Note: Descriptions are shown in the official language in which they were submitted.
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Ferroelectric Thin Films of Reduced Tetragonality
FIELD OF THE INVENTION
S The invention relates generally to perovskite materials. In particular, the
invention
relates ferroelectric materials usable in ferroelectric memory cells.
BACKGROUND ART
Ferroelectric random access memories (FRAMs) offer the possibility of a non-
volatile
memory to replace silicon ones since FRAMs do not require energy to retain
their electrically
impressed polarization state. The schematized general structure of an FRAM 10
is illustrated
in FIG. 1 and includes two capacitor plates 12, 14 between which is placed a
body 16 of
ferroelectric material. Not only does the ferroelectric material 16 have a
dielectric constant
substantially in excess of unity, but also under the proper conditions the
ferroelectric is
bistable. Once the capacitor plates 12, 14 have poled the ferroelectric into
either the
1 S upwardly or downwardly directed polarization state, the ferroelectric body
16 remains in that
state even after the poling voltage is removed. That is, a charge (or voltage)
remains on the
cell 10 without any power being currently applied. Sometime later, the charge
can be
measured. Thereby, the FRAM 10 forms a non-volatile memory.
Conventionally, the FRAM has included a polycrystalline ferroelectric material
sandwiched between two metallic electrodes in a capacitor structure. Such a
design however
has suffered from reliability and aging problems.
More recently, Ramesh and coworkers have been developing crystallographically
oriented ferroelectric cells using metal oxide electrodes. Dhote et al. have
disclosed a
platinum-based lower electrode in U.S. Patent Application, Serial No.
08/578,499, filed
December 26, 1995, also published as PCT Publication 97/23886 on July 3, 1997.
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An exemplary structure of Dhote et al. for a ferroelectric random access
memory
(FRAM) 20, similar to a silicon dynamic RAM, is illustrated in cross section
in FIG. 2. It is
understood that this FRAM structure is replicated many times to form a large
FRAM
integrated circuit and that other support circuitry needs to be formed in the
same chip. The
overall FRAM structure, with a few exceptions, is known and has been disclosed
by Ramesh
in the previously cited U.S. patents and applications. Kinney provides a good
overview of
FRAM integrated circuits in "Signal magnitudes in high density ferroelectric
memories,"
Integrated Ferroelectrics, vol. 4, 1994, pp. 131-144. The FRAM 20 is formed on
a
(001)-oriented crystalline silicon substrate 22 so that other silicon
circuitry can easily be
incorporated. A metal-oxide-semiconductor (MOS) transistor is formed by
diffusing or
implanting dopants of conductivity type opposite to that of the substrate 22
into source and
drain wells 24, 26. The intervening gate region is overlaid with a gate
structure 28 including a
lower gate oxide and an upper metal gate line, e.g., aluminum, to control the
gate.
A first inter-level dielectric layer 30, for example of silicon dioxide, is
deposited over
the substrate 22 and the transistor structure. A contact hole 32 is
photolithographically etched
through the first inter-level dielectric layer 30 over the source well 24, and
polysilicon is
filled therein to form a polysilicon contact plug to the transistor source 24.
A metal source
line 34 is photolithographically delineated on top of the first inter-level
dielectric layer 30 and
electrically contacts the polysilicon plug 32.
A second inter-level dielectric layer 36 is then deposited over the first
inter-level
dielectric layer 30. Another contact hole 38 is etched through both the first
and second inter-
level dielectric layers 30, 36 over the area of drain well 26, and polysilicon
is filled therein to
form a contact to the transistor drain 26. The processing up to this point is
very standard in
silicon technology.
A lift-off mask is then deposited and defined to have an aperture over the
drain
contact hole 38 but of a larger area for the desired size of capacitor,
although in commercial
manufacture a masked dry plasma etch would typically be performed. Over the
mask and
into the aperture are deposited a sequence of layers. A polysilicon layer 40
provides good
electrical contact to the polysilicon plug 38. A TiN layer 42 and a platinum
layer 44 form
conductive barrier layers between the polysilicon and the oxidizing metal-
oxide contacts.
