# Patent

## Title
Deposition system using sealed replenishment container

## Abstract

A method for vaporizing particulate material and depositing it onto a surface to form a layer, includes providing a supply of particulate material in a replenishment container, the replenishment container having a sealed interface fitting; mounting the replenishment container to a supply hopper defining at least one feed opening, and breaking the seal at the interface fitting; transferring particulate material from the replenishment container to the supply hopper; and transferring such particulate material through the feed opening along a feeding path to a vaporization zone where at least a component portion of the particulate material is vaporized and delivered to the surface to form the layer.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
Reference is made to commonly assigned U.S. patent application Ser. No. 10/805,980 filed Mar. 22, 2004 entitled “Vaporizing Fluidized Organic Materials” by Long et al.; U.S. patent application Ser. No. 10/784,585 filed Feb. 23, 2004, entitled “Device and Method for Vaporizing Temperature Sensitive Materials” by Long et al.; U.S. patent application Ser. No. 10/945,940, filed Sep. 21, 2004, entitled “Delivering Organic Power to a Vaporization Zone” by Long et al; U.S. patent application Ser. No. 11/134,654 filed May 20, 2005, entitled “Delivering Particulate Material to a Vaporization Zone” by Long et al; U.S. patent application Ser. No. 10/945,941 filed Sep. 21, 2004 entitled “Delivering Organic Powder to a Vaporization Zone” by Long et al.; U.S. patent application Ser. No. 11/134,139 filed May 20, 2005, entitled “Delivering Particulate Material to a Vaporization Zone” by Long et al and U.S. patent application Ser. No. 11/272,320 filed concurrently herewith, entitled “Purifiying Organic Materials for Physical Vapor Deposition” by Michael L. Boroson, the disclosures of which are incorporated herein.
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 hole-transporting 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. Pat. 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. Pat. No. 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.
FIG. 1 shows a cross-sectional view of a conventional vaporization device 5, which includes three individual sources 6, 7, and 8, commonly termed “heating boats”, for vaporizing organic material. Vapor plume 9 is preferably homogeneous in the materials from the different sources, but in fact varies in composition from side to side resulting in a non-homogeneous coating on substrate 15.
Among the acknowledged problems of conventional approaches to vapor deposition are material purity and the difficulty in maintaining a continuous fabrication sequence that would allow deposition apparatus to operate for extended periods of time, without costly down-time for cleaning, for replenishment or recharging of material, and for pre-heating. Both of these problems present significant constraints on deposition system design. Conventional solutions reflect the assumption that there would be no suitable solution that would allow both continuous (or, at least, longer term) deposition processing and maintenance of a high level of material purity.
Conventionally, for example, the problem of maintaining high material purity is solved somewhat indirectly. As source 6 (FIG. 1), a crucible or “boat” is initially charged with material in an unheated state. Then, before deposition can begin, a “bake-out” of the material occurs in a pre-treatment or pre-heating cycle as the deposition chamber heats up. During this bake-out period, moisture and volatile impurities are thus effectively drawn off from the material. Then, when vaporization device 5 is up to operating temperature, the material in source 6 is relatively pure. With this type of solution, the material to be deposited requires careful handling, but generally need not be hermetically sealed beforehand against contamination, such as in shipping or during preparation, for example.
With the intention of reducing this bake-out time period and improving overall deposition efficiency, there have been a number of proposed solutions for providing material in a more purified form. For example, U.S. Published Patent Application No. 2004/0255857 entitled “Thin-Film Deposition Evaporator” by Chow et al. discloses a moving vessel that acts as a type of “shuttle” for replenishing the supply of vaporizable material in a deposition chamber. The method of the '5857 Chow et al. solution addresses the problems of maintaining a suitable vacuum level in the deposition system during replenishment and reducing the overall likelihood of contamination of the material. However, the solution proposed in the '5857 Chow et al. disclosure is not advantaged for any type of continuous processing because this batch replenishment process still requires a pre-heating period during which material in the deposition chamber heats up to deposition temperature.
Another proposed solution for improving the purity of materials used in replenishment is given in U.S. Patent Published Application No. 2004/0139914 by Yamazaki et al. As one part of the '9914 Yamazaki et al. solution, it is proposed to provide a supply crucible or other source that already contains replenishment material, hermetically sealed to prevent contamination, for placement directly into the crucible for deposition. While this type of solution can help to improve overall material purity, however, it still requires that the deposition process be stopped in order to allow replenishment, then restarted again once the sealed source is placed into position, the seal broken, and the material heated to deposition temperatures.
Thus, it can be seen that while solutions such as those proposed in the '5857 Chow et al. and '9914 Yamazaki et al. disclosures may serve to improve material purity to some degree and even minimize bake-out pre-treatment requirements, these solutions do not wholly eliminate the pre-heating cycle. Moreover, neither of these solutions would be suitable for use with a materials replenishment system that supports continuous operation, so that processing can continue while materials recharging takes place.
A shortcoming that is inherent to any method that requires a pre-treatment or pre-heating cycle relates to the need for simultaneous deposition of multiple component materials. In some applications, it is advantageous to deposit more than one material at a time. It may even be beneficial to mix two or more materials in the same container for vaporization. However, because some amount of pre-heating or bake-out time is required with conventional techniques, both materials must be substantially of the same sublimation temperature (to within a small tolerance in the range of no more than about ±20 degrees C. difference). Where materials differ in vaporization temperature by more than a few degrees, conditions for pre-heating or bake-out may not be optimal.
Thus, it can be seen that there is a need for a replenishment solution in a vapor deposition system that allows recharging of material without interrupting the deposition operation and that allows material to be provided in a highly purified form so that pre-treatment, bake-out, or pre-heating requirements are effectively eliminated.
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 A method for vaporizing particulate material and depositing it onto a surface to form a layer, comprising:
(a) providing a supply of particulate material in a replenishment container, the replenishment container having a sealed interface fitting;
(b) mounting the replenishment container to a supply hopper defining at least one feed opening, and breaking the seal at the interface fitting;
(c) transferring particulate material from the replenishment container to the supply hopper; and
(d) transferring such particulate material through the feed opening along a feeding path to a vaporization zone where at least a component portion of the particulate material is vaporized and delivered 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-dependent 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 highly 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, reducing 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 typically 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 material is conveyed through the device.



