Photo-electron spectrometer in air

Model AC-2

The counting mechanism of the photoelectron

and
The application to studies of
The Organic Light Emitting Diode (OLED)

RIKEN KEIKI CO., LTD 1

 Contents
1. The outline of AC-2
applications, features
2. The mechanism of counting photoelectrons
How does the open counter detect the electrons in the air?
3. The data analysis
What do the photoelectron spectrums mean?
4. The application to the OLED
The measurements of the IPs and WFs of
the Organic materials.
5. Conclusion

RIKEN KEIKI CO., LTD 2

 Contents
1. The outline of AC-2
applications, features
2. The mechanism of counting photoelectrons
How does the open counter detect the electrons in the air?
3. The data analysis
What do the photoelectron spectrums mean?
4. The application to the OLED
The measurements of the IPs and WFs of
the Organic materials.
5. Conclusion

RIKEN KEIKI CO., LTD 3

1. Outline of Spectrometer in Air (PESA)
Photo-Electron
MODEL AC-2
More than 170sets are used in Japan and world market.

36cm

45cm Light source part 120cm

Measuring part Personal computer
Mainly applications Latest applications
•Material research of the OLED . •Organic transistor
•The quality check of an ITO cleaning. •Organic solar battery
•The surface research of an MgO film for the PDP. •Catalyst of fuel cell
RIKEN KEIKI CO., LTD 4
 The features of AC-2
•Measurements can be done in the air.
Usually a photoelectron spectrometer needs a vacuum.
Because it is very difficult to detect and to count electrons in air.
•The work function and ionization potential can be
measured in the air in very high resolution.
•Measurement of contamination or film thickness on
a sample surface of 1mono layer-20nm.
•Easy operation & short measuring time.
RIKEN KEIKI CO., LTD 5
 Contents
1. The outline of AC-2
applications, features
2. The mechanism of counting photoelectrons
We employed the open counter for the detector of AC-2.
3. The data and the analysis
What do the photoelectron spectrums mean?
4. The application to the OLED
The measurements of the IPs and WFs of
the Organic materials.
5. Conclusion

RIKEN KEIKI CO., LTD 6

Conventional methods for detecting electrons
Picoammeter Channeltron
A pulse of 10 million electrons
Pulse counter
1pA (10-12A )

HV

Sample
Collector
UV Light Vacuum chamber
e
e

UV light e Sample

6.24x106cps (62 million/s)

This method is are

Photoelectrons not detected
sensitive A photoelectron
The
This electrons
device works isonly
strike detected
the channel
in a vacuum.
walls
enough
as quiteforsmall
photoelectron
amount of as an
and electricadditional
produce pulse. electrons.
spectroscopy.
electric current.

RIKEN KEIKI CO., LTD 7

The open counter Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

Open counter was invented in 1979 by Uda and Kirihata.

High Voltage Supply

Preamplifier
Scaling circuit
and Rate meter
Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid
e
O2 1 count
UV Light

e
Sample

Sample holder

The open counter is employed the photoelectron spectrometer in air. The open
counter is unique counter which can detect and count photoelectrons in the air.
RIKEN KEIKI CO., LTD 8
Structure Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

80mm

High Voltage Supply

Preamplifier
14mm Scaling circuit
and Rate meter
Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid 0 count

The open counter is composed of an anode, a quenching grid,

suppresser grid and electric circuits.

RIKEN KEIKI CO., LTD 9

Structure Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

Preamplifier
Scaling circuit
and Rate meter
Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid 0 count
15mm

Sample

Sample holder

The test sample is mounted on the sample stage which is kept at earth potential (0V).

RIKEN KEIKI CO., LTD 10

Structure Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 0 count

Sample

Sample holder

Suppresser Grid is kept at +80V, Quenching Grid is +100V, Anode is +2900V.

RIKEN KEIKI CO., LTD 11

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 0 count
UV Light

Sample

Sample holder

Monochromatized UV photons are used to excite photoelectrons from the sample surface.

