IEEE TRANSACTIONS ON MAGNETICS, VOL. MAG-23, NO.

2, MARCH 1987 847

THERMAL ANNEALING OF RF SPUTTERED NbN

W. L. Carter and E. J. Cukauskas

Electronics Technology Division
Naval Research Laboratory
Washington, DC 20375-5000

Abstract temperatures ranging from 150°C to 65OoC have been

annealed for times ranging from one sec to 12 hours.
The effects of thermal annealing on RF sputtered The vacuum system and procedures used to deposit the
NbCN films and completed NbN-based tunnel junctions films have been described i n . detail el~ewhere.~ In
has been investigated. The starting films were RF brief, preheating, presputtering and sputter etching
sputtered at temperatures from 150'C to 650°C. After steps precede film deposition in a premixed reactive
a vacuum anneal at 600°C for six hours the transition Ar/N2/CH4 sputtering gas. The resulting NbCN films
temperature reached a maximum of 14.6K and depended have been characterized by measurements of transition
only on the carbon concentration, for those films temperature Tc and width ATc, resistivity p , and
deposited at 200°C and 4OO0C. Vacuum annealing for resistivity ratio RR using standard 4-wire and 2-can
one hour at temperatures of 900°C or more caused the cryostat techniques which have also been described in
formation
additional
of phases.
Rapid
thermal detail elsewhere.8 X-ray diffractometry has been used
annealing, RTA, at temperatures from 600°C to 1200°C to characterize the structure of the films before and
for times from one to 100 sec resulted in increased Tc afterannealing. Two typesofthermalannealing
with increased annealing temperature. The maximum Tc treatments were given to the films.
produced by RTA was 16.6K. The lattice parameter of
annealed 6-phase NbCNwasdecreasedtowardthe Vacuum Annealing
accepted value of 4.41A. Resistivity of the annealed
films decreased except when the films cracked during NbCN films received thermal anneals under vacuum
annealing. RTA for 10 sec at 750°C of a completed for times ranging from one to 12 hours at temperatures
NbN/Si/NbN edge junction increased the electrode gaps from 60Q°C to 1200°C. Six and 12 hours anneals at
butforNbN/Si/Nbplanarjunctionsthesumgap 600'C and 10-6 Pa were done in the same vacuum system
decreased. Microshorts also appeared in both types of as were the film depositions. The films annealed at
junctions after annealing. 600'C were deposited on quartz substrates at different
substrate temperatures and CH4 concentrations in the
Introduction sputtering gas in order to determine the effects of
lowtemperatureannealingonawidevarietyof
Attempts to develop a high quality all refractory differentNbCNstartingmaterials. In additiona
high Tc Josephson junction technology based on NbN series of anneals were done at temperatures of 900,
represent one of the most active research areas in 1000, 1100 and 1200°C for one hour inUHVa MBE system
superconducting microelectronics. Several researchers at pressures of 10-7 Pa or lower. Details of this
have made considerable progress in this in area
recent system can be found elsewhere.9 The film used in this
years.1-5 At NRLweareinvestigatingNbN/Nband study was deposited onto a sapphire substrate which
NbN/NbNjunctionswithsemiconductorbarriersfor was
subsequentlybroken
into
four
pieces
for
applicationas SIS mixers. Two problemareasin annealing.
current NbN based all refractory junctions are the
width A V of the rise in quasi particle current at the Rapid Thermal Annealing
sum of tfe electrode energy gaps and the magnitude of
Rsg, the subgap resistance. Large AVg and small hg The
second
type
annealing
of which
was
result from degraded superconductive properties of the investigated was rapid thermal annealing, RTA. In this
NbN at the junction interfaces as well as from poor caseannealsrangingfrom600°Cto1200°Cwere
barriermaterialproperties. We
have also
seen performed in one atmosphere of N2 Arorafter a20 min
indications of non-ideal superconductive properties in purge for times ranging from one to 100 seconds. RTA
the bulk through specific heat measurements made at is used in semiconductor processing, for. example, to
Stanford University and in upper critical field, Hc2, anneal out local implant damage without allowing large
measurementsmadeat NRL.6
X-ray diffractometry scaleredistributionoftheimplanteddopants. In
indicates our films, while single 6-phaseY have a this case it was expected local ordering of the high
largerthan expected lattice parameter ao, and Tcfcc 6-phase NbN could be accomplished without
distorted latticein thatthe (111) and (200) significantamountsoftheequilibriumhexagonal
reflections give a, which differ typically by 1% or c-phase NbN being created. RTA was performed in a
more. Since appropriate thermal annealing treatments Heatpulse 210 unit from AG Associates in which high
can improve the
superconductive properties
of temperaturesandfasttemperaturerisetimesare
materials, we are investigating the effects of thermal achieved by means of thirteen 1.5 kW quartz halogen
annealing on NbNfilmsandNbNbasedjunction lamps. The samples used for RTA were made in four
structures. depositions, one at 150°C onto silicon and oxidized
silicon substrates, one at400'C onto silicon, one at
Thermal Annealing of NbCN 4OOOC onto sapphire and one at 65OoC onto oxidized
silicon. The film grown at 150'C was similar to those
NbCN films of thickness 250 to 500 nm have been used as counter electrodes in our NbN/NbN junctions
deposited by RF sputtering on substrates of sapphire, while the film grown at 650°C was similar to films
quartzandoxidizedandunoxidizedsilicon,and used as base electrodes in our junctions.10
subsequently annealed. Films deposited at substrate

