Sample

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

Contents
3. The data analysis
5. Conclusion

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
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.
Contents
We employed the open counter for the detector of AC-2.
3. The data and the analysis
5. Conclusion

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.

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.
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

Quenching Grid
Suppresser Grid 0 count
The open counter is composed of an anode, a quenching grid,

suppresser grid and electric circuits.

High Voltage Supply

Preamplifier
Scaling circuit
and Rate meter
Quenching circuit

Quenching Grid
15mm
Sample
Sample holder
The test sample is mounted on the sample stage which is kept at earth potential (0V).

High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+100V Quenching circuit
+80V
Quenching Grid
Sample
Sample holder
Suppresser Grid is kept at +80V, Quenching Grid is +100V, Anode is +2900V.

Measurement Reference: H.Kirihata, and M.Uda; Rev. Sci. Instrum. 52 (1981) 68.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
Quenching Grid
UV Light
Sample
Sample holder
Monochromatized UV photons are used to excite photoelectrons from the sample surface.

High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
Quenching Grid
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.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
Quenching Grid
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.
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.

High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
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.
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.
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.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
Quenching Grid
UV Light
Sample
Sample holder
The electron avalanche makes a small electric pulse on anode.

This pulse is detected and counted as one electron.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter

Quenching Grid
UV Light
Sample
Sample holder
When the quenching circuit detects the electric pulse, +400V is applied in place of
+100V to the quenching grid.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter

Quenching Grid
UV Light
Sample
Sample holder
This reduction of the electric field around the anode causes the electron avalanche to be
quenched.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
-30V
Quenching Grid
UV Light
Sample
Sample holder
On the other hand, -30V is applied in place of +80V to the suppressor grid.

Ion
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
-30V
Quenching Grid
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.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
Anode
3ms
+400V
-30V
Quenching circuit
Suppresser circuit Display

Quenching Grid
UV Light
Sample
Sample holder
Such voltages applied to the quenching grid and suppressor grid are kept for 3msec
i.e. the quenching time.
High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
Anode
3ms
+400V
-30V
Quenching circuit

Quenching Grid
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.

High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
Anode
3ms
+400V
-30V
Quenching circuit

Quenching Grid
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.

High Voltage Supply
+2900V Preamplifier
Scaling circuit
and Rate meter
+80V
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.

High Voltage Supply

Preamplifier
Scaling circuit
and Rate meter
Quenching circuit

Quenching Grid
Suppresser Grid
e
O2 21 count
UV Light
e
Sample
Sample holder
Now the counter is ready to count the next electron.

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.

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

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

Contents
5. Conclusion

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

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

Vacuum level
Work function
Ionization Work function
Ionization Ionization
Work function
potential potential potential
Energy
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.

UV photon e Photoelectron e
e
Vacuum level
Energy
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.

e
Vacuum level
Ionization
Ionization Ionization
potential
potential potential
Energy
Fermi Level
Therefore, the photoemission threshold energy is the ionization potential.

e
Vacuum level
Ionization
Work function Ionization Ionization
potential
potential potential
Energy
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.

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.

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.

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

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.

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.

The relationship between the slope and film thickness
- - Thin contamination film

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

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

Contents
5. Conclusion

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

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)

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)

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.

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

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.

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.

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.

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Photo-electron spectrometer in air

The counting mechanism of the photoelectron

RIKEN KEIKI CO., LTD 1

RIKEN KEIKI CO., LTD 2

RIKEN KEIKI CO., LTD 3

45cm Light source part 120cm

RIKEN KEIKI CO., LTD 6

6.24x106cps (62 million/s)

This method is are

RIKEN KEIKI CO., LTD 7

Open counter was invented in 1979 by Uda and Kirihata.

High Voltage Supply

Anode Suppresser circuit Display

High Voltage Supply

Anode Suppresser circuit Display

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

RIKEN KEIKI CO., LTD 9

High Voltage Supply

Anode Suppresser circuit Display

RIKEN KEIKI CO., LTD 10

High Voltage Supply

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

RIKEN KEIKI CO., LTD 11

High Voltage Supply

RIKEN KEIKI CO., LTD 12

High Voltage Supply

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

High Voltage Supply

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

RIKEN KEIKI CO., LTD 15

High Voltage Supply

Electric Anode surface

Electric Anode surface

N2+ N+2 O+2

High Voltage Supply

The electron avalanche makes a small electric pulse on anode.

High Voltage Supply

Anode Suppresser circuit Display

High Voltage Supply

Anode Suppresser circuit Display

High Voltage Supply

RIKEN KEIKI CO., LTD 22

High Voltage Supply

High Voltage Supply

Suppresser circuit Display

High Voltage Supply

Suppresser circuit Display

RIKEN KEIKI CO., LTD 25

High Voltage Supply

Suppresser circuit Display

RIKEN KEIKI CO., LTD 26

High Voltage Supply

RIKEN KEIKI CO., LTD 27

High Voltage Supply

Anode Suppresser circuit Display

Now the counter is ready to count the next electron.

RIKEN KEIKI CO., LTD 28

RIKEN KEIKI CO., LTD 29

3.4eV 6.2eV sample photodiode

Light source part Measuring part

RIKEN KEIKI CO., LTD 30

3.4eV 6.2eV photodiode