On the phase control of CuInS2 nanoparticles from Cu-/In-xanthates

Article abstract of DOI:10.1039/c8dt00653a

In this paper we report the synthesis and single-crystal X-ray characterisation of six novel indium(iii) xanthate complexes. These xanthates have been used as an In-source for the synthesis of highly crystalline CuInS₂ nanoparticles in conjunction with a Cu(i)-xanthate. In synthesising the nanoparticles we have also demonstrated an ability to control the phase of the material through choice of solvent.

Full text of DOI:10.1039/c8dt00653a

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DOI: 10.1039/C8DT00653A.
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January 2016 Pages 1–398
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ARTICLE
On the Phase Control of CuInS Nanoparticles from Cu-/In-
2
Xanthates
a
c
a
b
Received 00th January 20xx,
Accepted 00th January 20xx
Mundher Al-Shakban, Peter D Matthews, Xiang L. Zhong, Inigo Vitorica-Yrezabal, James
b
a
a,b
Raftery, David J. Lewis and Paul O’Brien*
DOI: 10.1039/x0xx00000x
In this paper we report the synthesis and single-crystal X-ray characterisation of six novel indium(III) xanthate complexes.
These xanthates have been used as an In-source for the synthesis of highly crystalline CuInS nanoparticles in conjunction
2
www.rsc.org/
with a Cu(I)-xanthate. In synthesising the nanoparticles we have also demonstrated an ability to control the phase of the
material through choice of solvent.
1
4–26
alkaline earth metal sulfides.
The xanthates breakdown
Introduction
cleanly to form metal sulfides via a Chugaev elimination
2
7
mechanism, in which volatile gases are the only by-products.
Previous synthetic routes to CIS nanoparticles have
Transition metal chalcogenides (TMCs) have witnessed a
remarkable surge in interest in recent years, owing to
extensive investigations into their exciting properties and wide
ranging applications. These applications, which include playing
key roles in sensors, photovoltaics, photocatalysts and other
electronics, are driven by the presence of a controllable band
included the reaction of metal salts (e.g. CuI, CuOAc, In(OAc)
8–32
3
2
or indium stearate) with thiols/elemental sulfur,
+
cation
3+
x y
exchange of Cu for In into previously prepared Cu S
3
3–35
nanoparticles,
[(PPh CuIn(SEt)
SEt) In(SEt)
or the use of single source precursors like
3
6
37
1
–3
3
)
2
4
],
thiobenzoates,
3 2
and [(Ph P) Cu-(µ-
gap which causes the semi-conductor properties of TMCs.
I-III-VI ternary TMCs, such as CuInS (CIS), offer an
environmentally benign alternative to the more common II-VI
3
8
2
2
]. However, these procedures are relatively
2
2
complex, requiring fine control of the reaction conditions.
Additionally, there have been some reports of the use of
4
binary systems like PbS or CdS. CIS has been explored as the
5
3
9–41
–7
active light harvesting component in photovoltaic devices as
it has a direct band gap of 1.5 eV, an absorption coefficient
simple, previously known xanthates to make CIS.
Here we
present a robust synthetic route which demonstrates control
over the phase of the obtained CIS through choice of the
reaction solvent.
5
10 cm and a good defect tolerance.
-1
8–10
>
However, it is
synthetically challenging to make pure CIS owing to the
difference in reactivity of Cu(I) (soft Lewis acid) and In(III) (hard
Lewis acid) to sulfur. Additionally, the phase diagram of CuInS2
Results and Discussion
is complex, and the window to form CuInS at temperatures
2
1
1
Precursors
lower than 800 °C is narrow. These challenges mean that the
formation of contaminating Cu S phases is often observed.
