Appl. Phys.
A (2017) 123:547
DOI 10.1007/s00339-017-1163-3
Factors influencing the tunability of the near-IR absorption band
of CuS nanoparticles
Delfino Cornejo-Monroy1 • Luis A. Martı́nez-Ortega1 • Zaira Y. Castillo-Morán1
Rey D. Molina-Arredondo1 • Salvador Noriega1 • Vianey Torres-Argüelles1 •
Jose L. Enriquez-Carrejo1
Received: 13 January 2017 / Accepted: 20 July 2017 / Published online: 27 July 2017
Ó Springer-Verlag GmbH Germany 2017
Abstract Owing to the importance of the correct selection
of the synthesis parameters when fabricating nanoparticles, a
general full factorial design with three factors: pH, thioac-
etamide/CuCl2 H2 O ratio, and stirring time was performed
to find the factors affecting the spectral position of the near-
infrared (NIR) absorption band of CuS nanoparticles. Based
on the results, there is evidence that the peak position
depends on one significant interaction, as well as on two
main factors. Additionally, taking into account R2 , we argue
that the variability of the wavelength corresponding to peak
position of the NIR absorption band can be explained by a
linear model with an accuracy above 93%.
1 Introduction
Nanomaterials are of great interest in many areas of science
and technology, owing to their unique physical and chem-
ical properties [1–4]. Noble metal nanoparticles such as
gold, silver, and copper are of particular interest due to their
novel properties which make them useful in catalysis,
electronics, plasmonics, and medicine [5–8]. Among noble
materials, gold and silver nanoparticles are the most studied
nanomaterials mainly due to their high stability and optical,
electrical and thermal properties along with their potential
applications in medicine and solar cells. On the other hand,
copper nanoparticles are unstable, highly sensitive to oxy-
gen, and easily oxidized [9–11]. These characteristics could
& Jose L. Enriquez-Carrejo
jose.enriquez@uacj.mx
1 (TGA), and thioacetamide ACS reagent (CH3 CSNH2 ) 
Instituto de Ingenierı́a y Tecnologı́a, Universidad Autónoma
de Cd. Juárez, Av. del Charro #450 N, 32310 Ciudad Juárez,
Chihuahua, Mexico
•
be the main reasons why copper nanoparticles are less
attractive. Despite those disadvantages, copper nanoparti-
cles are widely used in lubricants, polymers, metallic
coatings, and inks [12, 13]. Recently, copper sulfide, a
copper compound, has attracted attention at the nanoscale
mainly because copper sulfide nanoparticles (CuS NPs)
exhibit a strong absorption band in the near-infrared region
(NIR). CuS NPs with optical properties in the NIR are
useful for solar cells, infrared detectors, lubricants, and
biomedical applications [14–16]. Furthermore, synthesis of
CuS NPs is cheaper than gold and silver nanostructures with
optical properties in the NIR. At the present time, CdSe,
CdS, and PdS nanostructures exhibit interesting properties
which can be used to replace nanogold and nanosilver
[16–18]; however, these are toxic materials. Additionally,
other nanomaterials such as amorphous silicon, gallium
arsenide, indium compounds, and sulfide salts can be used
to replace expensive noble metals, but their manufacturing
process requires high temperature and high vacuum
[17, 18]. As a result, CuS NPs are cheaper, as well as
environmentally friendly. Despite great advantages of CuS
NPs with their absorption band in the NIR, the experimental
conditions affecting the tunability of the NIR absorption
band are not well understood.
2 Methods and experimental details
2.1 Materials
Copper (II) chloride dihydrate reagent grade
(CuCl2 2H2 O), thioglycolic acid (HSCH2 COOH)  98%
99.0% were purchased from Sigma-Aldrich and sodium
hydroxide pellets from Macron. Ultrapure water with a
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547 Page 2 of 6 D. Cornejo-Monroy et al.

