Multivariate Synthesis of Tin Phosphide Nanoparticles: Temperature ...
Multivariate Synthesis of Tin Phosphide Nanoparticles: Temperature, Time, and Ligand Control of Size, Shape, and Crystal Structure Venkatesham Tallapally,† Richard J Alan Esteves,† Lamia Nahar, and Indika U. Arachchige* Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 232842006, United States
Supporting Information †
These authors contributed equally to this work.
Corresponding author E-mail: [email protected]
S1
Intensity (arb. units)
a b
20
30
40 50 2(degrees)
60
70
Figure S1. (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and TOP in OLA/OA/ODE at 350 ºC for 3 h along with the (b) ICDD-PDF overlay of tetragonal Sn (JCPDS No. 00-004-0673).
S2
[B]
Intensity (arb. units)
[A]
20
a b
30
40 50 60 2(degrees)
70
80
Figure S2. (A) (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min along with the (b) ICDD-PDF overlay of rhombohedral Sn4P3 (JCPDS No. 01-073-1820). (B) A representative TEM image of the asprepared particles.
S3
Intensity (arb. units)
a b c 20
30
40
50
60
2(degrees) Figure S3. (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and (TMSi)3P in OLA/OA/ODE with DDT at 180 ºC for 12 h along with the ICDD- PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) orthorhombic SnS (JCPDS No. 390354).
S4
[A]
[B]
Figure S4. Representative TEM images of (A) rhombohedral Sn4P3 NPs synthesized at 180 °C and (B) hexagonal SnP NCs synthesized at 250 °C with no use of oleic acid.
S5
Intensity (arb. units)
[A]
20
[B]
30
40 50 2(degrees)
60
70
[C]
[D] 0.31 nm
0.198 nm (110) 0.298 nm (0012)
0.31 nm
Figure S5. (A) A representative powder XRD pattern of amorphous to partially crystalline Sn4P3 NPs produced at 180 °C for 5 min using SnI4 and (TMSi)3P precursors, without the use of alkylphosphines (TBP or TOP). (B) SEM/EDS spectrum of the corresponding Sn4P3 NPs along with (C) HRTEM, and (D) the selected area electron diffraction pattern recorded from 200 nm x 200 nm area of the sample indicating short-range crystalline order of rhombohedral Sn4P3. The broad and not well defined peaks in the PXRD is due to lack of long-range crystalline order. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown suggesting the growth of Sn4P3 particles. S6
Intensity (arb. units)
a b c d
30
40 50 2(degrees)
60
70
Figure S6. (a) Powder XRD pattern of the product obtained from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min in the presence of 12 mM TBP. ICDD-PDF overlays of (b) tetragonal tin (JCPDS No. 00-004-0673), (c) rhombohedral Sn4P3 (JCPDS No. 01073-1820), and (d) hexagonal SnP (JCPDS No. 03-065-9787) are also shown.
S7
Intensity (arb. units)
a b c
30
40 50 2(degrees)
60
70
Figure S7. (a) Powder XRD pattern of the product obtained from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min in the presence of 4 mM of TOP. ICDD-PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) hexagonal SnP (JCPDS No. 03-065-9787) are also shown.
S8
[B]
Intensity (arb. units)
[A]
a b c
20
30
40
50
60
70
2(degrees)
Figure S8. (A) Powder XRD pattern of (a) the product obtianed from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 220 ºC for 15 min. ICDD-PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) hexagonal SnP (JCPDS No. 03-065-9787) are also shown. (B) A representative TEM image of the as-prepared particles.
S9
[A]
[B]
[C]
[D]
Figure S9. Representative TEM images of the phase pure hexagonal SnP NCs synthesized in OLA/OA/ODE at 250 ºC for (a) 5, (b) 30, (c) 60, and (c) 180 seconds.
S10
[A]
[B]
[C]
[D]
Figure S10. Low resolution and high resolution TEM images of the hexagonal SnP NCs prepared in OLA/OA/ODE at 250 ºC for (a) 5, (b) 30, (c) 60, and (c) 180 seconds showing the presence of a crystalline SnP core and amorphous shell with varying thickness.
S11
Figure S11. A representative SEM/EDS spectrum of the hexagonal SnP NCs synthesized at 250 ºC without the use of TBP for 60 seconds. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown.
