Dopant Activation and Deactivation Phenomena
During Advanced Millisecond Anneal Cycles
P. J. Timans*, M. Hagedorn, C. Pfahler, A. Cosceev,
and M. Zwissler
Mattson Thermal Products GmbH
Daimlerstrasse 10, 89160 Dornstadt, Germany
*paul.timans@mattson.com
A. Joshi
Active Layer Parametrics, Inc.
Los Angeles, CA 90024, USA
Abstract—Achieving very high concentrations of electrically
active dopants is essential for minimizing parasitic resistances in
advanced CMOS devices. Existing methods are severely
challenged by the limits on electrical activation of dopants
imposed by their solid solubility, electrical deactivation,
segregation at silicon/SiO2 interfaces and by the need to limit
process temperatures to allow integration of new materials. This
paper investigates the factors in the design of millisecond
annealing (MSA) temperature cycles with peak temperatures
below 1200ºC that can still improve electrical activation of high
doses of As or P atoms ion-implanted in preamorphized silicon.
High dose P doping was found to display better activation than
could be achieved with As, where activation decreased for higher
doses. MSA pulse length was found to have a weak influence on
activation. Higher preheat temperatures degraded activation, as
might be expected from the consequent increase in the post-pulse
thermal budget. The effects of different cooling profiles after the
pulsed heating were investigated, but were found to be
insignificant for cooling cycle temperatures < 725ºC. The
preheating conditions offer further room for optimization
because they can affect dopant diffusion and activation during
the regrowth of the amorphized layer.
Keywords—Millisecond annealing, doping, electrical activation,
deactivation, diffusion, segregation, SPE, arsenic, phosphorus
I. INTRODUCTION
The continuing progress of scaling CMOS technology to
smaller feature sizes faces a severe challenge from
performance loss caused by increasingly significant parasitic
resistances in the transistor source/drain (s/d) regions,
especially at the contacts [1]. Fermi-level pinning at the metal-
semiconductor interface makes it difficult to decrease the
contact resistance by reducing the potential barrier. A very high
concentration of electrically active doping would help, but
traditional doping methods face difficulties, including the need
to exceed the equilibrium dopant solubility while strongly
limiting the thermal budget to prevent excessive dopant
diffusion [2]. Millisecond annealing at high temperatures
allows efficient dopant activation with well controlled limits on
978-1-5090-2024-9/16/$31.00 ©2016 IEEE
L. Rubin
Axcelis Technologies
108 Cherry Hill Drive, Beverly, MA 01915, USA
diffusion, but integration of materials such as SiGe requires
lower annealing temperatures [3]. Furthermore, subsequent
thermal exposure tends to deactivate high concentrations of As
or P, which form electrically inactive complexes through
interaction with point defects [2-8]. Dopants can also segregate
to interfaces, reducing the effective doping [9-14]. There have
been remarkably few experimental studies of deactivation
during very short high temperature cycles, such as the cooling
period immediately after the peak temperature of a millisecond
anneal. This paper investigates the effects of various features of
the MSA cycle, including the preheat temperature, the pulse
shape and the post-pulse cooling cycle on heavily-doped n-type
layers formed by ion implantation of As or P in silicon.
II. EXPERIMENT
300 mm p-type (100) Si wafers with resistivity of 1-50
Ωcm were preamorphized by a combination of 6 and 15 keV
implants of 2x1015 Si+/cm2, creating a 50 nm-thick amorphous
layer to suppress channeling of subsequent doping implants.
The wafers were dipped for 30 seconds in 200:1 HF to remove
any native oxide immediately prior to the As and P implants.
As was implanted at 2 keV at a beam current of 8.5 mA, and P
was implanted at 1 keV at a beam current of 10.5 mA. Doses
were either 1015/cm2 (samples As1 and P1) or 3x1015/cm2
(samples As3 and P3) to simulate n+ s/d implant conditions.
The wafers were annealed in Mattson Technology’s Millios®
MSA tool, which provides real-time measurement and control
of the temperatures of both the front and the back surfaces of
the wafer. A variety of thermal cycles was explored, as
summarized in Table I. The “centre” condition was with a
preheat ramp at 150 K/s where the two lamps below the wafer
uniformly heat it to an intermediate temperature (Ti ) of 725ºC,
and then a pulse of energy from the bank of four lamps above
the wafer heats the surface to a peak temperature (Tp) of
1175ºC for a nominal 0.7 ms duration, defined by the pulse
width 50 K below the peak temperature. After the pulse, the
surface cools rapidly by thermal conduction to the substrate
beneath it, until the wafer reaches a uniform temperature, Tpost,
below which it cools at a slower rate limited by radiative heat
 TABLE I. MATRIX OF EXPERIMENTS AND MEASURED RS VALUES (SAMPLES WITH RS IN BOLD WERE ALSO CHARACTERIZED BY SIMS)
Anneal Type Anneal Conditions Rs (Ω/sq.)
Tp (ºC) Ti (ºC) Pulse Length (ms) Cooling Cycle P1 P3 As1 As3
Centre 1175 725 0.7 Normal 621.5 437.2 614.6 657.4
Tp=1200C 1200 725 0.7 Normal 609.4 422.4 611.1 613.5
Ti=775C 1175 775 0.7 Normal 693.0 527.2 685.8 759.1
0.2 ms 1175 725 0.2 Normal 648.5 488.7 629.2 646.6
1.0 ms 1175 725 1.0 Normal 600.3 436.1 616.8 659.1
0.2 ms, Slow 1175 725 0.2 Slower 648.5 488.8 636.5 642.4
0.7 ms, Slow 1175 725 0.7 Slower 614.8 444.1 624.1 647.4
1.0 ms, Slow 1175 725 1.0 Slower 605.5 430.1 621.6 668.6