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 organic 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 organic 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 three-dimensional view of a portion of another embodiment of an apparatus according to the present invention for vaporizing particulate organic materials and condensing them onto a surface to form a layer, including an apparatus to drive off adsorbed gasses or impurities;
FIG. 10 is a cross-sectional view of a device according to the present invention including a deposition chamber enclosing a substrate;
FIG. 11 is a cross-sectional view of an OLED device structure that can be prepared with the present invention;
FIG. 12A is a cross-sectional side view of a replenishment container in one embodiment, prior to dispensing material;
FIG. 12B is a side view of a replenishment container in position for dispensing material;
FIG. 13 is a cross-sectional side view of a replenishment container using a slide valve mechanism;
FIG. 14 is a top view of an alternate rotatable valve mechanism in an alternate embodiment;
FIG. 15 is a cross-sectional side view of a replenishment container using a pressure differential to feed material;
FIG. 16 is a cross-sectional side view of a replenishment container with an agitator mechanism in another embodiment;
FIG. 17 is a cross-sectional side view of a replenishment container using a piston mechanism for feeding material; and
FIG. 18 is a cross-sectional side view of a replenishment container using an alternate type of piston for feeding material.



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 organic particulate materials and condensing them onto a surface to form a layer. A vaporization apparatus 10 includes a manifold 20 and an attached feeding apparatus 40. Feeding apparatus 40 includes a feed container 50 and a feeding path 60. Feed container 50 is provided with a quantity of organic or other material in a particulate form, such as a powder in one embodiment.
Manifold 20 includes one or more apertures 30 through which vaporized organic material can exit to a substrate surface. Manifold 20 is shown in an orientation whereby it can form a layer on a vertically-oriented substrate, but it is not limited to this orientation. For example, manifold 20 can be oriented horizontally and can form a layer on a horizontal substrate. Manifold 20 has been described in detail by Long et al. in commonly-assigned, above-cited U.S. patent application Ser. No. 10/784,585. Feeding apparatus 40 is shown attached to the bottom of manifold 20, that is, opposite to apertures 30; however, feeding apparatus 40 can also be attached to a side of manifold 20. The nature of the attachment of feeding apparatus 40 to manifold 20 is described in more detail subsequently.
To allow continuous (or, more precisely, long-term) operation, a replenishment container 72 provides a supply of particulate material to a supply hopper 52 that acts as a source of material for feed container 50. Replenishment container 72 is a replaceable unit, positioned in place at interface fitting 54 that provides a sealed fitting as described subsequently. For efficient recharging of the particulate material in feeding apparatus 40, in many cases it is preferable for replenishment container 72 to be larger in volume than supply hopper 52.
Turning now to FIG. 3, there is shown a cross-sectional view of one embodiment of a portion of feeding apparatus 40 for feeding particulate material according to the present invention, whereby particulate material is effectively fluidized and transferred to feeding path 60. In a replenishment apparatus 400, replenishment container 72 holds a supply of organic particulate material 100 that is provided to supply hopper 52 and, from there, feeds feed container 50 and the overall feeding path 60. Sealed interface fitting 54 helps to prevent material contamination and to maintain vacuum levels or other ambient conditions needed for feeding apparatus 40. Replenishment container 72 may also include a sensor 450 for detecting the amount of particulate material 100 remaining. Sensor 450 would be in communication with control logic components (not shown) in order to report a low level of particulate material 100 so that a replacement replenishment container 72 could be readied for use.
Supply hopper 52 defines an opening 230 for feeding particulate material 100 to an intermediate containment structure such as feed container 50 or, in other embodiments, directly to feeding path 60. First container 50 holds organic particulate material 100, which is preferably in the form of a finely divided powder and is desirably of a uniform size, and which feeds into an auger structure 80, or some other feed mechanism, in feeding path 60. In the embodiment of FIG. 3, auger structure 80 passes through the interior of feed container 50 and feeds into the manifold components described above (not shown in FIG. 3 for clarity). At least a portion of auger structure 80 is rotated by motor 90 in order to transfer an organic particulate material 100 at a controlled volumetric rate or pressure along feeding path 60 to a vaporization zone. In the vaporization zone, the organic component material is vaporized and subsequently delivered to a substrate to form a layer. Feeding path 60, and therefore organic particulate material 100 flowing in feeding path 60, can be maintained at a temperature below the desired vaporization temperature of the organic component material. To facilitate the movement of organic particulate material 100 to auger structure 80, organic particulate material 100 may be fluidized by agitating organic particulate material 100 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 replenishment container 72 to provide a continuous supply of organic particulate material 100 provides several advantages. Using this component, a large quantity of organic particulate material 100 can be charged in feeding apparatus 40 at one time, allowing continuous operation of the device for extended periods. By sensing the quantity of organic particulate material 100 in replenishment container 72, for example, by measuring the height of the column of organic particulate material 100, it would be possible to selectively meter the amount of organic particulate material 100 transferred to first container 50 and to provide a substantially constant volume of organic particulate material 100 in first container 50, for example, ±5 cm3. In practice, 10 cm3 of organic particulate material 100 is loaded in first container 50. Some embodiments described herein allow great process latitude with respect to reliable feeding of particulate material 100 over a wide range of material height in the container and can be run nearly to exhaustion without failing to feed additional organic particulate material 100 in feeding path 60. However, it is believed that multi-component mixing homogeneity is fostered if an optimum material height is established and maintained in first container 50 to within ±10%. This reduces variations in the feeding rate of organic particulate material 100 along feeding path 60.