S12
[A]
[B]
0.31 nm
0.20 nm
[C]
0.20 nm
Intensity (arb. units)
[D]
10
20
30
40
50
2(degrees)
60
70
80
Figure S12. (A-B) HRTEM images of trigonal Sn3P4 NPs synthesized at 100 °C for 3 min using SnI4 and (TMSi)3P in OLA/OA/ODE in the presence of TBP. (C) SAED and (D) PXRD patterns of the corresponding sample along with ICDD-PDF overlay of trigonal Sn3P4 generated from crystal maker (black lines).1
S13
Figure S13. Representative SEM/EDS spectrum of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE at 100 ºC with 4 mM TBP for 60 sec. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown.
S14
Absorbance (arb. units)
c
b a
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Energy (eV) Figure S14. Diffuse reflectance spectra (converted to absorption using Kubelka-Munk remission function) of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE without TBP at 100 ºC for (a) 1, (b) 2, and (c) 3 minutes.
S15
Figure S13
[A]
[B]
[C]
[D]
[E]
[F]
Figure S15. Representiavtive TEM images of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE at 100 ºC without TBP for (A) 5 sec, (B) 1 min, (C) 2 min, and (D) 3 min. (E) and (F) are electron diffraction patterns of NPs shown in (C) and (D), respectively.
S16
Transmittance (arb. units) 4000
c b [Si(CH3)3]
(N-H) 3500
(C=C) (CH2)
(CHx) 3000
a
2500
2000
1500 -1
(SiC)
(POx)
1000
500
Wavenumber (cm )
Figure S16. FT-IR spectra of tin phosphide NPs synthesized OLA/OA/ODE. (a) rhombohedral Sn4P3 NCs produced at 180 °C for 3 min, (b) hexagonal SnP NCs at 250 °C for 5 seconds, and (c) trigonal Sn3P4 NPs produced at 100 °C for 3 min.
S17
40
x10
4
Intensity (counts)
Sn(3d)
32
O(1s) Sn(MN2)
24
Sn(MN1)
Sn(3p1)
Sn(3p3)
C(1s)
16
P(2s) Si(2s) P(2p)
8
N(1s)
1000
800
600
400
200
Si(2p) Sn(4d)
0
Binding Energy (eV) Figure S17. X-ray photoelectron spectrum (survey scan) of rhombohedral Sn4P3 NCs produced at 180 ºC for 3 min.
S18
x10
4
Sn(3d)
Intensity (counts)
48 40
Sn(MN2) Sn(3p3)
32
O(1s)
Sn(3p1) Sn(MN1) I (3d)
24 P(2s) Si(2p) Si(2s) I (3d) C(1s) P(2p) Sn(4d)
16 8
N(1s)
1000
800
600
400
200
0
Binding Energy (eV) Figure S18. X-ray photoelectron spectrum (survey scan) of hexagonal SnP NCs produced at 250 °C for 5 seconds.
S19
Intensity (counts)
40
x10
4
Sn(3d)
32
O(1s)
Sn(MN2) Sn(3p3) Sn(3p1)
24
Sn(MN1) I(3d) C(1s)
16
P(2s) Si(2s) P(2p)
8
Si(2p) I(4d) Sn(4d)
In(3d)
1000
800
600
400
200
0
Binding Energy (eV) Figure S19. X-ray photoelectron spectrum (survey scan) of trigonal Sn3P4 NPs produced at 100 ºC for 3 min.
S20
[A]
O(1s)
Internsity (arb. units)
(c) O-Sn Bonds O-Adsorbed Species PxOx Impurities
(b)
(a) 536
N-Sn Bonds N-H Bonds
Intensity (arb. units)
[B]
534 532 530 Binding Energy (eV)
406
528
N(1s) (c)
(b)
(a) 404
402 400 398 Binding Energy (eV)
396
Figure S20. X-ray photoelectron spectra of (A) O(1s) and (B) N(1s) regions of (a) rhombohedral Sn4P3 NCs produced at 180 °C for 3 min., (b) hexagonal SnP NCs produced at 250 °C for 5 seconds, and (c) trigonal Sn3P4 NPs produced at 100 °C for 3 min.
S21
Figure S21. A photograph showing the colloidal stability of tin phosphide NPs in hexane. (A) trigonal Sn3P4 NPs synthesized at 100 °C, (B) rhombohedral Sn4P3 NCs synthesized at 180 °C, and (C) hexagonal SnP NCs synthesized at 250 °C.
References (1) Ganesan, R.; Richter, K. W.; Schmetterer, C.; Effenberger, H.; Ipser, H. Synthesis of SinglePhase Sn3P4 by an Isopiestic Method. Chem. Mater. 2009, 21, 4108–4110.
S22
Supporting Information †
These authors contributed equally to this work.
