Received: 5 June 2020 Revised: 11 July 2020 Accepted: 18 August 2020

DOI: 10.1002/jrs.6003

RESEARCH ARTICLE

Reliable estimation of Raman shift and its uncertainty for a

non-doped Si substrate (NMIJ CRM 5606-a)

Nobuyasu Itoh | Katsuhiro Shirono

National Metrology Institute of Japan

(NMIJ), National Institute of Advanced
Industrial Science and Technology (AIST),
Japan
Correspondence
Nobuyasu Itoh, National Metrology
Institute of Japan (NMIJ), National
Institute of Advanced Industrial Science
and Technology (AIST), Central 3, 1-1-1
Umezono, Tsukuba, Ibaraki 305-8563.
Japan.
Email: nobuyasu-itoh@aist.go.jp
Abstract
Raman shift is one of the most important parameters in Raman spectroscopy
and is theoretically calculated from the difference in the wavenumbers of
excitation and Raman scattering. At present, there are no standard procedures
available to reliably estimate the Raman shift and evaluate its uncertainty from
experimental results. In this study, we reliably estimated the Raman shift and
evaluated its uncertainty for a non-doped crystalline Si substrate (NMIJ
CRM5606-a) using a He-Ne laser and its plasma lines (Ne emission lines). The
Raman scattering wavenumber of NMIJ CRM 5606-a was estimated by the
bracket calibration method using the wavenumbers of the closest Ne emission
lines. The Raman shift was determined from the differences in the theoretical
wavenumbers of a He-Ne laser and the observed Raman scattering. To
evaluate the combined standard uncertainty, we considered the uncertainty
originating from the He-Ne laser and the Ne emission lines, the repeatability
of experimental results, inhomogeneity of measuring points and spectral
dispersion. The estimated Raman shift was 520.45 cm−1 ± 0.28 cm−1 (coverage
factor k = 2). The Raman shift was validated by the other estimated Raman
shifts obtained with other two Raman spectrometers.

KEYWORDS
He-Ne laser, Ne emission lines, Raman shift, Si substrate, uncertainty

1 | INTRODUCTION using a common material to calibrate all the Raman

Raman shift originates from the difference between
the energies of excitation and Raman scattering.[1–4]
Although Raman shifts are theoretically independent of
the Raman spectrometer used, in practice, the observed
shifts are strongly dependent on the Raman spectrome-
ter. Furthermore, users must calibrate their Raman
spectrometers according to the references and protocols
provided by the manufactures because there are no
standardized protocols available for calibration. Under
these circumstances, Raman shifts obtained from differ-
ent Raman spectrometers are not so consistent; however,
their consistency can be significantly improved when
spectrometers.[5]
Wavelengths/wavenumbers of elemental emission
lines such as Ne and Raman shift values of
well-characterized materials are commonly used for
calibration.[1–3] Use of elemental emission lines are suit-
able for accurate calibration and well-characterized mate-
rials are convenient for daily calibration. Materials
provided in ASTM E1840 were obtained from 8 laborato-
ries and are widely used to calibrate Raman spectrome-
ters.[1,3,4,6] Some of these materials (polystyrene,
cyclohexane, and paracetamol) are also described in
European Pharmacopoeia (Ph. Eur.) along with their tol-
erance standards.[7] Although the Raman shift of some

2496 © 2020 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jrs J Raman Spectrosc. 2020;51:2496–2504.