loss. Other test conditions included a higher Tp (1200ºC), a
higher Ti (775ºC), and different pulse lengths. In some cycles,
the normal cooling cycle was delayed by adding a 1 s-duration
“soak” step at 725ºC. Fig. 1 shows pyrometer readings of the
wafer’s surface temperature for some typical anneals. Fig. 1(a)
emphasizes the “slower” parts of the heating cycle, including
the ramp to Ti and the cooling from Tpost, which is higher than
Ti because of the energy absorbed from the pulse. Longer
pulses and larger temperature jumps, (Tp-Ti), require larger
pulse energies, and as a result Tpost varies with the type of
anneal. Fig.1(b) shows the three types of pulsed heating used
here, with nominal durations of 0.2, 0.7 and 1.0 ms. The As-
implanted wafers were annealed in N2 with 4% O2, whereas the
P-implanted wafers were annealed in N2 with <20 ppm O2.
After annealing, the sheet resistance (Rs) was measured by a
KLA-Tencor RS100 4-point probe with type-D probes. Doping
profiles were characterized by secondary ion mass
spectrometry (SIMS), using a PHI ADEPT 1010 SIMS tool
under low energy Cs primary ion bombardment. SIMS was
850
(a)
Temperature (ºC)
also used to deduce the surface oxide thicknesses, by assuming
that these equal the depths where the oxygen signal drops to
half its peak value.
III. RESULTS AND DISCUSSION
Fig. 2 shows SIMS profiles from the four types of implant
for a subset of the annealing conditions in Table I, together
with approximate locations of the Si/oxide interfaces. The
oxides on the as-implanted samples were ~1.2 nm thick. After
annealing they varied between 1.2 and 1.9 nm. The very
shallow doping conditions lead to large fractions of the
implanted doses being in the surface oxides or at the interface.
For as-implanted samples, the fractions are ~5% and ~20% for
As and P respectively and they rise to ~10% and ~30% after
annealing. The total doses after annealing were within 10% of
the as-implanted doses for most samples, suggesting that that
there is relatively little dopant loss to the gas ambient. The
exact nature of the MSA cycle had little impact on the profiles.
All the profiles show diffusion after annealing, with a shift of
dopant towards the surface, causing a pile-up of dopants at the
Centre Si/oxide interface. There is also some diffusion in the tails of