In addition to sensor 450, it may be advantageous to provide other internal components, such as to support uniform particle sizing and supply, for example. One or more internal screens can be employed within replenishment container 72, with suitable mesh sizes for helping to control the feed rate. Agitation devices, such as moving arms or vibrating piezoelectric actuators, could also be built into replenishment container 72, working in cooperation with screens, for example.
Agitating devices such as piezoelectric structures 140 shown fitted against the wall of supply hopper 52 in FIG. 3, could alternately be positioned within or against replenishment container 72 for preventing the buildup of organic particulate material 100 in 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 organic particulate material 100 at vibrational nodes.
For proper operation of feeding apparatus 40, it is important to maintain a uniform feed rate of organic particulate material 100 in feeding path 60. Organic particulate material 100 is generally provided in a powdered form. One important strategy for providing a free flow of organic particulate material 100 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 feed hopper 52 and feed container 50, as shown in FIG. 3, must be sufficiently sized to overcome the bridging characteristics of the powdered material. This sizing requirement is best determined empirically, taking into account worst-case conditions for the particular particulate material 100 that must be supplied, in a free flowing manner, to feeding path 60. Maintaining a nearly constant volume of organic particulate material 100 in first container 50 also helps to promote a constant feed rate of organic particulate material 100 to auger structure 80. By properly sizing opening 230 and maintaining a sufficient volume of organic particulate material 100 in first container 50, a uniform feed rate can be achieved for many types of powdered organic particulate material 100, 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 organic particulate material 100 that is in proximity to the infeed portion of screw auger structure 80 is maintained in a fluidized state by an agitating device. This can be accomplished by slowly agitating organic particulate material 100 immediately above the auger screw or by inducing vibration, e.g. by piezoelectric structure 130 (FIG. 3), into organic particulate material 100 that is tuned to induce liquid-like behavior of the powdered organic particulate material 100 but is not so energetic as to cause gas-like behavior.
Turning now to FIG. 4, there is shown in further detail a cross-sectional view of a portion of vaporization apparatus 10 in an alternate embodiment of the present invention. Here, feeding apparatus 40 has supply hopper 52 supplying feeding path 60 without an intermediary feed container 50 as in the embodiment of FIGS. 2 and 3. Auger structure 80 transfers powdered organic particulate material 100 along feeding path 60 into a heating element 170 in manifold 20. Heating element 170 can be, for example, a heated screen as has been previously described in detail in the Long et al. disclosures cited earlier. 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 powdered organic particulate material 100 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 powdered organic particulate material 100 vaporizes to be delivered to a substrate surface to form a layer. Auger structure 80 and its rotation rate control the rate at which organic particulate material 100 is fed to heating element 170. This provides linear control of the rate of vaporization and therefore of the rate at which organic particulate material 100 leaves manifold 20 in the vapor state. Thus the feed rate of organic particulate material 100 to auger structure 80 and to the vaporization zone controls the deposition rate of vaporized organic particulate material 100 onto the desired surface.
Additionally, a base 180 can be included. Base 180 is a heat-dissipating structure that helps to prevent radiated heat from heating element 170 from traversing the length of feeding path 60, and thus significantly cools the bulk of organic particulate material 100 before it reaches the vaporization zone immediately adjacent to heating element 170. Means of heat dissipation for base 180 have been described by Long et al. in commonly-assigned, U.S. patent application Ser. No. 10/784,585 cited above. The steep thermal gradient that is thereby created protects material in feeding path 60 that is not yet to be vaporized from the high temperatures.
With this heating arrangement, the vaporized organic vapors rapidly pass through heating element 170 and can enter into heated manifold 20. The residence duration of organic particulate material 100 at the desired vaporization temperature is very short and, as a result, thermal degradation is greatly reduced. The residence duration of the organic particulate material 100 at elevated temperature, that is, at the rate-dependent vaporization temperature, is orders of magnitude less with this arrangement than with prior art devices and methods. This duration is in seconds vs. hours or days with conventional approaches. This permits heating organic particulate material 100 to higher temperatures than with conventional approaches. Thus, the device and method of the present invention can achieve substantially higher vaporization rates, without causing appreciable degradation of the components of organic particulate material 100.
Organic particulate material 100 can include a single component, or can include two or more different organic or other 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 component organic materials commonly used in OLED devices. The vaporization rate is proportional to the vapor pressure, so that 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 organic particulate material 100 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 vaporize at the same time.
