Journal of Electron Spectroscopy and Related Phenomena, 2 (1973) 75-86

@ Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

’ studied Mg and MgO and found

an Auger line shift of 6.2 eV compared to a binding energy shift of only 0.8 eV.
These results imply that more attention should be paid to Auger signals in ESCA
studies.
In this work we have studied Zn, ZnO, Ga and Gaz03. It will be shown again
that the Auger electron spectrum is more sensitive to the chemical environment than
the direct electron spectrum.
Auger electron spectroscopy also became an important analytical tool via the
LEED technique, where a retarding field analyzer easily could be incorporated in the
LEED optics. In these studies, an electron beam is used as exciting radiation. How-
76

ever, a retarding field analyzer or an electrostatic cylindrical analyzer as normally

designed for Auger studies do not give the resolution obtainable with the hemispherical
analyzers normally used in ESCA instruments. This is a disadvantage for the study of
Auger electron energy shifts or the fine structure of an Auger signal. Nevertheless,
it has been possible to detect changes in Auger electron spectra. A direct comparison
with electron binding energy shifts (ESCA shifts) is not possible in this technique,
where only Auger electrons are studied. Most reports deal with changes due to metal-
oxygen interaction: Be14* 15, Mg16, A1’7-20, Si20-24, Ti25, 26, V27-30, Cr25, 27,
~~16 ~31 Nb32 Mo31, 32 ~~32, 33 ~32
and U34. Also changes in the carbon Auger
spect!rum have been studied32 ’ 35- 3‘:

EXPERIMENTAL

The experiments were performed with an AEI ES 100 electron spectrometer

equipped with a hemispherical electrostatic analyzer which uses a preretardation
field. Oil diffusion pumps fitted with cold traps produce a vacuum of lo- 7 torr during
the experiments. All spectra presented here were obtained with Al Kcr,, 2 radiation
(1486.6 eV). The instrumental resolution for the gold 4f7,2 signal is 1.30 eV during the
experimental conditions in this work. The instrumental calibration has already been
described in detail12. According to this, the binding energy of Au 4f7,2 electrons is
84.0 eV.
Metallic zinc was studied as foil (BDH, 0.38 mm thick) and zinc oxide as
powder (BDH, Analytical Reagent) fastened to a copper gauze. Mechanically
cleaned zinc was studied at 25 “C and at 200°C and zinc oxide at 25 “C and at 400°C.
The results obtained at different temperatures were consistent within 0.1 eV. Gallium
(BDH, Analytical Reagent) was melted and placed on a copper sample holder and
studied at 25 “C. Ga,O, (BDH, Analytical Reagent) was studied at 25 “C as powder
fastened to a double-coated tape.
A charging effect of at most 0.3 eV for ZnO and 1.3 eV for Ga,O, was
observed from the position of the contamination carbon peak. The results presented
here are corrected for this charging. Binding energies and Auger electron energies are
given in relation to the Fermi level throughout this work.

RESULTS AND DISCUSSION

Direct electron spectra from zinc and zinc oxide

The measured core electron binding energies in Zn and ZnO are given in
Table 1 together with the values reported by Siegbahn et al.’ for zinc and by Vesely
and Langer 38 for zinc oxide. We have also included the values for 0 1s and C 1s
electrons. Vesely and Langer 38 resolved the 3d level by a DuPont curve resolver.
The only difference between the Zn spectra at 25°C and at 200°C was found
in the oxygen signal. Figure 1 shows oxygen 1s signals from Zn at 25 “C and at 200 “C
 77

TABLE 1

BINDING ENERGIES (eV) IN ZINC AND ZINC OXIDE

Electron Zn zno Zn zno

level This work This work Siegbuhn Vesely and Lange+
et al.’

