Title of Invention

"A METHOD FOR VAPORIZING AN ORGANIC MATERIAL"

Abstract A method for vaporizing an organic material and condensing it onto a surface of a substrate to form a layer of organic material on the surface of the substrate, comprising: (a) providing a quantity of a first organic material in a powdered form in a first container and a quantity of a second organic material in a powdered form in a second container spaced (b) fluidizing the first organic material in the first container by agitating the first organic material with a first agitating device placed in proximity of the infeed portion of a first auger structure, and transferring the fluidized first organic material from the first container into a manifold with the first auger structure along a first feeding path, and vaporizing the first organic material in the manifold; (c) fluidizing the second organic material by agitating the second organic material with a second agitating device placed in proximity of the infeed portion of a second auger structure, and transferring the fluidized second organic material into the manifold, and vaporizing the second organic material in the manifold, the first and second vaporized organic materials being mixed in the manifold; and (d) delivering through at least one aperture of the manifold the mixed vaporized organic materials to the substrate surface to form the layer.
Full Text DELIVERING PARTICULATE MATERIAL
TO A VAPORIZATION ZONE
FIELD OF THE INVENTION
The present invention relates to the field of physical vapor
deposition of particulate material.
BACKGROUND OF THE INVENTION
An OLED device includes a substrate, an anode, a holetransporting
layer made of an organic compound, an organic luminescent layer
with suitable dopants, an organic electron-transporting layer, and a cathode.
OLED devices are attractive because of their low driving voltage, high luminance,
wide-angle viewing and capability for full-color flat emission displays. Tang et
al. described this multilayer OLED device in their U.S. Patent Nos. 4,769,292 and
4,885,211.
Physical vapor deposition in a vacuum environment is the principal
means of depositing thin organic material films as used in small molecule OLED
devices. Such methods are well known, for example Barr in U.S. 2,447,789 and
Tanabe et al. in EP 0 982 411. The organic materials used in the manufacture of
OLED devices are often subject to degradation when maintained at or near the
desired rate dependant vaporization temperature for extended periods of time.
Exposure of sensitive organic materials to higher temperatures can cause changes
in the structure of the molecules and associated changes in material properties.
To overcome the thermal sensitivity of these materials, only small
quantities of organic materials have been loaded in sources and they are heated as
little as possible. In this manner, the material is consumed before it has reached
the temperature exposure threshold to cause significant degradation. The
limitations with this practice are that the available vaporization rate is very low
due to the limitation on heater temperature, and the operation time of the source is
very short due to the small quantity of material present in the source. In the prior
art, it has been necessary to vent the deposition chamber, disassemble and clean
the vapor source, refill the source, reestablish vacuum in the deposition chamber
and degas the just-introduced organic material over several hours before resuming
operation. The low deposition rate and the frequent and time consuming process
associated with recharging a source has placed substantial limitations on the
throughput of OLED manufacturing facilities.
A secondary consequence of heating the entire organic material
charge to roughly the same temperature is that it is impractical to mix additional
organic materials, such as dopants, with a host material unless the vaporization
behavior and vapor pressure of the dopant is very close to that of the host material.
This is generally not the case and as a result, prior art devices frequently require
the use of separate sources to co-deposit host and dopant materials.
A consequence of using single component sources is that many
sources are required in order to produce films containing a host and multiple
dopants. These sources are arrayed one next to the other with the outer sources
angled toward the center to approximate a co-deposition condition. In practice,
the number of linear sources used to co-deposit different materials has been
limited to three. This restriction has imposed a substantial limitation on the
architecture of OLED devices, increases the necessary size and cost of the vacuum
deposition chamber and decreases the reliability of the system.
Additionally, the use of separate sources creates a gradient effect in
the deposited film where the material in the source closest to the advancing
substrate is over represented in the initial film immediately adjacent the substrate
while the material in the last source is over represented in the final film surface.
This gradient co-deposition is unavoidable in prior art sources where a single
material is vaporized from each of multiple sources. The gradient in the deposited
film is especially evident when the contribution of either of the end sources is
more than a few percent of the central source, such as when a co-host is used.
FIG. 1 shows a cross-sectional view of such a prior-art vaporization device 5,
which includes three individual sources 6, 7, and 8 for vaporizing organic
material. Vapor plume 9 is preferably homogeneous in the materials from the
different sources, but in fact varies in composition from sided to side resulting in a
non-homogeneous coating on substrate 15.
A further limitation of prior art sources is that the geometry of the
vapor manifold changes as the organic material charge is consumed. This change
requires that the heater temperature change to maintain a constant vaporization
rate and it is observed that the overall plume shape of the vapor exiting the
orifices can change as a function of the organic material thickness and distribution
in the source, particularly when the conductance to vapor flow in the source with a
full charge of material is low enough to sustain pressure gradients from nonuniform
vaporization within the source. In this case, as the material charge is
consumed, the conductance increases and the pressure distribution and hence
overall plume shape improve.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an effective way
of transferring particulate material from a container to a vaporization zone.
This object is achieved by 1. A method for vaporizing particulate
material and condensing it onto a surface to form a layer, comprising:
(a) providing a quantity of first particulate material in a first
container and a quantity of second particulate material in a second container
spaced apart from the first container, the first and second containers respectively
having first and second openings;
(b) transferring the first particulate material through the first
opening in the first container into a manifold and vaporizing the first particulate
material in the manifold;
(c) transferring the second particulate material through the
second opening in the second container into the manifold and vaporizing the
second particulate material in the manifold, whereby the first and second
vaporized particulate materials are mixed; and
(d) delivering the mixed vaporized materials from the manifold
to the surface to form the layer.
It is an advantage of the present invention that the continuous
heating of material during operation of prior art devices is eliminated in that only
a small portion of particulate material is heated, for a short period of time and at a
controlled rate. The bulk of particulate material is maintained at a temperature
that can be as much as 300°C cooler than the desired rate-dependant vaporization
temperature. This can be particularly advantageous when vaporizing organic
materials.
It is a further advantage of the present invention that it can
maintain a steady vaporization rate with a continuously replenished charge of
particulate material and with a steady heater temperature. The device thus allows
extended operation of the source with substantially reduced risk of degrading even
very temperature-sensitive organic materials.
It is a further advantage of the present invention that it permits
materials having different vaporization rates and degradation temperature
thresholds to be co-sublimated in the same source.
It is a further advantage of the present invention that it permits
linear vaporization rate control by controlling the volumetric metering rate or
controlling the feed pressure of the compacted particulate material.
It is a further advantage of the present invention that it can rapidly
stop and reinitiate vaporization and achieve a steady vaporization rate quickly by
controlling the metering rate of the particulate material, minimizing contamination
of the deposition chamber walls and conserving the particulate materials when a
substrate is not being coated.
It is a further advantage that the present device achieves
substantially higher vaporization rates than in prior art devices with substantially
reduced material degradation. Further still, no heater temperature change is
required as the source material is consumed.
It is a further advantage of the present invention that it can provide
a vapor source in any orientation, which is frequently not possible with prior-art
devices.
It is a further advantage of some embodiments of this invention
that it can remove adsorbed gases from the particulate material through the use of
heat and vacuum as a much smaller quantity of particulate material is conveyed
through the device.
It is a further advantage of some embodiments of this invention
that it can permit a temporal gradation in concentration of one or more of the
particulate material components by varying the feed rate of one or more of the
components relative to the other material components.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a prior-art vaporization device;
FIG. 2 is a three-dimensional view of one embodiment of an
apparatus according to the present invention for vaporizing particulate materials
and condensing them onto a surface to form a layer;
FIG. 3 is a cross-sectional view of one embodiment of a portion of
the above apparatus for feeding particulate material according to the present
invention, including one embodiment of an agitating device useful in the present
invention;
FIG. 4 is a cross-sectional view of one embodiment of a portion of
the above apparatus for feeding and vaporizing particulate material according to
the present invention;
FIG. 5 shows a graphical representation of vapor pressure vs.
temperature for two organic particulate materials;
FIG. 6a is a cross-sectional view showing one embodiment of an
auger structure useful in this invention;
FIG. 6b is a cross-sectional view of the terminal end of the auger
structure in FIG. 6a;
FIG. 6c is a relief view showing another embodiment of an auger
structure useful in this invention;
FIG. 6d is a cross-sectional view showing another embodiment of
an auger structure useful in this invention;
FIG. 7 is a cutaway view of another embodiment of an agitating
device useful in the present invention;
FIG. 8 is a cutaway view of another embodiment of an agitating
device useful in the present invention;
FIG. 9 is a cross-sectional view of a portion of another embodiment
of an apparatus according to the present invention for vaporizing particulate
materials and condensing them onto a surface to form a layer;
FIG. 10 is a cross-sectional view of a device according to the
present invention including a deposition chamber enclosing a substrate; and
FIG. 11 is a cross-sectional view of an OLED device structure that
can be prepared with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to FIG. 2, there is shown a three-dimensional view of
one embodiment of an apparatus according to the present invention for vaporizing
particulate materials and condensing them onto a surface to form a layer.
Vaporization apparatus 10 includes manifold 20, attached feeding apparatus 40,
and attached feeding apparatus 45. Feeding apparatus 40 includes at least first
container 50 and feeding path 60. Feeding apparatus 45 includes at least second
container 55 spaced from first container 50 and feeding path 65. First container
50 is provided with a quantity of a first particulate material, such as a powder in
one embodiment. Second container 55 is provided with a quantity of second
particulate material. Feeding apparatus 40 can also include third container 70, and
feeding apparatus 45 can also include fourth container 75. Third container 70 is
associated with first container 50 and the first particulate material. Fourth
container 75 is associated with second container 55 and the second particulate
material. Third container 70 and fourth container 75 can receive first and second
particulate materials, respectively, and transfer them to first container 50 and
second container 55, respectively, as will become apparent. Manifold 20 includes