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Polysilicon is semiconductive, but, if its surface is oxidized into SiOz, a
stable, insulating
layer is formed that prevents electrical contact. Over the platinum layer 44
is deposited a
layer 46 of a conductive metal oxide, preferably a perovskite, such as
lanthanum strontium
cobalt oxide (LSCO), although other metal oxides may be used, especially
layered
perovskites. This material has a composition nominally given by
Lao,SSro.5Co03, although
compositions of approximately La,_XSrxCoO~ are possible with 0.15>_xz0.85. It
is now well
known that LSCO forms an acceptable electrical contact, and it further
promotes highly
oriented growth of perovskite ferroelectric materials.
The photomask is then lifted off leaving the lower stack of layers 40, 42, 44,
46
shown in FIG. 2. Another photomask is then defined allowing the conformal
deposition of a
Z-shaped field-oxide layer 48, which covers the sides of the previously
defined lower stack,
has a rim extending over the edge of the upper surface of the lower stack, and
has a foot
extending outwardly from the bottom of the lower stack, but leaves a central
aperture for the
after deposited upper ferroelectric stack. The field-oxide layer 48
electrically insulates the
after deposited ferroelectric from the side portions of the lower electrode.
In the past, the field-oxide layer 48 has been formed of SiOz or TiOz, but
neither of
these materials are ideal. Perovskite ferroelectrics when deposited over these
materials tend
to form in a mixture of perovskite and pyrochlore phases, which then
differentially etch,
resulting in unreliable etching. A better material for the field oxide layer
48 is bismuth
titanate (approximately of the stoichiometric composition Bi4Ti30,z), which is
a perovskite
and can be grown by the same growth process as the other perovskite layers.
Ramesh in U.S.
Patent 5,248,564 discloses that Bi4Ti30,z is a powerful templating layer for
promoting the
growth of crystallographically oriented perovskites over unoriented substrates
so a Bi4Ti~Olz
field oxide layer 48 assures good quality ferroelectrics are grown over it.
Other perovskite
materials may be substituted for the bismuth titanate as long as they are not
highly conducting
and they display a low dielectric constant, e.g., not be a ferroelectric. For
most effective
templating, the perovskite forms of the Bi4Ti30,z should have a layered
structure, that is, have
a c-axis lattice that is at least twice those of the a- and b-axes.
After the formation of the field oxide 48, another photomask is deposited and
defined
that includes an aperture around the lower stack 40, 42, 44, 46 but the outer
periphery of its
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bottom overlies the feet 49 of the field-oxide layer 48. A ferroelectric layer
50 is then
deposited under conditions favoring crystallographically oriented growth.
Preferably, the
ferroelectric layer 50 comprises lead lanthanum zirconium titanate (PI,ZT) or
lead niobium
zirconium titanate (PNZT). The deposition of the perovskite ferroelectric
layer over LSCO or
other similar perovskite conductive electrodes allows the ferroelectric to be
deposited at a
relatively low temperature but still manifest favorable crystallinity. Over
the ferroelectric
layer 50 is deposited an upper conductive metal-oxide layer 52, preferably
symmetrically
formed with the lower conductive metal-oxide layer 44, of a perovskite, such
as LSCO. An
upper platinum layer 54 is deposited over the upper conductive metal-oxide
layer 52. This
layer 54 is not considered to involve critical technology, and its platinum
composition was
selected only as an interim solution. It is anticipated that the composition
will be changed to
TiW or other metallizations common in silicon technology. After the upper
platinum layer 54
is deposited, the photomask is lifted off leaving the structure of the upper
stack illustrated in
FIG. 2.
A third inter-level dielectric layer 56 is deposited and etched to cover the
ferroelectric
stack. This layer 56 is intended more as a passivation layer than as an inter-
level dielectric.
The upper electrode 54 is then electrically contacted by etching a via 60
through the
third inter-level dielectric layer 56 overlying the ferroelectric stack,
filling the via 60 with
Ti/W, and delineating a metal capacitor line 62 of A1 that electrically
contacts the Ti/W plug
60.
Dhote et al. found that depositing the lower platinum layer 44 at a relatively
high
temperature, in the neighborhood of 500-550°C, allows the deposition of
the ferroelectric
stack (the ferroelectric and the two sandwiching metal-oxide layers) at a
higher thermal
budget, which is defined as the integral of the temperature (measured in
°C) and the time the
sample is at that temperature. Since the three layers, that is, the PNZT layer
50, the upper
I,SCO electrode 52, and the upper Pt layer 54, are typically deposited in a
single chamber at a
single temperature, the thermal budget becomes the product of the deposition
temperature and
the total deposition time.
