Reineck, Gibson - All-Optical Thermometry With Infrared Emitting Defects in Nanodiamonds

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RESEARCH ARTICLE

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All-Optical Thermometry with Infrared Emitting Defects in


Diamond
Mitchell O. de Vries, Blanca del Rosal, Kibret A. Messalea, Brant C. Gibson,
Philipp Reineck, and Brett C. Johnson*

biotechnology and other fields.[1] Elec-


Diamond color centers (optically active defects) can be used for all-optical tronic devices and batteries may bene-
thermometry for non-invasive and localized temperature measurement. The fit from such diagnostics to understand
visible to near-infrared photoluminescence of these defects is greatly durability, efficiency, and function.[2] In
attenuated in optical fibres and biological samples and therefore limits their biology, luminescence thermometry can
also provide insights into temperature
use. This study have recently uncovered a defect in Si-doped diamond with sensitive biological phenomena such as
emission coinciding with the O-band and a major biological transparency reactions catalyzed by enzymes[3] and de-
window. It has a zero phonon line (ZPL) at 1221 nm and well-resolved phonon naturation of protein behavior[4] to name
side-band features. In this work, a strong temperature dependence above a few.
150 K is observed, allowing for accurate temperature measurements up to Recently, optically active point defects
in diamond, also known as color centers,
approximately 420 K. The temperature can be determined via spectral shifts or
have shown promise in nanoscale pho-
thermal broadening of the ZPL and through the intensity ratio between the toluminescence (PL) thermometry. The
ZPL and√the phonon side-band to a maximum temperature resolution of wide bandgap and high Debye temper-
0.57 K/ Hz. Thermometry using these micro-diamonds is demonstrated for ature of diamond results in PL that is
both electronics and biological applications highlighting their versatility. The often bright, stable and with emission
potential for further enhancements in sensitivity is discussed. in a narrow spectral band. In addition,
diamond does not contain any toxic el-
ements making it compatible with bi-
ological applications.[5] Furthermore, its
1. Introduction excellent thermal properties ensures intimate thermal contact
with its environment.
Luminescence thermometry involves the measurement of lo- Common color centers in diamond with temperature depen-
cal temperature variations with possible nanometer spatial dent PL are the negatively charged nitrogen-vacancy (NV),[6–8] the
resolution and has important applications in nanotechnology, Ni complex[9,10] and a range of group-IV-vacancy defects includ-
ing the negatively charged silicon vacancy (SiV− ),[11,12] Ge vacancy
M. O. de Vries, B. C. Johnson (GeV),[13,14] , and tin vacancy (SnV).[15] The temperature depen-
School of Science dence may manifest as shifts or broadening in the zero phonon
RMIT University line (ZPL) component of the spectrum, changes in intensity or
VIC 3001, Australia the intensity ratio between separate spectral components of the
E-mail: brett.johnson2@rmit.edu.au
PL. Spin-based resonance methods are also possible with the
B. del Rosal, B. C. Gibson, P. Reineck
ARC Centre of Excellence for Nanoscale BioPhotonics
NV center albeit at the expense of a more complex experimen-
School of Science tal setup.[16]
RMIT University For optical-based sensing in biological environments (espe-
Melbourne, Victoria 3001, Australia cially in small animal models) the NIR-II window (1000 – 1700
K. A. Messalea nm) is unquestionably superior to shorter wavelengths at which
ARC Centre of Excellence for Quantum Computation and Communication these color centers emit light. First, the visible to near-infrared
Technology
RMIT University spectral range can be strongly attenuated by both optical fibres
Melbourne, Victoria 3001, Australia and biological tissues.[17,18] This impacts the time required to col-
lect the emitted light and hence affects the temperature
√ resolu-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adsr.202300086
tion (as defined in [19] and measured in Kelvin/ Hz). Excitation
with short wavelength light can also cause heating for some ma-
© 2023 The Authors. Advanced Sensor Research published by
Wiley-VCH GmbH. This is an open access article under the terms of the terials and auto-fluorescence of biological compounds. The lat-
Creative Commons Attribution License, which permits use, distribution ter can distort the detected spectral line-shape[20] but is virtually
and reproduction in any medium, provided the original work is properly nonexistent for wavelengths longer than 1200 nm.[21] While ab-
cited. sorption is not necessarily lower than in the NIR-I (700–1000 nm)
DOI: 10.1002/adsr.202300086 window due to the vibrational bands of water, the reduction in