ITOH AND SHIRONO
materials described in ASTM E1840 (polystyrene, cyclo-
hexane, and benzonitrile) were in good agreement with
the most of independent interlaboratory comparison
data,[5] Raman shifts of materials provided in ASTM
E1840 are not associated with uncertainty information,
which is essential for obtaining reliable values. Thus, it is
necessary to reliably estimate the Raman shifts and eval-
uate their uncertainty for materials; however, requisite
procedures have not been provided.
To evaluate the uncertainty in Raman shifts, the
uncertainty in the wavenumbers of excitation and Raman
scattering should be known. International Committee for
Weights and Measures (CIPM) provides the reliable
frequency (f = 473.6127 THz) and wavelength in vacuum
(λ = 632.9908 nm), along with their relative uncertainty
(1.5 × 10−6), for unstabilised He-Ne lasers.[8,9] Thus, the
use of an unstabilised He-Ne laser (He-Ne laser com-
monly used for Raman spectrometers) is important for
evaluating the uncertainty in the Raman shift. Ne emis-
sion lines are also widely used for the calibration of
Raman spectrometers, and their reliable wavenumbers in
vacuum, along with their uncertainties, are also avail-
able.[10] The bracket calibration method allows the esti-
mation of the wavenumbers and the evaluation
uncertainties of unknown peaks from those of the Ne
emission lines in vacuum.[11,12] Thus, reliable Raman
shifts of unknown peaks may be able to be estimated by
using the wavenumbers and the uncertainties of He-Ne
laser and Ne emission lines.
Crystalline Si substrates are widely used for the daily
calibration of Raman microscopes because they give a
single strong peak at 520 cm−1.[4,5] On the other hand,
the Raman shift of Si substrates is not provided in ASTM
E1840 partly because of the differences in the Raman
shifts that arise from not only the residual stresses and
preparation processes[13–16] but also the inapplicability in
calibration for a wide spectral range.[5] Thus, reliable esti-
mation of Raman shift for Si substrate is important for
users of Raman microscopes.
In this study, we reliably estimated the Raman shift
of Si substrate (NMIJ CRM 5606-a) using an unstabilised
He-Ne laser and its plasma lines (Ne emission lines). This
CRM can be reasonably used as a typical Si substrate
because NMIJ CRM 5606-a (single-crystal silicon for posi-
tron defect measurements) is fabricated from a non-
doped Si substrate.[17] The combined standard uncer-
tainty was evaluated from the uncertainties in the
wavenumbers of the He-Ne laser and the Ne emission
lines, the repeatability of experimental results, inhomoge-
neity of measuring points and spectral dispersion. The
obtained Raman shift of NMIJ CRM 5606-a was validated
by the other estimated Raman shifts obtained with other
Raman spectrometers.
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2497
2 | EXPERIMENTAL
2.1 | Materials
The non-doped Si substrate for positron defect measure-
ments (NMIJ CRM 5606-a, No. 003) was obtained from
National Metrology Institute of Japan (NMIJ). This CRM
constitutes two pieces, each of which is 15 mm × 15 mm
with 1 mm thickness, with a crystal orientation of
{100} ± 1
.[17] One side of the substrate is mirror-finished,
while the other side has a rough surface. The measure-
ments were performed on the mirror-finished side.
2.2 | Raman spectrometers
Three types of independent Raman spectrometers were
employed in this study. One of them was for the estima-
tion of the Raman shift of NMIJ CRM 5606-a and uncer-
tainty evaluation (System A), while the other two were
for the validation of that estimation (Systems B and C).
System A is a LabRAM HR Evolution Raman spectrome-
ter, and Systems B and C are an NRS-7100 Raman spec-
trometer and an NRS-5500 Raman spectrometer,
respectively. Unstabilised He-Ne lasers were used for all
the systems to apply its reliable wavenumber and uncer-
tainty provided from CIPM. Ne emission lines used in
this study were originated from the He-Ne laser itself
(plasma lines) in all the analytical systems. These lines
are more reliable than Ne emission lines using another
Ne lamp because their optical path is the same as that of
the He-Ne laser and Raman scattered light.
A LabRAM HR Evolution Raman spectrometer (focal
length: 800 mm, objective: 100×, laser power at sample:
1 mW; HORIBA, Kyoto, Japan) with a 1800 gr/mm
(System A) was used to estimate the Raman shift of NMIJ
CRM 5606-a. The measurement range was
15123.29–15445.66 cm−1 (wavelength: 647.43–661.23 nm)
in air.
To validate the Raman shift of NMIJ CRM 5606-a, an
NRS-7100 Raman spectrometer (focal length: 500 mm,
objective: 100×, laser power at sample: 1 mW; JASCO,
Tokyo, Japan) equipped with a 1800 gr/mm grating
(Systems B) and an NRS-5500 Raman spectrometer
(focal length: 300 mm, objective: 100×, laser power at
sample: 1 mW; JASCO) equipped with a 1800 gr/mm
grating (System C) were also used. The measurement
ranges in air were 15021.94–15534.75 cm−1
(wavelength: 643.72–665.69 nm) for System B and
14953.90–15648.14 cm−1 (wavelength: 639.05–668.72 nm)
for System C.
Five points on a piece of Si substrate (four points
close to the corners and a point around the centre) were

