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Reineck, Gibson - All-Optical Thermometry With Infrared Emitting Defects in Nanodiamonds
Reineck, Gibson - All-Optical Thermometry With Infrared Emitting Defects in Nanodiamonds
Reineck, Gibson - All-Optical Thermometry With Infrared Emitting Defects in Nanodiamonds
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Adv. Sensor Res. 2023, 2300086 2300086 (1 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
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Adv. Sensor Res. 2023, 2300086 2300086 (2 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
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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
Adv. Sensor Res. 2023, 2300086 2300086 (3 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
27511219, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adsr.202300086 by Cochrane Czech Republic, Wiley Online Library on [09/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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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.
Adv. Sensor Res. 2023, 2300086 2300086 (4 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
27511219, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adsr.202300086 by Cochrane Czech Republic, Wiley Online Library on [09/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Adv. Sensor Res. 2023, 2300086 2300086 (5 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
27511219, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adsr.202300086 by Cochrane Czech Republic, Wiley Online Library on [09/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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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:
Adv. Sensor Res. 2023, 2300086 2300086 (6 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH
27511219, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adsr.202300086 by Cochrane Czech Republic, Wiley Online Library on [09/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Adv. Sensor Res. 2023, 2300086 2300086 (7 of 7) © 2023 The Authors. Advanced Sensor Research published by Wiley-VCH GmbH