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the scattering coefficient with increasing wavelength[22] makes it


possible to obtain higher resolution fluorescence images at larger
tissue depths.[23,24]
In this work, we consider a recently discovered color center
in diamond that emits in the second near-infrared transparency
window, 1000–1700 nm (NIR-II).[25] In this wavelength range ab-
sorption and scattering issues of biological tissue are significantly
lower than in the spectral region below 1000 nm.[22,26] This de-
fect center has a ZPL at 1221 nm (T = 0 K value) and a number
of distinct quasi-local vibrations that dominate the phonon side-
band (PSB). These have an energy of 42 meV suggesting a weak
coupling to the diamond lattice. Visible spectra from these par-
ticles has also been reported previously showing strong PL from
the SiV− , silicon–boron (SiB), and negatively charged substitu-
tional nickel center (Ni−s ).[27] The strong intensity of the 1221 nm
defect also suggests that it consists of one or more of the main
impurities in the diamond and has been tentatively assigned to
a SiV2 :H(− ) defect.[25,28] It is also interesting to note that the PL
lineshape is similar to the so-called 1.660 eV (746.9 nm) line
with a phonon sideband energy of 59 meV found in Ni-doped
diamond.[29]
Further to previous work on this defect, we present a detailed
analysis of the PL temperature dependence and consider a num-
ber of methods to extract the temperature from the PL line-shape.
Potential applications as local temperature probes for electronic
devices and biological specimens are also explored.

2. Results and Discussion


A schematic of the custom-built confocal microscope used to
study the temperature dependence of the 1221 nm defect PL in
Si-doped micro-diamonds is shown in Figure 1a. Further details
are provided in the experimental section below. Figure 1b) shows
the PL spectra at three different temperatures. These spectra are
normalized to the intensity of the ZPL. The main features of the
PSB of this defect are labeled as PSB1 and PSB2. A third phonon
replica appears around 1400 nm but its intensity is much reduced
and is not considered further here. The PL emission is stable and
increases linearly with excitation power, characteristic of a large
ensemble of color centers.
Additional peaks at shorter wavelengths are also observed. The
peak at 1170 nm is attributed to the same 1221 nm defect system
(marked with an asterisk in Figure 1b). The remaining peaks at
1110 and 1150 nm are associated with an as-yet unidentified de-
fect. These peaks have intensities that vary independently of the
1221 nm defect when observed in different micro-diamonds. We
also note that these shorter wavelength PL features do not appear
in bulk diamonds that also contain the 1221 nm defect.[25] Dia-
mond particles made from such material could be beneficial for
reducing the background within the 1221 nm defect PL range but Figure 1. a) Schematic of the confocal microscope employed in this work.
is not considered here. It consists of a 980 nm laser, which is directed onto a dichroic mirror (DM)
Figure 1c shows a typical fit of the spectra with the sum of three and NIR optimized objective mounted on an XYZ piezoelectric stage. The
Lorentzians, PL is collected with the same objective and passes through a 1075 nm long
pass (LP) filter. b) PL spectra of the Si-doped micro-diamonds in the NIR

3 range, measured at temperatures of 5, 288, and 352 K. The zero phonon
Ii line (ZPL, 1221 nm), first (PSB1, 1275 nm), and second (PSB2, 1330 nm)
S(𝜆) = (1)
i=1 1 + xi2 phonon side-band features are indicated. Features at shorter wavelengths
arise from a separate defect system, except for the 1170 nm feature identi-
where x = (𝜆 − 𝜆i )/(Γi /2). The values Ii , 𝜆i , and Γi are the inten- fied with an asterisk, which is also a part of the 1221 nm system. c) Typical
sity, peak position, and full width at half maximum of the ith peak fit to data using Equation (1) and a linear background.

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Figure 2. The temperature dependence of a) the ZPL peak position, b) width and c) the PSB1/ZPL intensity ratio. Data from ref. [25] is included for
comparison. Lines are fits using the models discussed in the text.

