Beruflich Dokumente
Kultur Dokumente
Article
Just Accepted
Just Accepted manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides Just Accepted as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. Just Accepted manuscripts
appear in full in PDF format accompanied by an HTML abstract. Just Accepted manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI). Just Accepted is an optional service offered
to authors. Therefore, the Just Accepted Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the Just
Accepted Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these Just Accepted manuscripts.
Page 1 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic
Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-sen University,
Guangzhou 510275, P.R. China.
E-mail: cesbin@mail.sysu.edu.cn;
b
The Hong Kong Institute of Education (Education University of Hong Kong, designate), 10 Lo Ping
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1. INTRODUCTION
The World Energy Outlook 2015 released in November 20151 calls for the
understanding of the implications of the shifting energy landscape for economic and
environmental goals and for energy security. Oil price collapse, geopolitical
instability, trends in CO2 emissions and energy inefficiency all provoke us to seek
renewable and stable energy resources. Recent developments in flexible copper
indium gallium selenide,2 transparent solar cells,3 upconversion multicolor tuning4
and lanthanide ion-doped quantum dots5 provide optimism in this respect. Our goal
has been to harness as much of the solar flux as possible and herein we report a
wideband harvester with an emission profile tailored to the response of the silicon
solar cell.
The cubic silicate garnet host Ca3Sc2Si3O12 (CSS) is endowed with unique and
versatile spectroscopic properties. Its structure comprises Ca2+ in dodecahedral (8-)
and Sc3+ in octahedral 6-coordination to oxygen.6 Upon doping with Eu3+, the bands
of the transition 5D0 7F4 located between 800-900 nm are unusually strong,7
attributed to the selection rules for the distorted EuO8 coordination.8,9 The Tb3+-doped
CSS exhibits strong green luminescence with a lifetime of 3 ms and a rather slow
population of 5D4 from 5D3.7 The afterglow of the scintillator CSS:Pr3+ can be
removed by co-doping with Mg2+ and hence the performance is improved.10 A
phosphor with color rendering index Ra > 90 for white light-emitting diode (wLED)
use was synthesized by co-doping CSS with Ce3+, Mn2+ and a charge-compensating
lanthanide ion.11 Perhaps the most striking property of the host is that it can extend the
2
Page 2 of 37
Page 3 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
luminescence of divalent europium into the near infrared spectral region12 and this is
exploited in the present work.
The synthesis of the CSS host material may be problematic due to the presence
of various secondary phases when using solid state methods.6,8 Wu et al. have
proposed that the substitution of Sc3+ by Al3+ (below 40%) in CSS:Ce3+ in solid state
synthesis at 1450 oC can inhibit the formation of the impurity phases Sc2O3 and CeO2,
improve crystallinity, and enhance the photoluminescence intensity.13 Recently, a
freeze-drying method and increased heat treatment temperature have been utilized to
reduce the presence of secondary phases.14 The X-ray diffraction pattern of a sample
prepared by sol-gel combustion synthesis and subsequently fired at 1100 oC does not
exhibit other phases.15,16 Several candidates are available for the doping of this host
with divalent lanthanide ions, of which Eu2+ and Yb2+ are the most promising.17
The luminescence and excitation spectra of some Ce3+-activated silicate garnets
have previously been reported at room temperature.18,19 The Ce3+ electronic energies
were interpreted on the basis of two factors: the centroid shift from the free ion and
the 5d crystal field splitting. There have been numerous studies regarding of the
energy transfer between Ce3+ and Eu2+ in various solid-state hosts. To our knowledge,
the aim of these studies has been the development of near-ultraviolet-pumped white
light emitting diodes (wLEDs). For example, the Ca1.65Sr0.35SiO4:Ce3+, Li+, Eu2+
phosphor has been recommended as a candidate for color-tunable blue-green
components of wLEDs, with emission between 465-550nm;20 Ba2ZnS3:Ce3+, Eu2+ has
application as a blue-converting phosphor for wLEDs, with emission maximum
3
Chemistry of Materials
intensity at ~650 nm.21 The Ca4(PO4)2O:Ce3+, Eu2+ wLED phosphor has Eu2+
emission maximum at 650 nm.22
The format of this work is as follows. The structure and luminescence of the
host material, luminescence of Ce3+ or Eu2+-doped systems, and the energy transfer
from Ce3+ to Eu2+ in the CSS host material are presented and discussed in Section 2.
