462 IEEE ELECTRON DEVICE LETTERS, VOL. EDLd, NO.

9, SEPTEMBER 1985

High-Barrier Al/p-Si Schottky Diodes

Abstract-Sequential implantationof argon ions and low-energy had been implanted to an Ar dose of l o L 4cm-2. Instead of the
hydrogen ions has been foundto yield Schottky barriers of exceptionally expected recovery from the Ar damage-induced high values of
high values on p-type silicon. The interaction of these ions in Si is quite
Al/p-Si Schottky barrier height, the barrier height increased
complex,involvingdonor defect generation,defectpassivation, and
acceptor dopant neutralization. The apparent synergism of these specific much further, with excellent rectification characteristics. It
implants has resulted in Al/p-Si Schottky diodes with an effective barrier appears that the hydrogen implant has had a synergistic effect
height as high as 0.83 eV,among the highest value reported for any with the earlier Ar implant, and the absence of the correspond-
metal/p-Si contact. ing changes for similarly implanted n-Si samples seems to
indicate additional specific interaction between hydrogen ions
I. INTRODUCTION and the boron acceptors in the p-Si. A thorough investigation
of the phenomenon is underway, and here we report on the
I T HAS now been universally observed that bombardment of
the silicon surface by inertireactive gas or dopant ions as
encountered in ion-assisted etchingideposition or ion implanta-
electrical properties of the resulting very high barrier Alip-Si
Schottky diodes.
tion results in the generation of donor-like defects in a 11. EXPERIMENTAL
PROCEDURE
modified surface region[ 11-[9]. The positive charge residing in
Boron-doped p-type and phosphorous-doped n-type Si
these donor states close to the Si surface alters the electrical
wafers of (100) orientation and 1-10 cm resistivity were
properties of subsequently formed Schottky barriers by lower-
etched and cleaned by standard procedures before implanting
ing the barrier height on n-Si (thereby making the junction
the front side with Ar in a commercial ion implanter. The ion
more leaky) and increasing it onp-Si (thus making the
energy was chosen at 10 keV, the lowest value possible for
junction less leaky). Studies have established the threshold ion
energy and dose for these effects to be as low as 50 eV and- reasonable beam currents, and the dose was varied from 10l2
- 5 X 10” cm-*, respectively [3], [lo]. Removal of the
cm-’ to 1015cm-2 in decade increments SO as to encompass
the threshold dose for amorphization [lo]. The n-Si wafers had
damage-induced donor defects by thermal anneal requires
appropriate n + back implants for ease of ohmic contact
temperatures of the order of 900-1000°C, but alternately it
formation. The H‘ implant was performed in a Common-
has been shown that room temperature passivation of the
wealth Scientific Ion Beam Sputtering (IBS) system at an
defects is possible with a low-energy (-0.4-keV), high-dose
energy of 0.4 keV, with the beam current and implant time
(- lo1*cm-2) hydrogen ion implant following the etching/
selected to yield a net dose of about lo1*cm-2. There was no
implantation step [ 111, This hydrogen passivation process has
intentional heating of the wafers during either implant steps.
also been extended to reduce the dopant activation anneal
Control wafers withoutany implant, wafers withonly Ar+
temperature following ion implantation in Si p-n junction
implant and those with both Ar+ and the “passivating” H +
fabrication [121.
implants were all given a brief etch before A1 metallization
The primary role of atomic hydrogen in (hydrogenated)
step in order to remove any native oxide or other thin
amorphous Si is now quite clear from the numerous studies of
insulating film [ l l ] at the surface. A1 was thermally evapo-
the past decade, but in contrast its influence in crystalline Si
rated on the entire backside of the wafers for ohmic contact
has not been widely investigated andhas been a subject of
and through l-mm-diam shadow masks on the front for the
much controversy. Depending on the energy, dose, and implant
Schottky metallization.
temperature, hydrogen has been shown to create donor levels
[13], neutralize (not simply compensate) acceptors [14], and, 111. RESULTS
AND DISCUSSION
as outlined above, passivate defects created by its own prior
The current-voltage (I-V )data of the Al/Si Schottky diodes
bombardment [111. As a continuation of an investigation of the
made on the control wafers (no Ar+ or H’ implant) show the
dose dependence of the Ar ion implantation damage recovery
expected behavior-rectifying or high barrier onn-Siand
[ 151, we attempted to passivate the Ar ion damage in p-Si and
“ohmic”or low barrier on p-si. The Ar+-only implanted
n-Si withthe low-energy hydrogen implant passivation scheme
samples display progressive barrier height changes with Ar
of [l 11 and obtained startling results for p-type samples that
dose as discussed earlier [lo]. However the (Ar+ + H + )
implant samples show unexpected behavior with uncorrelated
Manuscript received April 17, 1985; revised June 24, 1985. This workwas changes for n-type and p-type material. While the A h - S i
supported in part by the National Science Foundation under Grant ECS- samples showed either modest changes in current or became
8305646 and by the General Electric Company.
The authors are with the Engineering Science Program, The Pennsylvania
very leaky depending on the Ar dose (instead of the anticipated
State University, University Park, PA 16802. passivation and the resultant large increase in barrier height),