2498
selected for the measurement. 10 times repetitions were
implemented on each point. Peak top wavenumbers of
Ne emission lines and Si substrate obtained as the output
data were used for the analysis without any curve fittings
in this paper.
2.3 | Estimation of Raman shift
The wavelength in vacuum (λ = 632.9908 nm), frequency
(f = 473.6127 THz), and relative standard uncertainty
(1.5 × 10−6) of the unstabilised He-Ne laser are
available.[8,9] Wavelengths of the Ne emission lines in air
and their wavenumber in vacuum are also available.[10]
In this study, we used wavenumbers in vacuum and their
corresponding uncertainties; the wavenumber of the
He-Ne laser in vacuum (15798.018 cm−1) was calculated
from the reciprocal of its wavelength in vacuum
(λ = 632.9908 nm).
Theoretical Raman scattering wavenumber of NMIJ
CRM 5606-a was estimated with the two closest Ne
emission lines using the bracket calibration method.
Then, the Raman shift was estimated from the difference
in the wavenumber of the He-Ne laser and that of the
Raman scattering of NMIJ CRM 5606-a.
2.4 | Evaluation of uncertainty
The uncertainty of the Raman shift was evaluated based
on ISO/IEC Guide98–3 “Evaluation of measurement
data -- Part 3: Guide to the expression of uncertainty in
measurement (GUM)”.[18] In Figure 1, we show the
summary of the uncertainty evaluation in this study.
The standard uncertainty of the Raman shift u (ΔνSi)
was evaluated step by step according to this figure. The
uncertainty sources taken into consideration are
follows:
i. Uncertainty due to the wavenumbers given in the
references
ii. Uncertainty due to the inhomogeneity (difference
between measurement points)
iii. Uncertainty due to the line selection
iv. Uncertainty due to the spectral dispersion
(wavenumber resolution)
v. Uncertainty due to the repetitions in
measurement
Finally, the expanded uncertainty was obtained by the
coverage factor (k = 2) for the 95% level of confidence.
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ITOH AND SHIRONO
3 | R E S U L T S AN D D I S C U S S I O N
3.1 | Estimation of Raman scattering
wavenumber of the Si substrate
It should be noted that the uncertainty evaluation
depends on not only the measurement procedure but also
the definition of the measurand. The definition should
be, therefore, given in an explicit way. The measurand in
this study is defined as the Raman shift on an arbitrary
point on a Si-substrate piece. The uncertainty evaluation
of the Raman shift on a specific point given by the posi-
tional information, and the general reference value for
the Raman shift of a bulk of NMIJ CRM 5606-a with the
uncertainty are different from what is evaluated in this
study. More information is given in 3.3 Uncertainty in the
inhomogeneity of the measurement points subsection.
Five points on a piece of Si substrate were selected for
the measurement. Specifically, four points close to the
corners and a point around the centre. 10 times
repetitions were implemented on each point. We use the
subscript j and k to mean the identifications for the
positions (j = 1, …, 5) and the repetitions (k = 1, …, 10),
respectively.
For this purpose, we applied the bracket calibration
method (Equation 1) to obtain the theoretical
wavenumber of the Si substrate[11,12] as there is only one
target peak at 520 cm−1 in this study. We used the two
closest Ne emission lines (lines 2 and 3, Table 1 and
Figure 2) to obtain the Raman shift of the Si substrate for
the k-th repetition at the j-th position, ΔνSi, j, k, as follows:
2
  Ob  3
νTh
Ne2 −ν Th
Ne3 × ν Si,j,k −ν Ob
Ne3,j,k
ΔνSi,j,k = νTh 4 5
HeNe − + νTh
Ne3 ,
νOb
Ne2,j,k −νNe3,j,k
Ob
ð1Þ
−1 −1
where νThNe2 (cm ), νNe3 (cm ) and νHeNe are the theoreti-
Th Th
cal wavenumbers of Ne emission line-2, Ne emission
line-3 and He-Ne laser, respectively. Table 1 gives the
−1 −1
Si (cm ) and νSi,j,k (cm ) are
specific values of them. νTh Ob
the theoretical and observed wavenumbers, respectively,
−1
Si,j,k , νNe2,j,k (cm )
of Raman scattering for Si substrate. νOb Ob
−1
and νNe3,j,k (cm ) are Raman scattering of the Si
Ob
substrate, the observed wavenumbers of Ne emission
line-2 and Ne emission line-3, respectively.
The average of the 50 values are computed as the
the measurement value as follows:
1X 5 X 10
ΔνSi = ΔνSi, j, k : ð2Þ
50 j = 1 k = 1
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ITOH AND SHIRONO 2499