Manuscript received September30, 1986

0018-9464/87/0300-0847$01.0001987 IEEE
848

Resuits and Discussion 111

Vacuum Annealing Results 10 SEC RTA

Films deposited at both 200'C and 4OO0C on quartz
substrates have been given thermal anneals at 6OO0C
under vacuum in the 10-6 Pa range for periods of six
and 12 hours. Fig. 1 shows the Tc dependence of the
1
1

I
I AS
AS DEPOSITED
DEPOSITED x-
2 %%
0
X
X
AA

films before and after annealingon the concentration

of CHq in the sputtering gas during deposition. For
A 2bO"C ON Si
o 400°C ON Si
0 T ~ 2 0 0 " C 1 0 %N2 13
AT^ 400°C 13% N2 0 200 400 600 800 1000 1200
2 ANNEALING TEMPERATURE ("C)

31
15
,.a*---
14 Figure 2. The RTA temperature dependence of Tc for
similar films deposited on different substrates at
2 dp'-\/ different temperatures. The error bars represent ATc
when larger than the plotting symbol.

-AS DEPOSITED materialshadsimilarcompositionsbased on Auger

-___ ANNEALEDAT 600°C 6 HR. composition analyses from previous depositions.8 The
, I I I I I I I I I J
Tc of the annealed films increased with increasing
annealing temperature. The minimum RTA temperature
0 2 4 6 8 10
that caused Tc to increase was less than 600'C for
PERCENTCH, films deposited at150'C but was 8OO0C for films grown
at 400°C. The maximum Tc achieved by RTA was 16.6K,
Figure 1. Thetransitiontemperature of vacuum as high as the best material we can make by RF bias
sputteringat 850'C substratetemperatures.3RTA
annealed NbCN films as a function of the percentage of
CH4 inthesputteringgas.Ts
temperature during deposition.
is thesubstrate -
above 900°C usually led to increased A Tc. Another
problem with RTA was that films occasionally did not
adheretothesubstrateorcrackedduringthe
annealing. The films deposited at 150'C on silicon
films deposited at 2OO0C a six hour anneal caused Tc and oxidized silicon were particularly susceptible to
to increase -0.8-1.3K to a maximum of 14.6K. For this problem. This may be due to stress in the film
thosefilmswhichoriginallyhadunusuallylarge due
to
the low deposition temperature. Films
transition widths, annealing sharpened the transition. depositedat 4OO0CadheredQelltothesubstrate
Other films which began with sharp transitions (ATc< during RTA. However, the films deposited on silicon
.05K) showed little or no increase inATc. A second at 400'C cracked when annealed at 1000°C or more for
anneal at 6OO0C for six hours (not plotted) caused timesofthreeormoreseconds.Thiswaseasily
additional increases in Tc of up to 0.2K arid generally determined by an increase in the room temperature
slight increases inATc-as well. For films deposited resistivityofthosefilmsafterannealing.The
at 4OO0C the Tc after annealing had the same CH4 resistivity of films which remained intact initially
concentration dependence as for the films deposited at decreasedandthenwasconstantwithincreasing