A comment is included in Section 3 concerning the applicability of Ce3+-Eu2+
co-doped CSS in the field of solar energy conversion. Some conclusions from the
experimental results and data analyses are made in the final Section 4.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 4 of 37
Ca2.54Ce0.2Eu0.06Na0.2Sc2Si3O12
Ca2.97Eu0.03Sc2Si3O12
Ca2.94Ce0.03Na0.03Sc2Si3O12
Ca3Sc2Si3O12
20
30
40
50
60
2
(degree)
70
80
(x
0.001-0.2),
Ca3-xEuxSc2Si3O12
(x
0-0.09),
Page 5 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Chemistry of Materials
fine structure analysis that the Ce3+ ion replaces the Ca2+ position of the CSS host
crystal, and mentioned that a Ca2+ vacancy could compensate for the charge of two
Ce3+ ions. X-ray absorption near edge spectra6 showed that all Ce ions are trivalent, in
agreement with the calculated value of 2.9 from the bond valence model.25
The SEM images of the CSS precursor and final product at the magnification of
100000 were measured and these are shown in Figure S3. The precursor calcined at
700 oC exhibits irregular fragmented morphology within the size of several hundred
nm. The final product sintered at 1400 oC for 6 h comprises oblatoid grains united
together with the entire size being ~ 20 m. The larger particle size obtained in the
present study than when firing at 1100 oC for 2 h15,16 results from the growth at higher
temperature and holding time in the reducing atmosphere. We consider that the higher
temperature and holding time is required in order to remove impurity phases and
obtain purer samples (Figure S4).
0.7
Ca3Sc2Si3O12 15 K
em = 385 nm
ex = 206 nm
0.6
6.02 eV
(206 nm)
0.5
3.23 eV
(385 nm)
0.8
ex = 206 nm;
em = 385 nm
= 5.5 s
(b)
25
0.4
Normalized intensity (arb. units)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 6 of 37
0.3
0.2
0.1
6.74 eV
(184 nm)
(a)
0.0
100
200
300
400
500
600
50
Time (s)
75
em = 385 nm
15 K
70 K
120 K
296 K
(c)
125 150 175 200 225 250
Wavelength (nm)
Wavelength (nm)
Page 7 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
(ex = 206 nm; em = 385 nm) at room temperature. (c) The excitation spectra (em =
385 nm) at different temperatures.
2.2 The luminescence of Ca3Sc2Si3O12 host. The vacuum ultraviolet (VUV)
spectroscopy of pure Ca3Sc2Si3O12 was investigated as a prerequisite for the study of
the luminescence properties of doped samples. The emission spectrum upon
synchrotron radiation excitation at 206 nm and the VUV excitation spectrum by
monitoring at the wavelength of 385 nm emission at 15 K are shown in Figure 2(a). A
broad excitation band was observed with a maximum at 206 nm (6.02 eV) and is
associated with near-defect excitons. At higher energy, a broad shoulder band (184 nm,
6.74 eV) is present and is assigned to self-trapped exciton (STE) absorption. Upon
206 nm excitation, the emission exhibits a broad band with maximum at 385 nm. The
spectrum is similar to that reported by Ivanovskikh et al.26 who pointed out that the
broad emission band in the time-integrated excitation spectrum is attributed to
excitons localized near defects or to direct electronhole recombination. These
authors also reported several other weak bands which are not present in Figure 2(a).
Figure 2(b) shows the monoexponential decay curve of the emission intensity I,
fitted to Eq (1).
ln(I) = lnA - kt
(1)
where the slope k is the reciprocal of the intrinsic lifetime (0) and A is a constant.
The lifetime is fitted to be 5.5 s. The decay is little slower than that previously
reported for CSS at 10 K (2 s27) and also in comparison with the decay time of
self-trapped exciton luminescence in pure LaCl3 (3.5 s at room temperature28).