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 organic particulate material 100—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, for example, stopping the movement of auger structure 80. This can be done when a substrate surface is not being coated so as to conserve organic particulate material 100 and reduce 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 downwards so as to coat a substrate placed below it. This is an advantage not found using 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 80 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 powdered organic particulate material 100 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 auger screw 85 and the auger tube. For example, an auger screw 85 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 powdered organic particulate material 100 in a horizontal orientation.
It has been 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 organic particulate material 100.
It has also been found that the angle of auger screw threads can be optimized to facilitate free flow of organic particulate material 100 along feeding path 60. While optimal screw thread angle may vary somewhat depending on the particular component materials of powdered organic particulate material 100, 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 80 provide optimal flow conditions for the types of organic materials 100 that are most often deposited.
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 organic particulate material 100 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 80 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, the organic particulate material 100 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 the organic particulate material 100 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 its source at first container 50. 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 organic particulate material 100 to form a narrow annular or tubular shape. This narrow annular shape substantially improves the thermal contact and temperature uniformity through the organic particulate material 100, between the temperature-controlled auger screw 85 and the temperature-controlled feeding path 60. This configuration additionally assures good temperature uniformity of the organic particulate material 100 at a given transverse cross section relative to a circular cross section and substantially increases the attainable temperature gradient in the organic particulate material 100 between the auger structure 80 and the heating element 170. The powdered organic particulate material 100 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 80 and enables the powdered organic particulate material 100 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 μm from the end of the auger structure 80 indicates that an average axial thermal gradient of 0.5° C./μm can be achieved through the organic particulate material 100 spanning heating element 170 and the terminal end of the auger structure 80 when the temperature differential between the two is 270° C. There can therefore be a 100° C. temperature drop through the first 200 μm of consolidated powdered organic particulate material 100. 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 component organic materials. This large gradient is further instrumental in maintaining the organic particulate material 100 in a consolidated powder form at the exit of the auger tube even when component organic materials that liquefy before vaporizing are employed.
The arrangement of auger structure 80 shown in FIG. 6a is effective at transporting powdered organic particulate material 100 horizontally, but is not as effective in transporting powdered organic particulate material 100 vertically, since the powdered organic particulate material 100 tends to simply rotate with the screw rather than 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 in an alternate embodiment. Auger structure 95 includes two or more auger screws, e.g. auger screws 85a, 85b, and 85c, with identical interlaced helical threads. Auger screws 85a, 85b, and 85c all rotate in the same direction. Organic material 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 the powdered organic particulate material 100 into a solid shape and to 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 manifold 20 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. 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 including helical threads 115—rotates and is turned by motor 90 Powdered organic particulate material 100 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 non-circular 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 organic particulate material 100. Stationary center portion 125, in cooperation with feeding path 60, substantially prevents all but a thin film of powdered organic particulate material 100 from rotating with the auger. Advantageously, auger structure 105 does not rely on gravity to accumulate powdered organic particulate material 100 and will operate in any orientation. Auger structure 105 also consolidates the powdered organic particulate material 100 into a thin annular shape that substantially improves the thermal contact between the powdered organic particulate material 100 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 component 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 organic particulate material 100 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 organic particulate material 100 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 organic particulate material 100 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 150 and 155 have high vibration amplitude and are effective in fluidizing powdered organic particulate material 100 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 150 and 155. 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 low-pressure conditions. Opening 230 represents the lower end of the above-described supply hopper 52 or, alternately, an opening at the base of 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 a gear driver 220, by motor 90, which also turns auger structure 80. In practice, the rotational speed of rotating thread type device 210 can vary depending on the particle size and properties of the particular powdered organic particulate material 100, 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 powdered organic particulate material 100 toward the center of opening 230 and prevent powder bridging over auger structure 80. 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 powdered organic particulate material 100 and is therefore not likely to cause particle separation by size or density.