one or more apertures 30 through which vaporized particulate material can exit to
a substrate surface. Manifold 20 is shown in an orientation whereby it can form a
layer on a horizontally-oriented substrate, but it is not limited to this orientation.
Manifold 20 can be oriented vertically and can form a layer on a vertical substrate.
Manifold 20 had been described in detail by Long et al. in commonly-assigned,
above-cited U.S. Patent Application No. 10/784,585. Feeding apparatus 40 and
feeding apparatus 45 are shown attached to opposite sides of manifold 20, but they
can also be attached to the same side of manifold 20, or to the bottom of manifold
20 if the manifold is in a vertical orientation. The nature of the attachment of
feeding apparatus 40 to manifold 20 will become clear.
Turning now to FIG. 3, there is shown a cross-sectional view of
one embodiment of a portion of the above vaporization apparatus for feeding
particulate material according to the present invention whereby particulate
material is effectively fluidized and transferred to the auger structure. First
container 50 holds first particulate material 160, which can be in the form of a
finely divided powder and is desirably of a uniform size, and which feeds into
auger structure 80 in feeding path 60. Auger structure 80 passes through the
interior of first container 50 and feeds into the manifold described above (not
shown for clarity). At least a portion of auger structure 80 is rotated by motor 90
so as to transfer the first particulate material at a controlled volumetric rate or
pressure along feeding path 60 to a vaporization zone where the component
material is vaporized and subsequently delivered to a substrate to form a layer.
Feeding path 60, and therefore first particulate material in feeding path 60, can be
maintained at a temperature below the desired vaporization temperature of the
component material. To facilitate the movement of first particulate material 160
to auger structure 80, first particulate material 160 is fluidized by agitating first
particulate material 160 by using an agitating device, e.g. piezoelectric structure
130 or an electromechanical vibrator. Such fluidized material is more readily
transferred to auger structure 80 by gravity feed.
The addition of optional third container 70 to hold additional first
particulate material 100 provides several additional advantages. A large quantity
of first particuliate material 100 can be charged in the apparatus, allowing
continuous operation of the device for extended periods of time. By sensing the
quantity of particulate material in first container 50, e.g. by measuring the height
of the column of first particulate material 160, one can selectively meter the
amount of first particulate material transferred from second container 70 to first
container 50 and provide a substantially constant volume of first particulate
material 160 iri first container 50, e.g. ±5 cm3. In practice, 10 cm3 of particulate
material is loaded in first container 50. Some embodiments described herein have
great process latitude with respect to reliable particulate material feeding over a
wide range of particulate material height in the container and can be run nearly to
exhaustion without failing to feed particulate material. However, it is believed
that multi-component mixing homogeneity is fostered if an optimum powder
height is established and maintained in first container 50 to within ±10%. This
minimizes variations in the feeding rate of first particulate material 160 to feeding
path 60. Also, third container 70 can be arranged to be refillable without affecting
the operation of first container 50, allowing the device to be continuously operated
for even longer periods of time. First particulate material 100 is maintained in
third container 70 by e.g. screens 110 and 120, whose mesh size is chosen to
prevent the free flow of particulate material. Screens 110 and 120 can also be the
mechanism for providing measured quantities of first particulate material 100 to
move from third container 70 to first container 50. Screens 110 and 120 may be
contacted by agitating devices (not shown) that can be actuated to cause a quantity
of particulate material 100 to pass through the screen mesh. Such devices include
those to vibrate the screen, or a movable arm immediately above or below the
screen to allow selective agitation of screens 110 and 120. A commercial flour
sifter is one sqch device well adapted for use in this application. In these sifters,
three screens are used and the top surface of each screen is contacted by rotatable
anns that extend radially from the center of the sifter. The arms have a V shaped
cross section so as to force the powdered particulate material 100 into a
converging space between the ami and the screen as the aim rotates to thereby
force a controlled volume of powder through the screen. A sensing system based
on the height of first particulate material 160 in first container 50 (or on an
integrated signal derived from the deposition rate and time of operation) can serve
to actuate the devices agitating screens 110 and 120 so as to maintain a nearly
constant volume of particulate material 160 in first container 50. Agitating
devices such as piezoelectric structures 140 prevent the buildup of particulate
material 100 m the feed path to first container 50. Piezoelectric structures can be
vibrated with multiple frequencies, e.g. a siren effect, to prevent the buildup of
particulate material 100 at vibrational nodes. Feeding apparatus 45 of FIG. 2
operates in an analogous manner with second container 55, fourth container 75,
feeding path 65, and motor 35. Feeding apparatus 45 may also include an
analogous separate agitating device for fluidizing the second particulate material
by agitating it and thereby transferring it to an auger structure, an analogous
means for measuring the height of the column of second particulate material in
second container 55 and for metering the amount of second particulate material
transferred from fourth container 75 to second container 55, and an analogous
separate second auger structure that passes through the interior of second
container 55 to move the second particulate material down feeding path 65 and
transfer it to manifold 20.
For proper operation of feeding apparatus 40 and 45, it is important
to maintain a uniform feed rate of particulate material 160. Particulate material
160 is generally provided in a powdered form. One important strategy for
providing a free flow of particulate material 160 is to prevent bridging, a
characteristic behavior of particulate materials such as powders that can occur
when the powder particles self-assemble into a load-bearing structure about an
opening or aperture and thereby obstruct the flow of powder through the opening.
Bridging effects can occur, for example, when the dimensions of an aperture are
too small to overcome a tendency of a particulate material to resist flow. Factors
that may cause bridging can include particulate size relative to the aperture
dimensions, humidity, electrostatic attraction between particles, vacuum levels,
and friction. To alleviate this problem, the dimensions of an opening 230 at the
interface of first container 50 and feeding path 60, as shown in FIG. 3 for
example, must be sufficiently sized to overcome the bridging characteristics of the
powdered material. This sizing requirement is best detennined empirically, taking
into account worst-case conditions for the particular particulate material 160 that
must be supplied, in a free flowing manner, to feeding path 60. Maintaining a
nearly constant volume of particulate material 160 in first container 50 also helps
to promote a constant feed rate of particulate material 160 to auger structure 80.
By properly sizing opening 230 and maintaining a sufficient volume of particulate
material 160 in first container 50, a uniform feed rate can be achieved for many
types of powdered particulate material 160, providing a fluidized flow without
requiring any supplemental form of agitation.
Where the opening 230 must be narrow, feed rate uniformity can
be assured when the particulate material 160 in proximity to the infeed portion of
the screw auger is maintained in a fluidized state by an agitating device. This can
be accomplished by slowly agitating particulate material 160 immediately above
the auger screw or by inducing vibration, e.g. by piezoelectric structure 130, into
particulate material 160 that is tuned to induce liquid-like behavior of the
powdered particulate material 160 but is not so energetic as to cause gas-like
behavior.
Turning now to FIG. 4, there is shown in farther detail a crosssectional
view of one embodiment of a portion of the above apparatus for feeding
and vaporizing particulate material 160 according to the present invention. Auger
structure 80 transfers first particulate material 160 along feeding path 60 into
manifold 20 and heating element 170. Heating element 170 can be e.g. a heated
screen and has been previously described in detail by Long et al. Manifold 20
includes a vaporization zone which is defined as the region of feeding path 60
immediately adjacent to heating element 170. A thin cross-section of particulate
material 160 is heated to the desired rate-dependent temperature, which is the
temperature of heating element 170, by virtue of contact and thermal conduction,
whereby the thin cross-section of first particulate material 160 vaporizes.
Similarly, feeding apparatus 45 of FIG. 2 transfers the second particulate material
160 into manifold 20 at a second heating element, where the second particulate
material 160 vaporizes in manifold 20. The first and second vaporized particulate
materials 160 are mixed in manifold 20, and subsequently delivered to a substrate
surface to form a layer. The auger structure 80 and its rotation rate control the
rate at which particulate material 160 is fed to heating element 170. This linearly
controls the rate of vaporization and therefore the rate at which particulate
material 160 leaves the manifold in the vapor state. Thus the feed rate of
particulate material 160 to the auger structure and to the vaporization zone
controls the deposition rate of the vaporized component material onto the desired
surface. With two such structures, as in FIG. 1, the relative feed rates of the first
and second particulate materials 160 to the respective auger structures and the
respective vaporization zones controls the relative partial pressures of the first and
second particulate materials 160 in the manifold, and hence their relative
deposition rates and concentrations in the deposited layer. One useful example is
wherein one of particulate materials 160 is a host material and the other is a
dopant.
Additionally, base 180 can be included. Base 180 is a heatdissipating
structure to prevent much of the heat from heating element 170 from
traversing the length of feeding path 60, and thus keeps the bulk of particulate
material 160 significantly cooler than the conditions it experiences in the
vaporization zone immediately adjacent to heating element 170. Means of heat
dissipation for base 180 have been described by Long et al. in commonlyassigned,
above-cited U.S. Patent Application 10/784,585. A steep thermal
gradient thereby created protects all but the immediately vaporizing material from
the high temperatures. The vaporized component vapors rapidly pass through
heating element 170 and can enter into the heated manifold 20. The residence
time of particulate material 160 at the desired vaporization temperature is very
short and as a result, thermal degradation is greatly reduced. The residence time
of particulate material 160 at elevated temperature, that is, at the rate-dependent
vaporization temperature, is orders of magnitude less than prior art devices and
methods (seconds vs. hours or days in the prior art), which permits heating
organic particulate materials 160 to higher temperatures than in the prior art.
Thus, the current device and method can achieve substantially higher vaporization
rates, without causing appreciable degradation of organic components of
particulate material 160.
Particulate material 160 can include a single component, or can
include two or more different vaporizable components, such as organic material
components, each one having a different vaporization temperature. The
vaporization temperature can be determined by various means. For example, FIG.
5 shows a graphical representation of vapor pressure versus temperature for two
organic materials commonly used in OLED devices. The vaporization rate is
proportional to the vapor pressure, so for a desired vaporization rate, the data in
FIG. 5 can be used to define the required heating temperature corresponding to the
desired vaporization rate. In the case where particulate material 160 includes two
or more organic components, the temperature of heating element 170 is chosen
such that the vaporization is feed-rate limited, that is, the vapor pressure at the
heating element temperature is substantially above the desired partial pressure of
that component in the manifold, so that each of the organic material components
simultaneously vaporizes.
