38 Nuclear Instruments and Methods in Physics Research B37/38 (1989) 38-44

North-Holland, Amsterdam

A HEAVY NEGATIVE ION SPU’ITER SOURCE: PRODUCTION MECHANISM OF NEGATIVE

IONS AND THEIR APPLICATIONS

Junzo ISHIKAWA
Department of Electronics, Kyoto Vnioersity, Sakyo-ku Kyoto 606, Japan

Heavy negative ions can be produced by sputtering a metal surface at high efficiency by means of a secondary ion emission
process. The most important factor for obtaining high negative ion production efficiencies is to maintain approximately one-half
monolayer of Cs on the sputter target which produces a minimum in the surface work function. In a dynamic situation in which the
surface is being bombarded by heavy ions, the cesium coverage is determined by a balance between the incoming and outgoing
cesium fluxes. The supply of additional cesium to the surface and control of the target temperature are then essential for high
negative ion production efficiency. The Neutral and Ionized Alkaline metal Bombardment type heavy Negative Ion Source
(NIABNIS) in which a continuous negative ion current of a few hundred pA for several elements can be extracted, can be directly
used for applications in materials science, such as negative ion beam deposition and negative ion implantation.

1. Introduction metal surface at a velocity quite a bit higher than the

thermal velocity. This phenomenon, called secondary
Recently, heavy negative ion sources [l-3] whose negative ion emission, is the primary production mecha-
currents range from a few pA to a few hundred yA nism in sputter-type heavy negative ion sources.
(continuous) or to 10 mA (pulsed), have been developed Consider, for example, an extractable ion current
for producing negative ion beam from various elements produced by means of secondary negative ion emission
by means of a secondary negative ion emission process. as illustrated in fig. 1. The negative ion current ex-
The current densities from such sources are comparable tracted after passing a low gas pressure region is given
to those of positive ion sources. This means that the by
ionization efficiency for negative ions is relatively high
I-= I+Sn- exp( -nOLo,), (1)
although negative ions are considered fragile because of
their low electron affinities in comparison with ioniza- where I+ is the positive ion current for sputtering, S is
tion potentials. Negative ions are formed by a shift of the sputtering yield at the sputter target by the positive
an electron between the Fermi level of the metal surface ion, 7)- is the negative ion production probability on a
and the electron affinity level of the metal atom during metal target surface, or is the total electron detachment
the sputter ejection process [4,5].
Since high heavy negative ion currents are easily
obtained, the source can be used not only for tandem SPUTTERING METAL INCIDENT ION

accelerators but also in various fields, including in-

dustrial applications, such as negative ion beam deposi-
tion and negative ion implantation. However, only a INCIDENT ANGLE
few examples of negative ion applications in materials
science have been reported.
Heavy negative ion production in the NIABNIS has
been investigated for optimum conditions for produc-
tion. In order that negative ion beams can be more
widely used, investigations of heavy negative ion pro-
0.0..
duction and the interaction between negative ions and LOW GAS PRESSURE REGION
solids and gases are also included in this report. ( GAS DENSITY : no )
4--L_
SPUTTERING
2. Mechanism of heavy negative ion production (SPUTTERING )
\
VIELD : S NEGATIVE ION PRODUCTION
ON METAL SURFACE
2.1. Secondary negative ion emission ( PROBABILITV : ‘L- )

The negative ion production efficiency may be rela- Fig. 1. Illustration of the secondary negative ion emission
tively high when an atom leaves a low work function processes by sputtering.

0168-583X/89/$03.50 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
 J. Ishikowa / A heavy negative ion sputter source 39

cross section for the negative ion, and no is the gas with respect to the normal of the target surface, showing
density in the path of the negative ion beam of length a maximum at an incident angle of 50”~80” in prac-
L. To obtain an intense negative ion beam, If, S and tice. For example, the sputtering yield at an incident
Q- should be high, and no and L as low as possible. angle of 60” is 2-3 times that at O”. Therefore, the
sputtering yield is increased when a large incident angle
2.2. Sputtering and/or a rough target surface is used.