1
2
x
y
We report here the synthesis and single crystal structures
n
i
The challenge that we address in this manuscript is one of
how to reliably and easily synthesise CuInS2, whilst
demonstrating a certain level of control. In order to do this, we
of six novel indium xanthates: [In(S CO Pr) ] (8), [In(S CO Bu) ]
2 3
2
3
(
[
[
10), [In(S CO(CH ) OEt) ] (11), [In(S CO(CH ) OMe) ] (12
)
and
as
2
2 2
3
2
2 2
3
In(S CO(CH ) C(OMe)(Me) ) ]
2
(
13)
2 2
2 3
1
3
turned to a combination of copper(I) xanthates and novel
indium(III) xanthates. Metal xanthates [M(S COR) ] have been
In(S COC(H)(Me)CH OMe) ]
2
(
14
)
as
well
2
3
2
x
[K(S CO(CH ) C(OMe)(Me) )] (ESI Tables S2 and S3). We also
2 2 2 2
i
prepared [In(S CO Pr) ]
shown to be excellent precursors to an array of metal
chalcogenides previously, including complex materials such as
(9), which has previously been
2
3
4
2
reported. These complexes were prepared from the reaction
of a previously prepared potassium xanthate (from the
insertion of CS2 into the relevant potassium alkoxide) and
indium(III) chloride. Crystals suitable for X-ray analysis can be
grown from the slow evaporation of chloroform at room
temperature.
Compounds 8, 11, 12 and 13 adopt a monoclinic crystal
system with space groups P2 /c1, C2/c, P21/n, and P21/n
1
respectively, whilst 10 is orthorhombic Pbca and 14 is trigonal
R-3.
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In all cases the central In ions are 6-coordinate, bound by
three chelating xanthate ligands in a distorted octahedral via thermogravimetric analysis (TGA, ESI Figure S1). Complexes
manner (Figure 1). The In-S bond lengths show little variation 10, i.e. those with a pure hydrocarbon xanthate backbone,
across the series: 2.5650(8)-2.6166(8) Å ( ), 2.575(1)-2.626(1) decompose cleanly in one-step to form InS at 120-150 C. In
Å (10), 2.5577(9)-2.655(1) Å (11), 2.5683(6)-2.6298(6) Å (12), contrast, 11 14, which have an ether moiety within the
.558(2)-2.634(2) Å (13) and 2.576(2)-2.63(2) Å (14). This is xanthate chain undergo a two-step process, initially forming
also mirrored in the S-In-S bond angles of 69.93(2)-70.51(3) In before the remaining sulfur is driven off to leave InS.
), 69.68(3)-70.27(3) 10), 69.71(3)-70.30(3) 11), 70.06(2)-
0.44(2) 12), 69.72(6)-70.03(5) 13) and 69.66(3) 14) and Synthesis of Nanoparticles
S-C-S bond angles of the xanthates: 122.0(2)-122.2(2) ),
11), 121.8(1)-
13) and 121.9(3) 14).
It is clear from the bond angles, that the distortion around
The decomposition of the indium complexes was assessed
8
-
8
°
-
2
°
2 3
S
(
8
°
(
° (
7
°
(
°
(
° (
° (8
We initially chose complex 11, [In(S CO(CH ) OEt) ], as our
2
2 2
3
1
21.3(2)-122.4(3)
° (10), 122.1(2)-123.2(2)° (
source of In, reasoning that the two-step decomposition
process would give rise to a control handle for the phase
122.4(1) 12), 121.4(4)-123.0(4)
°
(
°
(
° (
produced. We selected triphenylphosphine copper(I) 2-
the In centre, noted above, is due to the sharp ligand bite
13
ethoxyethylxanthate (15
)
as the copper source to avoid any
angle and associated formation of a CS In 4-membered chelate
2
potential problems involving ligand exchange.
ring. This results in an acute S-In-S intraligand bond angle, in
turn forcing the S-In-S interligand bond angle to become
obtuse.
We prepared CuInS nanoparticles using the hot-injection
2
method in two distinct solvent systems. Firstly, we suspended
a 1:1 ratio of 11
preheated to 260
hexagonal phase CuInS (Figures 2a and 2b), with unit cells
:15 in octadecene and injected it into castor oil
°
C. This resulted in the formation of
2
4
3
comparable to the literature (ESI Table S4).
Figure 2. The pXRD patterns and Raman spectra of CIS prepared at 260 °C via hot
injection, (a, b) hexagonal CIS and (c, d) cubic CIS. In each case the upper pattern
corresponds to a 45 minute reaction, whilst the lower corresponds to a 10 minute
43
reaction length. Hexagonal CIS reference pattern generated from Qi et al., cubic CIS
44
reference pattern generated from Pan et al.