Tp=1200C
Ti=775C
the implants. In the As1 and P1 cases, the annealed profiles are
800 0.2 ms all rather similar, with just small differences in the tails of the
1.0 ms P1 doping distributions. For the As3 and P3 data, the
0.7 ms, differences are slightly greater. For most samples, the peak in
750 Slow Cool dopant concentration near the surface is slightly larger for the
Ti=775ºC condition. In the P3 sample with Ti=775ºC there is
700 less tail diffusion and it had also lost almost 20% of the P dose
after the anneal. Shifts of dopants towards the surfaces have
-0.5 0 0.5 1 1.5 2 2.5 3 frequently been observed in studies of low-energy As and P
Time (s) implanted silicon [9-14]. One explanation involves “snow-
1200
Centre (0.7 ms) ploughing” of dopant into the amorphous silicon (a-Si) as it
(b) crystallizes by solid-phase epitaxy (SPE) [10,11]. Other studies
Temperature (ºC)

1100 0.2 ms
1.0 ms have focused on traps that could immobilize dopant diffusing
1000 towards the surface, or the influence of point defect fluxes that
could also drive uphill diffusion towards the surface [12-14].
900 There is evidence that some of the surface doping peak may be
electrically active [9].
800
Table I includes Rs results for the four implants and the
700 different annealing schemes. The Rs values for the As1, P1 and
1 2 3 4 5 6 7 As3 cases are quite similar, but Rs is notably lower for the P3
Time (ms) samples. One difficulty in interpreting Rs values is that they are
Fig. 1. Temperature-time profiles of typical MSA cycles, as measured affected both by the degree of electrical activation and by the
by the pyrometer on the Millios. (a): Detail of the “slow parts” of the shapes of the doping profiles. However, Rs data can be
millisecond annealing cycles. The pulsed surface heating occurs at 0 s., combined with the SIMS profiles to estimate the peak values of
but is too short to seen on this timescale. (b): The three types of surface
heating pulses used in the experiments.
the electrically active dopant concentrations, although this
 22
10
As-Imp. As-Imp. As-Imp. As-Imp.
Centre Centre Centre Centre
Concentration (cm )

21 Tp=1200C Tp=1200C
-3

10 Tp=1200C Tp=1200C
Ti=775C Ti=775C

Oxide Interface

Oxide Interface
Ti=775C Ti=775C
1.0 ms 1.0 ms
Oxide Interface

Oxide Interface
1.0 ms 0.7 ms, 1.0 ms 0.7 ms,
20
10 Slow Slow

19
10

P1 P3 As1 As3
18
10
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
Depth (nm) Depth (nm) Depth (nm) Depth (nm)

Fig. 2. SIMS profiles for the four types of n-type doping samples and different types of MSA cycle.

approach requires several assumptions [11]. The first is that the and As1 cases and much lower for the As3 cases. Increasing
carrier profile matches the SIMS profile up to a fixed electrical the As dose decreased the carrier density, suggesting that it is
activation limit, Cmax, above which the As or P is electrically not just inefficient, but also counterproductive. Previous
inactive. The second assumption is the validity of the published studies have shown that SPE gives similar activation for a wide
data linking the doping concentration and the electron mobility, variety of implants, so one might expect SPE regrowth of the
which may not apply in these samples [15]. The third a-Si layers here to also give similar activation [8]. However,
assumption is that the carrier distribution starts at a depth equal the final activation could be reduced by dopant deactivation
to the surface oxide thickness deduced from SIMS. Fig. 3 processes and by segregation to the oxide interface. For
shows examples of the analysis for each type of implant, for anneals with Ti=725ºC, the activation is only weakly affected
the “centre” annealing condition. Where SIMS profiles were by the anneal condition. Higher Tp (1200ºC) improves Cmax,
not available, the analysis was performed by relying on SIMS but this condition may be ruled out by integration
data from similar anneals, recognizing that the chemical doping requirements. The pulse length has a weak influence, although
profiles are relatively insensitive to the anneal conditions. activation tends to be lower for the 0.2 ms pulse. Fig. 4(b)
Some samples were also analysed using the ALPro system compares Cmax for normal and delayed cooling profiles. The 1 s
developed by ALP Inc., which is based on the differential Hall delay in cooling at 725ºC had almost no effect on Cmax,
effect [16]. The ALPro technique implements the Hall effect suggesting that deactivation is relatively slow at 725ºC and that
measurements in conjunction with Angstrom-level material the nature of the cooling curve below 725ºC is unlikely to
modification. The approach provides measurements of both the influence the final activation. The Ti=775ºC condition resulted
carrier concentration and the mobility as functions of depth. in low Cmax in all the samples. This might be expected, since
ALPro system profiles for carrier activation are included in Fig. 1(a) shows that this case gives the highest post-pulse
Fig. 3. Although not identical, these completely independent thermal budget, which should increase dopant deactivation.
measurements give comparable Cmax values. Mobility values However, this experiment is somewhat ambiguous, because
were typically somewhat lower than those derived from the Rs these samples also experience the largest pre-pulse thermal
analysis method. budget, which could affect the activation achieved during SPE.
Fig. 5 compares simulations of how the a-Si layer thickness is
Fig. 4(a) shows Cmax values from the Rs analysis for anneals expected to change, as a function of the wafer temperature,
with normal cooling profiles. While the doping distributions in during the “centre” condition anneal (Ti=725ºC), as compared
Fig. 2 are fairly similar for the different anneals, Fig. 4(a) to the Ti=775ºC case. The simulations used measured
shows that Cmax is sensitive to annealing conditions. Cmax temperature-time profiles combined with the SPE kinetics for
tended to be highest for the P3 samples, a little lower in the P1 self-amorphized silicon [17]. For Ti=725ºC, the a-Si has not
22
10
P1 P3 As1 As3
21
Concentration (cm )