(i.e., the ZPL, PSB1, and PSB2 peaks). A linear fit is employed to of the ZPL peak. At these temperatures the signal to noise ratio
account for the background signal which most likely arises from is much reduced (spectra included in Figure S2, Supporting In-
the PL from other defects with ZPL at shorter wavelengths. This formation). For our confocal system this temperature represents
Lorentzian model provides an excellent fit over the full tempera- an approximate upper limit at which this PL can be used as an
ture range considered (5–420 K) and was employed throughout optical thermometer.
this work (see Figure S1, Supporting Information for a compari- The thermal quenching is expected to be proportional to the
son with other models). empirical relation, (1 − Cexp (ΔEa /kB T))−1 where ΔE is the ac-
The temperature dependence of the PL line-shape was inves- tivation energy, kB is Boltzmann’s constant, and C is a dimen-
tigated over the 5–420 K temperature range. The variation in 𝜆i , sionless constant. Since the 1221 nm defect has a well-resolved
𝜔i and the intensity ratio, PSB1/ZPL, with temperature is shown PSB, the intensity ratio, PSB1/ZPL can also be used to deter-
in Figure 2. These will now be discussed in turn. mine a temperature. The advantage of taking a ratio is that the
Generally, the ZPL red-shift is a consequence of lattice expan- measurement will be less susceptible to fluctuations due to exci-
sion and electron phonon coupling. For the case of the 1221 nm tation laser intensity and variations in the optical absorption of
line, this shift can be described by the equation, biological samples over time. The total PL intensity also varies
depending on the number of defects that are addressed during
ΔE = 𝜇T 4 + 𝜈T 2 (2) measurement. Furthermore, the integrated intensity in the ZPL
and PSB spectral bands may be collected simultaneously via ap-
The fit shown in Figure 2a (with energy scale indicated on propriate band pass filters to determine temperature without any
the right axis) results in fitting parameters of 𝜇 = (−2.7 ± 0.1) × post-processing, although the accuracy then becomes more sen-
10−10 meVK−4 and 𝜈 = (−6 ± 2) × 10−6 meVK−2 . Here, the T2 sitive to background PL.
term, which is related to the softening of bonds dominates the The intensity ratio, follows the Arrhenius equation,[34]
T4 term, related to hard phonon modes.[30] Our data agree well
with those reported previously in ref. [25] (crosses in Figure 2a). A exp(−ΔE∕kB T) + B (4)
Equation (2) can also be conveniently solved for temperature.
A fit with a modified Varshni equation with a similar T4 scal- where A is the proportionality factor and B is an offset. For the fit
ing (ΔE = (𝛼T4 )/(T + 𝛽)2 with 𝛼 = 1.1 ×−6 eV.K−4 and 𝛽 = 1.5 × in Figure 2c A = 2.2 ± 0.4 and ΔE = (55 ± 6) meV. This is in good
103 K) is also included for comparison as it has been employed agreement with the ZPL - PSB energy separation, ΔE = 42.8 ±
previously to describe ZPL line shifts in diamond.[31] It can be 1.9 meV.[25] The scatter in the intensity ratio data appears to be
observed here that 𝛽 is of the same order of magnitude as the slightly greater than that observed for the ZPL position and width
Debye temperature (2300 K for diamond). These values are also data. The intensity ratio determined with Equation (1) inherently
comparable to those obtained for the NV center in diamond with contains more noise and is more susceptible to background sig-
𝛼 = 5.3 × 10−7 eV.K−4 and 𝛽 = 725 K.[31] nals. This will be discussed further with reference to Figure 3.
A strong thermal broadening is also observed for the 1221 nm It is noted that the PL lineshape of small diamond particles
ZPL and presented in Figure 2b. We find the temperature depen- is susceptible to variations. This is a common issue where the
dence to be well-described by the expression,[32] peak position and width suffer from inhomogeneous broadening
caused by variations in the local strain around the defect due to
Γ = aT 3 + Γ0 (3) proximity of the surface, fabrication damage, or impurity density
fluctuations within the diamond lattice. The intensity ratio itself
with the fitting parameters a = 2.24 ± 0.05 × 10−7 nm K−3 and a may also vary due to phonon confinement effects.[35] We further
zero-temperature width of Γ0 = 3.81 nm. A similar T3 depen- note that the 1221 nm defect is fairly robust against environmen-
dence has been observed previously for both charge states of tal changes such as pH (data included in Figure S3, Supporting
the NV center and the SiV− center.[32] The T3 dependence has Information) or magnetic noise.
been attributed to defect–defect interactions[33] or the softening With the temperature dependence of the 1221 nm PL estab-
of the local phonon modes of the defect involved in the electronic lished, the temperature resolution, 𝜂, to changes in temperature
transition.[30] At temperatures above 400 K there is an apparent is now explored. A series of spectra were continuously collected
decrease in the broadening, which is actually due to the grow- with a 1 s exposure time while the sample was at room tempera-
ing uncertainties in the fit caused by heavy thermal quenching ture. The ZPL peak position, width and PSB1/ZPL intensity ratio