PNZT is a well known ferroelectric material. Dhote et al. give particular
examples of
the composition of PNZT as Pbo,~Nbo.,BZro.7gTi03 and PbNbo.~Zro.28Tio.680;,
that is, PNZT
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which is on one hand lead-poor or on the other hand lead-rich and zirconium-
rich.
A problem which needs to be addressed in ferroelectric memories of any sort is
their
fatigue behavior. It is generally observed that the ferroelectric or
polarization properties of a
ferroelectric cell degrade over a large number of read-write cycles. The
polycrystalline cells
suffer greatly from fatigue while the crystallographically oriented cells
exhibit much greater
resistance to fatigue. Nonetheless, fatigue is still believed to be problem
with
crystailographically oriented cells.
To be able to quantize fatigue and other operating characteristics in
ferroelectric cells,
it is necessary to understand the polarization characteristics of a
ferroelectric cell. A
ferroelectric hysteresis loop 64 is illustrated in FIG. 3. The horizontal axis
represents the
voltage across the cell. The vertical axis represents the polarization of the
material, whether
immediately impressed or residual (remanent), that is, without a voltage being
applied. The
polarization is proportionately related to the time integral of the charge
flowing into or from
the cell. The hysteresis curve is highly non-linear. For this discussion, it
is assumed that the
characteristics are symmetric although this is not usually true in practice.
The illustrated hysteresis curve implies that the hysteresis curve approaches
a
maximum polarization P~~ as the applied voltage asymptotically approaches a
saturation
voltage Vsa~. However, the poling is usually performed along the voltage
direction only to
Vm~, which yields a Pm~x of only about 90% of PS~~. The difference in the
polarization
between poling to tVmax is indicated by P*, that is P*=2PmuX for a symmetric
hysteresis curve.
When the cell has been pulsed to Vmax, with an accompanying polarization of
Pm~x, but
thereafter the voltage is reduced to V--0, the polarization is nonetheless
maintained at a
residual polarization P~. If the cell had been poled negatively, the
polarization is retained a
negative residual polarization, which for a symmetric hysteresis curve equal -
Pt. Assuming
that the reading is performed by positive poling with an applied voltage of
Vmax, the measured
charge upon poling corresponds to either a non-switched polarization P~ or a
switched
polarization P*. The reading circuitry must be able to distinguish the
difference between
them, which is the pulsed polarization DP = P* - P~. For a symmetric
hysteresis curve, the
pulsed polarization OP is equal to 2P~.
Generally, it is felt that for superior performance the hysteresis curve
should be as
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rectangular as possible. That is, the coercive voltage V~ should be maximized
for a given
V",ex. This feeling is based upon the facts that the remanent polarization Pr
should be made as
large as possible and that the remanent polarization increases with the
coercive voltage.
However, we believe that there are some countervailing considerations.
Another consideration is that if ferroelectric memories are to be
commercialized, they
must be compatible with other silicon integrated circuits used in, for
example, personal
computers, computer work stations, and other computer controlled applications.
For many
years, digital silicon integrated circuits, whether logic or memory, were
powered by a DC
voltage V~~ of SVDC. However, in recent years, advanced integrated circuits
have been
designed to be powered by lesser voltages, 3.OVDC, 2.3VDC and 1.8VDC for
example. The
decreased voltages both reduce the problems associated with thermal
dissipation in extremely
dense integrated circuits and also provide extended battery operation for
portable computers.
An example of the critical reading circuitry associated with a ferroelectric
cell 10 is
illustrated in the circuit diagram of FIG. 4. This embodiment follows the
description by
Kinney et al. Other equivalent circuitry is possible. Associated with each
ferroelectric cell
10 is a read transistor 66, corresponding to the MOS transistor 23 in FIG. 2.