F I G U R E 1 Summary of the
uncertainty evaluation in this
study [Colour figure can be
viewed at wileyonlinelibrary.
com]

TABLE 1 Wavenumbers used in this study and their

uncertainty

Wavenumber in Standard
vacuum (cm−1) uncertainty (cm−1)
He-Ne laser*1 15798.018 0.024
Ne line-1 15364.9354 0.0012
Ne line-2 15302.9512 0.0012
Ne line-3 15149.7353 0.0011
Ne line-4 15140.677 0.009

Wavenumbers and the uncertainties of Ne emission lines were

obtained from literature (Reference 10). F I G U R E 2 Raman spectrum of NMIJ 5606-a with Ne
*1 Calculated from the reciprocal of wavelength in vacuum and its emission lines obtained with System A. Labels correspond to those
relative uncertainty (References 8 and 9). in Table 1

Table 2 shows the averaged Raman shift on each mea- table. We applied the three-decimal-point expression,
surement point together with the total averaged values. and the total averaged value of ΔνSi = 520.446 cm−1 is
For later discussion, the standard deviations for the repe- employed as the reported value for the measurand in
titions on individual measurement points are given in the this study.
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2500 ITOH AND SHIRONO

T A B L E 2 Averaged Raman shifts and the standard deviations ∂ΔνSi 1

cTh
Ne3 = ≈ Ave Ave −1, ð8Þ
of a measured Raman shifts obtained on individual measurement ∂νNe3 νNe2 − νNe3
Th
points together with the total averaged Raman shift using System A

Averaged Raman Standard ∂ΔνSi

cTh
HeNe = ≈1: ð9Þ
shift (cm−1) deviation (cm−1) ∂νTh
HeNe
Top-right 520.4627 0.1583
Top-left 520.3944 0.0758
Thus, the uncertainty due to the wavenumbers can be
Centre 520.5076 0.1740
computed as follows:
Bottom-right 520.3703 0.0310
h

Th 2
Th
Th 2
Th
Th 2 i1=2
Bottom-left 520.4924 0.1761
uwave = cTh
Ne2 u νNe2 + cNe3 u νNe3 + cHeNe u νHeNe
Total average 520.4455
= 0:0237 cm − 1 :
Indices of top-right to bottom-left are given in convenience and no ð10Þ
absolute direction is defined for NMIJ CRM 5606-a.