0741-3106/85/0900-0462$01.00 0 1985 IEEE

ASHOK AND GIEWONT: HIGH-BARRIER SCHOTTKY DIODES 463

the Allp-Si devices became more rectifying with the best

rectifying behavior (i.e., the highest barrier height 4B)
occurring for an Ar dose of 10l 4 cm-*. The log I- V
characteristics of the Al/p-Si devices with 1014 cm-2 Ar dose
are shown in Fig. 1 with and without the H + implant. The
“ohmic” characteristics of the control samples are also shown
for comparison. The device with only the Ar+ implant shows
improving rectification due to the Ar damage-produced donors
(higher $B), while the one with the additional H + implant
displays excellent rectification with good diode ideality factor
n (1.08 at low currents and 1.25 at high currents) and nearly
voltage-independent reverse current. Using the standard
Schottky diode equation [16], the effective barrier height cpB
has been calculated from the room-temperature saturation
current to be 0.83 eV, quite a high value even for a Schottky
barrier on n-Si andexceptionally high for p-Si. It is among the
highest value reported for any metalip-Si contact [17], and is
exceeded only by the barrier between the refractory metal ‘Hf
(melting point 2230°C as against 660°C for Al)and p-Si,
01
. 0.2 0.3 0.4 0.5
reported at 0.90 eV [18]. The highest barrier height reported VOLTAGE I V )
for Allp-Si contacts is 0.75 eV, but with an intentional ultra- Fig. 1, Forward (FWD) and reverse (REV) log I- V characteristics of Alip-
thin insulating layer (MIS Schottky) [19]. Si Schottky diodes. (a) Control (no implant). (b) 10-keV loi4cm-2 Ar-
implant, (c) 10-keV l O I 4 cm-2 Ar-’ implant followed by 0.4-keV IO’*
Activation energy plots of both extrapolated forward and cm-2 H+implant, The diode area is 7.85 X lo-’ cm-2.
reverse currents yield a lower barrier height of 0.75 eV,
indicating possible presence of an interfacial layer between the
metal and the semiconductor [20]. However in many Schottky AVp-Si
applications the n-factor and saturation current are the most
crucial parameters and so the former effective 4 B of 0.83 eV is N- 14- Ar* ‘mplarp/
more meaningful for assessing the diode performance. Identi- IL

7
cally processed n-type Si wafers yielded Alln-Si Schottky
barrier diodes of effective barriers heights 0.70, 0.50, and N
-P 12-
/
/x N = I 05 x 1 0 cm-’
’~

y 10-
0.57 eV for control, Arf implant, and (Ar+ + H’) implant a
z / j YX , X/ Ar p/
AX. p l o n’
t
k E-N,: 4.6 x 10’4cm-?-’
samples, respectively, as determined from room-temperture
$
I- V data.
’ /’
0
Vi : 0 . 5 7 y x H+ lmplont
<tl.oz x 1015~~-3
Further evidence of the barrier modification is seen in the 1- 4 1 / Vi:0.70V
MHz capacitance-voltage (CV) characteristics ‘of the de-
Ax
vices. The 1/C2 plots for the devices of Fig. l (except the
control, which is too conductive to enable capacitance I
//.
-*
?
’‘-/
I I I I I
-I 0 I 2 3 4 5
measurements) are shown in Fig. 2. The Ar-only implant REVERSE VOLTAGE (VI
sample exhibits two straight-line segments with a higher slope Fig. 2 . 1/C2plots for the diodesof Fig. 1 (b) and (c). NAand V,indicate the
at low voltages, corresponding to compensation of the p-Si net acceptor concentration from the slope and the intercept voltage,
respectively.
acceptors close to the surface by the damage-generated donors
[lo]. In contrast, the 1/C2 plot for the (Ar + H) implant
sample isa single straight line with the slope yielding an electrical data. Clearly synergistic effects are under play since
acceptor dopant concentration of 1.02 x 10“ consist- such high-barrier increases are not seen onp-Siwith H +

ent with the known resistivity of the p-Si bulk. The intercept
voltage Viis determined to be 0.70 eV,giving a barrier height
of 0.94 eV [ 161. This higher value relative to’ the activation
energy is also indicative of the possible presence of a thin
interfacial layer.
The reverse recovery transient of the high-barrier diodes
was studied to detect any minority-carrier injection but the test
failed to reveal any charge storage effects. Thus the absence of
minority-carrier injection tends to confirm that the devices are
indeed Schottky barriers and that the (Ar+ + H + ) implants
have not led to the formation of a p-n junction.
The causes of the high barrier on p-Si under (Ar’ + H + )
implants can onlybe speculated on based solely on the
implant alone. Further the absence of complementary behavior
in the Alln-Si diodes seems to suggest direct interaction
between hydrogen and the boron acceptor as has been reported
in the literature [141. Alternatively the possibility exists for the
formation of a heterojunction betweeq a hydrogenated amor-
phous Si surface layer and the p-Si bulk. Efforts are underway
to understand the process with the use of additional electrical
and surface analytical measurements,
IV. SUMMARY
High-barrier Allp-Si Schottky diodes have been fabricated
using 10-keV Ar ion implantation followed on 0.4-keV atomic
hydrogen implantation. The technique is simple and involves
464
no thermal processing. The effective barrier height obtained is
0.63 eV, the highest value reported for any conventional
metal/p-Si contact. The exact cause of the observed barrier
changes is at present unknown and is being investigated.
ACKNOWLEDGMENT
The authors are grateful to Dr.A. Mogro-Camper0 of
General Electric Corporate Research and Development,
Schenectady, for furnishing the Ar-implanted samples and to
R. Singh for assistance with the hydrogen implants.
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