Secondly, we dissolved the precursors 11 and 15 in separate
mixtures of trioctylphosphine (1 ml) and oleylamine (1 ml).
These two solutions were then injected into oleylamine (20 ml)
that had been preheated to 260 °C and held at that
temperature for a set length of time before quenching. This
resulted in the formation of cubic CIS (i.e. zincblende
n
i
Figure 1. The structures of the indium xanthates. (a) [In(S
2
CO Pr)
] (11), (e) [In(S
(13) and (g) [In(S COC(H)(Me)CH
3
] (8), (b) [In(S
CO(CH OMe)
OMe) (14). H
2
CO Pr)
3
]
structure) again with unit cells comparable to the literature
44
42
i
(
(
9), (c) [In(S
2
CO Bu)
3
] (10), (d), [In(S
2
CO(CH
2
)
2
OEt)
3
2
2
)
2
3
] (12),
(Figures 2c and 2d and ESI Table S4).
f) [In(S CO(CH
2
2
)
2
C(OMe)(Me)
2 3
) ]
2
2
3
]
This intriguing result indicates that the choice of solvent has
atoms are omitted for clarity. Bronze = In, yellow = S, red = O, grey = C.
a remarkable impact on the phase that is formed. Octadecene
is of course a non-coordinating solvent, but the main
2
| J. Name., 2012, 00, 1-3
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component of castor oil is the triester of glycerol and ricinoleic close to the ideal CuInS
ARTICLE
2
ratios. Raman spectroscopy gave
acid, which does have pendant hydroxyl groups on the additional confirmation as to the purity of the phases We have
backbone and has been previously used as a ‘green’ capping also measured the optical properties of the nanoparticles and
4
5–47
ligand.
Oleylamine and trioctylphosphine on the other found them to be in the range 1.47-1.53 eV, but all within
hand are very much coordinating ligands that can act to error of each other (ESI Figure S7, Table S6). This result is
4
8
44,54
stabilise metal surfaces. It is interesting to note that in a consistent with the literature.
previous study oleic acid (i.e. an acid capping ligand) gave the In order to confirm the consistency of the phase control, we
cubic, zincblende structure, which is the reverse of what we also performed the experiment using the equivalent 2-
4
4
observe here. On the other hand, a reaction (of different methoxyethylxanthate (i.e. 12 and the corresponding copper(I)
precursors) in oleylamine gave the same cubic CIS that we analogue). We found that the precursors behaved identically
4
9
report.
In order to be sure that there was no exchange of the alkoxy
group of the xanthates for oleylamine (to make
dithiocarbamate) we heated a solution of 11 in oleylamine to
00 °C (i.e. just below the initial breakdown temperature) and
as 11 and 15 (ESI Figures S5-S6).
a
Conclusions
1
We have demonstrated an ability to generate highly crystalline
1
then ran a H NMR of the resulting mixture (ESI Figures S8 and
S9). For 11 + oleylamine, there was no evidence of any
exchange occurring with the oleylamine signals remaining
identical after heating (ESI Figure S8). There is some slight
shifting of the xanthate signals after heating (ESI Figure S9) but
this is most likely due to the beginnings of decomposition. We
2
CuInS from indium and copper xanthate precursors, whilst
exhibiting phase control through choice of solvent. We have
reported the crystal structures of six novel indium xanthates,
comprehensively extending this family of compounds.
have previously conducted a similar experiment for 15 and Experimental
seen no ligand exchange either.
1
3
Materials and Synthesis: All chemicals were purchased from
Figures 2b and 2d show the Raman spectra of CuInS2
nanoparticles. 240 (E mode), 258 (E/B modes), 289 (A mode),
Sigma Aldrich, and were used as received. Elemental analyses
2
1
(EA) and Thermogravimetric analyses (TGA) were carried out
2
97 (likely associated with lattice ordering) and 341 (B mode)
2
by the Microelemental Analysis service at the University of
Manchester. EA was performed using a Flash 2000 Thermo
Scientific elemental analyzer and TGA data was obtained with
-1 50–53
cm .