3.2 | Uncertainty of the wavenumbers 3.3 | Uncertainty in the inhomogeneity of

the measurement points
As mentioned, we evaluated the uncertainties of the
wavenumbers by converting those of the wavelengths The Raman shift of a Si substrate is affected by the
available from references.[8,9] Not only the standard changes in residual stresses[13–16]; thus, the estimated
uncertainties of individual sources but also the sensitivity Raman shifts can vary with the measuring points,
coefficients, the conversion factors of them to the depending on the cutting processes. Therefore, we
reporting Raman shift,[18] must be clarified in the compu- obtained data at five different measuring points.
tation. To compute the sensitivity coefficients, we need to The inhomogeneity of the measuring points was
give an approximate measurement model to specify the assessed by measuring the wavenumbers at five different
influence of individual wavenumbers. The following measuring points (four corners and the centre). The one-
approximate measurement model suggested in this study: way ANOVA was performed, and the mean squares for a
measurement point (Vrep) and among measurement


Ave Ave  
Ne2 − νNe3 × νSi − νNe3
νTh Th points (Vpoint) were calculated as follows:
ΔνSi ≈νTh
HeNe − + νNe3 ,
Th
ð3Þ
Ne2 −νNe3
νAve Ave

1X 5 X 10
2
V rep = ΔνSi, j −ΔνSi , ð11Þ
4 j=1 k=1
Si , νNe2 and νNe3 are given as follows:
where νAve Ave Ave

1X 5 X 10 1X 5 X 10
2
νAve = νOb , ð4Þ V point = ΔνSi, j, k −ΔνSi, j , ð12Þ
Ne2
50 j = 1 k = 1 Ne2,j,k 45 j = 1 k = 1

1X 5 X 10
where
νAve
Ne3 = νOb , ð5Þ
50 j = 1 k = 1 Ne3,j,k
1X 10
ΔνSi, j = ΔνSi, j, k : ð13Þ
1X 5 X 10 10 k = 1
νAve
Si = νOb : ð6Þ
50 j = 1 k = 1 Si, j, k
Vrep and Vpoint can be computed using the data in
Based on equation 3, the sensitivity coefficients for νTh
Ne2 , Table 2. Usually, the standard deviations between the
νTh
Ne3 and ν Th
, c , c
HeNe Ne2 Ne3 and c HeNe , are given as follows: points (spoint) were calculated as follows[19]:

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
∂ΔνSi 1 V point − V rep
cTh = Th ≈− Ave Ave , ð7Þ spoint = = 0:0423 cm − 1 : ð14Þ
Ne2
∂νNe2 νNe2 −νNe3 10
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ITOH AND SHIRONO 2501

