1. Field of the Invention
The disclosure relates to method and apparatus for efficiently depositing patterns of film on a substrate. More specifically, the disclosure relates to a method and apparatus for providing ink to a deposition apparatus for depositing an organic film on a substrate.
2. Description of Related Art
The manufacture of light emitting devices requires depositing one or more organic films on a substrate and coupling the top and bottom of the film stack to electrodes. The film thickness is a prime consideration and the deposition process must be optimized to deliver optimal thickness uniformity. The printing is typically accomplished by introducing liquid ink containing film material dissolved or suspended in a carrier fluid onto a discharge nozzle which then delivers all or part of the received film material onto the substrate.
The liquid ink is typically stored in a reservoir and is delivered to a discharge array. The discharge array comprises a multitude of interconnected discharge nozzles arranged in rows and columns. Each discharge nozzle prints a pixel on the substrate. The discharge nozzles typically comprise one or more micropores. The micropores receive liquid ink from the ink reservoir at a surface proximal thereto and dispense the ink material onto the substrate from their distal surface. The ink material can be dispensed in substantially vapor phase so as to allow formation of a film layer on the substrate in the absence of a carrier fluid.
Each discharge nozzle is spaced apart from its adjacent discharge nozzles. Although the liquid ink is intended to be delivered directly to the microarrays of each discharge nozzle, misalignment issues prevent complete delivery and only a fraction of the supplied ink makes its way to the micropores. The ratio of the quantity of liquid ink entering the pores compared to the quantity of liquid ink (including dissolved or suspended material) remaining or drying on the surface is called ink loading efficiency. When a large amount of liquid is supplied to the discharge array but only a small portion of the ink material makes its way into the micropores, the system is considered to have low loading efficiency. Moreover, when liquid ink material is finally delivered to the micropores, one or more solid particles can clog a micropore and thereby cause incomplete discharge.
Accordingly, there is a need for a method and apparatus that allows filling the micropores uniformly even if liquid ink is delivered some distance away from the region of interest with high loading efficiency.
The disclosure relates to a method and apparatus for efficiently depositing a film on a substrate. More specifically, the disclosure relates to a method and apparatus for directing liquid ink containing dissolved or suspended OLED material to a printhead surface in order to form an OLED film on the substrate. The OLED film can be substantially-free from carrier fluid and the delivery system is optimized to increase the loading efficiency.
An exemplary implementation of the disclosure relates to a method for loading film material into a discharge array. The discharge array includes a surface and a plurality of micropores extending through the surface. The discharge array is interposed between a liquid ink delivery system and a substrate. The liquid ink delivery system may include a plurality of nozzles which correspond to, and are aligned, with the plurality of micropores. The nozzles deliver liquid ink comprising of a carrier fluid having suspended or dissolved film material therein.
After a quantity of liquid ink is delivered to the discharge array, only a portion of the delivered ink is received at the micropores and the balance is received at the surface of the array. A pressurized gas knife is then moved over the discharge array to drive the delivered ink material to the micropores. The carrier fluid is removed from the delivered ink to form a substantially carrier-free ink material at the micropores prior to dispensing the substantially carrier-free film material from the micropores.
In another embodiment of the disclosure, the non-discharge surfaces and the micropores are treated such that the non-discharge surfaces repel liquid ink while the micropores attract the liquid ink. The treatment can be one of chemical treatments (i.e., coating with a repellant or attracting chemical), a physical treatment (i.e., differential surface roughness etching or other forms of solid surface treatment), an electrochemical treatment (i.e., anodic treatment) or a combination of these treatments.
In still another embodiment, the disclosure relates to an apparatus for loading ink material into discharge system. The apparatus comprises an ink discharge system defined by an array having a surface and at a first micropore extending through the surface; an ink supply for delivering liquid ink to the discharge system, the liquid ink can be defined by a carrier fluid containing dissolved or suspended film material therein; a gas knife for directing pressurized gas to the surface and the first micropore to distribute liquid ink across the surface and into the first micropore; and an energy source for evaporating the carrier fluid from the delivered liquid ink to thereby leave a substantially carrier-free film material in the first micropore. The energy source can comprise a heater. The micropore can be configured to receive the ink and the surrounding surfaces can be configured to repel the ink. The film that forms on the substrate can be a substantially carrier-free layer of an organic light emitting diode.
In yet another embodiment, the disclosure relates to a method for depositing a film material on a substrate by (1) supplying a quantity of liquid ink defined by a carrier fluid containing dissolved or suspended ink material to an array defined by a first surface having a plurality of blind micropores extending therethrough; (2) repelling the liquid ink from the first surface of the array toward a first of the plurality of blind micropores; (3) receiving the liquid ink at the first micropore; (4) flowing a pressurized gas over the surface to drive the liquid ink into the first micropore; (5) removing the carrier fluid from the delivered ink to form a substantially carrier-free ink material at the first micropore; and (6) dispensing the substantially carrier-free ink material from the at least one micropore to form the film on a substrate.
These and other embodiments of the disclosure will be discussed with reference to the following exemplary and non-limiting illustrations, in which like elements are numbered similarly, and where:
In one embodiment, the disclosure relates to a method and apparatus for depositing a film substantially free from carrier liquid on a substrate. In another embodiment, the disclosure relates to a method and apparatus for depositing a film of material in a substantially solid form on a substrate. In another embodiment, the disclosure relates to a method and apparatus for depositing a film of material substantially free of solvent onto a substrate. Such films can be used, for example, in the design and construction of OLEDs and large area transistor circuits. The materials that may be deposited by the apparatuses and methods described herein include organic materials, metal materials, and inorganic semiconductors and insulators, such as inorganic oxides, chalcogenides, Group IV semiconductors, Group III-V compound semiconductors, and Group II-VI semiconductors.