Pressure develops in manifold 20 as vaporization proceeds, and
streams of vapor exit manifold 20 through the series of apertures 30 shown in
FIG. 2. Because only a small portion of particulate material 160—the portion
resident in the vaporization zone—is heated to the rate-dependent vaporization
temperature, while the bulk of the material is kept well below the vaporization
temperature, it is possible to interrupt the vaporization by a means for interrupting
heating at heating element 170, e.g. stopping the movement of auger structure 80.
This can be done when a substrate surface is not being coated so as to conserve
particulate material 160 and minimize contamination of any associated apparatus,
such as the walls of a deposition chamber, which will be described below.
Because heating element 170 can be a fine mesh screen that
prevents powder or compacted material from passing freely through it, the
manifold can be used in any orientation. For example, manifold 20 of FIG. 2 can
be oriented down so as to coat a substrate placed below it. This is an advantage
not found in the heating boats of the prior art.
Turning now to FIG. 6a, there is shown a cross-sectional view of
one embodiment of an auger structure useful in this invention. The auger
structure 80 includes an auger screw 85 that is turned by motor 90. The distance
between the threads of the screw helix and the thread height are chosen to be
sufficiently large that powder tends not to pack into and rotate with the helix, but
rather to remain at the bottom of a horizontally oriented auger tube and be
transported linearly by virtue of the relative motion between the screw and the
auger tube. For example, an auger screw with a 2.5 mm pitch screw lead and a
0.8 mm thread height has been found to be an effective combination in
transporting and consolidating organic material powders in a horizontal
orientation.
The inventors have found that auger dimensions have an affect on
maintaining a uniform flow rate. Similar to the bridging effects noted above with
respect to the size of opening 230, proper auger sizing and screw thread pitch is
best determined empirically, considering worst-case conditions for the particular
composition of particulate material 160.
The inventors have also found that the angle of auger screw threads
can be optimized to facilitate free flow of particulate material 160 along feeding
path 60. While optimal screw thread angle may vary somewhat depending on the
particular component materials of powdered particulate material 160, it has been
determined that screw thread angles ranging from not less than about 4 degrees to
no more than about 15 degrees relative to the rotational axis of auger structure 85
provide optimal flow conditions for particulate materials 160 that are
conventionally used.
Various materials and surface treatments of the auger shaft have
been found to facilitate auger operation, allowing increased feed rates. While
stainless steel may provide acceptable performance, additional benefit may be
obtained by surface treatments such as electropolishing or by coatings, such as a
coating of titanium nitride.
While continuous auger rotation at a sustained rate may provide an
acceptable level of performance, added benefits may be obtained by pulsing the
auger, providing rotation of the auger shaft in a repeated incremental fashion. A
pulsing action reduces the tendency for powdered particulate material 160 to
rotate with the auger screw by reducing the effective coefficient of friction
between the auger screw and the particulate material. The powder feeding
efficiency of auger structure 85 is thereby improved. Pulsing behavior may also
be advantageous where it becomes useful to vary the feed rate over an interval, for
example.
In the horizontal orientation, particulate material 160 travels along
the bottom of auger screw 85 in a tumbling and dispersed form. At the terminal
end of auger screw 85, a powder pressure of 1 Mpa can be developed that
increases the bulk density of particulate material 160 to the point where it serves
as a vapor seal, preventing vaporized material in the manifold having a pressure
greater than the ambient vacuum level from flowing back along the auger screw to
the powder source container. As shown in FIG. 6b, the terminal end of auger
screw 85 is configured to have a thread-free portion 135 having a constant circular
cross section over a small length to constrain the consolidated powdered
participate material 160 to form a narrow annular or tubular shape. This narrow
annular shape substantially improves the thermal contact and temperature
uniformity through particulate material 160, between the temperature-controlled
auger screw 85 and the temperature-controlled feeding path 60. This
configuration additionally assures good temperature uniformity of particulate
material 160 at a given transverse cross section relative to a circular cross section
and substantially increases the attainable temperature gradient in particulate
material 160 between the auger structure and the heating element. The powdered
particulate material 160 is extruded from the auger structure in a tubular shape and
is sufficiently consolidated that it can maintain the tubular extruded form for at
least several millimeters upon exiting the support of the auger tube. This solid
form prevents pressurized vapor, resulting from organic material vaporization,
from flowing back into the auger structure and enables the powdered particulate
material 160 to bridge the short gap between the end of the temperature-controlled
auger structure and the heating element.
Thermal modeling of a powder dispensing system having this
annular configuration where the heating element is spaced 130 |im from the end of
the auger structure 85 indicates that an average axial thermal gradient of 0.5°C/|im
can be achieved through that portion of particulate material 160 spanning heating
element 170 and the terminal end of the auger structure when the temperature
differential between the two is 270°C. There can therefore be a 100°C
temperature drop through the first 200 |im of consolidated powdered particulate
material 160. This gradient prevents the usual leaching of more volatile
constituents from bulk volumes of mixed-component organic materials and
enables a single source to co-deposit multiple organic materials. This large
gradient is further instrumental in maintaining particulate material 160 in a
consolidated powder form at the exit of the auger tube even when organic
component materials that liquefy before vaporizing are employed.
The auger structure 80 shown in FIG. 6a is effective at transporting
particulate material 160 powders horizontally, but is not as effective in
transporting particulate material 160 vertically, since the particulate tends to
simply rotate with the screw and not advance along the length of the structure.
Turning now to FIG. 6c, there is a relief view of another embodiment of an auger
structure 95 useful in this invention. In this embodiment, auger structure 95
includes two or more auger screws, e.g. auger screws 85a, 85b, and 85c, with
identical interlaced helical threads. All of the auger screws 85a, 85b, and S5c
rotate in the same direction. Particulate material 160 that is packed between the
threads of one auger screw, e.g. 85a, will be removed as the material rotates into
contact with the interlaced thread of the second rotating auger screw, e.g. 85b,
because the facing portions of adjacent screws move in opposite directions.
Auger structure 95 thus overcomes the orientation restrictions of the single-screw
auger structure of FIG. 6a while retaining the ability to consolidate powdered
particulate material 160 into a solid shape and form a vapor seal. The discharge
portion of auger structure 95 would have an elongated cross-section that can
extend across the entire length of the manifold so as to inject material
substantially uniformly along its length.
Turning now to FIG. 6d, there is a cross-sectional view of another
embodiment of an auger structure 105 useful in this invention. Auger structure
105 includes a rotating helical thread 115, a stationary center portion 125, and a
stationary outer tube, which in this case is feeding path 60. In this embodiment,
only a portion of auger structure 105—the portion comprising helical threads
115—rotates and is turned by motor 90. Powdered particulate material 160
feeding with circular cross section helical threads has been demonstrated. The
thread consisted of a steel wire 0.7 mm diameter formed into a helix of 5 mm
outside diameter and 2.5 mm pitch. Smooth wires of other materials such as
titanium and stainless steel are also suitable. The wire can also have a noncircular
cross section, with a rectangular cross section being particularly
advantageous as it provides additional rigidity to prevent the helical thread from
changing dimensions as it encounters torsional resistance while pushing the
powdered particulate material 160. Stationary center portion 125, in cooperation
with feeding path 60, substantially prevents all but a thin film of powdered
particulate material 160 from rotating with the auger. Auger structure 105 does
not rely on gravity to accumulate powdered particulate material 160 and will
operate in any orientation. Auger structure 105 also consolidates the powdered
particulate material 160 into a thin annular shape that substantially improves the
thermal contact between particulate material 160 and temperature-controlled
feeding path 60 and stationary center portion 125. These characteristics are
significant in enabling the controlled vaporization of mixed component organic
materials, and organic materials that liquefy before vaporizing. Thus this
embodiment overcomes the orientation restrictions of the first auger structure
while retaining the ability to consolidate the powdered particulate material 160
into a solid shape and form a vapor seal.
The above embodiments of this invention, based primarily on
vaporization apparatus 10 of FIG. 2, are useful at atmospheric pressure and
pressures down to about one-half atmosphere. Experimentally, it has been
observed that fine powder is considerably more difficult to meter in a partial
vacuum below half an atmosphere. The powdered particulate material 160
agglomerates as residual air molecules are removed, and undergoes a reduction of
the elastic coupling between particles that is effective in communicating
vibrational energy through powdered particulate material 160 under atmospheric
conditions. This effect negatively influences the powder-feeding uniformity of
the auger structure. Therefore, a different agitating device can be necessary.
Turning now to FIG. 7, there is shown a cutaway view of another embodiment of
an agitating device useful in the present invention for overcoming the limitations
in low-pressure conditions. This embodiment employs three piezoelectric
structures as the agitating device. Piezoelectric structures 150 and 155 are
inclined at a steep angle and form opposite walls of a funnel at the bottom of first
container 50. The bottom portion 190 of these two piezoelectric structures is not
supported and leads directly to the infeed portion of auger structure 80. The
unsupported portions of the piezoelectric structures have high vibration amplitude
and are effective in fluidizing particulate material 160 in proximity to their
surfaces. The third piezoelectric structure 130 is mounted below auger structure
80 and imparts vibration whose amplitude is essentially perpendicular to the
vibration of the other two piezoelectric structures. The piezoelectric structures are
driven by a frequency sweeping circuit. The changing frequency is instrumental
in preventing the formation of nodes and improves the powder feeding efficiency
considerably. Auger structure 80 can be any of the above-described auger
structures.
FIG. 8 is a cutaway view of another embodiment of an agitating
device useful in the present invention for overcoming the limitations in lowpressure
conditions. Opening 230 represents the lower end of the above-described
first container 50. Rotating thread type device 210 includes left- and right-hand
helically wound wires on a common shaft. Rotating thread type device 210 is
positioned above the infeed portion of the auger structure such that the wires are
substantially tangent to the threads of auger structure 80. The rotating thread
should not interfere with the auger screw threads, but it will continue to operate
effectively with as much as 1 mm clearance. Rotating thread type device 210 is
slowly rotated via gear drive 220, by motor 90, which also turns auger structure
80. In practice, the rotational speed of the rotating thread type device 210 can
vary depending on the particle size and properties of the particular particulate
material 160, but a practical guide is to have the axial slew rate of the rotating
thread match the axial slew rate of the threads of the auger screw. The wires of
rotating thread type device 210 tend to push particulate material 160 toward the
center of opening 230 and prevent powder bridging over auger structure SO.
Auger structure 80 can be any of the above-described auger structures. This
agitating device is well adapted to feeding mixed-component organic materials as