resistivity of 18.2 MXcm was obtained from Labconco
WaterPro PS polishing system.
2.2 Equipment
Absorbance spectra were collected using a single-beam
UV–Vis spectrophotometer (190–1100 nm, ±1 nm,
0.5 nm), pH was measured using a pH checker from Hanna
Instruments, chemical reactions were performed using a
digital stirring hot plate with external temperature probe
from Corning. An analytic balance 65 g  0.0001 g from
Ohaus Pioneer series was used for weighing.
2.3 Design of experiment (DOE)
experimental conditions shown in Table 2. In detail, under
constant stirring (700 rpm), 0.017048 g of CuCl2 2H2 O
was dissolved in 100 ml of ultrapure water, followed by the
addition of 15 l of TGA; pH was adjusted by drop-wise
addition of a 0.5 M solution of NaOH. Finally, thioac-
etamide, dissolved separately in 20 ml of ultrapure water,
was added and the whole solution was heated at 50  C.
Stirring time (in hours) was measured after all ingredients
were mixed and target temperature was reached. For
example, sample 1 was prepared using 0.017048 g
(0.1 mmol) of CuCl2 2H2 O, 15 l of TGA, pH 8, 8.3 mg
(0.09 mmol) of TGA (TCR ¼ 0.09/0.1 ¼ 0.9), and the
stirring time was 1 h.

Based on the methodology proposed by others [15], a general 3 Results and discussion
full factorial experiment was designed using three factors:
pH (pH), thioacetamide:CuCl2 H2 O ratio (TCR), and stir- First, the absorbance spectra for each sample was obtained.
ring time (Time); each factor with three levels, except the The wavelength range of interest was 400–1100 nm. Fig-
stirring time with two levels. Details are given in Table 1. ures 1 and 2 show the absorbance spectra of CuS NPs
Using MinitabÓ, a non-replicated 22  32 general full
factorial design was created. The resulting eighteen ran-
domized runs or samples were synthesized according to the

Table 1 Factors and its levels

Factors Levels
used in the full factorial design
1 2 3

pH 8 9 10
TCR 0.9 1.3 2.0
Time (h) 1 2 –

Table 2 Run order of samples

Sample pH TCR Time (h)
and experimental conditions
9 9 1.3 1
13 10 0.9 1 Fig. 1 Absorbance spectra of CuS NPs synthesized with a stirring
time of 1 h
10 9 1.3 2
1 8 0.9 1
17 10 2.0 1
2 8 0.9 2
4 8 1.3 2
14 10 0.9 2
5 8 2.0 1
8 9 0.9 2
12 9 2.0 2
6 8 2.0 2
15 10 1.3 1
16 10 1.3 2
11 9 2.0 1
7 9 0.9 1
18 10 2.0 2
3 8 1.3 1 Fig. 2 Absorbance spectra of CuS NPs synthesized with a stirring
time of 2 h

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Factors influencing the tunability of the near-IR absorption band Page 3 of 6 547