Turning now to FIG. 9, there is shown a three-dimensional view of a portion of another embodiment of vaporization apparatus 10 according to the present invention for vaporizing powdered organic materials and condensing them onto a surface to form a layer, including an apparatus for pre-conditioning organic particulate material 100 to drive off adsorbed gasses or impurities. The apparatus includes replenishment container 72 in cooperation with feed container 50 as described above for holding a quantity of organic particulate material. The apparatus can also include agitating devices, as were described for embodiments shown in FIGS. 3 and 4. Organic particulate material 100 from feed container 50 is fed into a first feeding path 260 for pre-conditioning. First feeding path 260 includes an auger structure in association with feed container 50 for transferring the organic particulate material 100 from feed container 50 to first feeding path 260. At least a portion of the auger structure is turned by motor 90 to feed powdered organic particulate material 100 along first feeding path 260. First feeding path 260 includes a vacuum exposure opening 270, which is in communication with a source of partial vacuum. First feeding path 260 can alternately be heated so as to heat the powdered organic particulate material 100 while exposing it to a partial vacuum in order to drive off adsorbed gasses or impurities as the organic particulate material 100 is transferred along first feeding path 260 to the vaporization zone as pre-conditioned organic particulate material 100. For typical deposition rates, the free powdered organic particulate material 100 has several minutes to liberate adsorbed water vapor and gas molecules in this pre-conditioning phase, just prior to being compacted and vaporized. The pre-conditioned powdered organic particulate material 100 is then transferred to a second feeding path 265, which is defined by an auger structure as described above, in which it is consolidated, that is, it is compacted and evenly distributed around the auger structure. Powdered organic particulate material 100 is fed along second feeding path 265 by the auger structure to a manifold and vaporization zone (not shown) as described above, where the organic material is vaporized and subsequently condensed onto the surface of an OLED substrate to form an organic layer. Optional third container 250 can receive the exposed powdered organic particulate material 100 from first feeding path 260. In such a case, the auger structure that defines second feeding path 265 is also associated with third container 250 for feeding exposed powdered organic particulate material 100 to second feeding path 265, and such auger structure passes through the interior of third container 250. This apparatus also includes means for fluidizing the powdered organic particulate material 100, as already described. In an alternative embodiment, feeding path 260 includes vacuum exposure opening 270 and feeds directly to a manifold without the use of a second feeding path.
In practice, the apparatus described herein is operated as follows. A powdered organic particulate material 100, which is useful in forming a layer on an OLED device, is provided from material in replenishment container 72. The organic particulate material 100 is transferred in a controlled manner to feed container 50 in such a way as to maintain a substantially constant volume of powdered organic particulate material 100 in feed container 50. The powdered organic particulate material 100 is fluidized by means described herein and thereby transferred to auger structure 80, which transfers the powdered organic particulate material 100 to a vaporization zone as described herein. The organic particulate material 100 is vaporized in the vaporization zone into a manifold 20, which delivers the vaporized organic 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 100. Referring back to FIG. 2, it can be observed that a continuous column of organic particulate material 100 is maintained in feeding path 60. In one embodiment, this column of organic particulate material 100, if suitably compacted, can be utilized as a type of vacuum seal, where particulate characteristics of organic particulate material 100 allow. With this arrangement, a high vacuum level can be present for organic particulate material 100 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 100 in first container 50 and/or for organic particulate material 100 in replenishment container 72. 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 deposition apparatus 32 of the present invention using replenishment apparatus 400 and 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. Deposition chamber 280 is held under controlled conditions, e.g. a pressure of 1 Torr or less provided by a 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 10 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 19, including any container or containers for holding the powdered organic particulate material 100, is enclosed by deposition chamber 280.
In practice, OLED substrate 285 is placed in deposition chamber 280 via load lock 275 and held by translational apparatus 295 or associated apparatus. Vaporization apparatus 10 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 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 light-emitting 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 electron-injecting layer 360. Hole-injecting layer 335, hole-transporting layer 340, light-emitting 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.
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, iridium, 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 hole-transporting layer. Suitable materials for use in hole-injecting layer 335 include, but are not limited to, porphyrinic compounds as described in U.S. Pat. No. 4,720,432, plasma-deposited fluorocarbon polymers as described in U.S. Pat. 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 EP 0 891 121 A1 and EP 1 029 909 A1.
While not always necessary, it is often useful that a hole-transporting layer 340 be formed and disposed over anode 330. Desired hole-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. 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, triarylamine, or a polymeric arylamine. Exemplary monomeric triarylamines are illustrated by Klupfel et al. in U.S. Pat. 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. Pat. 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. Pat. Nos. 4,720,432 and 5,061,569. Such compounds include those represented by structural Formula A.