it imparts very little energy to particulate material 160 and is therefore not likely
to cause particle separation by size or density.
FIG. 9 is a cross-sectional view of another embodiment of an
apparatus according to the present invention for vaporizing particulate materials
160 and condensing them onto a surface to form a layer. In this embodiment, first
container 50 and second container 55 are spaced apart, but positioned in such a
way that the feeding paths (represented by first auger structure 250 and second
auger structure 255, respectively) terminate in close proximity. First particulate
material 240 in first container 50 is fluidized and then transferred by first auger
structure 250 into mixing chamber 260 in manifold 20. Second particulate
material 245 irt second container 55 is fluidized and then transferred by second
auger structure 255 into mixing chamber 260 in manifold 20, where it mixes with
first particulate material 240. The mixed first and second particulate materials
240 and 245 are vaporized by heating element 170, and can be delivered to a
substrate surface by manifold 20. The relative feed rates of the first and second
particulate material 240 and 245 to the respective auger structures and the
respective vaporization zones controls the relative concentrations of materials in
the deposited layer, as well as the deposition rate. Such an apparatus can enable a
gradient in dopant concentration through the thickness of a deposited layer, or can
create a smooth transition from one layer to the next by adjusting the
concentration of the first particulate material 240 from 100 % to 0 % while the
second host particulate material 245 concentration is simultaneously adjusted
from 0 % to 100 %. Multiple auger screw systems can be repeated along the
length of the source to independently feed different particulate materials so as to
deposit a series of layers in this way.
In practice, the apparatus described herein is operated as follows.
A first organic particulate material 160, which is useful in forming a layer on an
OLED device, is provided into third container 70, and a second organic particulate
material 160 is provided into fourth container 75. The first particulate material
160 is transferred in a controlled manner to first container 50 and the second
particulate material 160 to second container 55 in such a way as to maintain a
substantially constant volume of particulate materials in the first and second
containers. Each particulate material 160 can be fluidized by means described
herein and thereby transferred to a respective auger structure, which transfers the
particulate materials 160 to one or more vaporization zones as described herein.
At least one component of the particulate material 160 is vaporized in the
vaporization zone(s) into a manifold 20, which delivers the vaporized material to
the surface of an OLED substrate to form a layer, as will be described below.
As has been noted hereinabove, vacuum levels may tend to
complicate the problem of metering out uniform amounts of finely powdered
organic materials 160. Referring back to FIG. 2, it can be observed that a
continuous column of particulate material 160 is maintained in feeding path 60.
In one embodiment, this column of particulate material 160, if suitably
compacted, can be utilized as a type of vacuum seal, where particulate
characteristics of particulate material 160 allow. With this arrangement, a high
vacuum level can be present for particulate material 160 at heating element 170
and in the manifold 20. A lower vacuum level can then be maintained at first
container 50, which may even be at atmospheric pressure. Even a partial seal
could be advantageous. This sealing effect could also be used to isolate ambient
gases used for storage of organic particulate material 160 in first container 50
and/or for organic particulate material 100 in second container 70. With some
materials, for example, it is beneficial to store materials under an inert gas such as
argon or helium.
Turning now to FIG. 10, there is shown an embodiment of a device
of this disclosure including a deposition chamber enclosing a substrate.
Deposition chamber 280 is an enclosed apparatus that permits an OLED substrate
285 to be coated with organic material transferred from manifold 20. Manifold 20
is supplied with organic material via feeding path 60 as described above. For
clarity of illustration, only a single feeding path is shown. Deposition chamber
280 is held under controlled conditions, e.g. a pressure of 1 torr or less provided
by vacuum source 300. Deposition chamber 280 includes load lock 275 which
can be used to load uncoated OLED substrates 285, and unload coated OLED
substrates. OLED substrate 285 can be moved by translational apparatus 295 to
provide even coating of vaporized organic material over the entire surface of
OLED substrate 285. Although vaporization apparatus is shown as partially
enclosed by deposition chamber 280, it will be understood that other arrangements
are possible, including arrangements wherein the entire vaporization apparatus,
including any container or containers for holding powdered particulate material
160, is enclosed by deposition chamber 280.
In practice, an OLED substrate 285 is placed in deposition chamber
280 via load lock 275 and held by translational apparatus 295 or associated
apparatus. The vaporization apparatus is operated as described above, and
translational apparatus 295 moves OLED substrate 285 perpendicular to the
direction of emission of organic material vapors from manifold 20, thus delivering
mixed vaporized organic material to the surface of OLED substrate 285 to
condense and form a layer of organic material on the surface.
Turning now to FIG. 11, there is shown a cross-sectional view of a
pixel of a light-emitting OLED device 310 that can be prepared in part according
to the present invention. The OLED device 310 includes at a minimum a
substrate 320, a cathode 390, an anode 330 spaced from cathode 390, and a lightemitting
layer 350. The OLED device can also include a hole-injecting layer 335,
a hole-transporting layer 340, an electron-transporting layer 355, and an electroninjecting
layer 360. Hole-injecting layer 335, hole-transporting layer 340, lightemitting
layer 350, electron-transporting layer 355, and electron-injecting layer
360 include a series of organic layers 370 disposed between anode 330 and
cathode 390. Organic layers 370 are the organic material layers most desirably
deposited by the device and method of this invention. These components will be
described in more detail.
Substrate 320 can be an organic solid, an inorganic solid, or a
combination of organic and inorganic solids. Substrate 320 can be rigid or
flexible and can be processed as separate individual pieces, such as sheets or
wafers, or as a continuous roll. Typical substrate materials include glass, plastic,
metal, ceramic, semiconductor, metal oxide, semiconductor oxide, semiconductor
nitride, or combinations thereof. Substrate 320 can be a homogeneous mixture of
materials, a composite of materials, or multiple layers of materials. Substrate 320
can be an OLED substrate, that is a substrate commonly used for preparing OLED
devices, e.g. active-matrix low-temperature polysilicon or amorphous-silicon TFT
substrate. The substrate 320 can either be light transmissive or opaque, depending
on the intended direction of light emission. The light transmissive property is
desirable for viewing the EL emission through the substrate. Transparent glass or
plastic are commonly employed in such cases. For applications where the EL
emission is viewed through the top electrode, the transmissive characteristic of the
bottom support is immaterial, and therefore can be light transmissive, light
absorbing or light reflective. Substrates for use in this case include, but are not
limited to, glass, plastic, semiconductor materials, ceramics, and circuit board
materials, or any others commonly used in the formation of OLED devices, which
can be either passive-matrix devices or active-matrix devices.
-20-
An electrode is formed over substrate 320 and is most commonly
configured as an anode 330. When EL emission is viewed through the substrate
320, anode 330 should be transparent or substantially transparent to the emission
of interest. Common transparent anode materials useful in this invention are
indium-tin oxide and tin oxide, but other metal oxides can work including, but not
limited to, aluminum- or indium-doped zinc oxide, magnesium-indium oxide, and
nickel-tungsten oxide. In addition to these oxides, metal nitrides such as gallium
nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc
sulfide, can be used as an anode material. For applications where EL emission is
viewed through the top electrode, the transmissive characteristics of the anode
material are immaterial and any conductive material can be used, transparent,
opaque or reflective. Example conductors for this application include, but are not
limited to, gold, indium, molybdenum, palladium, and platinum. The preferred
anode materials, transmissive or otherwise, have a work function of 4.1 eV or
greater. Desired anode materials can be deposited by any suitable means such as
evaporation, sputtering, chemical vapor deposition, or electrochemical means.
Anode materials can be patterned using well known photolithographic processes.
While not always necessary, it is often useful that a hole-injecting
layer 335 be formed over anode 330 in an organic light-emitting display. The
hole-injecting material can serve to improve the film formation property of
subsequent organic layers and to facilitate injection of holes into the holetransporting
layer. Suitable materials for use in hole-injecting layer 335 include,
but are not limited to, porphyrinic compounds as described in U.S. Patent No.
4,720,432, plasma-deposited fluorocarbon polymers as described in U.S. Patent
No. 6,208,075, and inorganic oxides including vanadium oxide (VOx),
molybdenum oxide (MoOx), nickel oxide (NiOx), etc. Alternative hole-injecting
materials reportedly useful in organic EL devices are described in
EP0891 121 Al andEP 1 029 909 AJ.
While not always necessary, it is often useful that a holetransporting
layer 340 be formed and disposed over anode 330. Desired holetransporting
materials can be deposited by any suitable means such as
evaporation, sputtering, chemical vapor deposition, electrochemical means,
thermal transfer, or laser thermal transfer from a donor material, and can be
deposited by the device and method described herein. Hole-transporting materials
useful in hole-transporting layer 340 are well known to include compounds such
as an aromatic tertiary amine, where the latter is understood to be a compound
containing at least one trivalent nitrogen atom that is bonded only to carbon
atoms, at least one of which is a member of an aromatic ring. In one form the
aromatic tertiary amine can be an arylamine, such as a monoarylamine,
diarylamine, tiriarylamine, or a polymeric arylamine. Exemplary monomeric
triarylamines are illustrated by Klupfel et al. in U.S. Patent No. 3,180,730. Other
suitable triarylamines substituted with one or more vinyl radicals and/or
comprising at least one active hydrogen-containing group are disclosed by
Brantley et al. in U.S. Patent Nos. 3,567,450 and 3,658,520.
A more preferred class of aromatic tertiary amines are those which
include at least two aromatic tertiary amine moieties as described in U.S. Patent
Nos. 4,720,432 and 5,061,569. Such compounds include those represented by
structural Formula A.
(Figure Removed)
Qi and Ch are independently selected aromatic tertiary amine moieties; and
G is a linking group such as an arylene, cycloalkylene, or alkylene group
of a carbon to carbon bond.
In one embodiment, at least one of Ql or Q2 contains a polycyclic
fused ring structure, e.g., a naphthalene. When G is an aryl group, it is
conveniently a phenylene, biphenylene, or naphthalene moiety.
A useful class of triarylamines satisfying structural Formula A and
containing two triarylamine moieties is represented by structural Formula B.
(Figure Removed)
where:
RI and R2 each independently represent a hydrogen atom, an aryl group, or
an alkyl group or RI and R2 together represent the atoms completing a cycloalkyl
group; and
R3 and R4 each independently represent an aryl group, which is in turn
substituted with a diaryl substituted ammo group, as indicated by structural
Formula C.
wherein Rs and Rg are independently selected aryl groups. In one embodiment, at
least one of RS or R6 contains a polycyclic fused ring structure, e.g., a
naphthalene.
Another class of aromatic tertiary amines are the tetraaryldiamines.
Desirable tetraaryldiamines include two diarylamino groups, such as indicated by
Formula C, linked through an arylene group. Useful tetraaryldiamines include
those represented by Formula D.
each Are is an independently selected arylene group, such as a phenylene
or anthracene moiety;
n is an integer of from 1 to 4; and
Ar, R-j, RS, and Rg are independently selected aryl groups.
In a typical embodiment, at least one of Ar, R7, Rg, and R is a
polycyclic fused ring structure, e.g., a naphthalene.