7
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 8 of 37
Ca2.8Na0.1Ce0.1Sc2Si3O12 RT
F
ex = 440 nm
em = 550 nm (VUV)
em = 550 nm (UV)
A
C
B
E
100
200
300
400
500
Wavelength (nm)
600
700
Page 9 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
bands (A-F) are distinguished in the 125-530 nm range as labeled in Figure 3. The
bands A (182 nm, 6.81 eV) and B (215 nm, 5.77 eV) are analogous to the exciton
absorptions observed in the VUV-UV excitation spectrum of Ca3Sc2Si3O12 in Figure 2,
but with different relative intensities and a red-shift of the latter by several nm. With
an excess of 8% for exciton binding energy,29 the band gap of CSS:Ce3+ is estimated
to be 7.35 eV at room temperature.
The three lower energy bands C (239 nm, 5.18 eV), D (308 nm, 4.02 eV) and F
(440 nm, 2.82 eV) are attributed to 4f-5d transitions of Ce3+, in line with previous
studies.12,30 In CSS-Ce the Ce3+ ion occupies the D2 symmetry Ca2+ site, so that the 5d
level is initially split into a lower doublet (Eg) and a higher triplet (T2g) by the cubic
component of the crystal field and then further split by the distortion from cubic
symmetry. A first-principles study27 has calculated the energies of the 4f1 and 5d1
levels of Ce3+ in Ca3Sc2Si3O12 with different types of charge compensation
mechanisms. Assignments for the 5d(1)-5d(5) energy levels of Ce3+ in garnet host
lattices (mostly expressed as vibronic band maxima) are collected in Table 1 and in
the present case the assignments for 5d(1)-5d(3) appear secure. There is some
disagreement in the literature concerning the assignment of the higher 5d levels in
YAG:Ce3+. From the first principles calculation, the crystal field splitting (CFS) of
Ca3Sc2Si3O12:Ce3+, Na+ is calculated to be about 27773 cm-1 (3.44 eV).
Table 1. Calculated (calc.) and observed (obs.) energies (in eV) for selected garnets
doped with Ce3+. Values refer to band maxima except for the calculation of Ref. 32 for
9
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 10 of 37
YAG:Ce3+ which refers to zero phonon line energies. In YAG:Ce3+, the 5d(1) and 5d(2)
zero phonon lines are at 0.15 eV and 0.11 eV to low energy of the excitation band
maxima, respectively.32 Measurement temperatures are included, where appropriate.
Ref.
System
4.03
5.19
12, 77 K, obs.
Ca2.97Ce0.03Sc2Si3O12
2.79
4.03
5.23
27, calc.
Ca3Sc2Si3O12:Ce3+, Na+
2.87
3.94
5.59
6.10
31, obs./calc.
Y3Al5O12:Ce3+
2.71
3.65
5.50
~5.50 6.06
32, calc.
Y3Al5O12:Ce3+
2.53
3.57
5.39
6.09
6.31
7.51
Page 11 of 37
Ca2.8Ce0.1Na0.1Sc2Si3O12 RT
500
em = 390 nm
30
20
10
5d(1)
1
1.0
400
0.7
300
400
em = 550 nm
100
0.5
300
5d(2)
0.2
0
500
150
5d(2)
5d(1)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
50
400
500
600
700
Emission wavelength (nm)
300
400
0
500
Wavelength (nm)
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
emission from 340 nm to 700 nm, as shown in Figure 4. The remarkable intense
absorption between 400 - 500 nm corresponds to the vibronic band of the 4f - 5d(1)
transition of Ce3+. The transition to 5d(2) shows weak absorption intensity (as marked
in Figure 4), whilst three additional weaker bands at 296, 330 and 360 nm appear
when monitoring emission at ~390 nm (Figure 4: top right-hand panel), which is at a
similar wavelength to that of the host emission (Figure 2). These excitation bands are
more prominent when monitoring the emission at 390 nm than at 550 nm, as shown
Figure 4, right-hand panels, Figure S7 and Figure S8. Furthermore, excitation at 330
nm or 360 nm gives an emission band ~390 nm in addition to the Ce3+ emission at
longer wavelength (Figure S9). The former emission band is shifted a few nm to
higher energy, at 385 nm, when exciting at 237 nm and 206 nm at 15 K (Figure S10).
The decay curves of the Ce3+ and defect site emissions are compared in Figure S11.