Similar peak positions were observed for both
hexagonal and cubic CIS with a slight shift for some individual
peaks.
e
Mettler Toledo TGA/DSC1 star system between the range of
-1
0 - 600 °C at a heating rate of 10 °C min under nitrogen flow.
The particles themselves are highly crystalline, though of an
indeterminate shape for both solvent systems (Figure 3).
3
3 2
NMR spectra were recorded in CDCl and D O solutions on a
Lattice fringes for hexagonal CuInS can be indexed to the
2
Bruker Ascend spectrometer operating at 400 MHz.
Transmission electron microscope (TEM) images were
collected using an FEI Tecnai G2 F30 with Schottky Field
Emitter operated at 300keV. Powder X-ray diffraction (pXRD)
analyses were carried out using an X-Pert diffractometer with
a Cu-Kα1 source (λ = 1.54059 Å), the samples were scanned
between 10 and 80°, the applied voltage was 40 kV and the
current 30 mA. Raman spectra were measured using a
Renishaw 1000 Micro-Raman System equipped with a 514 nm
laser. UV-Vis spectra were collected on a Shimadzu UV-1800,
(
100) plane (Figure 3b), and for cubic CuInS can be indexed to
2
the (111) plane. There is little discernible difference from a 10
min reaction (Figure 3) and a 45 min reaction (ESI Figure S4)
using 3.09 mM solution of CuInS
2
nanoparticles in methanol.
), Potassium
4), potassium 2-ethoxyethylxanthate
Potassium
iso-butylxanthate
(
3
2-
methoxyethylxanthate (
(
5), potassium 3-methoxy-3-methyl-1-butylxanthate
(6)
potassium 1-methoxy-2-propylxanthate (7) and
triphenylphosphine copper(I) 2-ethoxyethylxanthate (15) were
all prepared according to our previously published
1
procedure.
3
Figure 3. TEM images and associated selected area electron diffraction (SAED) patterns
Synthesis of potassium n-propylxanthate (1): Potassium n-
for (a)-(c) hexagonal CuInS
min reaction.
2 2
from a 10 min reaction and (d)-(f) cubic CuInS from a 10
5
5
propylxanthate was prepared following a literature method.
Potassium hydroxide (11.2 g, 0.20 mol) and n-propanol (150
ml) were stirred for 2 h at room temperature and then CS
15.2 g, 12.0 ml, 0.20 mol) was added dropwise to the
Energy dispersive x-ray spectroscopy (EDX) indicates that the
composition of the particles is consistent across the different
solvent systems and reaction times (ESI Table S5, Figure S3),
2
(
reaction, resulting in an orange solution. The unreacted
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alcohol was removed in vacuo and the yellow solid product (2.25 g, 0.0037 mol, 82% yield). M.p. = 81-84 °C. Calc.
n
was dried to give [K(S
2
CO Pr)] (27.3 g, 0.157 mol, 78.4% yield). for C15
KOS (%):C 27.6, H 4.05, S 29.5, H 4.36, S 31.2, In 18.7. FT-IR (cm ): 2971 (m), 2865 (w),
6.7, K 22.5; found: C 27.8, H 3.99, S 37.0, K 22.9. FT-IR (cm ): 1441 (m), 1384 (m), 1352 (w), 1214 (s), 1116 (s), 1035 (s),
6 6
H27InO S (%): C 29.5, H 4.46, S 31.5, In 18.8; found: C
-
1
M.p. = 228-230 °C. Calc. for C
4
H
7
2
-
1
3
2
1
1
965 (m), 2937(w), 2873 (w), 1453 (m), 1445 (w), 1270 (m), 998.5 (s), 936.1 (m), 863.3 (m), 836.1 (m). H NMR (400 MHz,
148 (s), 1087 (s), 1061 (s), 925 (m), 902 (m), 765.0 (s), 660.1 CDCl (ppm): 1.17 (t, 3H, OCH ), 3.51 (q, 2H, OC CH ),
), 3.74 (t, 2H, CH O), 4.49(t, 2H, C CH O).
