)

Li K too low

<figure><img src="image_13.png" /></figure>
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
# AlCuLi quasi-crystal – Al<sub>60</sub>Cu<sub>23</sub>Li<sub>17</sub> wt. – Al<sub>52</sub>Cu<sub>8</sub>Li<sub>40</sub> at.

<figure><img src="image_14.png" /></figure>
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
LiF electronic structure

<figure><img src="image_15.png" /></figure>

Arakawa (1976)

“standard” emission band
2p – 1s electron transition
Spectra obtained at 1 kV

<figure><img src="image_16.png" /></figure>

different positions

same position

5 minutes

10 minutes

<figure><img src="image_17.png" /></figure>

Intensity of peaks at 47 and 62 eV decreases: damaging of LiF, fluorine removal

Intensity of 49 eV shoulder and O Kα peak increases: oxidation of sample

Decrease of overall background intensity and of intensity of 55 eV feature:
evolution of the cathodoluminescence / no metal formation
Comparison with synchrotron measurement

<figure><img src="image_18.png" /></figure>

Tsang (1987)

Intensity (arbitrary unit)

Background subtraction
0.5 eV shift

<figure><img src="image_19.png" /></figure>

2p-1s
emission band

core
exciton

Relative intensities
band / exciton
electrons / x-rays
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
# Silicates

* Petalite

LiAlSi<sub>4</sub>O<sub>10</sub>

* Spodumene

LiAlSi<sub>2</sub>O<sub>6</sub>

Spectral interference with Si L
Impossible to observe
Li K emission band

1 kV - 900 nA - 300 s

<figure><img src="image_20.png" /></figure>
# Phosphates

* Amblygonite
(Li,Na)AlPO4(F,OH)
no silicon

3 kV

<figure><img src="image_21.png" /></figure>
# Phosphates

* Amblygonite
  (Li,Na)AlPO₄(F,OH)
  no silicon

**Li K spectrum** calculated with

- Li 2p local and partial density of states

- Broadening with Li 1s core hole

- Experimental broadening

- Weighting matrix elements

- **Alignment** exp. and calc. energy scales
  with Li 1s binding energy (relative to E_F)

<figure><img src="image_22.png" /></figure>
# Phosphates

* Amblygonite
  (Li,Na)AlPO₄(F,OH)
  no silicon

**Al L spectrum** calculated with

- Al 3sd local and partial density of states

- Broadening with Al 2p core hole lifetime

- Experimental broadening

- Weighting matrix elements

- **Alignment** exp. and calc. energy scales
  with Al 2p binding energy (relative to E_F)

<figure><img src="image_23.png" /></figure>
# Phosphates

* Amblygonite
  (Li,Na)AlPO₄(F,OH)
  no silicon

**P L spectrum** calculated with

- P 3sd local and partial density of states

- Broadening with P 2p core hole lifetime

- Experimental broadening

- Weighting matrix elements

- **Alignment** exp. and calc. energy scales
  with P 2p binding energy (relative to E_F)

<figure><img src="image_24.png" /></figure>
# Outline of the presentation

* Introduction

* Li metal

* Li alloy

* Li quasi-crystal

* Li fluoride

* Li minerals

* Other line of investigation
# Other line of investigation

* Lithium Z=3

* Standard recombination processes after Li 1s ionization

* Fluorescence yield = 9 $10^{-5}$ / Auger yield = 1

<figure><img src="image_25.png" /></figure>

Auger yield should be 0
Fluorescence yield should be 1

Auger process forbidden!
Not enough energy
to emit an Auger electron
# Other line of investigation

* Enough energy of the incident particles to generate a shake process

* Fluorescence yield = 9 $10^{-5}$ / Auger yield = 1

<figure><img src="image_26.png" /></figure>

## Work at low acceleration voltage

* To close the shake up channel

* Reach a fluorescence yield = 1

* Intensity increase x 10 000

Following shake up process
Auger emission possible

**Atomic point of view**
**Valid for the solid?**
Thank you!

<figure><img src="image_27.png" /></figure>

<figure><img src="image_28.png" /></figure>

<figure><img src="image_29.png" /></figure>

<figure><img src="image_30.png" /></figure>

<figure><img src="image_31.png" /></figure>