The life time of this defect site emission is 202 ns which is shorter than the 67 ns
decay of Ce3+. The defect sites may arise from aliovalent substitutions near Ce3+ ions
since their population leads not only to self-trapped excitonic emission but also to
Ce3+ emission. Since the relevant spectral features of these defect sites are at high
energy, their presence does not interfere with our study on Ce3+- Eu2+ energy transfer
and application.
12
Page 12 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Page 13 of 37
ex = 440 nm
Ca3-2xCexNaxSc2Si3O12 RT
x = 0.001
x = 0.03
em = 550 nm
x = 0.10
x = 0.15
x = 0.20
300
400
500
600
700
Wavelength (nm)
ex = 440 nm, em = 550 nm
b
100
200
300
Time (ns)
400
500
Figure 5. (a) The normalized excitation spectra (em = 550 nm) and emission spectra
(ex = 440 nm) for Ca3-2xCexNaxSc2Si3O12 (x = 0.001-0.2) at room temperature. (b)
The corresponding decay curves of these samples.
Chemistry of Materials
Ca2.8Ce0.1Na0.1Sc2Si3O12
1.0
ex = 440 nm
0.8
0.2
320 K
340 K
360 K
380 K
400 K
420 K
440 K
460 K
480 K
0.0
400
450
0.6
0.4
1.2
Normalized intensity (arb. units)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 14 of 37
1.0
0.8
0.6
0.4
81.1%
0.2
0.0
300 350 400 450 500
Temperature (K)
500
550
600
Wavelength (nm)
650
700
et
al.6
have
pointed
out
that
the
thermal
14
performance
of
Page 15 of 37
0
CB
-1
-2
3+
Ln E
LS
-3
VRBE (eV)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
-4
HS
-5
-6
4 5
2+
Ln G
-7
-8
-9
-10
3+
Ln G
La
Ce
Pr
Nd
Pm Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
VB
9 10 11 12 13 14
3+
number of electrons n in Ln 4f
Figure 7. VRBE scheme for lanthanide Ln3+ 4fn and 4fn-15d states (blue color), and
Ln2+ 4fn states (red color) in Ca3Sc2Si3O12. The excited energy levels of lanthanide
ions are taken from Refs. 33,34. Refer to the text for explanation.
2.6. Vacuum referred binding energy scheme (VRBE) scheme. The vacuum
referred binding energy (VRBE) scheme for Ln3+ 4fn and 4fn-15d states and Ln2+ 4fn
states in Ca3Sc2Si3O12 is displayed in Figure 7 by using published methods.33,34
Various approximations are involved, including the use of the same band gap for all
15
Chemistry of Materials
ions, the use of band maxima instead of zero phonon line energies, and the separations
of high and low-spin states. The required data for the construction in the CSS host are
(i) the energy of the lowest 4f - 5d transition of Ce3+ (arrow 1: 2.84 eV); (ii) the host
band gap energy (arrow 2: 7.35 eV); (iii) the energy of the charge transfer band of
Eu3+ (arrow 3, see Figure S13: 4.86 eV); (iv) the Coulomb correlation energy, i.e.,
energy difference between the ground states of Eu2+ and that of Eu3+ (not shown, 6.93
eV); and (v) the centroid shift (Figure S5: 1.4 eV). The exchange splitting energy
between the low spin and high spin 4f - 5d transitions of Tb3+ in CSS is taken from
Velzquez et al.14 (arrows 4 and 5: 0.79 eV). The ground state of Eu2+ is found to be
above the Fermi energy level in Figure 7, indicating that the Eu2+ is unstable in this
host with respect to oxidation. This fact is supported by the calculated sum of the
bond valences (Eq. (1) in Ref. 35) coordinating Eu2+ in the CSS host (equal to the
oxidation number of Eu) and found to be 3.1 in the present case from the Ca-O bond
distances in CSS.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ca2.94Eu0.06Sc2Si3O12 RT
ex = 360 nm
ex = 520 nm
em = 873 nm
a
300
400
500
600
700
800
900
1000
1100
1200
Wavelength (nm)
ex = 405 nm, em = 873 nm
~ 95.1 ns
b
150
300
450
600
750
900
1050
Time (ns)
Page 16 of 37
Page 17 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Chemistry of Materials
assuming the same Stokes shift, and this is far from the observed peak wavelength.
