6.8 Diamond Structured Si and Pb
129
104
106
108
110
112
(a)
BE (eV)
N
-1/3
Si
+
N
2p
BOLS
4
6
8
10
12
14
BE (eV)
Si +
N
VB
BOLS
N
-1/3
(b)
0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.0 0.1 0.2 0.3 0.4 0.5 0.6
2.5
3.0
3.5
4.0
4.5
80
100
120
140
Measurement
BOLS
m = 4.88, dot
(c)
Δ E
2p
K
-12
-9
-6
-3
0
3
0
5
10
15
20
DOS
E-E F
(100) skin
(210) skin
(d)
Fig. 6.22 Size trends of a, b the 2p and the valence band for Si +
N clusters [96] and c the 2p band for
the porous Si [97]. The p-Si increases its size from K = 2.7 (A, 1.4 nm) to 4.0 (2.1 nm, E) in radius.
DFT optimized (d) edge-entrapment of valence DOS for Si(210) (inset) with respect to that of the
Si(100) surface. DFT revealed distances between atom E and its neighbors denoted 1, 2, and 3 are
0.2577, 0.3572, and 0.3394 nm with respect to the bulk distance of 0.3840, 0.4503, and 0.3840 nm.
Reprinted with permission from [98]. Copyright 2014 American Institute of Physics
6.8.2 Pb 5d Binding Energy Shift
Figure 6.23a–d shows the BOLS-TB decomposed Pb 5d 3/2 spectra collected from
the (111) skin and Pd film deposited on the Si(100) substrate as well as Pb 3000 and
Pb 1000 clusters. Figure 6.23e is the BOLS linearization of the measured and the DFT
calculated size dependence of the 5d CLS with respect to E F (offset).
Table 6.10 summarizes the optimal z and E ν (z) components, and the energy levels
E ν (0) and their bulk shift ν (12) for Pb and Si skins and clusters. One electron
short of the Si
+
N offsets the E ν (0) from that derived from the skin by 4.87 eV without
changing the ν (12) value of 2.46 eV. This observation exemplifies how to correct
the charging effect in calibrating and analyzing the XPS spectra. Reprinted with
permission from [103]. Copyright 2014 The Royal Society of Chemistry.
129
104
106
108
110
112
(a)
BE (eV)
N
-1/3
Si
+
N
2p
BOLS
4
6
8
10
12
14
BE (eV)
Si +
N
VB
BOLS
N
-1/3
(b)
0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.0 0.1 0.2 0.3 0.4 0.5 0.6
2.5
3.0
3.5
4.0
4.5
80
100
120
140
Measurement
BOLS
m = 4.88, dot
(c)
Δ E
2p
K
-12
-9
-6
-3
0
3
0
5
10
15
20
DOS
E-E F
(100) skin
(210) skin
(d)
Fig. 6.22 Size trends of a, b the 2p and the valence band for Si +
N clusters [96] and c the 2p band for
the porous Si [97]. The p-Si increases its size from K = 2.7 (A, 1.4 nm) to 4.0 (2.1 nm, E) in radius.
DFT optimized (d) edge-entrapment of valence DOS for Si(210) (inset) with respect to that of the
Si(100) surface. DFT revealed distances between atom E and its neighbors denoted 1, 2, and 3 are
0.2577, 0.3572, and 0.3394 nm with respect to the bulk distance of 0.3840, 0.4503, and 0.3840 nm.
Reprinted with permission from [98]. Copyright 2014 American Institute of Physics
6.8.2 Pb 5d Binding Energy Shift
Figure 6.23a–d shows the BOLS-TB decomposed Pb 5d 3/2 spectra collected from
the (111) skin and Pd film deposited on the Si(100) substrate as well as Pb 3000 and
Pb 1000 clusters. Figure 6.23e is the BOLS linearization of the measured and the DFT
calculated size dependence of the 5d CLS with respect to E F (offset).
Table 6.10 summarizes the optimal z and E ν (z) components, and the energy levels
E ν (0) and their bulk shift ν (12) for Pb and Si skins and clusters. One electron
short of the Si
+
N offsets the E ν (0) from that derived from the skin by 4.87 eV without
changing the ν (12) value of 2.46 eV. This observation exemplifies how to correct
the charging effect in calibrating and analyzing the XPS spectra. Reprinted with
permission from [103]. Copyright 2014 The Royal Society of Chemistry.