10
-3

20
10
Oxide Interface

Oxide Interface

Oxide Interface
Oxide Interface

19
10 Doping Doping Doping Doping
Carriers Carriers Carriers Carriers
ALPro Carriers ALPro Carriers ALPro Carriers ALPro Carriers
18
10
0 5 10 15 0 5 10 15 0 5 10 15 0 5 10 15
Depth (nm) Depth (nm) Depth (nm) Depth (nm)

Fig. 3. Comparisons of the chemical doping profiles and the active carrier profiles derived by combining the Rs measurements with the SIMS profile analysis,
assuming a “flat-top” electrical activation limit. The graphs also include results from differential Hall effect carrier profiling (ALP Inc.’s ALPro system).
 IV. CONCLUSIONS
4 (a) As1 As3 P1 P3
cm )
High dose P doping provided better activation than could
-3

3 be achieved with As, where activation degraded for the higher

dose condition. Higher MSA peak temperatures help
20
(10

2 activation, but will be limited by integration requirements.

Once the MSA pulse length exceeded 0.2 ms, it had a weak
max

1
influence on activation. Higher preheat temperatures degraded
C

0
activation. This might be expected from the higher post-pulse
thermal budget but the role of the preheat cycle deserves

1200C

775C
(0.7ms)
0.2ms

1.0ms
Centre

Ti=
Tp=
further study, since it may affect the behaviour of the dopants
before SPE is complete. The effects of different cooling
3 (b) profiles after the pulsed heating were checked, but were found
cm )
-3

to be insignificant for temperatures < 725ºC. The interaction of

2 activation and deactivation kinetics at relatively high
20
(10

temperatures and short times deserves deeper investigation,

1
since improved understanding of those phenomena, especially
max

for high-concentration shallow doping, could enable a fuller

C

0
optimization of both doping and annealing conditions.
0.2ms,

0.7ms,

1.0ms,
0.7ms

1.0ms
0.2ms

Slow

Slow

Slow
Anneal Type
Fig. 4. (a) Peak active carrier concentrations (Cmax) derived from
combined Rs/SIMS profile analysis for various annealing recipes. (b) Cmax
for cycles with or without the extra delay of 1 s at 725ºC during the cool-
down. The delay appears to have almost no effect on electrical activation.
fully crystallized by the time the wafer reaches Ti, and SPE
finishes during the pulsed surface heating, at ~1070ºC. The
simulation does not include the effect of the extremely heavy
doping, which can greatly decrease the SPE rate near the
surface, which would raise the temperature when SPE regrowth
is complete [11]. Previous studies showed improved activation
for fast ramps to the SPE temperature [2], and a lower Ti could
increase activation by this route. The diffusion and segregation
at the Si/oxide interface may also be affected by the ramp-up
conditions. The small, but consistent, shifts seen in all the
doping profiles for the Ti=775ºC cases also hint that the role of
the heating cycle before the pulse requires clarification.
60
Centre (T=725°C)
i [9]
50 T =775°C
i [10]
Pulsed heating
40
(nm)
ACKNOWLEDGEMENT
The authors would like to thank Dr Michael Ameen of
Axcelis Technologies for providing the implants.
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