The decay curve of Eu2+ emission in Ca2.94Eu0.06Sc2Si3O12 was excited by 405 nm
radiation (Figure 8(b)) and can be well fitted by the monoexponential Eq. (1) with the
Ca3-xEuxSc2Si3O12 RT
Intensity
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 18 of 37
0.00
0.04
0.08
Concentration x
ex = 520 nm
873 nm
700
800
x=0
x = 0.001
x = 0.01
x = 0.03
x = 0.06
x = 0.09
900
1000
Wavelength (nm)
1100
1200
Page 19 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
19
Chemistry of Materials
Ca2.94-2xCexEu0.06NaxSc2Si3O12
3+
Ce emission
2+
Eu emission
0.0
0.1
ex = 440 nm
x=0
x = 0.001
x = 0.03
x = 0.10
x = 0.20
0.2
Content (x)
400
500
600
800
RT
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 20 of 37
900
1000
1100
1200
Wavelength (nm)
2.8. Energy transfer between Ce3+ and Eu2+ in CSS. There is a large spectral
overlap between the emission of Ce3+ (Figure 2) and the absorption of Eu2+ (Figure
8(a)), suggesting that efficient energy transfer may occur from the sensitizer Ce3+ to
the activator Eu2+. In order to investigate this energy transfer, Ce3+ and Eu2+ co-doped
samples Ca2.94-2xCexEu0.06NaxSc2Si3O12 and Ca2.8-2xCe0.1EuxNa0.1Sc2Si3O12 (where x is
the nominal synthesis concentration) were prepared and the spectra and decay curves
were
recorded
separately.
Figure
10
shows
the
emission
spectra
of
Page 21 of 37
Normalized intensity
Ca2.94-2xCexEu0.06NaxSc2Si3O12
1.0
(a)
em = 870 nm
RT
0.8
0.6
x=0
x = 0.001
x = 0.03
x = 0.10
x = 0.20
0.4
0.2
350
400
450
500
550
600
650
700
750
Wavelength (nm)
0.9
(b)
0.8
Relative intensity
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
0.7
Ca2.94-2xCexEu0.06NaxSc2Si3O12
0.6
0.5
0.4
0.3
0.00
0.05
0.10
0.15
0.20
3+
Ce content (x)
Figure 11. (a) The normalized excitation spectra (em = 873 nm) of
Ca2.94-2xCexEu0.06NaxSc2Si3O12 at room temperature. (b) Excitation intensity at 370 nm
relative to that at 520 nm.
The excitation spectra, normalized at 520 nm, of Eu2+ emission (em = 873 nm)
from Ca2.94-2xCexEu0.06NaxSc2Si3O12 at room temperature (Figure 11(a)) show a
21
Chemistry of Materials
of
the
Ce3+
emission
at
550
nm
in
the
co-doped
system
Ca2.8-xCe0.1Na0.1EuxSc2Si3O12 (Figure S18) does not show the presence of the Eu2+
absorption band at 368 nm so that nonradiative energy transfer from Eu2+ to Ce3+ does
not occur. On the contrary, this excitation spectrum (Figure S18) and the emission
spectrum, Figure S19, show that the emission of Ce3+ is quenched with the addition of
Eu2+.
Ca2.8-xCe0.1EuxNa0.1Sc2Si3O12
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 22 of 37
RT
100
200
Time (ns)
300
400
Page 23 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
The energy transfer rates were estimated from the decay curves of the Ce3+:5d1
4f1 emission at 550 nm in Ca2.8-xCe0.1Na0.1EuxSc2Si3O12 (x = 0-0.09) (Figure 12) at
room temperature. With ascending Eu2+ concentration, the lifetimes decrease
markedly and deviate from the monoexponential behavior of the sample x = 0.
Therefore, the curves were fitted by the double-exponential equation:
= A e
+ A e
(2)
Where 1 and 2 are the fast and slow components of the luminescent lifetime,
respectively. A1 and A2 are the corresponding fitting parameters. The average lifetime
can be further evaluated by the following equation:
= (A
+ A
)/(A + A
)
(3)
The fitting results are presented in Table 2, with goodness of fit, for all the
samples. The Ce3+ lifetime is drastically reduced from 66.8 ns and follows a
monoexponential decay with Eu dopant ion concentration as shown in the top panel of
Figure 13. The linear relationship of kET with Eu2+ dopant ion concentration x as
shown in the bottom panel of this figure indicates a direct transfer from Ce3+ to Eu2+,
with the transfer efficiency rising as high as 88.9% (Table 2, final column).