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Figure 3. The variation in temperature measured with a) the peak shift, b) the peak width, and c) the PSB1 to ZPL intensity ratio extracted from fits of
spectra collected for 1 s with 3 mW of laser power. The corresponding histograms are shown in (d–f). g) The spectral noise density and h) the Allan
variance determined from (a–c) as a function of averaging time of the measurement, 𝜏. The dashed line indicates a slope proportional to 1/𝜏.

were extracted from a fit using Equation (1) and converted to tem- to 1/𝜏 (dashed line). This dependence is due to the uncertain-
perature (using the fits in Figure 2). The measured temperature ties related to the fitting procedure as confirmed with simulations
over time is plotted for the 1000 measurements in Figure 3a–c provided in Figure S4 (Supporting Information). The Allan vari-
with the corresponding histograms plotted in Figure 3d–f. The ance reaches a minimum between 10–40 s before the long term
FWHM of these histograms include drifts in temperature over drifts of the temperature during measurement start to become
the course of the measurement and have values of (0.958 ± noticeable. A with a value of around 0.014 K for the temperature
0.006) K, (0.93 ± 0.01) K, and (2.20 ± 0.03) K, respectively, in- determined with the ZPL position and width and 0.16 K for the
dicating that the peak position and width are the most accurate intensity ratio.
indicators of temperature using the 1221 nm defect. This is con- The√temperature resolution is expected to follow the relation,
sistent with the general scatter of data observed in Figure 2c. 𝜂 = 𝜎 Δt|df ∕dT|−1 , where t is the measurement time, 𝜎 is the
The spectral noise density is determined with a fast Fourier uncertainty, and f is 𝜆, Γ, or PSB1/ZPL intensity ratio.[36] The
transform of the experimental data in Figure 3a–c and plotted in |df/dT|−1 term increases dramatically below 150 K as observed in
Figure 3g. It shows no dependence on frequency as√expected and Figure 2. At higher temperatures thermal quenching will cause
has a geometric mean of 0.63, 0.57, and 1.36 K∕ Hz (dashed the uncertainty to increase due to a loss in the signal to noise ratio
lines), respectively. The Allan variance (Figure 3h), also deter- (SNR) of the measured spectrum. Indeed, the temperature reso-
mined from the experimental data, shows a decrease in the de- lution determined from √ any of the parameters considered here
tected RMS temperature with measurement time, proportional is proportional to 1∕ SNR (see Supporting Information). Thus,

Figure 4. a) Schematic of setup to test spectral responses to changes in temperature on-chip. Confocal maps in (b) reflectivity and (c) NIR PL modes
of the same region. The dashed lines in (c) denote the perimeter of the heater. d) The temperature as determined with the ZPL position and width of
the particle cluster circled in (c) as well as other particles at greater distances from the heater. The grey lines show linear fits to the data.

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optical thermometry using 1221 nm PL is best suited for temper-


