Application Note AN M134

Infrared Photoluminescence
Spectroscopy

Photoluminescence (PL) spectroscopy is an important semi-

conductor analysis technique in material sciences as well Keywords Instrumentation and Software
as for research and development of optoelectronic devices FTIR VERTEX, vacuum, INVENIO R
such as lasers, LEDs or sensors. PL is a valuable tool to
Photoluminescence PL module, PLII
study the band structure, exciton features, sample quality or
phonon modes of hetero structures (e.g. quantum wells) or Semiconductors Step-Scan
bulk samples. Based on decades of experience Bruker offers Infrared Cryostat, pulse tube
powerful PL solutions with the with the VERTEX or INVENIO
Photoreflectance Amplitude modulation
R FT-IR spectrometer forming the backbone.

Advantage of FT-IR technology It should be mentioned that due to the exceptional spec-
In the infrared spectral range FT-IR spectroscopy has major trometer sensitivity, Bruker is also number one supplier of
advantages over dispersive (e.g. grating or prism based) dedicated low temperature FT-IR PL systems for quality
systems. Due to the so-called Jaquinot (or throughput) control in Si industry (see AN M 55).
advantage [1] the sensitivity of FT-IR spectrometers is
significantly higher. Thanks to the so-called Fellget (or mul- Near Infrared Photoluminescence
tiplex) advantage FT-IR combines high spectral resolution For near infrared (NIR) PL Bruker offers the versatile PLII
and a broad spectral range in one measurement. In contrast module (fig. 1): it can be adapted to the right hand side of
for dispersive systems high resolution must typically be any VERTEX or INVENIO R spectrometer equipped with
paid with a much smaller spectral range and may require suitable optical components in order to spectrally analyze
to exchange gratings etc.. In FT-IR spectroscopy spectral PL. Since in the NIR atmospheric absorption (water vapor,
resolution is comfortably controlled via the software CO2) is rather weak, a vacuum spectrometer is not neces-
adjustable traveling distance of the moving interferometer sarily required. Highest spectral resolution of <0.06 cm -1
mirror. Also the spectral accuracy of FT-IR instruments is (<7.5 µeV) can be achieved with the VERTEX 80 / 80v
considerably higher thanks to the usage of a precise interfe- and high resolution option, corresponding to ~0.006 nm
rometer control laser. (0.024 nm) at a wavelength of 1 µm (2 µm). Since the PLII
 GaAs substrate PL
0.8
(~890 nm)

PL intensity/a.u.
0.6

InGaP PL
0.4
(~690 nm)

0.2

0.0
14000 12000 10000
680 nm Wavenumber/cm-1

Fig. 3: NIR/VIS PL spectrum of an InGaP solar cell, measured with

VERTEX 80, PLII module, NIR/VIS beam splitter T502/8, dedicated
Si avalanche diode and 532 nm cw excitation.

Fig. 1: Top: PLII module adapted to INVENIO R research FTIR spec- If spectrometer detector position shall be permanently
trometer. Lower left hand side: standard glass objective with vertical available for other applications (e.g. reflectance or trans-
sample mount. Lower right hand side: mirror objective and X-Y map- mittance), the PL detector can also be placed in the PLII
ping stage for convenient horizontal sample positioning.
module. In special cases utmost NIR sensitivity can be
module has its own sample compartment, the spectrometer achieved with a liquid Nitrogen cooled Ge detector.
itself can in addition be used for applications such as reflec-
tance or transmittance (see FT-IR semiconductor application As discussed, in the infrared spectral range FT-IR is supe-
brochure). rior to dispersive spectrometers while in the visible and
The PLII module can be equipped with up to two software ultraviolet spectral range (VIS/UV) typically the dispersive
controlled continuous wave (cw) excitation lasers. Standard approach is of advantage. However, for customers doing
wavelengths are 532 nm and 1064 nm with intensities in the mainly infrared and just occasionally VIS PL, systems
order of 100 mW, others are available on request. Suitable can also be extended to long wave VIS range (fig. 3). For
optical laser filters are crucial and available as well. Optionally this purpose a dedicated Si avalanche diode is available,
the PLII module can be operated with an external customer covering a range from approx. 9500 cm -1 (~1.05 µm) to
laser instead of internal ones. For NIR PL, high gain InGaAs ~20000 cm -1 (~500 nm). In addition the spectrometer must
detectors covering a range from either 4000 cm -1 (2.5 µm) or be equipped with aluminum coated mirrors and a suitable
5800 cm -1 (~1.7) up to ~12000 cm -1 (~0.84 µm) achieve excel- NIR/VIS/UV beam splitter. Mid infrared PL below ~4000 cm -1
lent sensitivity as e.g. shown by the various PL spectra in fig. (approx. >2.5 µm) typically requires dedicated solutions
2 with just a few seconds of measurement time. discussed in the next paragraph.