The various alkyl, alkylene, aryl, and arylene moieties of the
foregoing structural Formulae A, B, C, D, can each in turn be substituted. Typical
substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and
halogens such as fluoride, chloride, and bromide. The various alkyl and alkylene
moieties typically contain from 1 to about 6 carbon atoms. The cycloalkyl
moieties can contain from 3 to about 10 carbon atoms, but typically contain five,
six, or seven carbon atoms--e.g., cyclopentyl, cyclohexyl, and cycloheptyl ring
structures. The aryl and arylene moieties are usually phenyl and phenylene
moieties.
The hole-transporting layer in an OLED device can be formed of a
single or a mixture of aromatic tertiary amine compounds. Specifically, one can
employ a triarylamine, such as a triarylamine satisfying the Formula B, in
combination with a tetraaryldiamine, such as indicated by Formula D. When a
triarylamine is employed in combination with a tetraaryldiamine, the latter is
positioned as a layer inteiposed between the triarylamine and the electroninjecting
and transporting layer. The device and method described herein can be
used to deposit single- or multi-component layers, and can be used to sequentially
deposit multiple layers.
Another class of useful hole-transporting materials includes
polycyclic aromatic compounds as described in EP 1 009 041. In addition,
polymeric hole-transporting materials can be used such as poly(N-vinylcarbazole)
(PVK), polythiophenes, polypyrrole, polyaniline, and copolymers such as
poly(3,4-ethylenedioxytiiiophene)/poly(4-styrenesulfonate) also called
PEDOT/PSS.
Light-emitting layer 350 produces light in response to hole-electron
recombination. Light-emitting layer 350 is commonly disposed over holetransporting
layer 340. Desired organic light-emitting materials can be deposited
by any suitable means such as evaporation, sputtering, chemical vapor deposition,
electrochemical means, or radiation thermal transfer from a donor material, and
can be deposited by the device and method described herein. Useful organic lightemitting
materials are well known. As more fully described in U.S. Patent Nos.
4,769,292 and 5,935,721, the light-emitting layers of the organic EL element
include a luminescent or fluorescent material where electroluminescence is
produced as a result of electron-hole pair recombination in this region. The lightemitting
layers can include a single material, but more commonly include a host
material doped with a guest compound or dopant where light emission comes
primarily from the dopant. The dopant is selected to produce color light having a
particular spectrum. The host materials in the light-emitting layers can be an
electron-transporting material, as defined below, a hole-transporting material, as
defined above, or another material that supports hole-electron recombination. The
dopant is usually chosen from highly fluorescent dyes, but phosphorescent
compounds, e.g., transition metal complexes as described in WO 98/55561, WO
00/18851, WO 00/57676, and WO 00/70655 are also useful. Dopants are
typically coated as 0.01 to 10 % by weight into the host material. The device and
method described herein can be used to coat multi-component guest/host layers
without the need for multiple vaporization sources.
Host and emitting molecules known to be of use include, but are
not limited to, those disclosed in U.S. Patent Nos. 4,768,292; 5,141,671;
5,150,006; 5,151,629; 5,294,870; 5,405,709; 5,484,922; 5,593,788; 5,645,948;
5,683,823; 5,755,999; 5,928,802; 5,935,720; 5,935,721; and 6,020,078.
Metal complexes of 8-hydroxyquinoline and similar derivatives
(Formula E) constitute one class of useful host materials capable of supporting
electroluminescence, and are particularly suitable for light emission of
wavelengths longer than 500 nm, e.g., green, yellow, orange, and red.
wherein:
M represents a metal;
n is an integer of from 1 to 3; and
Z independently in each occurrence represents the atoms completing a
nucleus having at least two fused aromatic rings.
From the foregoing it is apparent that the metal can be a
monovalent, divalent, or trivalent metal. The metal can, for example, be an alkali
metal, such as lithium, sodium, or potassium; an alkaline earth metal, such as
magnesium or calcium; or an earth metal, such as boron or aluminum. Generally
any monovalent, divalent, or trivalent metal known to be a useful chelating metal
can be employed.
Z completes a heterocyclic nucleus containing at least two fused
aromatic rings, at least one of which is an azole or azine ring. Additional rings,
including both aliphatic and aromatic rings, can be fused with the two required
rings, if required. To avoid adding molecular bulk without improving on function
the number of ring atoms is usually maintained at 18 or less.
The host material in light-emitting layer 350 can be an anthracene
derivative having hydrocarbon or substituted hydrocarbon substituents at the 9 and
10 positions. For example, derivatives of 9,10-di-(2-naphthyl)anthracene
constitute one class of useful host materials capable of supporting
electroluminescence, and are particularly suitable for light emission of
wavelengths longer than 400 nm, e.g., blue, green, yellow, orange or red.
Benzazole derivatives constitute another class of useful host
materials capable of supporting electroluminescence, and are particularly suitable
for light emission of wavelengths longer than 400 nm, e.g., blue, green, yellow,
orange or red. An example of a useful benzazole is 2, 2', 2"-(l,3,5~
phenylene)tris[l -phenyl-1 H-benzimidazolej.
Desirable fluorescent dopants include perylene or derivatives of
perylene, derivatives of anthracene, tetracene, xanthene, rubrene, coumarin,
rhodainine, quinacridone, dicyanomethylenepyran compounds, thiopyran
compounds, polymethine compounds, pyrilium and thiapyrilium compounds,
derivatives of distryrylbenzene or distyrylbiphenyl, bis(azinyl)methane boron
complex compounds, and carbostyryl compounds.
Other organic emissive materials can be polymeric substances, e.g.
polyphenylenevinylene derivatives, dialkoxy-polyphenylenevinylenes, poly-paraphenylene
derivatives, and polyfluorene derivatives, as taught by Wolk et al. in
commonly assigned U.S. Patent No. 6,194,119 Bl and references cited therein.
While not always necessary, it is often useful that OLED device
310 includes an electron-transporting layer 355 disposed over light-emitting layer
350. Desired electron-transporting materials can be deposited by any suitable
means such as evaporation, sputtering, chemical vapor deposition, electrochemical
means, thermal transfer, or laser thermal transfer from a donor material, and can
be deposited by the device and method described herein. Preferred electron-
transporting materials for use in electron-transporting layer 355 are metal chelated
oxinoid compounds, including chelates of oxine itself (also commonly referred to
as 8-quinolinol or 8-hydroxyquinoline). Such compounds help to inject and
transport electrons and exhibit both high levels of performance and are readily
fabricated in the form of thin films. Exemplary of contemplated oxinoid
compounds are those satisfying structural Formula E, previously described.
Other electron-transporting materials include various butadiene
derivatives as disclosed in U.S. Patent No. 4,356,429 and various heterocyclic
optical brighteners as described in U.S. Patent No. 4,539,507. Benzazoles
satisfying structural Formula G are also useful electron-transporting materials.
Other electron-transporting materials can be polymeric substances,
e.g. polyphenylenevinylene derivatives, poly-para-phenylene derivatives,
polyfluorene derivatives, polythiophenes, polyacetylenes, and other conductive
polymeric organic materials such as those listed in Handbook of Conductive
Molecules and Polymers, Vols. 1-4, H.S. Nalwa, ed., John Wiley and Sons,
Chichester(1997).
An electron-injecting layer 360 can also be present between the
cathode and the electron-transporting layer. Examples of electron-injecting
materials include alkaline or alkaline earth metals, alkali halide salts, such as LiF
mentioned above, or alkaline or alkaline earth metal doped organic layers.
Cathode 390 is formed over the electron-transporting layer 355 or
over light-emitting layer 350 if an electron-transporting layer is not used. When
light emission is through the anode 330, the cathode material can include nearly
any conductive material. Desirable materials have good film-forming properties
to ensure good contact with the underlying organic layer, promote electron
injection at low voltage, and have good stability. Useful cathode materials often
contain a low work function metal ( cathode material is include of a Mg:Ag alloy wherein the percentage of silver is in
the range of 1 to 20 %, as described in U.S. Patent No. 4,885,221. Another
suitable class of cathode materials includes bilayers includes a thin layer of a low
work function metal or metal salt capped with a thicker layer of conductive metal.
One such cathode includes a thin layer of LiF followed by a thicker layer of Al as
-27-
described in U.S. Patent No. 5,677,572. Other useful cathode materials include,
but are not limited to, those disclosed in U.S. Patent Nos. 5,059,861; 5,059,862;
and 6,140,763.
When light emission is viewed through cathode 390, it must be
transparent or nearly transparent. For such applications, metals must be thin or
one must use transparent conductive oxides, or a combination of these materials.
Optically transparent cathodes have been described in more detail in U.S. Patent
No. 5,776,623. Cathode materials can be deposited by evaporation, sputtering, or
chemical vapor deposition. When needed, patterning can be achieved through
many well known methods including, but not limited to, through-mask deposition,
integral shadow masking as described in U.S. Patent No. 5,276,380 and EP 0 732
868, laser ablation, and selective chemical vapor deposition.
Cathode materials can be deposited by evaporation, sputtering, or
chemical vapor deposition. When needed, patterning can be achieved through
many well known methods including, but not limited to, through-mask deposition,
integral shadow masking as described in U.S. Patent No. 5,276,380 and EP
0 732 868, laser ablation, and selective chemical vapor deposition.
The invention has been described in detail with particular reference
to certain preferred embodiments thereof, namely for delivery of organic
particulate materials to a vaporization zone. However, it can be appreciated that
the present invention applies more broadly to particulate materials, including
organic and other types of particulate materials. The term "particulate materials"
can include a broad range of substances in particulate form, including, but not
limited to, crystals, nanotubes, powders, needles, flakes, and other solid materials
that can be classified as discontinuous, for example. Moreover, the particulate
materials may be provided in a mixture containing a quantity of inert material or
materials acting as a carrier for the component material. Inert earners could
include other types of solid materials as well as pastes and liquids, particularly
liquid materials having higher viscosities. Any inert material selected must be
compatible with the vaporization process, such that the inert carrier is
appropriately discarded before or during the vaporization of the component
particulate material. For example, the inert carrier can be selected from materials
having a much higher vaporization temperature than the desired particulate
component material. As just one example, particulate material 100 (FIG. 3) could
be a mixture containing sand and the particulate component material that is to be
vaporized. The utilization of such an inert earner, with suitable mixing
techniques, would allow the metering of minute quantities of a component
particulate material, such as an organic particulate material, for vaporization.
PARTS LIST
5 vaporization device
6 source
7 source
8 source
9 vapor plume
10 vaporization apparatus
15 substrate
20 manifold
30 aperture
35 motor
40 feeding apparatus
45 feeding apparatus
50 first container
55 second container
60 feeding path
65 feeding path
70 third container
75 fourth container
80 auger structure
85 auger screw
85a auger screw
85b auger screw
85c auger screw
90 motor
95 auger structure
100 particulate material
105 auger structure
110 screen
115 helical thread
Parts List cont'd
120 screen
125 center portion
130 piezoelectric structure
135 thread-free portion
140 piezoelectric structure
150 piezoelectric structure
155 piezoelectric structure
160 particulate material
170 heating element
180 base
190 bottom portion
210 rotating thread type device
220 gear driver
230 opening
240 first particulate material
245 second particul ate materi al
250 first auger structure
255 second auger structure
260 mixing chamber
275 load lock
280 deposition chamber
285 OLED substrate
295 translational apparatus
300 vacuum source
310 OLED device
320 substrate
330 anode
335 hole-injecting layer
340 hole-transporting layer
Parts List cont'd
350 light-emitting layer
355 electron-transporting layer
360 electron-injecting layer
370 organic layers
390 cathode