atures between approximately 150-350 K. The upper limit can be
extended further by improving the collection efficiency or bright-
ness of the PL.
To investigate the potential for micro-scale thermometry, the
Si-doped micro-diamonds were drop-cast onto a micro-heater
fabricated on a Si platform, as shown in Figure 4a. Fabrication
details are included in the Experimental Section below. Confo-
cal maps of the surface using a 980 nm laser were then col-
lected in reflectivity and PL modes across the same region and
are shown in Figure 4b,c, respectively. The higher reflectivity of
the micro-heater circuit can clearly be seen with micro-diamonds
distributed over the entire field of view (both on and off the micro-
heater). In Figure 4c the outline of the micro-heater is indicated
by white dashed lines. An aggregate of bright micro-diamonds
located on the micro-heater is circled. Assuming that the resis-
tance for the micro-heater remains constant, and that all of the
power applied to the circuit is dissipated as an increase in tem-
perature, the applied current was used to control the temperature
produced by the micro-heater. The PL spectra were collected first
at room temperature and then as a function of an applied current
between 0–39 mA.
The change in the PSB1/ZPL intensity ratio is shown in
Figure 4d, as a function of the square of the applied current.
The temperature corresponding to the PSB1/ZPL intensity ratio
is indicated on the right axis. A linear fit (slope=(1.09 ± 0.07) ×
10−4 mA−2 and intercept=0.646 ± 0.007) is also shown, demon-
strating that the change in the PSB1/ZPL ratio is directly propor-
tional to the power applied to the micro-heater. The temperature
variation is approximately linear over this PSB1/ZPL ratio range.
This technique could be further extended to have mapping capa-
bilities as previously demonstrated for nano-diamond arrays in
ref. [36] for example.
To assess the suitability of the 1221 nm color center for deep
tissue imaging in biological applications, the PL from micro-
diamonds were imaged through a phantom (Figure 5). This
phantom is commonly used to mimic tissue-like materials since
it has similar optical properties.[37]
The micro-diamonds were first suspended in DI water and dis-
persed using sonication. The suspension was transferred to cu-
vette and immediately imaged. Sedimentation is expected over
minutes for these micron sized particles, but this has no effect
on the measurements performed here. Imaging was performed
with a 808 nm excitation laser and the PL was collected with a NIR
camera, through a 1200 nm longpass filter. The resultant map is
shown in Figure 5a. A tissue phantom with a thickness varying
from 5 – 12 mm (from left to right in Figure 5b) was then placed
on the cuvette and remeasured. The thicker part of the phantom
is at the right-side end of the cuvette in Figure 5b where the PL is
attenuation by around 60%. This attenuation plotted as the ratio
between the PL intensity with (IP , Figure 5b) and without the tis-
sue phantom (INoP , Figure 5a) is plotted in Figure 5c. The dashed

Figure 5. PL widefield images of micro-diamonds in a quartz cuvette


(shown by white dotted lines) a) without and b) with a tissue phantom
placed on top. c) The PL intensity ratio between (b) and (a) determined
in the region indicated by the dashed blue boxes in (b) and (a). d) The
intensity ratio versus the thickness of the phantom. A fit with exp (− 𝛼t) is
also shown giving an attenuation coefficient, 𝛼 = 1.75 ± 0.06 cm−1 .