RIKEN KEIKI CO., LTD 12

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 0 count
UV Light
e Electron
Sample

Sample holder

If the energy of an UV photon(=hn) becomes bigger than a work function of a

sample, a photoelectron is emitted from the sample surface.
RIKEN KEIKI CO., LTD 13
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 0 count
UV Light
e Electron
Sample

Sample holder

The electron is accelerated by a weak electric field applied between the sample (0V)
and the suppresser grid kept at +80V.
RIKEN KEIKI CO., LTD 14
Form the O2- ion
N2 N2
O2 N2
N2
e
O2-ion N2
N2 N2
N2 N2 N2
N2 O2
N2 N2 N2
N2
N2 N2
N2 O2 N2

Sample surface

The electron becomes attached to an oxygen molecule to form O2-

ion in the air during drift to the counter. Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

RIKEN KEIKI CO., LTD 15

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid
e
O2 0 count
UV Light

Sample

Sample holder

When an O2- ion reaches the inner cylinder of the open counter, the ion is accelerated again by a
strong electric field applied between the quenching grid ( +100V) and the anode kept at +2900V.
RIKEN KEIKI CO., LTD 16
The electron avalanche Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

Electric Anode surface

Field

N2 N2 O2
N2 N2
N2 N2
O2 N2 N2
N2 N2
O2 N2
N2 O2 N2
N2 e N2
N2 N2 N2
N2 O2 N2
N2 O2 N2
N2 N2 e
N2
O2
O2-ion
When the O2- ion arrives near the anode, the electron is detached from the O2- ion
and then the electron is accelerated again to the anode.
RIKEN KEIKI CO., LTD 17
The electron avalanche Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

Electric Anode surface

Field
e e e e e e e e e e e e

N2+ N+2 O+2

N2+ N+2
N2 N+2
+ O2 N2 N2+
N2 +N
N2
O2 2 e e
+N O2+ N2
N2 2e N2
N2 N2 N2
N2 O2 N2
N2 O2 N2
N2 N2 e
N2
O2
O2-ion
This causes an electron avalanche, which produces many electrons and positive
ions around the anode wire, where only the electrons are collected on the anode.
RIKEN KEIKI CO., LTD 18
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 10 count
UV Light

Sample

Sample holder

The electron avalanche makes a small electric pulse on anode.

This pulse is detected and counted as one electron.
RIKEN KEIKI CO., LTD 19
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+400V Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

When the quenching circuit detects the electric pulse, +400V is applied in place of
+100V to the quenching grid.
RIKEN KEIKI CO., LTD 20
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+400V Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

This reduction of the electric field around the anode causes the electron avalanche to be
quenched.
RIKEN KEIKI CO., LTD 21
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+400V Quenching circuit
-30V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

On the other hand, -30V is applied in place of +80V to the suppressor grid.

RIKEN KEIKI CO., LTD 22

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

Ion

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+400V Quenching circuit
-30V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

This voltage switch prevents leaving of the positive ions to the sample surface,
and entering of the next O2- ions into the counter during quenching.
RIKEN KEIKI CO., LTD 23
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter

Anode
3ms
+400V
-30V
Quenching circuit

Suppresser circuit Display

Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

Such voltages applied to the quenching grid and suppressor grid are kept for 3msec
i.e. the quenching time.
RIKEN KEIKI CO., LTD 24
Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter

Anode
3ms
+400V
-30V
Quenching circuit

Suppresser circuit Display

Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

All positive ions produced around the anode wire arrive and neutralize at the quenching
grid or suppressor grid during quenching time.

RIKEN KEIKI CO., LTD 25

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter

Anode
3ms
+400V
-30V
Quenching circuit

Suppresser circuit Display

Quenching Grid
Suppresser Grid 1 count
UV Light

Sample

Sample holder

If the next electron has emitted from the sample surface, the suppresser grid prevents
entering of the electron during quenching time.

RIKEN KEIKI CO., LTD 26

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Anode Suppresser circuit Display
Quenching Grid
Suppresser Grid
1 count
UV Light

Sample

Sample holder

After the quenching time (3ms), the initial voltages (+100V and +80V, respectively) are
restored and the quenching procedure is over.