WE CLAIM:
1. A method for vaporizing an organic material and condensing it onto a surface of a substrate to form a layer of organic material on the surface of the substrate, comprising:
(a) providing a quantity of a first organic material in a powdered form in a first container and a quantity of a second organic material in a powdered form in a second container spaced from the first container;
(b) fluidizing the first organic material in the first container by agitating the first organic material with a first agitating device placed in proximity of the infeed portion of a first auger structure, and transferring the fluidized first organic material from the first container into a manifold with the first auger structure along a first feeding path, the first auger structure passing through the interior of the first container and feeding into the manifold so as to transfer the fluidized first organic material to a first vaporization zone in the manifold, and vaporizing the first organic material in the manifold;
(c) fluidizing the second organic material in the second container by agitating the second organic material with a second agitating device placed in proximity of the infeed portion of a second auger structure, and transferring the fluidized second organic material from the second container into the manifold with the second auger structure along a second feeding path, the second auger structure passing through the interior of the second container and feeding into the manifold so as to transfer the fluidized second organic material to a second vaporization zone in the manifold, and vaporizing the second organic material in the manifold, the first and second vaporized organic materials being mixed in the manifold; and
(d) delivering through at least one aperture of the manifold the mixed vaporized organic materials to the substrate surface to form the layer.