A word line 68
controls the read transistors 66 of a column of memory cells 10, but in a
direction orthogonal
to the work line 68. The read transistor 66 selectively connects the
ferroelectric cell 10 to a
bit line 70, which is similarly connected to row of memory cells 10. That is,
the word lines
68 and bit lines 70 run in perpendicular directions over a rectangular array
of memory cells
10. Because of hysteretic effects in the ferroelectric material, it is
necessary to provide during
the read process selective biasing of the other electrode of the ferroelectric
cell 10 through a
plate line 72, which runs in parallel to the word line 68.
During the read process, the ferroeiectric cell 10 is temporarily connected to
the bit
line 70 and the charge stored on the cell 10, whether in the positive or
negative state, is shared
with a larger parasitic capacitance 74 associated with the bit line 70,
thereby generating two
possible voltages on the bit line 70. A sense amplifier 76 then compares this
voltage to a
reference voltage resulting from a charge stored on a reference capacitor 78
and input to the
sense amplifier 76 on line 79. The sense amplifier 76 outputs a digital signal
OUT
representing the charge state of the ferroelectric memory cell 10.
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Typically, the reference capacitor 78 is the parasitic capacitance associated
with the
complementary bit line -BL 79 not used in the current read cycle. The sense
amplifier 76 is
most often implemented as a cross-coupled bistable latch circuit that latches
in one of two
states depending upon which of the voltages on its two inputs lines 70, 79 is
the highest.
Hence, it is desirable to set the voltage on the reference capacitor 78 or
associated bit line 79
at a voltage intermediate the complementary voltages induced on the active bit
line 70 by the
complementary states of the ferroelectric cell 10. All the above described
operations are
controlled, pre-charged, and discharged by a logic circuitry 80 having two
power supply
inputs at ground and at the DC power supply voltage V~~. As a result, barring
the use of
complex voltage multiplying circuitry, all operations within the memory
circuit are limited to
a maximum voltage swing of V~~.
However, many designs for ferroelectric memories have been based on the power
supply voltage V~~ being SVDC. As a general but loose rule, for a
ferroelectric capacitor
memory cell, the applied poling voltage Vmax is limited to no more than
approximately half of
the power supply voltage V~~. The reading of a ferroelectric cell is typically
done by dividing
the charge stored on the ferroelectric capacitor with a larger capacitance
associated with the
bit line. On account of this voltage drop and other voltage losses across
various capacitors in
the reading and writing circuitry, it is common that VmuX or Vs~~ is five time
the coercive
voltage V~. In any case, low values of the coercive voltage V~ are reflected
in low values of
the saturation voltage V~,~. Assuming a power supply voltage V~~ of 1.8VDC, it
is desired that
the coercive voltage V~ be 0.5 to 0.6VDC, with everything being switched by
0.9VDC.
Generally, if the coercive voltage V~ is low, the saturation voltage Vsa, is
also low.
Theoretically, it is possible in view of the reduced voltage operating range
to simply
reduce the thickness of the ferroelectric layer in the ferroelectric cell
since the ferroelectric
effects are dependent upon the applied electric field, that is, the applied
potential divided by
the thickness of the ferroelectric layer. Thereby V~ and VmuX would scale
downward with the
ferroelectric thickness. However, present day ferroeiectric materials are
imperfect electrical
insulators, and an unacceptably high electrical conductivity will prevent the
ferroelectric cell
from operating in a realistic system. The problem is-linear, that is, not
ohmic, for example by
electronic quantum hopping. As a result, a small increase in local effective
electric field may
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result in a very large increase in electrical current. These effects result in
the commonly
accepted limitation that the ferroelectric layer have a minimum thickness of
0.23~m or at
least no less than 0.15pm. At lesser thicknesses, the leakage current across
the ferroelectric
becomes excessive. As a result of the minimum thickness, the voltage applied
across the
ferroelectric layer must exceed a minimum value producing adequate capacitive
charge
storage.
The physical operation of a ferroelectric cell is believed to follow the
mechanism
illustrated in FIG. 5 for a simple ferroelectric material such as PZT (
PbZrTi03), PLZT
(PbLa7rTi03, and other well known materials. These first three materials are
best
characterized as alloys of the compounds PbZr03, PbTiO~, LaZr03, and LaNb03,
in the case
of PLZT. Similar characterizations should be made for PNZT (PbNbZrTiO~). A
unit cell for
these materials is generally tetragonal, that is, a rectangular cell having
three perpendicular
unit vectors, one having a value c and the other two having the same value a.