wherein:

    
    
        Q1 and Q2 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 Q1 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.




where:

    
    
        R1 and R2 each independently represent a hydrogen atom, an aryl group, or an alkyl group or R1 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 amino group, as indicated by structural Formula C.
    
    






wherein R5 and R6 are independently selected aryl groups. In one embodiment, at least one of R5 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.




wherein:

    
    
        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, R7, R8, and R9 are independently selected aryl groups.
    
    


In a typical embodiment, at least one of Ar, R7, R8, and R9 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 interposed between the triarylamine and the electron-injecting 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-ethylenedioxythiophene)/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 hole-transporting 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 light-emitting materials are well known. As more fully described in U.S. Pat. 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 light-emitting 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. Pat. 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′′-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole].
Desirable fluorescent dopants include perylene or derivatives of perylene, derivatives of anthracene, tetracene, xanthene, rubrene, coumarin, rhodamine, 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-para-phenylene derivatives, and polyfluorene derivatives, as taught by Wolk et al. in commonly assigned U.S. Pat. No. 6,194,119 B1 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. Pat. No. 4,356,429 and various heterocyclic optical brighteners as described in U.S. Pat. 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 (<3.0 eV) or metal alloy. One preferred cathode material is comprised of a Mg:Ag alloy wherein the percentage of silver is in the range of 1 to 20 %, as described in U.S. Pat. No. 4,885,221. Another suitable class of cathode materials includes bilayers comprised of a thin layer of a low work function metal or metal salt capped with a thicker layer of conductive metal. One such cathode is comprised of a thin layer of LiF followed by a thicker layer of Al as described in U.S. Pat. No. 5,677,572. Other useful cathode materials include, but are not limited to, those disclosed in U.S. Pat. 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. Pat. 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. Pat. 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. Pat. No. 5,276,380 and EP 0 732 868, laser ablation, and selective chemical vapor deposition.
Replenishment Container Embodiments
Referring to FIGS. 12A and 12B, there is shown, in side view representation, the components and operation of replenishment apparatus 400 using a bottle 422 as replenishment container 72 in one embodiment wherein a vacuum seal can be maintained at interface fitting 54. A loaded bottle 422 is fitted into an adapter 424 that is fitted with O-ring seals 423 and 425. Prior to introduction to the transfer apparatus, replenishment container 72 has been loaded with material and evacuated. The vacuum seal is maintained by a primary O-ring seal 436 and a spring loaded hinge 434. Multiple versions of adapter 424 may be fabricated to accommodate different sized and shaped bottles 422 or other components serving as replenishment containers 72. Adapter 424 is loaded together with bottle 422 into a mechanical bellows 420 that is affixed by vacuum seal to a sliding gate valve assembly 406. When mounted, bellows 420 is evacuated by means of a vacuum pump connected to pressure control fitting 432. The reduction of pressure within bellows 420 allows the pressure to be equalized between bellows 420 and the inside of replenishment container 72. When the pressure in bellows 420 is equal or less than that in replenishment container 72, a cover 454 is held in place only by the spring tension of a spring-loaded hinge 434. At that pressure, a vacuum gate valve 448 is opened to the high vacuum environment of evaporation materials transfer vacuum chamber 430. In such an embodiment, a vacuum level can be maintained for the transport mechanisms of feeding path 60 (as shown in the examples of FIGS. 3, 4, 6A, 7, and 8) and manifold 20, for example. Here, it is important for the overall deposition process that the vacuum seal be maintained within bottle 422. To break the seal and feed the contents of bottle to display hopper 52, vacuum gate valve 448 is used as part of a seal 408. Positioned over an opening 428 as shown in FIG. 12A, vacuum gate valve 448, initially seated against O-rings 404 or other sealing components, is moved to the right (in the orientation shown in FIGS. 12A and 12B) in order to access bottle 422 through opening 428. Once vacuum gate valve 448 is moved out of the way, bottle 422 can be lowered by compressing flexible bellows 420 by mechanical means (not shown).