It should be noted that the uncertainty due to the
inhomogeneity is not spoint. We must take the two
matters into consideration: (i) The representative value
ΔνSi varies because of the inhomogeneity, and (ii) the
arbitral points on the target piece of Si substrate has the
Raman shift fluctuate with the standard deviation spoint.
For the first, we can evaluate the standard
pffiffiffi deviation in
the determination of ΔνSi as spoint/ 5 , because there
were the five measurement points. Thus, we can compute
the uncertainty due to the inhomogeneity in the
measurement points as follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
s2point
upoint = + s2point = 0:0464 cm − 1 :
5
In this study, the measurand is the Raman shift at an
arbitrary point on the target piece. However, if we specify
the measurement point with the positional information,
the uncertainty due to the inhomogeneity is not basically
required because the measured value is associated with
the specific point.
3.4 | Uncertainty in the selection among
the Ne emission lines
The Raman shifts computed with the different pairs of
the Ne emission lines varies from each other. Specific
values can be computed using the same data to obtain
ΔνSi with Ne lines 2 and 3. In Table 3, we show the three
values of the Raman shift with using three different pairs
of Ne emission lines (1, 3), (1, 4), and (2, 4). We can find
the difference of 0.0828 cm−1 at the maximum.
The uncertainty in variance between the Ne emission
because the standard uncertainty
pffiffiffi for the rectangular dis-
tribution is given as H/ 3 , where H means the half
width of the rectangular distribution.[18]
3.5 | Uncertainty originated from spectral
dispersion
We also considered spectral dispersion as a source of
uncertainty when estimating the Raman scattering
wavenumbers, because it depends on the grating sys-
tems under the same focal length and strongly affects
the accuracy of the experimental results. Here, we used
ð15Þ peak-top numbers of Ne emission lines and Si
substrate without any curve fitting to reasonably
evaluate the standard uncertainties originated from
spectral dispersion (udisp) using the standard deviation
of rectangular distributions with the half-width
corresponding to the resolution of the employed plots.
Table 4 shows the most frequently observed peak-tops
for Ne lines 2 and 3 and Si substrate together with the
two closest wavenumbers to the peak-tops in larger and
smaller sides. For each line, we computed the larger
value between the two differences (of the closest
wavenumbers and the peak-top), which is shown in
Table 4 as “larger interval”.
Since the interval of the observed wavelength vary
in the larger and the smaller sides of the peak-top, the
rectangular distribution may not be applied in a strict
sense. However, the differences of the intervals are
small enough to approximate the distribution to be
rectangular. In this approximation, we employ the
larger interval as the half-width of the rectangular dis-
tribution. Thus, we evaluate the standard uncertainties
Ne2 , νNe3 , and νSi as due to the spectral dispersion as
of νAve Ave Ave

lines (uline) was evaluated in this study. For this purpose, follows:
we assume the uniform distribution with the half width
of the maximum difference of 0.0828 cm−1. Thus, the
 0:3280 −1
Ne2 = pffiffiffi cm
u νAve = 0:0947 cm − 1 , ð17Þ
uncertainty uline is computed as follows: 3

0:0828
 0:3215
uline = pffiffiffi cm − 1 = 0:0478 cm − 1 , ð16Þ Ne3 = pffiffiffi cm
u νAve −1
= 0:0928 cm − 1 , ð18Þ
3 3

 0:3269
u νAve
Si = pffiffiffi cm − 1 = 0:0944 cm − 1 : ð19Þ
3
T A B L E 3 Averaged Raman shifts computed using different Ne
lines for System A The sensitivity coefficients for these values are
Averaged Raman Difference from evaluated using the approximation with equation 3 as
shift (cm−1) ΔνSi (cm−1) follows:
Ne lines 1 and 3 520.5283 0.0828


Ave Ave 
Ne lines 1 and 4 520.4940 0.0485 ∂ΔνSi νThNe2 −νNe3 × νSi −νNe3
Th
cAve = Ave ≈
Ave Ave 2 , ð20Þ
Ne lines 2 and 4 520.4308 – 0.0147
Ne2
∂νNe2 νNe2 −νNe3
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2502 ITOH AND SHIRONO

T A B L E 4 Most frequently observed peaktops for Ne lines 2 and 3 and Si substrate together with the two closest wavenumbers to the
peak-tops in larger and smaller sides, respectively, for System A. see text for the computation of the larger difference to the peak-top

Most frequently Closest wavenumber Closest wavenumber

observed the peaktop to the peaktop to the peaktop Larger interval to
(cm−1) (larger side) (cm−1) (smaller side) (cm−1) the peaktop (cm−1)
Ne line 2 15306.6926 15307.0206 15306.3645 0.3280
Ne line 3 15153.4667 15153.7882 15153.1682 0.3215
Si substrate 15281.4071 15281.7340 15281.1035 0.3269