Corresponding author E-mail: [email protected]
S1
Intensity (arb. units)
a b
20
30
40 50 2(degrees)
60
70
Figure S1. (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and TOP in OLA/OA/ODE at 350 ºC for 3 h along with the (b) ICDD-PDF overlay of tetragonal Sn (JCPDS No. 00-004-0673).
S2
[B]
Intensity (arb. units)
[A]
20
a b
30
40 50 60 2(degrees)
70
80
Figure S2. (A) (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min along with the (b) ICDD-PDF overlay of rhombohedral Sn4P3 (JCPDS No. 01-073-1820). (B) A representative TEM image of the asprepared particles.
S3
Intensity (arb. units)
a b c 20
30
40
50
60
2(degrees) Figure S3. (a) Powder XRD pattern of the product obtained from the reaction of SnCl2 and (TMSi)3P in OLA/OA/ODE with DDT at 180 ºC for 12 h along with the ICDD- PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) orthorhombic SnS (JCPDS No. 390354).
S4
[A]
[B]
Figure S4. Representative TEM images of (A) rhombohedral Sn4P3 NPs synthesized at 180 °C and (B) hexagonal SnP NCs synthesized at 250 °C with no use of oleic acid.
S5
Intensity (arb. units)
[A]
20
[B]
30
40 50 2(degrees)
60
70
[C]
[D] 0.31 nm
0.198 nm (110) 0.298 nm (0012)
0.31 nm
Figure S5. (A) A representative powder XRD pattern of amorphous to partially crystalline Sn4P3 NPs produced at 180 °C for 5 min using SnI4 and (TMSi)3P precursors, without the use of alkylphosphines (TBP or TOP). (B) SEM/EDS spectrum of the corresponding Sn4P3 NPs along with (C) HRTEM, and (D) the selected area electron diffraction pattern recorded from 200 nm x 200 nm area of the sample indicating short-range crystalline order of rhombohedral Sn4P3. The broad and not well defined peaks in the PXRD is due to lack of long-range crystalline order. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown suggesting the growth of Sn4P3 particles. S6
Intensity (arb. units)
a b c d
30
40 50 2(degrees)
60
70
Figure S6. (a) Powder XRD pattern of the product obtained from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min in the presence of 12 mM TBP. ICDD-PDF overlays of (b) tetragonal tin (JCPDS No. 00-004-0673), (c) rhombohedral Sn4P3 (JCPDS No. 01073-1820), and (d) hexagonal SnP (JCPDS No. 03-065-9787) are also shown.
S7
Intensity (arb. units)
a b c
30
40 50 2(degrees)
60
70
Figure S7. (a) Powder XRD pattern of the product obtained from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 180 ºC for 3 min in the presence of 4 mM of TOP. ICDD-PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) hexagonal SnP (JCPDS No. 03-065-9787) are also shown.
S8
[B]
Intensity (arb. units)
[A]
a b c
20
30
40
50
60
70
2(degrees)
Figure S8. (A) Powder XRD pattern of (a) the product obtianed from the reaction of SnI4 and (TMSi)3P in OLA/OA/ODE at 220 ºC for 15 min. ICDD-PDF overlays of (b) rhombohedral Sn4P3 (JCPDS No. 01-073-1820) and (c) hexagonal SnP (JCPDS No. 03-065-9787) are also shown. (B) A representative TEM image of the as-prepared particles.
S9
[A]
[B]
[C]
[D]
Figure S9. Representative TEM images of the phase pure hexagonal SnP NCs synthesized in OLA/OA/ODE at 250 ºC for (a) 5, (b) 30, (c) 60, and (c) 180 seconds.
S10
[A]
[B]
[C]
[D]
Figure S10. Low resolution and high resolution TEM images of the hexagonal SnP NCs prepared in OLA/OA/ODE at 250 ºC for (a) 5, (b) 30, (c) 60, and (c) 180 seconds showing the presence of a crystalline SnP core and amorphous shell with varying thickness.
S11
Figure S11. A representative SEM/EDS spectrum of the hexagonal SnP NCs synthesized at 250 ºC without the use of TBP for 60 seconds. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown.
