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In-SEM photoluminescence

In-SEM Photoluminescence (PL) enables high-resolution analysis of optical and electronic properties in SEM, useful for semiconductors and organic materials. It captures emitted light after laser excitation, revealing details on band structure, impurities, and defects.
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Introduction

Photoluminescence (PL) is a non-destructive technique used to study optical and electronic properties of materials, notably semiconductors. In a very broad sense, PL consists of measuring the light that is emitted by a sample when it is excited with a light source. PL signal can be used in imaging, intensity and spectral analysis in a tremendously wide range of applications. In solid state physics and semiconductor science, common applications include band gap measurement and impurity quantification. In-SEM photoluminescence is the integration of PL measurements in a scanning electron microscope (SEM). This enhances the capabilities of both techniques, by allowing to perform correlative and in-situ studies while observing samples with an ultra-high resolution.

Principles

When a material absorbs a photon, one of its electrons get excited to a higher energy state. As it returns to its ground state, sometimes another photon is emitted. An illustration of the principle is depicted in Figure 1 for both semiconductors with a direct band gap, where photon absorption and emission are directly allowed, and semiconductors with and an indirect band gap, where photon absorption and emission are not allowed unless mediated by absorption or emission of a phonon. Other types of samples, such as organic molecules, do not have a band structure where electrons are free to move. They exhibit photoluminescence through excited states present in the electronic orbitals themselves. In biosciences, PL is colloquially known as fluorescence.

Figure 1 Illustration of the PL principle in direct and indirect bandgap semiconductors

By analysing the emitted light, valuable information can be obtained about the material band structure, defects, impurities, and electronic transitions. PL signal is generally at longer wavelengths (lower energies) than the excitation source, as some energy is dissipated in the process.

Typical PL experiments consist of varying the excitation power and recording signal evolution, scanning the excitation source on the sample to perform PL maps, or varying sample temperature while recording PL spectra. In the context of in-SEM photoluminescence, additional insight is obtained from high-resolution SEM imaging. Luminescence can be correlated with structural properties resolved at nm resolution and completed with auxiliary characterization techniques offered by SEM.

Instrumentation

PL instruments rely on an excitation light source, a detection system and a dichroic mirror. The dichroic mirror is a special optical component engineered to split incoming light into reflected and transmitted spectral ranges. Laser light gets reflected towards the sample, and PL signal gets transmitted towards the detection system. This way, not only is the PL signal efficiently collected, but the detection system is protected from the excitation light source reflected from the sample, which is often bright enough to saturate or even damage the detection system. This principle is illustrated in Figure 2.  

A diagram of a laserDescription automatically generated
Figure 2 Dichroic filtering allowing for photoluminescence measurement. Left: illustration of laser (excitation) light path in the system with reflection on the dichroic mirror, absorption in the sample and reflection. Right: sketch in reduced units (laser wavelength=1.0) of the spectral filtering action, with reflected range of dichroic mirror containing laser wavelength and transmitted range containing the detected luminescent peaks.

Often, the excitation light source is insufficiently rejected by the dichroic mirror, and additional filters are placed in the path of the PL signal. Additional components are usually present in the system, for example to control excitation power and polarization, focus it on the sample, or redirect the signal between different detection systems. Excitation sources are usually lasers, which provide much higher brightness than any other light source and are available at wavelengths across the whole UV-VIS-NIR range. High performance PL detection systems typically consist in an imaging spectrometer equipped with a CCD camera specialized for spectroscopy, very similar to a cathodoluminescence spectroscopy system. The installation of the injection line / PL setup on the Allalin platform is sketched out in Figure 3.

Figure 3 Positioning of the injection line and dichroic optics on the Allalin platform applied for PL / TRPL / Raman experiments

Example results

Figure 4 Left:  PL spectrum of a Ruby sample, showing characteristic R line luminescence at 694.3 nm [1]. Right: Power series of the R line luminescence total intensity vs laser excitation power. Continuous line indicates linear dependency, which is probed over more than 4 orders of magnitude.

Figure 5 Broadband Nd:YAG room-temperature photoluminescence spectrum, showing 4F3/2 -> 4I9/2 (870-950 nm) and 4F3/2 -> 4I11/2 (1050-1130 nm) transition lines [2]

Benefits and Further Reading

  • The classic Physics of Semiconductor Devices book by Sze and Kwok contains a succinct, helpful introduction to radiative transitions and photoluminescence: Sze, SM and Kwok KN, Physics of Semiconductor Devices, 2007 John Wiley & Sons, ISBN 9780471143239
  • Theory of emission and semiconductor photoluminescence are described for a vast variety of materials in this multiply-re-edited book. Kalt H and Klingshirn CF, Semiconductor Optics 1 & 2 (5th edition), Springer, 2019 - 2024

References

  1. Yamaoka, Hitoshi, Yumiko Zekko, Ignace Jarrige, Jung-Fu Lin, Nozomu Hiraoka, Hirofumi Ishii, Ku-Ding Tsuei, and Jun’ichiro Mizuki. “Ruby Pressure Scale in a Low-Temperature Diamond Anvil Cell.” Journal of Applied Physics 112, no. 12 (December 17, 2012): 124503. https://doi.org/10.1063/1.4769305.
  2. Barnes, N.P., and B.M. Walsh. “Amplified Spontaneous Emission-Application to Nd:YAG Lasers.” IEEE Journal of Quantum Electronics 35, no. 1 (January 1999): 101–9. https://doi.org/10.1109/3.737626.
References

Latest Scientific Publications

Halide homogenization for low energy loss in 2-eV-bandgap perovskites and increased efficiency in all-perovskite triple-junction solar cells WANG, Junke, ZENG, Lewei, ZHANG, Dong, et al. Nature Energy, vol. 9, no 1, p. 70-80. 2024
Applications

In-SEM photoluminescence

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