RIKEN KEIKI CO., LTD 27

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

High Voltage Supply

Preamplifier
Scaling circuit
and Rate meter
Quenching circuit

Anode Suppresser circuit Display

Quenching Grid
Suppresser Grid
e
O2 21 count
UV Light

e
Sample

Sample holder

Now the counter is ready to count the next electron.

RIKEN KEIKI CO., LTD 28

 The calculation of counts
Electron counts may be lost during the quenching time. The
counting rates of electrons are estimated based on the counting
rates of counter pulses by calculation.
NO
N=
1-tNO
NO: Counting rate of counter pulses
N : Counting rate of photo electrons
t :Quenching time
Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.

RIKEN KEIKI CO., LTD 29

Structure and functions of AC-2
optical fiber

open personal
controller
deuterium grating counter computer
lamp monochromator
e

3.4eV 6.2eV sample photodiode

sample stage

Light source part Measuring part

: UV light e : photoelectron

RIKEN KEIKI CO., LTD 30

Structure and functions of AC-2
optical fiber

open personal
controller
deuterium grating counter computer
lamp monochromator

3.4eV 6.2eV photodiode

sample stage

Light source part Measuring part

: UV light e : photoelectron

RIKEN KEIKI CO., LTD 31

 Contents
1. The outline of AC-2
applications, features
2. The mechanism of counting photoelectrons
How does the open counter detect the electrons in the air?
3. The data and the analysis
What do the photoelectron spectrums mean?
4. The application to the OLED
The measurements of the IPs and WFs of
the Organic materials.
5. Conclusion

RIKEN KEIKI CO., LTD 32

 Photoelectron Spectrum
(Yield[cps])1/2

Photoemission
Threshold Energy[eV]

Incident Photon Energy [eV]

Yield :: the
Metal counting rate after
relationship calibtation
between the photon energy and yield 1/2 looks like a linear line.
Semiconductor yield1/3 gives a (E)
counting rate of: photoelectrons linear line. of UV-ray (E) x intensity of UV-ray (5.9eV)
/ intensity

RIKEN KEIKI CO., LTD 33

 The relationship between
the threshold energy and the energy diagrams
Vacuum level

Energy
Metal Semiconductor General material
Conduction Band Lowest unoccupied molecular orbital (LUMO)
Valence Band Highest occupied molecular orbital (HOMO)
Fermi Level

The energy level diagrams of metals, semiconductors and general materials

RIKEN KEIKI CO., LTD 34

 The relationship between
the threshold energy and the energy diagrams
Vacuum level

Work function
Ionization Work function
Ionization Ionization
Work function
potential potential potential

Energy
Metal Semiconductor General material
Conduction Band Lowest unoccupied molecular orbital (LUMO)
Valence Band Highest occupied molecular orbital (HOMO)
Fermi Level

A work function is an energy difference between a vacuum level and a Fermi level. On the other hand,
the ionization potential is an energy difference between a vacuum level and highest occupied molecular
orbital.

RIKEN KEIKI CO., LTD 35

 The relationship between
the threshold energy and the energy diagrams
UV photon e Photoelectron e
e

Vacuum level

Energy
Metal Semiconductor General material
Conduction Band Lowest unoccupied molecular orbital (LUMO)
Valence Band Highest occupied molecular orbital (HOMO)
Fermi Level

A UV photon excites an electron from the occupied states to the higher energy states than the vacuum level. And this
electron can be emitted from the sample surface. The electron is called the photoelectron.

RIKEN KEIKI CO., LTD 36

 The relationship between
the threshold energy and the energy diagrams
UV photon e Photoelectron e
e

Vacuum level

Ionization
Ionization Ionization
potential
potential potential

Energy
Metal Semiconductor General material
Conduction Band Lowest unoccupied molecular orbital (LUMO)
Valence Band Highest occupied molecular orbital (HOMO)
Fermi Level

Therefore, the photoemission threshold energy is the ionization potential.