2. The method as claimed in claim 1, wherein a third and a fourth container respectively associated with the first and second containers, each for transferring organic material to its corresponding first or second container.
3. The method as claimed in claim 2, comprising metering the amount of organic material transferred from the third and fourth containers to the first and second containers, respectively, to provide a constant volume of organic material in the first and second containers.
4. The method as claimed in claim 1, wherein the step of transferring the first organic material into the manifold comprises:

(a) transferring the first organic material through a first opening to the first auger structure, the first opening being placed at the interface of the first container and first feeding path; and
(b) rotating a portion to the first auger structure to transfer the first organic material from the first container along the first feeding path to the first vaporization zone wherein the first organic material is vaporized.
5. The method as claimed in claim 1, wherein the step of transferring the
second organic material into the manifold comprises:
(a) transferring the second organic material through a second opening to the second auger structure, the second opening being placed at the interface of the second container and second feeding path; and
(b) rotating a portion of the second auger structure to transfer the second organic material from the second container along the second feeding path to the second vaporization zone wherein the second organic material is vaporized.
6. The method as claimed in any one of claims 4 or 5, wherein the feed
rate of the first and second organic materials to the auger structures and to the
vaporization zones controls the deposition rate of the vaporized organic
materials and the concentration of the organic materials in the layer.