20OoC. Thus the Tc after annealing at 600'C depended annealingtemperature,reachingabout 90% ofthe
only on the stoichiometry and not on the substrate original resistivity after RTA at 900°C or more.
temperature. The crystal structure of these films has
been investigated using X-ray diffractometry. We have The lattice parameter and grain size of the film
observed previously that our as-deposited films have a after RTA are plotted in Figs. 3a 3band respectively.
distortedfccstructurewithanunusuallylarge The error bars in Fig. 3a represent the difference in
lattice parameter a0.3,8,10 After annealing at 6OO0C a calculated from the (111) and (200) reflections.
.
all films showed a decrease in a, toward a 'more The (111) reflection had the larger a0 in almost all
accepted value for NbCN and also a decrease in the cases. As can be seen in Fig. 3a, RTA both decreased
apparent distortion of the fcc lattice. No traces of the lattice parameter to the expected value of 4.4U
additional phases were observed. and decreased or even eliminated the distortion of the
lattice. In generalfilmsremainedsingle&-phase
Pieces of another film deposited at 4OO0C were afterRTA.Thegrainsizeasdeterminedbythe
annealed for one hour at temperatures ranging from Scherrer formula and plotted in Fig. 3b increased with
900°C to 1200'C under UHV in the 10-7 Pa range or increasing annealing temperature above about 75OoC.
lower.X-raydiffractometryrevealedthatallthe
films had multiple phases after annealing. Only the The time dependence of RTA was also investigated.
film annealed at 900°C appeared to remain largely A series of rapid anneals for times ranging from one
S -phase NbCN with Tc increased to 16.lK. This is in to 100 sec at 1000°C was performed. There was a slight
agreement with other results that indicate NbN is increaseinTcandingrainsizewithincreased
metastable below about 127OOC and cannot be annealed annealing time. However, the lattice parameter showed
higherthan-900°Cwithoutnucleatingequilibrium no dependerice on annealingtime.Oneinteresting
phases. 11 12 point was that the film annealed for one second did
not crack during annealing while those films annealed
RTA Results for longer times were cracked. This may simply mean
that the one second annealing time did not actually
In Fig. 2 the transition temperatureTc of NbCN allow the film to reach the nominal temperature. The
filmsafterRTAfor 10 secisillustratedasa thermal environmentsof the saniple and thermocouple in
function of the annealing temperature. The starting theHeatpulse210
are
slightly different.
The
 a49

I
4.48
- 4.46-
-4
@
n
E
It T
o AI203
o Si

2
s
2UI
4.44

-
-
4.42 -
-

d
DEPOSITED
AS

0
E 4.40 -
'--...I
4 go
0

4.38 I I I I I I I
200400600 800 10001200
VOLTAGE (mV)
ANNEALINGTEMPERATURE ("C)
Figure 4. The
differential
resistance
dV/dI
of
(4 NbN/Si/NbN edge junctions before and after RTA. Note
the increased gaps after annealing.