Flexible bellows 420 is used for breaking the seal and obtaining the contents of bottle 422. As bellows 420 collapses, the mouth of bottle 422 used as replenishment container 72 is drawn into opening 428 as is shown in FIG. 12B. Spring-loaded hinge 434, forcing against an O-ring seal 436, is actuated upon encountering an obstruction 438 that is within vacuum chamber 430. This action breaks the seal of bottle 422, dispensing material into supply hopper 52.
Referring now to FIG. 13, an alternate embodiment of replenishment apparatus 400 is shown. Seal 408 again uses slide valve 402 that seats against paired O-rings 404. With this arrangement, replenishment container 72 dispenses its supply of particulate material 100 under pressure. A valve 412 is actuated once seal 408 is broken, forcing a gas such as air or such as an inert gas into replenishment container 72.
Alternately, replenishment container 72 initially contains organic material and an inert gas. Prior to opening slide valve 402, valve 412 is used to evacuate replenishment container 72. Then, once slide valve 402 is opened, the material is dispensed through opening 428, using gravity or other means, such as mechanical feeding methods.
Referring to FIG. 14, there is shown an alternative configuration for a valve 410. Here, valve 410 is in the form of a rotatable disk 416 having an aperture 414. The outline of replenishment container 72 is shown for reference. Some mechanism can be used to rotate valve 410 to a feed position once replenishment container 72 is in position.
Referring to FIG. 15, there is shown an alternative embodiment of replenishment apparatus 400 that also employs a pressure differential for dispensing particulate material 100. Here, valve 412 controls the flow of a gas used to inflate a bladder 440 that propels the particulate material 100 through opening 428. This combination is particularly advantaged for allowing a vacuum level to be maintained in supply hopper 52.
Referring to FIG. 16, there is shown a rotary agitator 442 in another embodiment of replenishment apparatus 400. Rotary agitator 442 can be actuated to help force particulate material 100 out from replenishment container 72.
Referring to FIG. 17, there is shown an alternative embodiment of replenishment apparatus 400 that uses a piston 444 for dispensing particulate material 100 from replenishment container 72. FIG. 18 shows an alternative configuration of piston 444.
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 carriers 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, organic 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 carrier, with suitable mixing techniques, would allow the metering of minute quantities of a component particulate material, such as an organic particulate material, for vaporization.
It is to be understood that variations and modifications can be effected within the spirit and scope of the invention. For example, it can be readily appreciated that there can be a number of different types of seal used at interface fitting 54 for replenishment container 72. The various arrangements shown in FIGS. 12A through 18 are just some examples of the broad range of solutions for seals and fittings that can be used at interface fitting 54. Replenishment container 72 may store its particulate material 100 in vacuum, or in inert gas, or other suitable gas medium. The method and apparatus of the present invention allow particulate material 100 to be prepared and stored in a very pure form and with very low moisture content, thus eliminating the need for bake-out pre-heating or other pre-conditioning of the material prior to vaporization. The present invention also permits multiple component materials to be packaged together as particulate material 100, thereby simplifying the design of deposition process equipment where it is desirable to deposit multiple materials at the same time.
There are a number of ways to detect that the supply of particulate material 100 within replenishment container 72 is depleted. Various types of optical sensors or devices that sense weight, electrical conductivity, or other material characteristics could be employed as sensor 450 (FIG. 3).
The present invention is advantaged in that it enables the design of a rechargeable replenishment container 72. This can provide cost advantages and reduce waste. The volume of replenishment container 72 exceeds that of supply hopper 52, thus providing an efficient mechanism for supply to support a continuous deposition process.
Thus, what is provided is a method and apparatus for physical vapor deposition of particulate material, using a replaceable replenishment container.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
PARTS LIST