Ave Ave  srep

∂ΔνSi νThNe2 −νNe3 × νNe2 − νSi
Th
urep = pffiffiffiffiffi = 0:0193 cm − 1 , ð25Þ
cAve = Ave ≈
Ave Ave 2 , ð21Þ 50
Ne3
∂νNe3 νNe2 −νNe3

because 50 measurements were performed in total for

∂ΔνSi νTh −νTh
cAve = Ave ≈− Ne2 Ne3
: ð22Þ five points in 10 repetitions.
Si
∂νSi νAve
Ne2 −νNe3
Ave

Thus, the uncertainty due to the wavenumbers can be
computed as follows:
h

Ave 2
Ave
Ave 2
Ave
Ave 2 i1=2
udisp = Ne2 u νNe2
cAve + cNe3 u νNe3 + cSi u νSi
= 0:1214 cm −1 :
ð23Þ
Strictly, this spectral dispersion uncertainty is not per-
fectly systematic but partially randomly shown in the
repetition. However, the analysis on the separation of the
fluctuation into the systematic and the random effects
are complicated.[20] We hence regard the spectral disper-
sion uncertainty to be perfectly systematic and indepen-
dent of the variance in the repetitions evaluated in 3.6
Uncertainty originated from repetition subsection, and
allow some over-evaluation of the uncertainty caused by
this measure.
3.7 | Combined standard uncertainty and
the expanded uncertainty
The results of the uncertainty evaluation are summarized
in Table 5. The combined standard uncertainty u (ΔνSi) is
computed the square root of the sum of the square of the
five standard uncertainties, i.e. uwave, upoint, uline, udisp,
and urep, as follows:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uðΔνSi Þ = u2wave + u2point + u2line + u2disp + u2rep = 0:1418 cm −1 :
ð26Þ
The expanded uncertainty (U) in the Raman shift is equal
to k × uCRM, where k = 2 is the coverage factor, for the
95% level of confidence.
U = kuðΔνSi Þ = 0:28 cm − 1 : ð27Þ

Thus, the Raman shift of the Si substrate was estimated

3.6 | Uncertainty originated from to be 520.45 ± 0.28 cm−1.
repetition

As described in 3.5 Uncertainty originated from spectral
dispersion subsection, uncertainty originated from repeti-
tion was separately evaluated from uncertainty originated
from spectral dispersion (udisp). The standard deviation in
the repetition (srep) can be computed from the data
shown in 3.3 Uncertainty in the inhomogeneity of the mea-
surement points subsection as follows:
pffiffiffiffiffiffiffiffiffi
srep = V rep = 0:1364 cm − 1 :
Thus, we can compute the uncertainty due to the repeti-
tion as follows:
3.8 | Validation of the obtained Raman
shift with other systems
The obtained Raman shift with System A (focal length:
800 mm and grating: 1800 gr/mm) was validated with
other two different systems (System B, focal length:
500 mm, and groove density: 1800 gr/mm; System C,
focal length: 300 mm, and groove density: 1800 gr/mm).
ð24Þ As the same with System A, five points on a piece of Si
substrate (top-right, top-left, centre, bottom-right,
bottom-left) were selected and 10 times repetitions were
implemented on each point in Systems B and
C. Obtained averaged Raman shift at each point was from
 10974555, 2020, 12, Downloaded from https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/10.1002/jrs.6003 by Sabanci University, Wiley Online Library on [10/07/2024]. 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
ITOH AND SHIRONO 2503

TABLE 5 Uncertainty budget for the Raman shift of a Si substrate for System A

Sub-source

Standard Converted standard Standard and

uncertainty of uncertainty with expanded
Source sub-source Sensitivity the sensitivity uncertainty for
(symbol) Symbol (cm−1) coefficient coefficient (cm−1) ΔνSi (cm−1) Note
Wavenumber 0.0237
(uwave)


u νTh
Ne2 0.0012 0.0065 0.0000


u νTh
Ne3 0.0011 – 0.9935 0.0011

Th 
u νNeHe 0.0237 1 0.0237
Inhomogeneity 0.0061
(upoint)
Selection in the 0.0478
lines (uline)
Spectrum 0.1214
dispersion
(udisp)


u νAve
Ne2 0.0944 0.8089 0.0763


u νAve
Ne3 0.0947 0.1904 0.0180

Ave 
u νSi 0.0928 – 0.9993 0.0927
Repetition 0.0193
(upoint)
u(ΔνSi) 0.1418 Relative standard
uncertainty; 0.027%.
U 0.28 k = 2. Relative expanded
uncertainty; 0.054%.