During sputtering, neutral atoms of relatively high

22.4. Sputtered azom energy
velocity are generated at the sputter target surface. The
The energy distribution of sputtered particles shows
sputtering yield S should be large; this depends on the
a peak at an energy level of L&/2 j7,8J. The energy of
incident ionic mass, the incident ion energy and the
the sputtered particles cannot be changed intentionally.
incident angle with respect to the normal of the surface.
The velocity of the sputtered atom is also important in
negative ion production process. 2.3. Negative ion production probability on metal surface
In Sigmund’s model, the sputtering yield S is given
by 1671 Rasser et al. have introduced a fairly simple equation
giving the negative ion production probability applied
(2) in the case of a particle emitted from a metal surface.
The equation is expressed as follows [4]:
where U, is the sublimation energy, C, is the coefficient
related to the target, .S,( E) is the elastic stopping power
of the incident ion, and G( M,/M,) is the efficiency of
energy transfer. Ml and M2 are the atomic masses of where cp is the work function of the metal surface, E, is
the incident ion and the target material. respectively. the electron affinity, u,, is the velocity component
normal to the metal surface, and a is a coefficient.
2.2. I. Incident ionic mass
Theoretical values of v- have not been calculated for
The efficiency of energy transfer OLincreases with
various heavy atoms. However, from experiments, the
increasing M,/M, when M,/M, is larger than 1. How-
value of q- for a carbon atom can be estimated to
ever, a is nearly constant when M2/Ml is smaller than
reach about 0.1, which is comparable to or higher than
1. The elastic stopping power S,,(E) has an incident
the gas efficiency in plasma type positive ion sources.
projectile mass dependence, especially at relatively high
The negative ion production probability is strongly
projectile energies E. As a result, at an energy level
dependent on the work function of the metal surface,
higher than several keV, S,(E) increases largely with
the velocity of the emitted particles, and the electron
M,. Heavy ions such as Cs+ and Xe* should then be
affinity of the atom. The electron affinity is an inherent
used for sputtering. However, at an energy level lower
value of an atom, and a sputtered atom has an average
than about 1 keV the sputtering yields for various
velocity related to its sublimation energy. Thus, the
incident ions, for example, Ar+, Ne+, and Xe+, are not
negative ion production efficiency can be enhanced
so different because of the weak atomic mass depen-
significantly by lowering the work function of the metal
dence of S,(E).
surface intentionally.
2.2.2. Incident ion energy
Onfy the elastic stopping power S,,(E) depends on 2.3.1. Work function of ~~s~urn-covered metal surface
the incident ion energy E. It increases approximately Although cesium has the lowest work function (1.81
proportional to E to Eli3 at an energy level lower than eV) of all elements, the work function of the cesium-
about 1 keV and approaches a plateau at a few tens of covered surface is generally lower than that of bulk
keV when a heavy ion is used for sputtering. At low cesium [9-111. The work functions of the. cesium-covered
incident energies, the sputtering yield is increased effi- surface for various metals were calculated by Alton [9]
ciently with increasing incident energy. At high incident and measured by Graham [lo]. The general behavior of
energies, a high sputtering yield can be obtained but the the surface work function as a function of cesium
input power efficiency of the sputtering is decreased. coverage is illustrated in fig. 2. The work function of the
The sputtering yields for high energy heavy ions such as base metal substrate is $o. The surface work function
Xe+ and Cs+ are over a few atoms per ion for most decreases with increasing the cesium coverage, reaching
metals. a minimum value of +“,, (1.37-1.76 ev) at a coverage
of S,, (about 0.6 atomic layer) [lo]. It than increases
2.2.3. Incident angIe with the cesium coverage up to a value of +( B = 1) of
The efficiency of energy transfer a has approxi- 1.56-2.15 eV [lo]. Since no further cesium atoms adhere
mately a secant p dependence on the incident angle fi to the surface above approximately room temperature