Table 3 Wavelengths corresponding to peak position of the NIR NIR absorption band were used as response variable in the
absorption band of CuS NPs, along with factors and levels used in the DOE, see Table 3.
full factorial design
Sample pH TCR Time (h) Wavelength (nm) To determine the significance of these experiments, we
compared the maximum wavelength shift for the samples,
1 8 0.9 1 1047
which is 110 nm, to the average FWHM (full width at
2 8 0.9 2 1056
half maximum) of the Gaussian-fitted curves. The calcu-
3 8 1.3 1 977
lation of the average FWHM yielded 410 nm. This
4 8 1.3 2 972
indicates that the maximum wavelength shift corresponds
5 8 2.0 1 1031
to 27% of the average FWHM. This is a very significant
6 8 2.0 2 1032
value in this analysis since this percentage represents the
7 9 0.9 1 1070
amount of experimental tuning of the NIR absorption band
8 9 0.9 2 1060
that can be achieved by adjusting the studied factors
9 9 1.3 1 1021
(parameters).
10 9 1.3 2 1029 To estimate the effect of each factor, we performed
11 9 2.0 1 1012 statistical analysis using a general full factorial experiment.
12 9 2.0 2 974 To improve visualization, the interactions and factors
13 10 0.9 1 1079 affecting the tunability of the NIR absorption band are
14 10 0.9 2 1082 presented in Figs. 3 and 4. In Fig. 3a it can be seen that the
15 10 1.3 1 1007 pH effect on peak position of the NIR absorption band is
16 10 1.3 2 1028 strong and positive; thus, the peak position increases with
17 10 2.0 1 1050 increasing pH. On the contrary, Fig. 3b shows that the
18 10 2.0 2 1076 wavelength corresponding to peak position is minimum at
Samples are displayed in ascending order for easy identification a TCR of 1.3 and its effect appears to be quadratic, whereas
Fig. 3c shows that the Time factor has a very weak effect
on tunability of the NIR absorption band. Consequently,
pH and TCR are the main factors affecting tunability of the
produced according to the experimental conditions shown NIR absorption band of CuS NPs.
in Table 2. It should be noted that all spectra exhibit a Figure 4 shows the interaction plots for the response
strong NIR absorption band with a peak position ranging variable. As can be seen in Fig. 4a, there is a high degree of
from 900 and 1100 nm. Based on the absorbance spectra, interaction between pH and TCR, i.e., the TCR effect
the wavelengths corresponding to the peak position of the depends on the pH level. For pH 8 and 10 the TCR effect is

Fig. 3 Main effect plots on

response variable. a pH effects
on peak position of the NIR
absorption band, b TCR effects
on peak position of the NIR
absorption band, and c Time
effects on peak position of the
NIR absorption band

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547 Page 4 of 6 D. Cornejo-Monroy et al.

Fig. 4 Interaction plots for response variable. a Interaction plot between pH and TCR, b interaction plot between pH and Time, and c interaction
plot between TCR and Time

quadratic; however, TCR has a negative linear effect at pH factors, the pH and TCR which cannot be evaluated
9. The interaction plot also indicates that peak position of independently.
the NIR absorption band presents a minimum at a TCR of
1.3 for pH 8–10. Figure 4b shows a mild interaction Table 5 shows the refined ANOVA of Table 4. The
between pH and Time. The Time effect is negative at pH 9 results are consistent; the pH and TCR factors, and the
and positive for the other levels. Finally, Fig. 4c shows that pHTCR interaction have a significant effect. The linear
TCR and Time factors do not have strong interactions. As a model describing the tunability according to the pH and
result, pHTime and TCRTime interactions apparently TCR factors is shown in the following equation:
do not have a significant effect on the tunability of the NIR
absorption band of CuS NPs.
An analysis of variance (ANOVA) was performed to
know which factors have a significant effect on tunability
of the NIR absorption band of CuS NPs. First, the ANOVA
was conducted in the model up to the second-order term.
The third-order term (pHTCRTime) was regarded as
error, after proceeding to refine the model by removing
each non-significant factor. Figure 5 shows the square sum
(SS) percent contribution for each factor. The TCR factor
has the biggest contribution, as a result it has a greater
effect on peak position, followed by pHTCR interaction
and pH factor. The ANOVA data are presented in Table 4.
The variance results show an interaction between pHTCR
factors with a p value of 0.036, which is less than 0.05,
meaning that the interaction is significant for the tunability
of the NIR absorption band of CuS NPs. In addition to the Fig. 5 Pareto chart for the contribution to the sum of squares of each
above result, the statistical model contains two main term

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Factors influencing the tunability of the near-IR absorption band Page 5 of 6 547