3
)
δ
2
CH
3
H
2
3
1
(
s), 544 (s). H NMR (400 MHz, D
2
O)
δ
(ppm) = 0.89 (t, 3H, C
H
3
2
C
H
2
H
2
2
1
.68 (s, 2H, CH
2
C
H
2
CH
3
), 4.31 (t, 2H, OC
H
2
2
CH ).
Synthesis of indium(III) 2-methoxyethylxanthate (12)
CO Pr)] [In(S CO(CH OMe) ] was synthesized via the same method as
, using iso-propanol , using potassium 2-methoxyethylxanthate (2.56 g, 0.0135
150 ml). (25.8 g, 0.148 mol, 74.1% yield). M.p. = 223-227 °C. mol). (2.2 g, 0.0038 mol, 86.1% yield). M.p. = 95-98 °C. Calc. for
Calc. for C KOS (%):C 27.6, H 4.05, S 36.7, K 22.5; found: (%): C 25.4, H 3.73, S 33.8, In 20.2; found: C 25.4,
C 27.6, H 3.96, S 36.6, K 23.3. FT-IR (cm ): 2970 (m), 1460 (w), H 3.66, S 33.5, In 19.8. FT-IR (cm ): 2922 (m), 1438 (m), 1392
370 (m), 1182 (m), 1048 (s), 901 (s), 1092 (s), 662 (w), 583 (m), 1367 (m), 1212 (s), 1120 (s) 1092 (s), 1036 (s), 1021 (s),
:
i
Synthesis of potassium iso-propylxanthate (2): [K(S
was prepared via the same method as
2
2
2
)
2
3
1
8
(
4
H
7
2
12 6 6
C H21InO S
-1
-1
1
1
1
(w). H NMR (400 MHz, D
2
O)
δ
(ppm) = 1.25 (d, 6H, CH(C
H
3
)
2
), 976.2 (s), 845.6 (s), 661.6 (m), 575.8 (w). H NMR (400 MHz,
CDCl (ppm): 3.36 (s, 3H, OC ), 3.71 (t, 2H, CH O), 4.50
t, 2H, C CH O).
5.44 (s, 1H, CH(CH ) ).
3
2
3
)
δ
H
H
3
2 2
CH
(
2
2
Synthesis of indium(III) n-propylxanthate (8): A solution of
potassium n-propylxanthate (2.35 g, 0.0135 mol) in water (60 Synthesis of indium(III) 3-methoxy-3-methyl-1-butylxanthate
ml) was added to a solution of InCl (1.00 g, 0.0045 mol) in the (13): [In(S CO(CH C(OMe)(Me) ] was synthesized via the
same amount of water. A white precipitate was obtained after same method as , using potassium 3-methoxy-3-methyl-1-
continuous stirring for 30 min at room temperature. The solid butylxanthate (3.13 g, 0.0135 mol). (2.3 g, 0.0033 mol, 73.6%
was collected by vacuum filtration and washed three times yield). M.p. = 78-81 °C. Calc. for C21 (%): C 36.3, H
with water. The product was dried in vacuo and recrystallized 5.66, S 27.6, In 16.6; found: C 36.5, H 5.67, S 27.3, In 16.5. FT-
3
2
2
)
2
2 3
)
8
6 6
H39InO S
-1
from chloroform at room temperature to give (1.96 g, 0.0038 IR (cm ): 2975 (m), 2825 (w), 1466 (m), 1381 (m), 1366 (m),
mol, 83.76% yield). M.p. = 102-104 °C. Calc. for C12 1310 (w), 1227 (s), 1210 (s), 1173 (s), 1155 (s), 1074 (s), 1040
%): C 27.7, H 4.07, S 36.9, In 22.1; found: C 27.8, H 3.98, S (s), 1019 (s), 933.7 (m), 871.4 (m), 788.1 (w), 751.9 (m), 644.7
3 6
H21InO S
(
-
1
1
3
6.1, In 22.0. FT-IR (cm ): 2970 (m), 2875(w), 1453 (m) 1245 (w), 568.2 (w). H NMR (400 MHz, CDCl
3
)
δ
(ppm): 1.24 (s, 6H,
OCH ), 3.23 (s, 3H,
OCH ).