II. ION SOURCES

40 J. Ishikowa /A heavy negative ion sputter source

where J, is the heavy positive ion current density

before bombardment.
Point Be in fig. 2 takes place at the point where J,,
is equal to the thermal evaporation rate of cesium atoms
from the bulk cesium. The temperature corresponding
to 0, is between room temperature and 100° C, de-
pending on J,-,. This situation is illustrated in fig. 3; the
temperature is T,. On the other hand, point 0,, shown
in fig. 2, takes place at the crossing point of the Jcs line
and the curve where the bond between Cs and the target
atom (tungsten in the case of fig. 3) is broken. The
I I I I corresponding temperature is T2. When the target tem-
I I
emin ; O_O ; Cs multb-layer perature is kept between T, and T, the surface work
function is so low that heavy negative ions can be
CESIUM COVERAGE produced at the highest efficiency. For the crossing
Fig. 2. General behavior of the surface work function as a points Tl, T, to exist, J,, should be positive. S,, is
function of cesium coverage. considered to be greater than 1 under usual operating
conditions, except for low sputtering yield conditions in
due to the weak Cs-Cs binding energy (0.45 eV), no which especially low sputtering yield materials such as
further change in the surface work function is usually carbon are used, or the incident energy is quite low.
observed. When the target is cooled too much (for Additional neutral cesium supply or spray onto the
example, to 77 K), a cesium multilayer will be formed. sputter target is then essential.
In this case the work function is changed to the bulk Fig. 4 shows the C- ion current plotted for various
cesium work function +cc, (1.81 ev), and the sputtering methods of cooling the sputter target: by liquid nitro-
yield of the target material decreases because of the gen, by liquid carbon dioxide, and not cooled. When the
thick cesium atomic layer. carbon target was cooled too much, the surface temper-
Since a lower work function of the sputter target ature was below @a, so negative ion production yield
surface increases the negative ion production efficiency, was decreased. Fig. 5 shows C ion production yield as
the region of cesium coverage for high efficiency nega- a function of the sputter target temperature whose value
tive ion production is between 0, and 8, as shown in is relatively high. The fact that the negative ion produc-
fig. 2. tion efficiency is rapidly reduced at a temperature of
around 600° C implies that the cesium monolayer is
2.3.2. Quantity of cesium coverage at various target tem- broken at a temperature higher than 600°C. This tem-
peratures perature is related to the binding energy between Cs
In sputter-type heavy negative ion sources, cesium and the sintered graphite target.
atoms are continuously supplied onto the sputter target When the thermal conductivity of the target material
surface as neutral particles or from a cesium ion beam. is low, the temperature of the sputter target surface is
At the same time, cesium atoms on the sputter target increased by ion bombardment. In fig. 6 the “B- ion
surface are sputtered by cesium or heavy positive ion currents are plotted for the same three methods of
bombardment, and thermally evaporate from the
surface. Here, in order to easily understand the dynamic
situation of cesium coverage, first terms without ther-
mal evaporation are discussed. Assuming the thermal
evaporation is neglected, the difference between incom-
ing and outgoing cesium fluxes, which is recalculated as
equivalent current density, is given for cesium ion
bombardment by
J,, = J,-,+ + J,,o -J,,+&, >
where J,,+ is the cesium ion current density before
bombardment, J,,o the supplied neutral cesium, and
Sc, the sputtering yield of cesium atoms on the sputter
-200 0 200 LOO 600 800 1000 1200
target by ion bombardment.
METAL TEMPERATURE (‘C 1
For heavy positive ion bombardment the difference
between incoming an outgoing cesium fluxes is Fig. 3. Relationship between metal surface temperature and
cesium coverage as a function of the incident Cs flux. The
sputtering target material is assumed to be tungsten.
 J. Ishikawo /A heavy negatioe ran sputter wurce 41

l NOT COOLED /

0 :NOT COOLED

SUPPRESSOR VOLTAGE _
1.0 k”

I **,.I I I L t ‘_
05 1 5 10
TARGET CURRENT (mA)

Fig. 6. “B- ion current plotted for various methods of cool-

Fig. 4. C- ion current plotted for various methods of cooling
ing: (a) sintered boron target: liquid nitrogen (A). liquid carbon
the sputtering target; liquid nitrogen (A,), liquid carbon dioxide
dioxide (0) and not cooled (0): (b) sintered boron target
(o), and not cooled (0). The target current is about twice the
mixed with aluminum (0).
incident Cs+ ion current.