Zn 2s 1195.9+0.3 1195.9*0.3 1194 1195.11

Zn 2,01/s 1044.8 *0.2 1044.8 kO.2 1044 1044.46=kO.21
Zn 2~312 1021.7f0.2 1021.7f0.2 1021 1021.38&0.21
Zn 3s 139.6f0.3 139.9*0.3 137 139.60
Zn 3~112 91.4*0.3 91.7hO.3 87 91.91 ho.23
Zn 3~312 88.8f0.3 89.0*0.3 88.82
Zn 3d 10.1 kO.2 10.6*0.2 9 10.79kO.27 10.04
0 1s 530.6&0.2 530.6+0.2 530.60
c IS 285.1&0.2 285.1 kO.2

BINDING ENERGY (eV)

Figure 1. Oxygen Is electron spectra from metallic zinc covered with a surface oxide and from zinc
78

together with the oxygen 1s signal from zinc oxide. The spectra from ZnO at 25 “C and
at 400°C were identical. All three oxygen spectra have a peak at a binding energy of
530.6 eV, which is interpreted as due to lattice oxygen in zinc oxide. Thus there is a
surface oxide present on zinc as for most other metals. Zn at 25 “C has also a distinct
peak at 532.0 eV, which decreases in intensity upon raising the temperature to 200°C.
Also ZnO has a small peak at the high binding energy side of the 0 1s spectrum.
This high binding energy oxygen is probably due to adsorbed oxygen or another
oxygen-containing molecule39-41.
The surface oxide present on zinc also influences the zinc signals. As seen from
Table 1, the zinc binding energies in Zn and ZnO are very similar. The kinetic energy
of ejected Zn 2p electrons is about 450 eV, whereas ejected Zn 3d electrons have a
kinetic energy of about 1470 eV. This means that the mean free path length of excited
Zn 2p electrons is smaller than that of Zn 3d electrons. Thus the 2p signals originate
from a thinner layer than the 3d signal. Table 1 shows that the 2p binding energies are
identical for Zn and ZnO, whereas there is a shift of about 0.5 eV for 3d electrons.
The 2p signals from Zn and ZnO are symmetric. The only difference is that the half-
width of the Zn signal is 0.3 eV larger than that of the ZnO signal. Both signals almost
entirely relate to zinc oxide. The 3d signal from zinc is definitely asymmetric due to
contribution from both metal and oxide zinc atoms, whereas the ZnO 3d signal is
symmetric and narrower.
The chemical shift between Zn” in metallic zinc and Zn*+ in zinc oxide is very
small, which is the same relation as was found in copper and copper oxides13. Chemical
shifts of this order, a few tenths of an eV, are difficult to register and the interpretation
of ESCA results becomes difficult.

Direct electron spectra from gallium and gallium oxide

The element after Zn in the periodic system, Ga, shows a definite chemical

TABLE 2

BINDING ENERGIES (eV) IN GALLIUM AND GALLIUM OXIDE

Electron Ga GazOa Ga
level This work This work Siegbahn et al.1

Ga 2~112 1143.3 zto.2 1145.1 hO.2 1143

Ga 2~312 1116.3kO.2 1118.1*0.2 1116
Ga 3s 159.2*0.3 161.0rk0.3 158
Ga 3~112 106.9+0.3 108.8ztO.3 107
Ga 3P3/2 103.9+0.3 105.8&0.3 103
Ga 3d l&6+0.2 20.5 k0.2 18
0 1s 531.1 kO.2 531.1 kO.2
c 1s 285.1 kO.2 285.110.2
 79

1125 1120 1115 - 25 20 15

BINDING ENERGY (eV1

Figure 2. Ga &a and Ga 3d electron spectra from metallic gallium covered with a surface oxide
(upper curves) and from gallium oxide (lower curves).