RIKEN KEIKI CO., LTD 37

 The relationship between
the threshold energy and the energy diagrams
UV photon e Photoelectron e
e

Vacuum level

Ionization
Work function Ionization Ionization
potential
potential potential

Energy
Metal Semiconductor General material
Conduction Band Lowest unoccupied molecular orbital (LUMO)
Valence Band Highest occupied molecular orbital (HOMO)
Fermi Level

We can
The metal
estimate
is special
the material.
work functions
Because,
or ionization
the energypotentials
of highestofoccupied
the materials
molecular
from orbital
the photoemission
and the Fermi
threshold
level are
energy.
same.
Therefore the photoemission threshold energy of a metal is the work function.

RIKEN KEIKI CO., LTD 38

The shape of a photoelectron spectrum

DOS
Vacuum level

Energy
Potential energy

unoccupied molecular orbital

occupied molecular orbital

Energy level diagram

Reference: M.Uda, Y.Nakagawa, T.Yamamoto, M.Kawasaki,
A.Nakamura, T.Saito, and K.Hirose ”Successive change in
work function of Al exposed to air”, J. Electron. Spectrosc.
and Related Phenom. 88 (1998) 767.

RIKEN KEIKI CO., LTD 39

the relationship between an energy level diagram and
the photoelectron spectrum
dY
DOS = dE Photoemission yield (Y)
0
Potential energy

Energy level diagram Photon energy Photoelectron spectrum

The DOS is estimated by the differential of the photoelectron spectrum with respect to the photon energy E.

Reference: M.Uda, Y.Nakagawa, T.Yamamoto, M.Kawasaki,

A.Nakamura, T.Saito, and K.Hirose ”Successive change in
work function of Al exposed to air”, J. Electron. Spectrosc.
and Related Phenom. 88 (1998) 767.

RIKEN KEIKI CO., LTD 40

 The difference of a photoelectron spectrum
caused by the thickness of a surface film
Incident photon (E) - - -
E > sWFs
WFf> WF - - --
Contamination
or
Oxide film
(0-20nm)
WFf -
WFs
Substrate

The cross section of the sample surface covered with a thin film

RIKEN KEIKI CO., LTD 41

 The difference of a photoelectron spectrum
caused by the thickness of a surface film
Incident photon (E) - - -
E > sWFs
WFf> WF - - --
Contamination
or
Oxide film
(0-20nm)
WFf -
WFs
Substrate

When photoelectrons pass through a surface film, some electrons collide with a molecule
forming the surface film, and the photoelectrons are scattered.
So some of photoelectrons can not escape from the sample surface.

RIKEN KEIKI CO., LTD 42

 The difference of a photoelectron spectrum
caused by the thickness of a surface film
Incident photon (E) - - -
E > sWFs
WFf> WF - - --
Contamination
or
Oxide film
(0-20nm)
WFf -
WFs
Substrate

So, when the surface film is thick, many photoelectrons can not be emitted from the
sample surface.

RIKEN KEIKI CO., LTD 43

The relationship between the slope and film thickness

- - Thin contamination film

- -- -

(Yield[cps])n
- -
WFf - -
WFs Large slope

Incident Photon Energy [eV]

- -- -
- - Thick contamination film
- -- - - -

(Yield[cps])n
- -
WFf - -
WFs Small slope

WFf WFs

RIKEN KEIKI CO., LTD 44

 Contents
1. The outline of AC-2
applications, features
2. The mechanism of counting photoelectrons
How does the open counter detect the electrons in the air?
3. The data and the analysis
What do the photoelectron spectrums mean?
4. The application to the OLED
The measurements of the IPs and WFs of
the Organic materials.
5. Conclusion

RIKEN KEIKI CO., LTD 45

 The applications to the OLEDs
Glass Substrate
ITO transparence anode

Organic layers

Metal cathode Vacuum Level

WF
+ LUMO
Hole

Fermi Level + Ionization

Barrier Potential

Photon -
HOMO

ITO Organic
Energy diagram of
OLED device ITO and Organic Layer

RIKEN KEIKI CO., LTD 46

Work functions of several metals
In Air 1)[eV] In UHV2) [eV]
Fe 4.35 4.50
Ni 4.25 5.15
Cu 4.45 4.65
Al 3.60 4.20
Zn 3.80 -
Au 4.78 5.10
1) M. Uda ; Jpn. J.Appl.Phys. 24,284 (1985)
2) D.E. Eastman ; Phys.Rev. B2, 1 (1970)