efficiency of the *IBM ion production was substantially

cooling the sintered boron target as used in the case of
increased even when the target electrode was not cooled.
carbon, shown in fig. 4. Since boron has a very low
Fig. 7 shows the negative copper ion current as a
thermal conductivity of 0.32 W/(cm K), the target
function of the cesium oven temperature for neutral
temperature gradually rises without cooling. The “B-
cesium spray under the condition that the cesium ion
ion yield was small when the target was not cooled. On
current to the sputter target is constant. Since copper
the other hand, the efficiency was substantially in-
has a very high sputtering yield of more than 10 at an
creased by cooling the target with liquid nitrogen. In
incident cesium ion energy of 17 keV and the surface
fig. 6 the “B- ion current is also shown when the
cesium atoms would be sputtered with sputtered copper
sintered boron target was mixed with aluminum to
atoms, ScIs in also considered to be large. Therefore, the
improve the thermal conductivity, It is noted that the
effect of the neutral cesium spray is remarkable with
only a small increment in oven temperature (about
ZO”C), which corresponds to a few times increment of
the neutral cesium supply.
_ 0
There are two methods for supplying neutral cesium
to the surface: a neutral cesium flux is sprayed to the
sputter target surface in a high vacuum, or the sputter

220 230 240

SPUTTERING TARGET TEM~ATU~ (Y:f CS OVEN TEMPERATURE f%)
Fig. 5. C ion production yield as a function of the sputter Fig. 7. Cu- ion current as a function of cesium oven tempera-
target temperature for temperatures higher than 400 OC. ture for neutral cesium spray.

Il. ION SOURCES

42 J. Ishikawa / A heavy negative ion spatier source

target is placed under relatively high cesium vapor production are as follows:
pressure. In the latter case, since a high target voltage i) control of the target temperature;
cannot be applied, a high current density for sputtering ii) additional neutral cesium supply;
would be required. iii) high positive ion current for bombardment;
iv) high ion energy for bombardment;
2.4. Electron detachment of negative ions v) high incident bombardment angle with respect to
the normal of the target surface.
When negative ions pass through a low gas pressure By consideration of these requirements, a neutral
region, some suffer electron detachment by collisions and ionized alkaline metal bombardment type heavy
with the gas particles. The main interactions between a negative ion source (NIABNIS) has been developed
negative ion and a neutral particle are the following: [3,12-141. This ion source is operated in dc mode. Fig. 9
single electron detachment and double electron detach- shows a schematic diagram of the source. NIABNIS
ment. Thus, the total electron detachment cross section consists of a cesium plasma ion source, a suppressor, a
err shown in eq. (1) is given by the sum of these two target electrode (sputter target), a negative ion extrac-
electron detachment cross sections. tion electrode, and an einzel lens. The cesium plasma
Fig. 8 shows some examples of single and double ion source is an axial magnetic field extraction-type
electron detachment cross sections as a function of microwave ion source with a permanent magnet [15],
negative ion energy. The single electron detachment which can deliver a cesium ion current of l-10 mA; a
cross section up0 is quite a bit larger than the double controlled neutral cesium flux can also be delivered by
IL+, especially in the low energy range; thus (~_a is the varying the cesium oven temperature. Neutral cesium
most important value. Also the single electron detach- supply onto the sputter target surface helps to provide a
ment cross section is several times larger than the low work function surface.
charge exchange cross section of the positive ion for the The target electrode and the suppressor function as
same element at an energy of 5-50 keV. If a C- ion is an accel-decel ion extraction electrode system for the
passing through a region whose gas pressure and length cesium plasma ion source. With this configuration, the
are 5 X 10e3 Torr (argon) and 6 cm, respectively, the high energy cesium ion beam (lo-20 keV) can be trans-
C- current passing out of the region is decreased to ported to the sputter target without loss. The incident
about one-third the original current. Thus, negative ions angle of the cesium ion beam with respect to the normal
are easily broken, and must not be transported through of the sputter cone surface is about 60”. The tempera-
a high gas pressure region. ture of the target electrode is controllable by flowing a
coolant through a tube soldered to the cone holder.