For most
ferroelectric materials, c is greater than a. The ratio cla will be defined to
be the tetragonality
factor of the ferroelectric material. The unit cell includes eight rare-earth
atoms 82 of lead
(Pb), lanthanum (La), or niobium (Nb) at its corners, six oxygen (O) atoms 84
in the middle
of the six rectangular faces, and one cation atom of titanium (Ti), zirconium
(Zr), etc. located
generally at the center of the tetragonal cell. However, below the Curie
temperature, the low-
energy cation position is located either above or below the cell center at one
of the offset
positions 86a, 86b. The displacement of the cation from the cell center
provides the bistable
ferroelectric behavior. Which of the two offset positions 86a, 86b the cation
assumes
determines the polarization state of the cell.
It is desired to take advantage of the known characteristics, advantages, and
disadvantages of ferroelectric memory cells to produce a design for cells
particularly
advantageous for low-voltage operation.
SUMMARY OF THE INVENTION
The invention can be summarized as a ferroelectric capacitor cell having a
crystallographically oriented ferroelectric layer formed on a metal-oxide
eiectrode layer. The
ferroelectric material is chosen to have a composition that has a low
tetragonality factor, that
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is, a low cla ratio for a tetragonal perovskite. In particular, the
tetragonality factor may
indicate a composition of a complex ferroelectric alloy that provides less
than optimal
ferroelectric characteristics. Nonetheless, a ferroelectric cell is likely to
manifest better
fatigue characteristics because of the less stress of the lower tetragonality
factor, and the
better characteristics may not be polable with voltage levels used in densely
integrated
memories. The effect has been demonstrated for lead lanthanum zirconium
titanate (PLZT)
and lead niobium zirconium titanate (PNZT).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a ferroelectric memory cell.
FIG. 2 is a cross-sectional view of a ferroelectric memory cell to which the
invention
can be applied.
FIG. 3 is a graph illustrating the important ferroelectric parameters of a
ferroelectric
cell.
FIG. 4 is a electrical schematic diagram illustrating the readlwrite circuitry
associated
with a ferroelectric memory cell.
FIG. 5 is a schematic orthographic illustration of the crystalline structure
of
ferroelectric materials such as PZT, PLZT and other perovskites.
FIG. 6 is graph of hysteresis curves for two compositions of lead lanthanum
zircotitanate.
FIG. 7 is a graph of hysteresis curves for different poling voltages for a
PLZT
composition of the invention
FIG. 8 is a graph of hysteresis curves for three compositions of lead niobium
zircotitanate.
FIG. 9 is a graph of the switched polarization as a function of poling voltage
for cells
composed of PNZT with three values of niobium content.
FIG. 10 is a graph of coercive voltage as a function of poling voltage for the
three
PNZT cells.
FIG. 11 is a graph of bipolar switched polarization as a function of fatigue
cycles for
the three PNZT cells.
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
My conclusion based partially upon some of the considerations presented in the
background section is that, for advanced ferroelectric integrated circuits,
the coercive voltage
V~ and the maximum operating voltage VmaX should be no more than acceptably
high values,
contrary to the prior art which believed the coercive voltage should be as
high as possible.
The present invention attempts to take advantage of the countervailing
considerations
between large tetragonality promoting good ferroelectric behavior but poor
fatigue
characteristics and excessively high operating voltage and small tetragonality
exhibiting poor
ferroelectric characteristics but good fatigue characteristics and low
operating voltages.
The c/a factor of the ferroelectric material, illustrated in FIG. 5, has major
implications for the ferroelectric behavior and fatigue characteristics. A
small cla ratio means
the unit cell is closer to a cubic symmetry while a larger ratio results in
greater tetragonality
of the cell. Generally, the larger the cla ratio, the greater is the
polarizability of the material,
as manifested by large values of the maximum polarization PmaX and of the
remanent
polarization P~. It would also appear that a large cla ratio produces a more
rectangular
hysteresis loop 70, thus contributing to a large coercive voltage V~. However,
as explained
before, a large coercive voltage V~ may not always be desirable.