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blue lines indicate the region over which the attenuation was de- was typically kept below 1 mW. Laser heating became noticeable for pow-
termined. ers of 5 mW and above.
Finally, the the PL attenuation versus tissue phantom thick- The laser was directed through a NIR-optimized objective (Olympus, ×
50, 0.65 NA IR LCPlan N) mounted on a three-axis piezo scanning stage
ness is presented in Figure 5d. A exponential fit using, exp (−
(Physik Instrumente, PI P-545.xC8S). A 980 nm longpass dichroic mirror
𝛼t), with t the phantom thickness, gives an attenuation coeffi- was used to filter the PL emitted by the sample, before further filtering
cient of 𝛼 = 3.45 ± 0.15 cm−1 , which is comparable to reported with 980 and 1075 nm longpass filters. The PL was then focused into a
values.[17] For a thickness of 10 mm the PL intensity drops by 62.5 μm diameter core multimode fibre, which acted as the confocal pin-
about half. Under these conditions, we hole. The fibre could be directed into either an InGaAs/InP photon counter
√ may expect a temperature (ID Quantique ID230) for confocal PL mapping or a InGaAs spectrometer
resolution degradation by a factor of 2. PL emission may be fur-
(Princeton Instruments PyLoN-IR, IsoPlane SCT-320) for spectral analy-
ther improved by using a longer wavelength excitation source up sis. For the optical reflection confocal maps, the 1075 nm longpass was
to ≈1200 nm. replaced by a 1000/50 nm bandpass filter and the laser was heavily atten-
uated to avoid saturating the detector.
The temperature of the sample during measurement was controlled
with either a Montana cryostat (4-300 K) or a Linkam THMS600 (>300 K).
3. Conclusion and Outlook The on-chip heater patterns were defined using photolithography on a
1×1 cm2 silicon substrate with a 200 nm surface oxide. Ti and Au were
The temperature dependence of the 1221 nm defect PL in Si-
electron beam evaporated to thicknesses of 5 and 100 nm, respectively.
doped micro-diamonds was investigated in detail. The ZPL po- The phantom was prepared from 1% intralipid (Sigma–Aldrich, 20%
sition, width and intensity were all considered for thermometry emulsion) as described in ref. [37]. While still liquid, the phantom was
applications. The shift and width were found√to have the greatest poured into a right-angled triangular prism mold with a thickness increas-
temperature resolution at 0.63, and 0.57 K∕ Hz, respectively. ing from 0 to 12 mm over a length of 22 mm. This was placed over a cuvette
(Thorlabs, CV1Q035AE), which contained the microdiamonds suspended
Although the intensity ratio of the PSB to ZPL was less sen-
in water. A defocused 808 nm diode laser was used to illuminate the cu-
sitive, this metric may allow fast temperature sensing via spec- vette and the PL was captured with a Princeton Instruments NIRvana HS
tral filtering given the well resolved features of the PL line- focal plane array fitted with a 1200 nm longpass filter.
shape, without the need for a fitting routine and therefore have a
shot-noise limited sensitivity. In the case of our current micro-
diamond material this was not considered given the presence Supporting Information
of background PL from defects emitting at shorter wavelengths.
Higher sensitivities may be obtained with material that is fabri- Supporting Information is available from the Wiley Online Library or from
the author.
cated without these defects.
Demonstrations of local area temperature probes were ex-
plored for both electronic devices and biological contexts high-
lighting the versatility of these materials. This together with the
Acknowledgements
convenient wavelength range of the diamond color center make The authors thank Remy Johnson for the SEM analysis. This work
this sensor a competitive technology for local temperature sens- was supported by the Australian Research Council (ARC) through its
ing. Centre of Excellence for Nanoscale BioPhotonics (CE140100003), Dis-
covery Project (DP220102518) and the LIEF programs (LE140100131,
LE190100130). M.dV. acknowledged funding through RMIT’s Research
Stipend Scholarship (RRSS-SC). B.d.R. acknowledged funding through
4. Experimental Section the RMIT Vice-Chancellor’s Research Fellowship and the ARC DE-
CRA Fellowship schemes (DE200100985). P.R. acknowledged the RMIT
For all-optical NIR temperature sensing, high temperature-high pres- Vice-Chancellor’s Research Fellowship and the ARC DECRA Fellowship
sure (HPHT) silicon-doped micro-diamonds were used. The size distribu- schemes (DE200100279).
tion of the particles is presented in Figure S5 (Supporting Information).
The distribution was skewed with a mode, mean, and median of 89, 245,
and 193 nm, respectively. However, the larger particles, around 1 μm in di-
ameter, exhibited the brightest PL and tended to be studied in more detail Conflict of Interest
(the PL versus particle size is presented in Figures S5 and S6, Supporting The authors declare no conflict of interest.
Information ). The particles were obtained from Adḿas Nanotechnologies
and synthesized by Hyperion M&T.[25,27]
As noted in earlier work,[27] these particles did not contain any notice-
able amount of the nitrogen-vacancy defect but about 19 ppm of substi- Data Availability Statement
tutional nitrogen impurities were detected. The negatively charged silicon
The data that support the findings of this study are available from the cor-
vacancy center was present to about 76 ppm with smaller concentrations
responding author upon reasonable request.
of the neutral charge state (0.06 ppm). Given that Ni was a common sol-
vent catalyst used in diamond growth, around 1 ppm of the substitutional
negatively charged nickel defect was also present.
The diamonds were dispersed in deionized water and subjected to ultra- Keywords
sonication to break down large aggregates. The final solution was drop-
cast onto a substrate for study. color centers, diamond, infrared, NIR, thermometry
PL spectroscopy and mapping were conducted using the custom-built
confocal microscope with diffraction-limited spatial resolution schemati- Received: May 25, 2023
cally shown in Figure 1a. A 980 nm diode laser was employed for excitation Revised: September 14, 2023
filtered with a 980 nm notch and variable density filters. The laser power Published online:

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[20] Q. le Masne de Chermont, C. Chanéac, J. Seguin, F. Pellé, S.


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