3. High current heavy negative ion source NIABNIS

From the above-mentioned discussions, the neces-

sary requirements for high current heavy negative ion
$8 ;;‘;$f+ENT

0 F’F’f?$MA~GNETIC 0
0 NON-FERROMAGNETIC
\
UATWAL
’ o-‘+----7

LLL
0 INSULATOR
A : Si-+Ar
o C-+Ar

MAAAA A A A A *
~0000 00 0 0 0 0

SINGLE ELECTRON
DETACHMENT

A A’
A
af30°
LOO
om
OOA DOUBLE ELECTRON
DETACHMENT
0 A
h
Fig. 9. Neutral and ionized alkaline metal bombardment type
heavy negative ion source (NIABNIS). (1) Sealed coaxial con-
nector, (2) coolant, (3) sheath heater, (4) boron nitride, (5)
16’70hiYhEd+ coolant, (6) cesium vapor, (7) antenna, (8) permanent magnet,
ION ENERGY (keV 1 (9) boron nitride or Macor insulator, (10) suppressor, (11)
Fig. 8. Examples of single and double electron detachment sputter target, (12) target electrode, (13) cooling tube, (14)
cross sections as a function of negative ion energy. negative ion extraction electrode, and (15) einzel lens.
 J. Ishiknwa / A heouy negative ion sputter murce 43

Table 1 negative ion beam energy ranges used were 10-1000 eV

Negative ion currents obtained from the NIABNIS for C- ion beams and 40-400 eV for CT ion beams.
The current density was 30-100 PA cmm2. The depen-
Ion species Ion current
dence of carbon film properties on ion beam energy and
(PA)
ion species (C- and CT) is quite strong [14,16,17]. Most
C- 135
of the properties such as optical band gap, resistivity,
C; 200
atomic density and thermal conductivity show a peak at
CU_ 320
Si- 170 an ion beam energy of 100-200 eV; the maximum
Ni- 59 values of these properties for C; deposition films are
B- 15 quite a bit higher than those for C deposition films.
B, 20 Thus, with negative ion beam deposition optimum con-
ditions can easily be chosen for high quality film forma-
tion.

Table 1 lists the mass-separated negative ion cur- 4.2. Negative ion implantation
rents produced by the NIABNIS.
In a negative ion implanter, an electron beam, ex-
tracted from the negative ion source together with a
4. Applications of negative ion beams in materials sci- negative ion beam, should be removed before high
ence voltage acceleration.
A prototype negative ion implanter has been devel-
Sufficiently intense negative ion beams, as needed oped by the author et al. [13], whose maximum energy is
for applications in materials science, have been pro- 60 keV; some fundamental experiments have been con-
duced by NIABNIS or other sputter-type negative ion ducted. The distribution of implanted carbon atoms in
sources [l-3]. Advantages in using negative ion sources Si substrate, using negative ion implantation, follows
for materials science applications are as follows: i) the distribution predicted by the LSS theory and is,
intense negative ion currents of some elements can be thus, considered to be the same as that for positive ion
obtained more easily than equivalent currents from implantation. One electron of a negative ion is easily
positive ion sources; ii) no gas is required for sputter- detached by bombardment on a solid surface. Thus, the
type negative ion source operation; thus, beam losses secondary electron emission coefficient is roughly the
are reduced and it is not necessary to use a high speed sum of one and a value proportional to the momentum
pumping system. of the negative ion. Therefore, charge-up problems, in
Negative ion beams can be directly used for ion the case of negative ion implantation into insulators,
beam deposition and ion implantation, like positive ion would be smaller than those experienced with positive
beams. Here mass-separated negative carbon ion beam ion implantation into large insulating surfaces.
deposition and negative carbon ion implantation by
using NIABNIS are reviewed.
5. Concluding remarks
4.1. Negative ion beam deposition
Intense heavy negative ion beams can be obtained at
In a mass-separated negative ion beam deposition relatively high efficiencies by a rather simple method.
system, ion beam deceleration is needed to produce a The negative ion current densities for some elements
very low energy ion beam. Generally oppositely-charged from negative ion sources are comparable to or higher
particles in the deceleration field are accelerated to the than those positive ion current densities from positive
substrate; in positive ion beam deceleration, this phe- ion sources. Negative ion beam applications, such as ion
nomenon, that is, electron acceleration, may be present beam deposition and ion implantation, are expected to
because many secondary electrons are sometimes gen- be popular in the near future.
erated by ion beam bombardment on electrodes. How-
ever, in negative ion beam deceleration, the amount of
positive ions generated in the deceleration field region
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II. ION SOURCES

44 J. Ishikowa / A heavy negative ion sputter source

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