S12
[A]
[B]
0.31 nm
0.20 nm
[C]
0.20 nm
Intensity (arb. units)
[D]
10
20
30
40
50
2(degrees)
60
70
80
Figure S12. (A-B) HRTEM images of trigonal Sn3P4 NPs synthesized at 100 °C for 3 min using SnI4 and (TMSi)3P in OLA/OA/ODE in the presence of TBP. (C) SAED and (D) PXRD patterns of the corresponding sample along with ICDD-PDF overlay of trigonal Sn3P4 generated from crystal maker (black lines).1
S13
Figure S13. Representative SEM/EDS spectrum of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE at 100 ºC with 4 mM TBP for 60 sec. The average Sn: P atomic ratio obtained from 5 individual measurements of the same sample are also shown.
S14
Absorbance (arb. units)
c
b a
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Energy (eV) Figure S14. Diffuse reflectance spectra (converted to absorption using Kubelka-Munk remission function) of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE without TBP at 100 ºC for (a) 1, (b) 2, and (c) 3 minutes.
S15
Figure S13
[A]
[B]
[C]
[D]
[E]
[F]
Figure S15. Representiavtive TEM images of trigonal Sn3P4 NPs synthesized in OLA/OA/ODE at 100 ºC without TBP for (A) 5 sec, (B) 1 min, (C) 2 min, and (D) 3 min. (E) and (F) are electron diffraction patterns of NPs shown in (C) and (D), respectively.
S16
Transmittance (arb. units) 4000
c b [Si(CH3)3]
(N-H) 3500
(C=C) (CH2)
(CHx) 3000
a
2500
2000
1500 -1
(SiC)
(POx)
1000
500
Wavenumber (cm )
Figure S16. FT-IR spectra of tin phosphide NPs synthesized OLA/OA/ODE. (a) rhombohedral Sn4P3 NCs produced at 180 °C for 3 min, (b) hexagonal SnP NCs at 250 °C for 5 seconds, and (c) trigonal Sn3P4 NPs produced at 100 °C for 3 min.
S17
40
x10
4
Intensity (counts)
Sn(3d)
32
O(1s) Sn(MN2)
24
Sn(MN1)
Sn(3p1)
Sn(3p3)
C(1s)
16
P(2s) Si(2s) P(2p)
8
N(1s)
1000
800
600
400
200
Si(2p) Sn(4d)
0
Binding Energy (eV) Figure S17. X-ray photoelectron spectrum (survey scan) of rhombohedral Sn4P3 NCs produced at 180 ºC for 3 min.
S18
x10
4
Sn(3d)
Intensity (counts)
48 40
Sn(MN2) Sn(3p3)
32
O(1s)
Sn(3p1) Sn(MN1) I (3d)
24 P(2s) Si(2p) Si(2s) I (3d) C(1s) P(2p) Sn(4d)
16 8
N(1s)
1000
800
600
400
200
0
Binding Energy (eV) Figure S18. X-ray photoelectron spectrum (survey scan) of hexagonal SnP NCs produced at 250 °C for 5 seconds.
S19
Intensity (counts)
40
x10
4
Sn(3d)
32
O(1s)
Sn(MN2) Sn(3p3) Sn(3p1)
24
Sn(MN1) I(3d) C(1s)
16
P(2s) Si(2s) P(2p)
8
Si(2p) I(4d) Sn(4d)
In(3d)
1000
800
600
400
200
0
Binding Energy (eV) Figure S19. X-ray photoelectron spectrum (survey scan) of trigonal Sn3P4 NPs produced at 100 ºC for 3 min.
S20
[A]
O(1s)
Internsity (arb. units)
(c) O-Sn Bonds O-Adsorbed Species PxOx Impurities
(b)
(a) 536
N-Sn Bonds N-H Bonds
Intensity (arb. units)
[B]
534 532 530 Binding Energy (eV)
406
528
N(1s) (c)
(b)
(a) 404
402 400 398 Binding Energy (eV)
396
Figure S20. X-ray photoelectron spectra of (A) O(1s) and (B) N(1s) regions of (a) rhombohedral Sn4P3 NCs produced at 180 °C for 3 min., (b) hexagonal SnP NCs produced at 250 °C for 5 seconds, and (c) trigonal Sn3P4 NPs produced at 100 °C for 3 min.
S21
Figure S21. A photograph showing the colloidal stability of tin phosphide NPs in hexane. (A) trigonal Sn3P4 NPs synthesized at 100 °C, (B) rhombohedral Sn4P3 NCs synthesized at 180 °C, and (C) hexagonal SnP NCs synthesized at 250 °C.
References (1) Ganesan, R.; Richter, K. W.; Schmetterer, C.; Effenberger, H.; Ipser, H. Synthesis of SinglePhase Sn3P4 by an Isopiestic Method. Chem. Mater. 2009, 21, 4108–4110.
S22