thebarrier.Inallcases , however,cleargap
200 structure was apparent. The minima in the dV/dI-V at
the individual electrode gaps have moved to higher
4
I voltages after RTA indicating an improvement in the
fi 160 quality of the NbCN within a coherence length of the
junction interfaces in both electrodes. The counter
5 Ig electrode gap improved from 1.80 to 1.92 mV and the
base electrode gap improved from2.66 to 2.82 mV. The
0
- AS DEPOSITED X improvement in the base electrode, which was deposited

~801
/ \
f ' underoptimum
unexpectedat
the
RF biasconditionsat
750'C RTA
temperature.
85OoC, was
This
indicates that considerable damage was done to the
surfaceofthe NbN baseelectrodeinsubsequent
processing steps, either in plasma etching the edge or
I I I I I I I duringsputtercleaningandbarrierandcpunter
0 200400600
80010001200 electrodedepositions. Us? ofaplanartechnology
ANNEALING TEMPERATURE ("Cl wouldalleviatetheformerpossibility.However,
similar RTA of NbN/Si/Nb planar junctions did not
(b) produce improved gap values. In fact the sum gap in
this case decreased from 4.0 mV to 3.85 mV after
Figure 3. The RTA temperature dependence of (a) the annealing. This decrease was apparently in the Nb
lattice parameter and (b) the grain size after 10 sec gap. In both the planar and edge junctions the width
anneals.
The
errorbars
in
(a)
representthe of the current rise at the sum gap decreased and the
difference between .a calculated from the (111) and subgap leakage increased during RTA. We also made
(200) reflections. planar NbN/Si/Nb junctions on NbN bases produced in
the same depostion but after subjecting one of the
basestoRTAat 900°C for 10 sec.Thejunction
temperature rise time from 4OO0C to 1000°C of the barriers and counter electrodes were deposited in the
thermocouple assembly was two sec. The time constant samerun.Therewas nosignificantdifferencein

tobe 0.1-
for thermal equilibrium in the substrate was estimated thesejunctions.Thussurfacedamageduetothe
secat 1000°C.
annealed in flowing argon for
Onesamplewasalso
10 sec at 1000°C and
showed properties identical to those of the sample
annealed under similar conditionsin nitrogen.
RTA of Tunnel Junctions
We have investigated the effects of RTA at 750'C
for 10 sec on several completed junction structures
whosefabricationhasbeendescribedindetail
elsewhere.13 This temperature was chosen since NbN
counterelectrodefilmsdepositedat150°Cshowed
increased T, after RTA at 75O0C without substantially
increased grain size. Large increases in grain size
would presumably lead to punching through the barrier. second phase formation. However, the
Annealing at 75OoC would also cause the amorphous
silicon barrier to transform to polysilicsn provided
the reaction is not kinetically limited. Fig. 4 shows with high critical current densities. Rapid thermal
dV/dI-V characteristics of NbN/Si/NbN edge junctions
both before and after RTA at 750°C for 10 sec. While
these are not the same junction they are from the same
chip. The annealing treatment created microshorts in
sputter cleaning and barrier and counter electrode
deposition may be the limiting factor in our present
junction fabrication technology.
Conclusion
Wehaveinvestigatedtheeffectsofthermal
annealing of €3 sputtered NbCN films and completed
NbN-based tunnel junctions. Vacuum annealing at 600'C
for six hours increased the transition temperature of
films deposited at 200°C and 4OO0C to a value which
depended only on the carbon concentration. For films
grown at 400°C vacuum annealing at temperatures of
900°C to 12OO0C for one hour caused the onset of
T, of the film
annealed at 900°C was significantly improved. This
may be of some importancein producing NbN conductors
annealing of similar NbCN films grown at 150°C and
400°C
resulted in
increased T, with increased
annealingtemperature.Resistivitydecreasedafter
RTA. The maximum Tc produced by RTA was 16.6K while
850