shift between metal and oxide gallium signals. Figure 2 shows Ga 2p3,2 and Ga 3d
signals from metallic Ga covered with a surface oxide and from Ga,O,. The chemical
shift is 1.9 eV for both signals. Table 2 gives the gallium electron binding energies in
gallium metal and gallium oxide. The oxide results were obtained from both the metal
surface oxide and Ga,O, powder.
In this case, the surface sensitivity of ESCA is better illustrated than for zinc.
Ga 2p,,, electrons with a high binding energy (ejected with a low kinetic energy) and
thus a low mean free path length have a larger contribution from surface oxide atoms
compared to bulk metal atoms. On the contrary, the 3d electrons with a low binding
energy (ejected with a high kinetic energy) and thus a larger mean free path length
have a larger contribution from metal atoms than from surface oxide atoms. By
comparing signals with different kinetic energies it is possible to calculate the thickness
of the surface oxide. For the gallium sample in Figure 2 we have found an oxide
thickness of 10 A by using the mean free path length reported for A1,0,42 also for
Ga,0S4’.

Auger electron spectra from zinc and zinc oxide

Figure 3 shows the LJM4,5M4,5 Auger electron spectra from Zn and ZnO
and in Figure 4 the L2,3M,,,M4,, sp ectra are shown. LMM Auger signals detected
80

in this work are summarized in Table 3 together with results recently reported by
Yin et a1.44 for zinc metal and by Langer and Vesely45 for zinc oxide. The agreement
between different investigations is very good. The calculated values in Table 3 are
obtained in the same way as described earlier l2 . The calculation was performed for
ZnO since the data for Zn in Table 1 are not for pure zinc metal but for zinc covered
with a surface oxide. The binding energies in Table 2 for gallium oxide are used in the
calculation.

TABLE 3

ZINC AUGER ELECTRON ENERGIES (eV)

Assignment Zn zno ZnO Z?l ZnO

This work This work This work Yin et ~1.~~ Lunger and
Measured Measured Calculated Vesely45

LsMz,zMl 770.0+1.0 770.8

LsMlMz.3 783.351.0 775.0
LzMz,sMz,s 823.8*0.5 825.0 827 +1.5
831.1*0.5 833 l1
LzM2,d&.3 846.4kl.O 848.1 850 *2
855.1 *l.O
LsM4,5M2,3 905.1 zto.5 900.8*0.5 904.3 904.4f0.4
906 +l
L~M2,zsM.w 913.6kO.5 909.4kO.5 911.3 912.6+0.3 910.6
915 l 1
L2M4,5Mw 927.9zt0.5 923.6AO.5 927.4 927 xtl
LzMwM4.5 936.5+0.5 932.2k0.5 934.4 935 *1.5 932.3
986.3 rlrO.5
LsM4,sM.w 992.5 *0.2 988.2kO.2 990.6 990.9kO.2 990.1
995.860.2 991.4f0.3 994.3 *to.3
1009.6&0.5
LzMwMu 1015.7ztO.2 1011.5?cO.2 1013.7 1013.6&I-0.3 1012.6
1018.9&0.3 1014.7kO.3

As inferred from Figures 3 and 4, the Auger signals present in ZnO are also
present in the Zn spectra. These peaks are ascribed to the surface oxide and the
remaining peaks in the Zn spectra are ascribed to zinc metal. Thus the difference
between zinc metal and zinc oxide is much better revealed in the Auger electron
spectrum than in the direct electron spectrum. The Auger shift is 4.3 eV for both
L,M,,,M,,s and L,,,M2,JM4,, Auger electrons. Each metal and oxide signal
consists of two peaks. The L,M,,,M,,, separation is 3.3 eV and that of L2,,M2,3-
M 4,5 8.6 eV. The separation is the same for metal and oxide signals. The L,M,,,-
M 4,5 Auger spectra not shown here have the same character as the L,M4,,M4,,
spectra in Figure 3. This was not the case in the spectrum published by Yin et a1.44.
 81

Zn and ZnO

I I I
985 990 995

KINETIC ENERGY feV)

Figure 3. Zn L3M4.5M4.5 Auger electron spectra from metallic zinc covered with a surface oxide and
from zinc oxide.