It also appears that a large cla ratio contributes to fatigue characteristics
and may as a
result further reduce the squareness of the hysteresis. These perovskite
materials are almost
always grown above the Curie temperature so that the material as grown has a
cubic lattice
structure with a single lattice dimension of a '. In the crystallographically
oriented materials
needed for advanced ferroelectric integrated circuits, the cubic material as
grown is to some
degree epitaxially oriented to the underlying templating layer of, for
example, LSCO. As the
material is cooled to below the Curie temperature, the material converts to
the tetragonal
structure of FIG. 5. Ignoring thermal expansion effects at temperatures remote
from the
transition, as the material is cooled across the phase transition, the lattice
constant decreases
in two dimensions from a'to a while in the other dimension the lattice
constant increases
from a'to c. Nonetheless, the newly tetragonal material remains atomically
anchored to the
substrate that does not undergo such a transition. As a result, the transition
impresses a great
amount of stress in the ferroelectric material, particularly near the
interface with the
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templating layer, and the stress is larger for larger cla ratios. Such high
levels of stress are
expected to drive several mechanisms contributing to fatigue and imprint in
crystallographically oriented ferroelectrics. It is noted that in
polycrystalline ferroelectrics
typical in the prior art, there is no atomic templating, and the tetragonal
crystallites can
accommodate a much higher lattice mismatch on the crystallite faces. Thus,
particularly for
crystallographically oriented tetragonal perovskites, a large cla ratio
implies a great amount of
induced stress which may seriously increase fatigue. It is also believed that
a large cla ratio
leads to slower switching of the ferroelectric polarization.
A second effect is that there are three possible orientations for the
tetragonal structure
as the material is cooled from the growth temperature to below the Curie
temperature. The
structure of FIG. 5 is based upon the generally preferred orientation that the
c-axis is
perpendicular to the plane of the templating layer. This is referred to as a c-
domain.
However, on a local scale, it is also possible that one or the other of the
two a-axes is
perpendicular to the templating layer with the c-axis lying in the plane.
These orientations are
a-domains. The existence of both a- and c-orientations produce 90°
domain walls between
the two differentially oriented regions. Uniform c-domains are preferred, and
generally the
a-domains will anneal to the orientation of the neighboring c-domains and form
larger
domains. However, if there is large value of cla, any annealing at lower
temperature includes
a significant distortion from the existing crystal structure and the
transition, while favorable,
is difficult to activate. That is, the multiple orientations may be
metastable. Song et al. have
explained this effect in "Activation field of ferroelectric (Pb,La)(Zr,Ti)O~
capacitors,"
Applied Physics Letters, vol. 71, no. 15, October 1997, pp. 2211-2213.
Furthermore, the operation of ferroelectric cells ultimately depends upon the
switching of polarization domains. It is well known that ferroelectrics
containing multiple
domains with 90° domain walls between them require higher fields to
switch compared to
those with only 1$0° domain walls. Hence, it is desirable to suppress
the multiple
orientations arising from c-domains in the predominantly c-axis oriented
ferroelectric
material.
Based upon these considerations, we now believe that ferroelectric integrated
circuits
which need to be operated at lower voltages should include a ferroelectric
material of lower
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tetragonality, that is, a reduced cla ratio though one having a value above
unity. The cla ratio
may be described as a tetragonality factor for materials having the same or
nearly the same a-
axis lattice vectors in two directions. Although the polarization effects may
be degraded by a
lower cla ratio, they may still be quite adequate. At the same time, the
fatigue characteristics
are improved because of the reduced strain. Further, it is believed that the
material is easier
to anneal into a purely c-axis oriented material. Yet further, the
ferroelectric cells of lower
tetragonality are expect to be more easily switched. That is, the switching
speed is increased.
I believe, based on experiments presented below, that a c/a ratio of about
1.01 is most
preferred, and beneficial results are obtained with values of the
tetragonality factor extending
down to 1.005.
One favored class of ferroelectric material is PLZT, that is Pb,_XLaXZryTi,_y.
A more
compact designation is, for example, 7/65/35 where x=7%, y=65%, and 1-y=35%.
The
designation thus amounts to xlyll -y. Generally, a large value of x decreases
feiroelectric
effects but favors crystalline quality because of the decreased tetragonality.
PLZT with high
values of x around 65% are used for electrooptical devices, but at these
values of x, the
material is non-tetragonal. I believe that for reduced voltage operation, PLZT
should have a
La content x of between 6 and 12%.