7. The method as claimed in any one of claims 4 or 5, wherein the temperature of the organic material in the feeding paths is maintained below the desired vaporization temperature of the material.

Documents:

1899-delnp-2007-Abstract-(19-12-2011).pdf

1899-delnp-2007-abstract.pdf

1899-delnp-2007-Assignment-(09-08-2012).pdf

1899-delnp-2007-Claims-(19-12-2011).pdf

1899-delnp-2007-claims.pdf

1899-delnp-2007-coresspondence-others.pdf

1899-delnp-2007-Correspondence Others-(09-08-2012).pdf

1899-delnp-2007-Correspondence Others-(19-12-2011).pdf

1899-DELNP-2007-Correspondence Others-(27-12-2011).pdf

1899-delnp-2007-correspondence-others 1.pdf

1899-delnp-2007-description (complete).pdf

1899-delnp-2007-Drawings-(19-12-2011).pdf

1899-delnp-2007-drawings.pdf

1899-delnp-2007-Form-1-(19-12-2011).pdf

1899-delnp-2007-form-1.pdf

1899-delnp-2007-Form-16-(09-08-2012).pdf

1899-delnp-2007-form-18.pdf

1899-delnp-2007-Form-2-(19-12-2011).pdf

1899-delnp-2007-form-2.pdf

1899-DELNP-2007-Form-3-(27-12-2011).pdf

1899-delnp-2007-form-3.pdf

1899-delnp-2007-form-5.pdf

1899-delnp-2007-GPA-(09-08-2012).pdf

1899-delnp-2007-GPA-(19-12-2011).pdf

1899-delnp-2007-gpa.pdf

1899-delnp-2007-pct-101.pdf

1899-delnp-2007-pct-210.pdf

1899-delnp-2007-pct-220.pdf

1899-delnp-2007-pct-237.pdf

1899-delnp-2007-pct-304.pdf

1899-delnp-2007-pct-311.pdf

1899-DELNP-2007-Petition-137-(27-12-2011).pdf


Patent Number 252467
Indian Patent Application Number 1899/DELNP/2007
PG Journal Number 20/2012
Publication Date 18-May-2012
Grant Date 16-May-2012
Date of Filing 12-Mar-2007
Name of Patentee EASTMAN KODAK COMPANY
Applicant Address 343 STATE STREET, ROCHESTER, NEW YORK 14650-2201, USA
Inventors:
# Inventor's Name Inventor's Address
1 MICHAEL LONG 10 BLACK TERN TERRANCE, HILTON, NY 14468, USA
2 JEREMY MATTHEW GRACE 132 HOLLYBROOK DRIVE, PENFIELD, NY 14526, USA
3 BRUCE EDWARD KOPPE 702 COONEY ROAD, CALENDONIA, NY 14423, USA
PCT International Classification Number C23C 14/24
PCT International Application Number PCT/US2005/033154
PCT International Filing date 2005-09-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/945,941 2004-09-21 U.S.A.
2 11/134,139 2005-05-20 U.S.A.