(
s), 1217 (s), 1136 (m), 1039 (s), 1034 (s), 937.5 (m), 899.2 (w), CH
1
55.2 (m), 648.8 (m), 561.6 (w). H NMR (400 MHz, CDCl
2
C(C
H
3
)
2
OCH
OC
3
), 2.09 (t, 2H, C
H
2
C(CH
3
)
2
3
7
3
)
δ
), 4.43 (t, 2H,
CH
2
C(CH
3
)
2
H
3
), 4.59 (t, 2H, C
H
2
CH C(CH
2
3
)
2
3
(ppm) = 1.06 (t, 3H, C
H
3
), 1.91 (s, 2H, CH
2
CH
2
CH
3
OC
H
2
CH
2
).
Synthesis of indium(III) 1-methoxy-2-propylxanthate (14):
In(S COC(H)(Me)CH OMe) ] was synthesized via the same
method as , using potassium 1-methoxy-2-propylxanthate
[
2
2
3
i
Synthesis of indium(III) iso-propylxanthate (9): [In(S
was synthesized via the same method as
iso-propylxanthate (2.35 g, 0.0135 mol). (1.85 g, 0.0035 mol, 109-112 °C. Calc. for C15
2
CO Pr)
3
]
8
8
, using potassium (2.75 g, 0.0135 mol). (2.25 g, 0.0036 mol, 82% yield). M.p. =
H
6 6
27InO S
(%): C 29.5, H 4.46, S 31.5, In
-1
7
2
2
1
6
9.0% yield). M.p. = 142-144 °C. Calc. for C12
3 6
H21InO S (%): C 18.8; found: C 29.3, H 4.26, S 29.3, In 19.4. FT-IR (cm ): 2984
7.7, H 4.07, S 36.9, In 22.1; found: C 27.8, H 3.98, S 36.7, In (m), 2938 (w), 1448 (m), 1392 (w), 1344(w), 1236 (s), 1198 (s),
-
1
2.5. FT-IR (cm ): 2976 (m), 2930 (w), 1461 (m), 1373 (m), 1161 (m), 1121 (w), 1092 (w), 1055 (s), 1009 (s), 943.9 (m),
1
232 (s), 1142 (m), 1083 (s), 1011 (s), 899.3 (m), 808.4 (w), 815.6 (m), 643.1 (w), 574.0 (w). H NMR (400 MHz, CDCl ) δ
3
45.2 (m), 567.7 (w). H NMR (400 MHz, CDCl
), 5.14 (s, 1H, C (CH ).
1
3
)
δ
(ppm) = 1.5 (ppm): 1.39 (d, 3H, CHC
H
3
), 3.35 (s, 3H, OC
3
H ), 3.50-3.59 (m,
(d, 6H, CH(C
H
3
)
2
H
3
)
2
2H, CH O), 5.08 (m, 1H, C
2
3
HCH ).
i
Synthesis of indium(III) iso-butylxanthate (10): [In(S
was synthesized via the same method as , using potassium performed using a Bruker diffractometer with a Cu-K
iso- butylxanthate (2.54 g, 0.0135 mol). (1.94 g, 0.0034 mol, = 1.5418 Å) (10 12 13) and XtaLAB AFC11 (RINC): Kappa single
(%): C diffractometer with a Mo-K source (λ = 0.71073 Å) ( 14
2.0, H 4.84, S 34.1, In 20.4; found: C 32.0, H 4.79, S 34.1, In SuperNova, Single source at offset, Eos diffractometer with a
2
CO Bu)
3
]
X-ray Crystallography: Single crystal X-ray diffraction was
8
α
source (λ
,
,
7
3
2
1
6
6.7% yield). M.p. = 109-113 °C. Calc. for C15
H
27InO
3
S
6
α
6,
8,
)
-1
0.2. FT-IR (cm ): 2955 (m), 2870 (w), 1466 (m), 1454 (m), Mo-K source (11). Crystallographic data available from the
372 (m), 1221 (s), 1197 (m), 1025 (s), 958.3 (s), 822.5 (w), CCDC, numbers: 1812198-1812204.