Table 4 Minitab results for the

Source DF Seq SS Adj SS Adj MS F P
ANOVA using wavelength as
response variable pH 2 3877.0 3877.0 1938.5 12.33 12.33
TCR 2 10,969.0 10,969.0 5484.5 34.90 0.003
Time 1 12.5 12.5 12.5 0.08 0.792
pHTCR 4 4852.0 4852.0 1213.0 7.72 0.036
pHTime 2 675.0 675.0 337.5 2.15 0.233
TCRTime 2 104.3 104.3 52.2 0.33 0.736
Error 4 628.7 628.7 157.2
Total 17 21118.5
S ¼ 12:5366 R2 ¼ 97:02% R2 ðadjÞ ¼ 87:35%

Table 5 Minitab results for the

Source DF Seq SS Adj SS Adj MS F P
refined ANOVA using
wavelength as response variable pH 2 3877.0 3877.0 1938.5 15.60 0.003
TCR 2 10,969.0 10,969.0 5484.5 34.90 0.000
pHTCR 4 4852.0 4852.0 1213.0 7.72 0.006
Error 9 1421.0 1421.0 157.8
Total 17 21,118.5
S ¼ 12:5632 R2 ¼ 93:27% R2 ðadjÞ ¼ 87:29%

Fig. 6 Residual plots. a Normal probability plot of residuals, b residuals versus fits plot, c histogram of residuals, and d residuals versus order

123
547 Page 6 of 6
y ¼1033:50  14:33A1  5:83A2 þ 20:17A3
þ 32:17B1  27:83B2  4:33B3 þ 0:17A1  B1
 16:83A1  B1 þ 16:67A1  B3 þ 5:17A2  B1 ð1Þ
þ 25:17A2  B2  30:33A2  B3
 5:33A3  B1  8:33A3  B2 þ 13:67A3  B3
where y is the wavelength (nm), Ai and Bi represent pH and
TCR factors, respectively; the subscript i denotes the factor
level, i ¼ 1; 2; and 3, for low, medium and high level,
respectively. Ai and Bi are binary variables that indicate
whether the level of factor i is selected (variable ¼ 1) or
P P
not (variable ¼ 0) with 3i¼1 Ai ¼ 1 and 3i¼1 Bi ¼ 1.
The R2 value describes the amount of variation in the
response variable. The model predicts a 93.27% variability
of the wavelength. Contrasting with the pH and TCR fac-
tors, the Time factor along with its interactions does not
have a significant effect on the tunability of the NIR
absorption band. To assess the adequacy of the model and
the assumptions, the difference between the observed and
the fitted response values was analyzed by residual plots.
The results are shown in Fig. 6.
In Fig. 6a residuals versus expected values are dis-
played. As it is shown in the graph, residuals roughly
follow a straight line indicating that residuals are normally
distributed. Figure 6b displays residuals versus its fitted
values. Based on this plot, residuals appear to be randomly
scattered about zero indicating that the errors have a con-
stant variance. Figure 6c displays the histogram of resid-
uals which shows the distribution of the residuals for all
samples. As it can be observed, it is symmetrical even
though it does not have a bell shape. Finally, in the
residuals versus order plot (Fig. 6d) it can be seen that the
residuals are randomized about zero; as a result, no evi-
dence exists that the error terms are correlated with one
another. Based on these results, there is evidence that our
statistical model results are satisfactory.
4 Conclusions
Based on the full factorial design results we concluded that
pH and TCR are the main factors affecting the peak posi-
tion of the NIR absorption band. Furthermore, pHTCR
interaction is significant for the tunability of the NIR
absorption band of CuS nanoparticles, i.e., the effect of
TCR depends on the pH level. Taking R2 into account, we
argued that the variability of the wavelength corresponding
to the peak position of the NIR absorption band can be
123
D. Cornejo-Monroy et al.
explained 93.27% by the model. Finally, in contrast to the
pH and TCR factors, the Time factor and its levels do not
have a significant effect on the response variable.
The model presented by Eq. 1 can be used to estimate
the wavelength as a function of pH and TCR in the
experimental levels used in this analysis. Further work is
suggested using a response surface methodology (RSM) to
be able to account for curvature effects and be able to
estimate the resulting wavelength as a function of contin-
uous pH and TCR.
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