The origin of the doublets is probably to be found in L-S coupling as discussed

by Yin et al. 44. In this model the L,M,,,M,,, signal consists of five fine-structure
lines due to different final states in the Auger process.
It should also be pointed out that the distances between corresponding peaks
in the Lz and L, based spectra are 23 eV, which is the separation between the Zn
2P1/2 and 2p3,2 levels.
Figure 3 shows that the L3M4,5M4,5 p eaks from zinc metal are narrower
than those of zinc oxide. The main peak is even narrower than the direct electron
signals from involved levels. This was also observed for the main Cu L3M4,5M4,5
Auger peak12, which was said to be due to different transition probabilities in different
parts of the valence band (M,,, level). The full width at half maximum for the Cu 3d
signal was 3.2 eV compared to an Auger peak width of about 1.0 eV. The same ex-
planation can be applied to the narrow metal Zn Auger peak in Figure 3.
The width of an electron signal is due to the instrumental contribution and to
the inherent width of the electron level. This inherent width is related to the lifetime of
 900 920 940
KINETIC ENERGY Wj

Figure 4. Zn Lz,sM~,sM~,s Auger electron spectra from metallic zinc covered with a surface oxide
and from zinc oxide.

the excited state by the uncertainty relation, AE*At>,A. In an Auger process, the
inherent width of the Auger signal is determined by the lifetimes of both the primary
state (one vacancy) and the final state (two vacancies). In zinc, the full width at half
maximum of signals from ejected core electrons were almost the same for Zn and
ZnO. Thus the Auger signal width due to the lifetime of the primary state is the same,
and the difference in Auger line widths as observed in Figure 3 is to be found in the
lifetimes of the final states. The electron lines from an insulator can be broadened due
to local charges formed on the surface, but this cannot be the explanation here since
this effect would influence both Auger and direct electron lines.
Friedman et a1.46 recently studied chemical effects on linewidths in photo-
electron spectra. In Na$,O, the S 2p signals from ligand sulfur (S2-) have an FWHM
of 2.20 eV compared to 1.88 eV for central sulfur (S6+). This was explained by variation
in valence-shell density. The - 2 sulfur has more electrons in the valence shell available
for the filling process which decreases the lifetime and increases the line width in
agreement with the experimental result. If the same discussion is applied to the Zn
and ZnO Auger spectra, the Zn lines should be broader than the ZnO lines in con-
tradiction to the experimental results in Figure 3. Nevertheless, the valence band
properties influence the linewidths since the difference in the L,,,M,,,M,,, spectra
(Figure 4), where only one valence electron is involved, is not as pronounced as for
 83

the L2,3M4,5M4,5 spectra, where two valence electrons are involved. Chemical
effects on the lifetime of Is hole states have been discussed by Shaw and Thomas4’.
Spohr et al.* discussed the broadened Auger lines found in methane in terms of
dissociation.

Auger electron spectra from gallium and gallium oxide

In gallium, the chemical shift between metal and oxide signals (1.9 eV) is
easily detected (Figure 2). Figure 5 shows the Ga L,M,,,M,,, Auger spectra from
metallic gallium covered with a surface oxide and from Ga,O,. Again the Auger
electron shift (5.7 eV) is larger than the chemical shift obtained from the direct
electron spectrum. The general structure of the Ga Auger spectra is very similar to
those of Zn shown in Figure 3.
The kinetic energies of the L,M,,,M,,, Auger lines are 1068.3 and 1072.0 eV
for the metal spectrum and 1062.6 eV and 1066.3 eV for the oxide spectrum. The
separation of the peaks is 3.7 eV compared to 3.3 eV in zinc. From the binding
energies in Table 2 and a Ge 3d binding energy of 29 eV’, a metallic Auger electron
energy of 1068.7 eV is calculated, in agreement with the main metal Auger peak in
Figure 5. As for Zn, the metal Auger widths are smaller than those of the oxide. The
Ga L2M4,,M4,, Auger spectrum has the same structure as the L3M4,5M4,5

metal

1060 1066 1070

KINETIC ENERGY (eVv)