520.4161 cm−1 to 520.5284 cm−1 with System B and from
520.1723 cm−1 to 520.3132 cm−1 with System C. The
detailed information is given in the Electric Supplemen-
tary Information (Tables S1–S3 for System B and
Tables S5–S7 for System C). The obtained Raman shifts
with Systems B and C were 520.52 ± 0.38 cm−1 and
520.25 ± 0.51 cm−1, respectively (k = 2). The evaluated
Raman shifts with Systems B and C are referred to as
ΔνSi,B and ΔνSi,C, respectively, for the simplicity in the
description.
The uncertainty budgets of Systems B and C are sum-
marized in Tables S4 and S8, respectively. uwave
(0.0237 cm−1) is a common source for all systems because
all systems commonly used He-Ne laser and the same Ne
emission lines. upoint of Systems B (0.0133 cm−1) and C
(0.0461 cm−1) are larger than System A (0.0061 cm−1)
whereas uline of Systems B (0.0127 cm−1) and C
(0.0311 cm−1) are better than System A (0.0478 cm−1).
Commonly, udisp is originating from the combination of
focal length and groove density, and the largest uncer-
tainty source for all the systems. Thus, the combined
uncertainty increased following order: System A
(0.1418 cm−1) < System B (0.1884 cm−1) < System C
(0.2562 cm−1).
The significance of the differences in the obtained
results was evaluated using inequation (28)[19] for the
comparison between Systems A and B:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
jΔνSi − ΔνSi, B j ≤ k × u2 ðΔνSi Þ + u2 ðΔνSi, B Þ : ð28Þ
When evaluated using this method, the difference is not
significant if this equation is satisfied. For the compari-
son between Systems A and C, the evaluation can be
implemented with the similar inequation. The both
results obtained with Systems B and C satisfied these
inequations, respectively, meaning the obtained Raman
shift with System A (520.45 ± 0.28 cm−1) is reasonable.
4 | CONCLUSIONS
Raman shift and its expanded uncertainty (coverage fac-
tor k = 2) of a non-doped Si substrate (NMIJ CRM5606-a)

2504
was reliably evaluated to be 520.45 ± 0.28 cm−1 with an
unstabilized He-Ne laser and its plasma lines
(Ne emission lines) using a bracket calibration method.
To the best of our knowledge, this is the first estimation
of reliable Raman shift for a Si substrate. Although this
approach is also suitable for reliable estimation of Raman
shifts for specific peaks of other materials close to Ne
emission lines using fine dispersive resolution system,
reflective materials should be better to use Ne emission
lines originated from He-Ne lasers. For Raman shifts of
peaks without close Ne emission lines, using low disper-
sive resolution system, or the both, other approaches
should also be developed.
A C K N O WL E D G E M E N T
This work was partly performed by the VAMAS TWA42
corresponding committee in Japan. We are grateful to
Mr. Shinsuke Kashiwagi (HORIBA) and Mr. Kohei
Tamura (JASCO) for the measurements and valuable dis-
cussions. We thank Tottori Institute of Industrial Tech-
nology for the usage of the Raman spectrometer.
ORCID
Nobuyasu Itoh https://orcid.org/0000-0003-0163-4454
Katsuhiro Shirono https://orcid.org/0000-0002-4930-
799X
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SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Itoh N, Shirono K.
Reliable estimation of Raman shift and its
uncertainty for a non-doped Si substrate
(NMIJ CRM 5606-a). J Raman Spectrosc. 2020;51:
2496–2504. https://doi.org/10.1002/jrs.6003