One of the examples presented by Ramesh in U.S. Patent 5,270,298 includes a
ferroelectric cell structure with PLZT having a composition of x=10%, y=20%,
that is,
10/20/80. Note that the cited application uses different definitions for x and
y. Two
prototype capacitor structures were fabricated according the method of the
cited patent. One
composition was {0/20/80) and the other was ( 10/20/80), that x equals
alternatively 0% and
10%. The crystallographic parameters for thin films of these materials are
given in TABLE 1.
Yang et al. reports similar results in "Low voltage performance of Pb(Zr,
Ti)03 capacitors
through donor doping," Applied Physics Letters, vol. 71, no. 25, December
1997, pp. 3578-
3580.
x (%) c (nm) a (nm) c/a
0 0.411 0.395 1.034
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3 0.410 0.396 1.030
0.4025 ~ 0.396 1.016
TABLE 1
Pulsed hysteresis curves were measured for the two samples. The results are
shown in
5 FIG. 6. The PZT sample (x=0) in loop 90 shows a very square characteristic,
while the PLZT
sample with x=10% in loop 92 shows a less square behavior. Later measurements
of the
hysteresis curve for the x=0.3 PLZT capacitors show results intermediate the
graphs of
FIG. 6.
The x=0.1 PLZT sample was tested for a number of pulsed poling voltages. The
10 hysteresis loops are shown in FIG. 7: loop 94 for 5V poling; loop 96 for
2.3V poling; and
loop 98 for 2V poling. For the x=0.1 PLZT sample, the saturation polarization
is about
35pC/cm2 at 5V, and the coercive voltages V~ are all about 0.6V.
The x=0.1 PLZT capacitors were tested for fatigue at both room temperature and
at
100°C. Both the fatiguing and test pulses were at 2V. The samples
showed essentially no
fatigue out to 10' ' cycles. Other tests with x=0.03 PLZT capacitors showed
better initial
polarizability, but fatigue above 109 cycles degrade the polarizability to
below that for the
x=0.1 PLZT.
As suggested previously, it is believed that the higher-lanthanum
ferroelectrics will
switch with lower energies than the more highly polarized lower-lanthanum
ferroelectrics
because of the lesser occurrence of a-axis domains. In an operational cell,
this benefit is
believed to extend to switching with shorter pulse widths, an effect that
becomes important
with ferroelectric memories which should switch at substantially less than a
lpm when
incorporated into computer systems, for example, using pulse widths of 100ns.
Experimental results are not available for a direct comparison between
similarly fabricated
cells with ferroelectrics of differing tetragonality. However, pulse-width
measures show that
PLZT capacitors may have somewhat less switchable polarization at longer pulse
widths than
do PZT capacitors, presumably because PLZT has a lower tetragonality factor
than does PZT.
However, as the pulse width decreases towards 100ns, the switchable
polarization of PZT
substantially falls while PLZT suffers a lesser decrease. Thus, it is expected
that the higher-
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WO 00/17936 PCT/US99/22178
lanthanum PLZT will operate better with very short pulse widths.
These results for PLZT show that superior results are obtained with a
tetragonality
factor cla of 1.016 rather than 1.030. I believe that a tetragonality factor
of 1.01 should
provide even better results for low voltage operation of the ferroelectric
cell, and a
tetragonality factor of even 1.005 would be beneficial.
Another ferroelectric material of great interest is PNZT, that is,
Pb,_xNbxZryTi,_y03.
We observe that this material behaves similarly to PLZT, although less
dramatically in the
polarization effects, but the fatigue and timing effects are substantial.
A series of prototype test capacitor structures were fabricated using the now
conventional pulsed ablation deposition (PLD) technique. A ( 100)-oriented
silicon substrate
was covered first with a TiN barrier layer. The TiN-covered substrate was then
covered in a
PLD process with a platinum contact layer. The ferroelectric layers were then
grown by PLD
in an oxygen environment at 600°C. The ferroelectric stack consisted of
a lower
contacdtemplate layer of LSCO, a PNZT ferroelectric layer, and a top contact
layer of LSCO.