AlGaInAs MQW:
GaAs AlGaInAs GaInAsP GaSb 2.0 Main Emission at T=10 K
bulk MQW MQW MQW
Normalized PL intensity/a.u.

0.02
Barrier Emission:
PL intensity/a.u.

~170 mes weaker!

1.0 0.01

0
7400 7000 6600 6200 5800

0
13000 11000 9000 7000 5000 9000 8500 8000 7500 7000 6500
1.2 µm Wavenumber/cm-1 1.51 µm
830nm Wavenumber/cm-1 2µm
1 µm 2 µm
Fig. 4: Low temperature (10K) NIR PL spectrum of an AlGaInAs
multiple quantum well, measured with VERTEX, NIR beamsplitter
Fig. 2: NIR PL spectra of multiple quantum well samples (MQW) T401/3, high gain InGaAs detector, 532 nm excitation and liquid
and GaAs bulk sample, measured with VERTEX, PLII module, NIR/ He flow through cryostat adapted to PLII module. Inset: Although
VIS beam splitter, high gain InGaAs detector and 532 nm excitation. measurement time was only 7 s, even the approx. 170 times weaker
Measurement duration per spectrum was significantly <10 seconds. barrier emission was simultaneously detected.
The PLII sample compartment can be equipped with many dard approach, it becomes clear that for PL signals which
useful and easily exchangeable accessories. E.g. a mirror objec- are further in the MIR range and/or weaker, this approach
tive (with video option) and an automated room temperature (as well as subtraction of the 300 K background) will finally
X-Y mapping stage are available and recommended to place fail.
the sample horizontally beneath the objective (fig. 1). For low The proper solution is to modulate the excitation laser e.g. by a
temperature PL (fig. 4) a liquid He or N2 flow through cryo- chopper wheel [4, 5]: hence the PL signal will be modulated
stat including adaption is available. Further measurement with the same frequency and can be amplified via a lock-in
examples can be found in [2] and [3]. amplifier, while the constant thermal background contribu-
tion is blocked. Because laser modulation would interfere
Mid Infrared Photoluminescence with the modulation created by the interferometer scanner,
For mid infrared (MIR) PL two additional challenges occur, MIR PL typically requires step-scan operation (so-called
making the application much more sophisticated. Firstly amplitude modulation) achieving highest accuracy under
atmospheric absorption (water vapor, CO2) is significantly vacuum conditions [6].
stronger: while in case of e.g. reflectance or transmittance Fig. 6 shows the ideal MIR PL system consisting of a
the main part of atmospheric artifacts is compensated by VERTEX 80v vacuum spectrometer and a dedicated vacuum
the reference measurement, PL typically means single PL module: it can either be used with external customer
channel spectroscopy without reference measurement. laser or is available with up to two preinstalled lasers. A
Therefore, even under good purge conditions, the spectrum liquid He or N2 flow through or a cryogen free pulse tube
can contain strong atmospheric absorption bands as illustra- cryostat is available including adaption. The PL detector
ted in fig. 5. Thus in order to get good quality MIR PL spec- requires dual channel electronics in order to send/receive
tra, it is practically a must to use a vacuum FT-IR system the signal to/from the lock-in amplifier and to finally digitize
with evacuated PL beam path. it via integrated dual channel ADC.
The second challenge concerns the mid infrared 300 K
background radiation surrounding us. The required high
gain LN2 cooled detectors are sensitive to this radiation and
weak MIR PL signals can therefore completely get lost. The
red curve on the right hand side of fig. 5 shows the harmful
effect of background radiation, using the borderline case of
an InGaAs sample emitting at ~4000 cm -1 (2.5 µm).
Although this sample could still be measured via the stan-

- “Dry“ Air Purge: atmos- - cw Excitaon & connuous

pheric Arfacts Scanner Movement.
- Modulated Excitaon VERTEX 80v Vacuum PL Module
- Vacuum:
PL Intensity/a.u.