1
54.6 (m), 575.3 (w). H NMR (400 MHz, CDCl
3
)
δ
(ppm): 0.96
(
d, 6H, CH(C
H
3
)
2
), 2.12 (s, 1H, C
H
(CH
3
)
2
), 4.15 (d, 2H,OC CH).
H
2
Synthesis of CuInS
synthesized via the hot injection method and a typical
Synthesis of indium(III) 2-ethoxyethylxanthate (11): procedure is described. A stoichiometric mixture of 15 (0.0752
In(S CO(CH OEt) ] was synthesized via the same method as g, 0.0001 mol) and 11 (0.0609 g, 0.0001mol) were used. The
, using potassium 2-ethoxyethylxanthate (2.75 g, 0.0135 mol). reactions were performed under nitrogen. To obtain a
2 2
nanoparticles: CuInS nanocrystals were
[
2
2
)
2
3
8
4
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ARTICLE
hexagonal phase, the mixture was suspended in octadecene (2
ml) and injected into 20 ml castrol oil preheated to 260 °C. To
2010, 20, 4031–4040.
E. A. Lewis, S. Haigh and P. O’Brien, J. Mater. Chem. A,
014, 2, 570–580.
E. A. Lewis, P. D. McNaughter, Z. Yin, Y. Chen, J. R. Brent, S.
A. Saah, J. Raftery, J. A. M. Awudza, M. A. Malik, P. O’Brien
and S. J. Haigh, Chem. Mater., 2015, 27, 2127–2136.
P. D. McNaughter, S. A. Saah, M. Akhtar, K. Abdulwahab,
M. A. Malik, J. Raftery, J. A. M. Awudza and P. O’Brien,
Dalton Trans., 2016, 45, 16345–16353.
P. D. Matthews, M. Akhtar, M. A. Malik, N. Revaprasadu
and P. O’Brien, Dalton Trans., 2016, 45, 18803–18812.
N. Alam, M. S. Hill, G. Kociok-Köhn, M. Zeller, M. Mazhar
and K. C. Molloy, Chem. Mater., 2008, 20, 6157–6162.
J. M. Clark, G. Kociok-Köhn, N. J. Harnett, M. S. Hill, R. Hill,
K. C. Molloy, H. Saponia, D. Stanton and A. Sudlow, Dalton
Trans., 2011, 40, 6893–6900.
1
1
7.
8.
2
2
form a zinc blende CuInS , the precursors were dissolved into
trioctylphosphine (1 ml) and oleylamine (1 ml) and injected
into oleylamine (20 ml) preheated to 260 °C. After a set period
of time (10 or 45 min), the solution was cooled to room
temperature with the addition of iso-propanol and the
particles separated by centrifugation. The nanoparticles were
extracted by diluting the resultant product with 30ml
methanol (three times) and 30ml acetone (two times).
1
9.
2
2
0.
1.
Acknowledgements
22.
The authors would like to acknowledge the Iraqi Culture
Attaché in London for financial support (M.A.S.). Some of the
equipment used in this study were provided by the EPSRC Core
Capability in Chemistry grant EP/K039547/1. P.D.M. would like
2
3.
M. Al-Shakban, P. D. Matthews, N. Savjani, X. L. Zhong, Y.
Wang, M. Missous and P. O’Brien, J. Mater. Sci., 2017, 52,
1
2761–12771.
to acknowledge the UK Government and European Union as 24.
contributors to the Smart Energy Network Demonstrator, ERDF
T. Rath, A. J. MacLachlan, M. D. Brown and S. A. Haque, J.
Mater. Chem. A, 2015, 3, 24155–24162.
project number 32R16P00706).
25.
M. Al-Shakban, P. D. Matthews and P. O’Brien, Chem.
Commun., 2017, 53, 10058–10061.
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2
2
2
6.
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8.
9.
S. H. Lu, T. F. Chen, A. J. Wang, D. Zheng, Y. L. Li and Y. S.
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On the Phase Control of CuInS Nanoparticles from Cu-/In-Xanthates
2
a
b,c
a
b
b
a
Mundher Al-Shakban, Peter D Matthews, Xiang L. Zhong, Inigo Vitorica-Yrezabal, James Raftery, Daivd J. Lewis and Paul
O’Brien*
a,b
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