23
Chemistry of Materials
Table 2. Lifetimes, fitting parameters, energy transfer rates and efficiency for
Ca2.8-2xCe0.1Na0.1EuxSc2Si3O12 from measurements of Ce3+ emission at 295 K.
Eu2+
A1
A2
R2adj
66.8 0
66.8 0
0.4874
0.4874
0.9984
66.8
0.0
0.0
0.001
18.0 0.6
55.4 0.5
0.2965
0.6886
0.9987
50.8
4.7
24.0
0.01
14.8 0.3
48.1 0.5
0.3855
0.5820
0.9984
42.4
8.6
36.5
0.03
6.9 0.08
27.4 0.2
0.5336
0.4332
0.9985
22.5
29.4
66.3
0.06
4.3 0.04
17.1 0.2
0.5995
0.2903
0.9985
12.8
63.4
80.9
0.09
2.6 0.02
10.60.1
0.7053
0.2602
0.9990
7.4
120.4
88.9
kET (s)-1
(%)
Lifetime, (ns)
60
y = (52.96.7)exp[-x/(0.0240.009)]+(7.26.2)
40
RT
Ca2.8-xCe0.1EuxNa0.1Sc2Si3O12
2
20
adj
= 0.9395
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 24 of 37
0.00
0.02
0.04
0.06
0.08
0.10
RT
120
y` = ( 1269100)x`- (2.64.6)
80
2
R
40
adj
= 0.9700
Ca2.8-xCe0.1EuxNa0.1Sc2Si3O12
0.00
0.02
0.04
0.06
Doping level, x
0.08
0.10
Figure 13. The Ce3+ emission lifetimes and the energy transfer rate as a function of
Eu2+ dopant ion concentration in Ca2.8-xCe0.1EuxNa0.1Sc2Si3O12.
24
Page 25 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
decay
of
donor
Ce3+
luminescence
is
attributed
to
multipole-multipole interaction between the donor Ce3+ ions and acceptor Eu2+ ions at
different distances and can be described by the following equation:39
()
#
$
(4)
where '( is the acceptor concentration; ' is the critical concentration; and
(1 3/*) is the gamma function. A value of 66.8 ns was taken for the lifetime (0)
of Ce3+ as fitted above. The s value depends on the mechanism of transfer and for the
following interactions it is: 6 (electric dipole-electric dipole or magnetic
dipole-magnetic dipole); 8 (electric dipole-electric quadrupole); and 10 (electric
quadrupole-electric quadrupole). Since the expression for energy transfer between a
donor and acceptor can be written to involve individual matrix elements for the
respective radiative transitions, 40 and both of the Ce3+ and Eu2+ transitions are from 4f
to 5d states, the appropriate value of s is 6 (refer to the Supporting Information).
Indeed, the decay curves plotted in Figure 12 closely resemble the plot for the regime
of dipole-dipole energy transfer without donor migration.40 The fitted curves and the
obtained fitting parameters are presented in Figure 12 and Table 3, respectively. The
fits using other values of s are inferior (for s = 10, see Figure S20(a) for example).
25
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 26 of 37
Table 3. The fitting parameters and the CA/C0 ratios obtained from the I-H model.
Ca2.8-xCe0.1Na0.1EuxSc2Si3O12
CA(Eu2+)
Radj2
CA/C0
0.9984
0.001
0.9839
0.34
0.01
0.9973
0.55
0.03
0.9944
1.31
0.06
0.8466
2.10
0.09
0.9806
2.94
Neglecting the value for x = 0.001 in Table 3, the average value of C0, the critical
transfer concentration, is x = 0.0250.006. Taking the intrinsic lifetime 0 as 66.8 ns,
with the corresponding deactivation rate is 15 (s)-1, then from the equation in the
lower Figure 13, the value of C0 is calculated to be slightly lower at x = 0.014.