& Step-Scan
no Arfacts
VERTEX80V

300 K Background Refl/Trans

Radiaon Detector
PL
Sample
InGaAs PL 1 2 Posion
PL PL Refl
Oponal Laser
Detector
3000 2000 1000 Trans Adapon Box
4000 3000 2000
Wavenumber/cm-1
3 µm 4 µm
Lock-in Laser L1
Amplifier Chopper
Fig. 5: Left hand side: Bad influence of atmospheric absorption (red L2
curve) on MIR PL which can even occur for well purged spectrome-
ters.Using a vacuum spectrometer instead, atmospheric artifacts
can completely be removed (green curve). Right hand side: InGaAs
PL measured with VERTEX 80v, liquid N2 InSb detector, vacuum PL Fig. 6: Top: VERTEX 80v with vacuum PL module and LHe flow
module and 1064 nm excitation. For cw excitation 300 K background through cryostat. Bottom: sketch of vacuum PL module with laser
radiation covers the MIR spectral range (red curve). With modulated adaption and beam paths for PL (orange), reflectance (red) and trans-
excitation, step-scan and lock-in detection thermal background can mittance (blue). The OPUS software allows to comfortably switch
be completely removed (blue curve). between the 3 different modes.
 Summary
Finally it should be added that experienced customers

PL Intensity/a.u.
1.0 PbS Room
1.0 might also be able to build their own external PL setup
Temperature PL
and use the spectrometer only for spectral analysis. But
3 µm
0.6 0.6 fmod, laser = 720Hz certainly this is non-trivial and the achieved sensitivity as
0.2 4 µm well as the usability is at least questionable. With the PLII
15000 0.2 module, comfortable NIR PL measurements with highest
2000
3000 5000
4000 sensitivity are readily available. Vacuum spectrometers such
4000 3000 2000 1000
Wavenumber/cm-1
as the VERTEX 80v with dedicated vacuum PL module
open the door to sophisticated and challenging applications
Fig. 7: Room temperature MIR PL of PbS bulk sample, measured like MIR PL or photomodulated reflectance.
with VERTEX 80v, vacuum PL module, modulated 1064 nm exci-
tation, step-scan and lock-in demodulation. Left hand side: After
demodulation the MIR PL spectrum is constant in time and thermal
background is suppressed. Right hand side: resulting PbS MIR room References
temperature PL spectrum.
[1] P.R. Griffiths, “Fourier Transform Infrared Spectroscopy”,
An example MIR PL measurement of PbS at room tempera- 2nd edition, Wiley-Interscience (2007)
ture is shown in fig. 7: after demodulation the signal is con- [2] T. Gründl et al., “GaInAsN growth studies for InP-based long-
stant in time and MIR PL can be extracted without thermal wavelength laser applications”, Journal of Crystal Growth
background radiation. 311 (2009) 1719–1722
Many scientific publications include MIR PL spectra measu- [3] A. Jaffrès et al., “Photon management in La2BaZnO5:
red with VERTEX 80v and vacuum PL modules such as e.g. Tm3+, Yb3+ and La2BaZnO5:Pr3+, Yb3+ by two step
[7] and [8] and a spectral range down to at least ~600 cm -1 cross-relaxation and energy transfer”, Chemical Physics
(> 16 µm) can be reached. In the MIR spectral range the Letters 527 (2012) 42–46
VERTEX 80v high resolution option (<0.06 cm -1, respectively [4] S. Sauvage et al., ”Midinfrared unipolar photoluminescence
<7.5 µeV) corresponds to 0.038 nm (0.6 nm) at a wavelength in InAs/GaAs self-assembled quantum dots”, Physical
of 2.5 µm (10 µm). Review B Volume 60 Number 23 (1999), 15589-15592
The vacuum PL module also includes two additional beam [5] J. Shao et al., “Modulated photoluminescence spectroscopy
paths for transmittance and reflectance (see fig. 6) with with a step-scan Fourier transform infrared spectrometer”,
comfortable switching controlled by the OPUS software. Review of Scientific Instruments 77 (2006)
This also allows for sophisticated measurements such as [6] C.J. Manning and P.R. Griffiths, “Noise Sources in FT-IR
photomodulated reflectance (PR) where weak reflectance Spectrometry”, Applied Spectroscopy Volume 51 Number 8
changes due to modulated excitation are analyzed in order (1997), 1092-1101
to explore the band structure [9]. Also PR experiments [7] M. Motyka, “Fourier Transformed Photoreflectance and
are typically done in step-scan mode and require special Photoluminescence of Mid Infrared GaSb-Based Type II
electronics to simultaneously measure the constant and Quantum Wells”, Applied Physics Express 2 (2009), 126505
the modulated part of reflectance. Vacuum is still strongly [8] D. Stange et al., “Optical Transitions in Direct-Bandgap
recommended and various publications with Bruker vacuum Ge1−x Snx Alloys”, ACS Photonics (2015)
spectrometers can be found such as e.g. [10] and [7]. [9] T.J.C. Hosea et al., “A new Fourier transform photo-
modulation spectroscopic technique for narrow band-gap
materials in the mid- to far- infra-red”, Physica Status Solidi
(a) Volume 202 Issue 7 (2005), 1233-1243
[10] Ma Li-Li et al., “Spectral Resolution Effects on the
Lineshape of Photoreflectance “, Volume 28 Number
4 (2011), 047801

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