The crystallographic parameters for thin films of Pb,.xNbxZro.2Tio.g03, that
is, {x/80/20)
PNZT, are given in TABLE 2. are given in TABLE 2.
x (%) c (nm) a (nm) c/a
0 0.4103 0.3968 1.034
6 0.4088 0.3975 1.0284
10 0.4083 0.3991 1.0233
TABLE 2
Hysteresis curves for capacitor structures for the three compositions were
measured
with a poling voltage of 4.SV, as shown in FIG. 8. Loop 100 shows the
hysteresis curve for
~0, that is, PZT; loop 102, for x=6%; and loop 104, for X10%. The polarization
properties
decrease somewhat for x=6% and substantially more for x=10%. Nonetheless the
niobium-
rich sample exhibit good hysteretic characteristics.
Similar hysteretic characteristics were obtained using a barrier layer of
(Tio.9Alo.,)N
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WO 00/17936 PCT/US99/22178
with a varying niobium content. Close analysis of these curves show
interesting results as the
maximum applied voltages are reduced and as the devices are fatigued. In FIG.
9 are
illustrated curves for the switched polarization OP=P*-P~ as a function of the
maximum
applied voltage VmaX. Curve 110 gives the switch polarization for a Nb content
of x=0%;
S curve 112, for x=6%; and curve 114 for x=10%. The Nb-free sample, that is,
of PZT, exhibits
the largest switched polarization at the highest switching voltage of SV. The
sample with
x=6% is somewhat reduced, and the highest content of niobium exhibits the
least switched
polarization. At 4V, the difference is even larger. However, as the maximum
voltages are
reduced below 3V, the situation changes. At 2V, the results are the same for
6% and 10%. In
FIG. 10 are shown the coercive voltages V~ as a function of maximum applied
voltage VmaX
for the same three values of Nb content. Curve 120 gives the value for x=0;
curve 122, for
x=6%; and curve 124, for x=10%. The low values of V~ correspond to low values
of Vs~~ and
to better low-voltage properties.
The fatigue results are even more interesting. The memory cells were fatigued
with
bipolar pulses of t3V at IMHz. Their bipolar switched polarizations ~P were
measured at
various times during the fatigue cycling, and the results are shown in FIG.
11. Curves 130
gives the switched polarizations for x=0; curves 132, for x=6%; and curves
134, for x=10%.
With no fatigue, the cells with lower Nb content showed somewhat better
switched
polarization than the cell with x=10%. However, after extended fatiguing, the
cells with x=0
began to severely degrade, and those with Nb content of 6% and higher showed
better overall
results.
Thus, it is seen that the La or Nb content should be raised to levels above
those
normally recommended for commercially viable ferroelectric memory cells. For
PLZT, the
lanthanum fraction x should be at least 3% and preferably more than 6% up to
12% when the
Zr fraction is approximately 20%. I believe that 15% is the maximum preferred
La fraction if
reasonable polarizabilities are to be achieved. The highest value of the La
content is limited
by the PLZT forming in a non-ferroelectric phase. The Zr fraction can be
increased to 50%,
for which the La fraction is much less, preferably around 2%.
For PNZT, I believe the same numbers apply to the Zr and Nb fractions.
Expressed in
terms of the tetragonality factor cla, for PNZT it should be reduced to below
1.029 and
CA 02343129 2001-03-07
WO 00/17936 PCT/US99/Z2178
preferably below 1.025. Beneficial results are expected with the PNZT
tetragonality factor
having a value in a range extending down to 1.020.
The memory cell presented in FIG. 1 is presented only to explain the exact
structure
used in the examples. Other structures of crystallographically oriented
ferroelectrics may be
used. Particularly preferred are those not requiring any platinum, such as the
one
incorporating an intermetallic barrier, disclosed by Dhote et al. in U.S.
Patent Application
08/582,545, filed January 3, 1996 and by Dhote et al. in U.S. Patent
Application 08/871,059,
filed June 19, 1997. The former corresponds to PCT Publication WO 97/25745.
Though the invention has been described with respect to particular
compositions of
PLZT and PNZT, it is not limited thereto. Rare-earth elements other than
lanthanum and
niobium may be used in fractions that reduce the tetragonality relative to a
fraction that
produces higher polarization effects.
The invention thus provides a ferroelectric cell that trades off unneeded
polarization
for needed stress reduction, resulting in less fatigue and higher switching
speeds.
16