There are 8x Eu2+ acceptors in the unit cell volume of 1837. 8 3, so that with
the use of Eq. 25 in Ref. 39:
C0 =
3
4R03
(5)
Page 27 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Figure 14. Spectral conversion design for solar cell applications, involving the AM
1.5 solar spectrum, spectral response of c-Si, and the PLE and PL spectra of
Ca2.88Ce0.03Eu0.06Na0.03Sc2Si3O12.
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
emission is located in the region of highest spectral response of the c-Si solar cell, the
CSS: Ce, Eu phosphor could be a solar energy converter material for application
together with the c-Si photovoltaic solar cell. The energy transfer efficiency from Ce3+
to Eu2+ is nearly 90%. The two main drawbacks have been identified herein: the poor
valence stability of Eu2+ in the CSS host and the luminescence quenching with
temperature increase.
4. CONCLUSIONS
This study has comprised two facets: the spectral properties and energy transfer of
Ce3+ and Eu2+ in the garnet host and the suitability for solar energy harvesting. Indeed,
the CSS garnet host exhibits many unique characteristics. The energy levels of Ce3+
are subject to a strong crystal field so that the 4f1 -5d1 lowest energy zero phonon line
is located in the blue spectral region. The Ce3+ ion occupies the Ca2+ site and charge
compensation by Na+ has been included. The monoexponential emission decay does
not exhibit noticeable quenching for Ce3+ concentration below x = 0.2 in
Ca3-2xCexNaxSc2Si3O12, and the intensity only decreases by 20% at 460 K. By contrast,
the emission of Eu2+-doped CSS is more sensitive to concentration and temperature
quenching. However, the emission band is located in the near infrared spectral region
and broad, intense 4f7 4f65d absorption bands span the visible and ultraviolet
regions. The spectral overlap between Ce3+ emission and Eu2+ absorption promotes
resonant energy transfer and the Ce3+ decay kinetics have been fitted by the
Inokuti-Hirayama formalism for electric dipole electric dipole energy transfer, in
28
Page 28 of 37
Page 29 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
ACKNOWLEDGMENTS
This work is financially supported by the National Natural Science Foundation of
China (21171176, U1232108, and U1432249).
29
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 30 of 37
SUPPORTING INFORMATION
Experimental details; Centroid shift of Ce3+ in CSS; Energy transfer formulae; Figures
and Tables.
REFERENCES
(1)
International
Energy
Agency,
World
Energy
Outlook
2015,
Page 31 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 32 of 37
Lukowiak, A.; Chiappini, A.; Chiasera, A.; Ferrari, M.; Nez, P. Structural and
Luminescence Study of Ce3+ and Tb3+ Doped Ca3Sc2Si3O12 Garnets Obtained by
Freeze-Drying Synthesis Method. Opt. Mater., 2015, 46, 109-114.
(15) Liu, Y.; Zhuang, W.; Hu, Y.; Gao, W.; Hao, J. Synthesis and Luminescence of
Sub-Micron Sized Ca3Sc2Si3O12 Green Phosphors for White Light-Emitting Diode
and Field-Emission Display Applications. J. Alloys Compd., 2010, 504, 488-492.
(16) Liu, Y.; Hao, J.; Zhuang, W.; Hu, Y. Structural and Luminescent Properties of
Gel-Combustion Synthesized Green-Emitting Ca3Sc2Si3O12:Ce3+ Phosphor for
Solid-State Lighting. J. Phys. D: Appl. Phys., 2009, 42, 245102.
(17) MacDonald, M. R.; Bates, J. E.; Ziller, J. W.; Furche, F.; Evans, W. J. Completing
the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes
of Pr2+, Gd2+, Tb2+, and Lu2+. J. Am. Chem. Soc., 2013, 135, 9857-9868.
(18) Kishore, S. M.; Kumar, N. P.; Chandran, R. G.; Setlurb, A. A. Solid Solution
Formation and Ce3+ Luminescence in Silicate Garnets. Electrochem. Solid-State Lett.,
2010, 13, J77-J80.
(19) Xia, Z.; Ma, C.; Molokeev, M. S.; Liu, Q.; Rickert, K.; Poeppelmeier, K. R.
Chemical
Unit
Cosubstitution
and
Tuning
of
Photoluminescence
in
the
Page 33 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 34 of 37
Page 35 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials
Chemistry of Materials
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
36
Page 36 of 37
Page 37 of 37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chemistry of Materials