Figure 5. Ga LsM4.sM4.s Auger electron spectra from metallic gallium covered with a surface oxide
and from gallium oxide.
84

spectrum in Figure 5. An Auger shift of 5.7 is also found in the L2,3M2,3M,,, Auger
spectrum.
Although the L, and L, based Auger spectra are identical in zinc and gallium,
this was not the case in copper I’, where the structure of the L,M,,,M,,, Auger
spectrum was different from that of L,M,,SM,,S.

THE RELATION BETWEEN AUGER AND BINDING ENERGY SHIFTS

The results obtained here from Zn and Ga show that the Auger electron energy
shift can be larger than the direct electron shift. For Zn-ZnO the Auger shift is 4.3 eV
whereas the direct electron shift is about 0.5 eV and difficult to determine with
accuracy. For Ga-Ga,O,, the binding energy shift is 1.9 eV, but the Auger shift is
three times as large. The Auger shifts were identical for L,,,M,,,M,,, and L,,,-
M,,,M,,, signals. Cu-Cu,O showed an Auger shift of about 2 eV compared to no
binding energy shift at all l3 . For Mg-MgO, Wagner and Biloen l1 found an Auger
shift of 6.2 eV compared to a binding energy shift of only 0.8 eV.
However, it cannot be concluded from these results that Auger shifts are
always larger than binding energy shifts. Fahlman et al.’ found a sulfur KL,L, Auger
shift of 4.3 eV between S6+ and S2- in sodium thiosulfate. The measured K electron
binding energy shift was 6.7 eV and the L,,, shift was 5.5 eV. Here the Auger shift
is smaller than the binding energy shift. Ramquist et al.’ reported KL,L, shifts in
titanium compounds which were close to the binding energy shifts.
The kinetic energy of an Auger electron is expressed by eqn. (1) after Burhop48
E vxy(z) = E u(z) - E,(z) - Eyw (1)

where Ev(=) and Ex(=) are binding energies of the atomic electron levels v and .Yof the
neutral atom and Eyecz, is the binding energy of electron y in an atom already singly
ionized in an inner level. Different approximations of eqn. (1) were discussed by Chung
and Jenkins4’. By differentiation of eqn. (1) we obtain:

AEvxy(zj = AE,,,, - AE+, - AE,Y,, (2)

AE,(,, and AE,,,, are the appropriate electron binding energy shifts (ESCA shifts).
The shift is almost equal for different levels which means that the difference AE,,,, -
AE,,,, vanishes. Thus the Auger electron shift is equal to AE,,,,,. The experimentally
demonstrated differences between electron binding energy shifts and Auger electron
energy shifts indicate that the shift in an already singly ionized atom (AEyroj) can be
larger than the shift in a neutral atom (AE,(,,). The sensitivity to the chemical en-
vironment is thus larger in an already ionized atom than in an atom in its ground state.

CONCLUSIONS

The difference between metal and oxide zinc atoms is much better revealed in
 85

the Auger electron spectrum than in the direct electron spectrum. In gallium, the
metal and oxide signals are well separated (1.9 eV) but the Auger electron shift is
three times as large as the chemical shift obtained from the direct electron spectrum.
Therefore, attention should be paid to Auger electrons in ESCA studies both from
analytical and theoretical points of view. In future tables concerning binding energies
and chemical shifts, it would be of great value to include Auger electron energy
characteristics as well.

ACKNOWLEDGEMENTS

The author is grateful to Professor Sten T. Lundin for his generous support
during the course of this work. Collaboration with Docent R. Larsson and Dr. B.
Folkesson is greatly appreciated. The work is supported by the Swedish Board for
Technical Development and the Bank of Sweden Tercentenary Fund.

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