    
    
        5 vaporization device
        6 source
        7 source
        8 source
        9 vapor plume
        10 vaporization apparatus
        15 substrate
        20 manifold
        30 aperture
        32 deposition apparatus
        40 feeding apparatus
        50 feed container
        52 supply hopper
        54 interface fitting
        60 feeding path
        72 replenishment 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
        120 screen
        125 center portion
        130 piezoelectric structure
        135 thread-free portion
        140 piezoelectric structure
        150 piezoelectric structure
        155 piezoelectric structure
        170 heating element
        180 base
        190 bottom portion
        210 rotating thread type device
        220 gear driver
        230 opening
        240 motor
        250 third container
        260 first feeding path
        265 second feeding path
        270 vacuum exposure opening
        275 loadlock
        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
        350 light-emitting layer
        355 electron-transporting layer
        360 electron-injecting layer
        370 organic layers
        390 cathode
        400 replenishment apparatus
        402 slide valve
        404 O-ring
        406 valve assembly
        408 seal
        410 valve
        412 valve
        414 aperture
        416 disk
        420 bellows
        422 bottle
        423, 425 seal
        424 adapter
        428 opening
        430 vacuum chamber
        432 pressure control fitting
        434 hinge
        436 seal
        438 obstruction
        440 bladder
        442 agitator
        444 piston
        448 valve
        450 Sensor
        454 cover

## Claims

1. A method for vaporizing particulate material and depositing it onto a surface to form a layer, comprising:
(a) providing a supply of particulate material in a replenishment container under conditions that reduce oxygen moisture, the replenishment container having a seal and a sealed interface fitting;
(b) mounting the replenishment container at the interface fitting to a supply hopper defining at least one feed opening under conditions that reduce oxygen and moisture, and breaking the seal to expose the material of the replenishment container to the hopper;
(c) transferring particulate material under conditions that reduce oxygen and moisture from the replenishment container to the supply hopper; and
(d) transferring such particulate material under conditions that reduce oxygen and moisture through the feed opening along a feeding path to a vaporization zone where at least a component portion of the particulate material is vaporized and delivered to the surface to form the layer, thereby reducing environmental contamination.

2. The method of claim 1 wherein the replenishment container is larger in volume than the supply hopper.

3. The method of claim 1 wherein the feeding path is defined by an auger.

4. The method of claim 1 wherein the interface fitting provides a vacuum seal.

5. The method of claim 1 wherein the interface fitting provides an inert gas seal.

6. The method of claim 1 wherein the interface fitting includes a bellows.

7. The method of claim 1 wherein the particulate material comprises one or more organic components.

8. The method of claim 1 wherein the wherein the supply hopper feed opening is dimensioned to facilitate the free flow of the particulate material through the opening.

9. The method of claim 1 wherein transferring such particulate material through the feed opening comprises the step of agitating the particulate material.

10. The method of claim 1 wherein the supply hopper is maintained at a pressure below atmospheric pressure.

11. The method of claim 3 comprising the step of rotating the auger in a repeated incremental fashion for feeding material.

12. The method of claim 1 wherein the vaporization zone includes a heating element.

13. The method of claim 1 wherein the temperature of the particulate material in the feeding path is maintained below the desired vaporization temperature.

14. The method of claim 1 further including metering, at a controlled volumetric rate or pressure, the particulate material into the vaporization zone.

15. The method of claim 1 further including sensing the quantity of particulate material in the replenishment container.

16. The method of claim 1 wherein the step of transferring the particulate material through the feed opening includes agitating the particulate material by using an agitating device.

17. The method of claim 16 wherein the agitating device includes a piezoelectric structure or a rotating thread type device.

18. The method of claim 1 further comprising heating the particulate material while in transfer along the feeding path.

19. The method of claim 1 wherein the particulate material includes two or more different organic material components.