the maximum Tc after vacuum annealing was 16.1K. We 10. E. J. Cukauskas, W. L. Carter and S. B. Qadri,
attribute thisdifference to the lack of second phase "Superconducting
and
StructureProperties
of
formation due to kinetic limitations during RTA. The Niobium
Nitride
Prepared
by RF Magnetron
lattice parameter of both vacuum annealed and rapid Sputtering," J. Appl. Phys., E, 2538-2542, 1985.
thermal annealed&-phase NbCN was decreased toward the
accepted value of 4.418. The distortion of the fcc 11. A. M. Cuculo, L. Maritato, A. Saggeseand R.
structure seen in our films was decreased and often Vaglio,
"Properties
ofNiobium
Nitride-based
eliminated by annealing. RTA of completed NbN/Si/NbN Josephson
Tunnel
Junctions," Cryogenics 6,
tunnel junctions at 75OoC for 10 sec increased both 45-47, 1984.
electrode gaps, but for NbN/Si/Nb junctions the sum
gap
was
decreased. In both
cases,
however, 12. E. K. Storms, "Inorganic Chemistry Series One,
microshorts appeared after annealing. RTA at 900°C SolidStateChemistry,"Butterworths,London,
for 10 sec of a NbN base electrode deposited at 400'C Vol. 10, p. 37, 1972.
before completion of the junction did not increase the
sum
gap.
This
indication
an
is that
our 13. E. J. Cukauskasand W. L. Carter,"Niobium
barrierlcounterelectrodedepositiontechniqueis Nitride Based Josephson Junctions with Unoxidized
limiting our junction quality. Further RTA studies are Silicon Barriers," this volume.
in progress.

Acknowledgements

The authors wish to thank John Claassen for the

high temperature vacuum anneals, Carl Vold for use of
his x-ray diffractometer, Phillip Thompson and Harold
Hughes for use of the rapid thermal annealer and
MartinNisenoffformanyusefuldiscussions.This
work was partially supported by the Office of Naval
Research.

References

1. A. Shoji, M. Aoyagi, S. Kosaka, F. Shinoki and H.

Hayakawa,
"Niobium
Nitride
Josephson
Tunnel
Junctions with Magnesium Oxide Barriers," Appl.
Phys. Lett, 5, 1098-1100, 1985.

2. J. C. Villegier, L. Vieux-Rochaz, M. Goniche, P.

Renard and M. Vabre, "NbN Tunnel Junctions, IEEE
"

Trans. Magn., MAG-21, 498-504, 1985.

3. E. J. Cukauskas and W. L. Carter, "Superconducting

and
Structural
Properties
of RF Magnetron
Sputtered
Niobium
Nitride
Josephson
for
Junctions," Adv.CryogenicEng., 3 2 , 643-650,
1986.

4. J. Talvacchio
and A. I. Braginski, "Tunnel
Junctions Fabricated from Coherent NbN/MgO/NbN
and NbN/Al203/NbN Structures," this volume.

5. H.G. LeDuc, J. Stern, S. Thakoor and S. K. Khanna,

"All Refractory NbN/MgO/NbN Tunnel Junctions,"
this volume.

6. W. L. Carter, to be published.

7. E. J. Cukauskas, "The Effects of Methane in the

DepositionofSuperconductingNiobiumNitride
ThinFilmsatAmbientSubstrateTemperature,"
J. Appl. Phys, 54, 1013-1017, 1983.

8. W. L. Carter, E. J. Cukauskas, S. B. Qadri, A. S.

Lewis and R. J. Mattauch, "Effects ofRF Bias on
the Superconducting and Structural Properties of
RF Magnetron Sputtered NbN," J. Appl. Phys., 2,
2905-2907, 1986.

9. S. A. Wolf, S. B. Qadri, J. H. Claassen, T.L.

Francavillaand B. J. Dalrymple,"Epitaxial
Growth of Superconducting Niobium Thin Films by
UltrahighVacuumEvaporation," J. Vac.
Sci.
Technol., &, 524-527, 1986.