RIKEN KEIKI CO., LTD 47

 Work functions or Ionization
potentials of EL materials

AC-2 [eV] UPS 1) [eV]

Alq3 5.84 5.8
a-NPD 5.50 5.4
CuPc 4.99 5.2

1) I.G.Hill and A.Kahn, J.Appl.Phys. 86,4515 (1999)

RIKEN KEIKI CO., LTD 48

The temporal change in the work function of
ITO treated with UV-ozone

5.5
Work function (eV)

5.3 UV-ozone 60min

UV-ozone 20min
5.1
UV-ozone 10min
4.9 before cleaning UV-ozone 0min
(boiling in IPA )
4.7
0 10 20 30 40 50 60
duration time after treatment (min)
Reference: Y. Nakajima, T. Wakimoto, T. Tuji, T. Watanabe,
M.Uda, The 10th International Workshop on Inorganic and Organic
Electroluminescence (2000.12.4), Hamamatu, Japan.

RIKEN KEIKI CO., LTD 49

 Change in WF of Al by Cl2 Contamination

Al exposed mixed gas 20sec

(Yield[cps])0.5

(Cl21.34ppm + air) : 4.33eV

Al in air : 4.05eV

Incident Photon Energy [eV]

RIKEN KEIKI CO., LTD 50
 5. Conclusion

1. We can detect and count photoelectrons in the air by

the open counter.
2. We can measure the work function or the ionization
potential of the OLED materials easily.

3. We can estimate the amount of the contamination on

the ITO surface from 1mono-layer to 20nm in the thick.
4. AC-2 is the de facto standard equipment of the work
function measurement on the OLED development.

RIKEN KEIKI CO., LTD 51

 References

[1] H.Kirihata, and M.Uda “Externally quenched air counter for low-energy electron
emission measurements”, Rev. Sci. Instrum. 52 (1981) 68.

[2] M.Uda “Open counter for low energy electron detection”, Jpn. J.Appl. Phys. 24
(1985) 284.

[3] T. Noguch, S. Nagashima and M. Uda “An electron counting mechanism for the
open counter operated in air” , Nucl. Instr. Meth. A342 (1994) 521.

[4] S. Nagashima, T. Tsunekawa, N, Shiroguchi, H. Zenba, M. Uda “Double

cylindrical open counter of pocket size”, Nucl. Instr. Meth. A373 (1996) 148.

[5] A. Koyama, M. Kawai, H. Zenba, Y. Nakajima, A. Yoneda and M. Uda “Electron

counting by a double cylindrical open counter in mixtures of N2 and inert gases of
various concentrations” , Nucl. Instr. and Meth. in Phys. Res. A422 (1999) 309.

RIKEN KEIKI CO., LTD 52

 References

[6] M.Uda, Y.Nakagawa, T.Yamamoto, M.Kawasaki, A.Nakamura, T.Saito, and

K.Hirose ”Successive change in work function of Al exposed to air”, J. Electron.
Spectrosc. and Related Phenom. 88 (1998) 767.

[7] Y. Nakajima, M. Hoshino, D. Yamashita and M. Uda “ Near Edge Structures of

Tetraphenylporphyrins Measured by PESA and Calculated with DV-Xα” , Adv.
Quantum Chem. 42 (2003) 399.

[8] Y. Nakajima, T. Wakimoto, T. Tuji, T. Watanabe, M.Uda “Measurements of the

work function of ITO Using an electron spectroscopy in air and a contact potential
difference method” ,The 10th International Workshop on Inorganic and Organic
Electroluminescence (2000.12.4), Hamamatu, Japan.

RIKEN KEIKI CO., LTD 53