While reservoir 130 appears in alignment with discharge nozzle 180, in practice the two may be misaligned. Consequently, the ink liquid ink is dropped over the exposed surface area adjacent discharge nozzle 180 and not into micropores 160. This misalignment causes poor loading efficiency as significantly less ink or film material makes its way to the micropore and ultimately onto the substrate.
The thermal jet print-head of
Discharge nozzle 180 includes partitions (or rigid portions) 165 separated by micropores 160. Micropores 160 and rigid portions 165 can collectively define a micro porous environment. The micro-porous environment can be composed of a variety of materials, including, micro-porous alumina or solid membranes of silicon or silicon carbide and having micro-fabricated pores. Micropores 160 prevent the material dissolved or suspended in the liquid from escaping through discharge nozzle 180 until the medium is appropriately activated. When the discharged droplet of liquid encounters discharge nozzle 180, the liquid is drawn into micropores 160 with assistance from capillary action. The carrier fluid in the quantity of ink may evaporate prior to activation of discharge nozzle 180, leaving behind a coating of the dissolved or suspended film material on the micropore walls. The carrier fluid may comprise one or more solvents with a relatively low vapor pressure. The carrier fluid may also comprise one or move solvents with a relatively high vapor pressure.
The evaporation of the carrier fluid may be accelerated by heating the discharge nozzle. The evaporated carrier fluid can be removed from the reservoir and subsequently collected (not shown), for instance, by flowing gas over one or more of the discharge nozzle faces. Depending on the desired application, micropores 160 can provide conduits (or passages) having a maximum linear cross sectional distance W of a few nanometers to hundreds of micrometers. The microporous region comprising discharge nozzle 180 will take a different a shape and cover a different area depending on the desired application, with a typical maximum linear cross-sectional dimension D ranging from a few hundred nanometers to tens of millimeters. In one embodiment, the ratio of W/D is in a range of about 1/10 to about 1/1000.
In the exemplary apparatus of
Dislodging the dissolved or suspended film material may include vaporization, either through sublimation or melting and subsequent boiling. It should be noted again that the term dissolved or suspended film material is used generally, and includes anything from a single molecule or atom to a cluster of molecules or atoms. In general, one can employ any energy source coupled to the discharge nozzle that is capable of energizing discharge nozzle 180 and thereby discharging the film material from micropores 160; for instance, mechanical (e.g., vibrational).
Referring again to
In another exemplary embodiment, piezoelectric elements (not shown) can be positioned at or near reservoir 130 to meter out the desired quantity of ink 101 through orifice 170, thereby forming droplet 102. In yet another exemplary embodiment, liquid can be streamed out of reservoir 130 through orifice 170 (by, for instance, maintaining a positive ink pressure) and this stream can be pulsatingly interrupted by a mechanical or electrostatic force such that metered droplets created from this stream and further directed onto discharge nozzle 180. If mechanical force is utilized, it can be provided by introducing a paddle (not shown) that pulsatingly intersects the stream. If electrostatic force is utilized, it can be provided by introducing a capacitor (not shown) around the stream that pulsatingly applies an electromagnetic field across the stream. Thus, any pulsating energy source that activates a dispensing mechanism and thereby meters liquid ink 101 delivered from reservoir 130 through orifice 170 and to discharge nozzle 180 can be utilized. The intensity and the duration of each energy pulse can be defined by a controller (not shown) which is discussed below. Furthermore, as noted above, this metering can occur primarily when the ink is ejected from reservoir 130 through orifice 170; alternatively, this metering can occur primarily while the ink is traveling from orifice 170 to discharge nozzle 180.
As discussed in the exemplary embodiments of
Discharge nozzle 180 has a proximal surface (alternatively, inlet port) 181 and a distal surface (alternatively, outlet port) 182. Proximal surface 181 and distal surface 182 are separated by a plurality of partitions 160 and micropores 165. Proximal surface 181 faces reservoir 130 and distal surface 182 faces substrate 190. Nozzle heater 150 can be activated such that the temperature of discharge nozzle 180 exceeds the ambient temperature which enables rapid evaporation of the carrier liquid from droplet 102 which is now lodged in conduits 160. Nozzle heater 150 may also be activated prior to energizing the ink dispenser (and metering ink droplet 102 as it travels from reservoir 130 through orifice 170 to discharge nozzle 180) or after droplet 102 lands on discharge nozzle 180. In other words, reservoir heater 110 and discharge heater 150 can be choreographed to pulsate simultaneously or sequentially.
In the next step of the process, liquid ink 103 (previously liquid ink droplet 102) is directed to inlet port 181 of discharge nozzle 180 between confining walls 145. Liquid ink 103 is then drawn through conduits 160 toward outlet port 182. The carrier fluid in liquid ink 103, which may fill conduits 160 extends onto the surrounding surface, with the extent of this extension controlled in part by the engineering of confining walls 145, may evaporate prior to activation of discharge nozzle 180, leaving behind on the micropore walls the dissolved or suspended film material (herein, solid ink material) 104 (
Activating nozzle heater 150 in
In an exemplary embodiment, ink material 104 is heated so as to evaporate the solid ink material and direct a vapor stream containing ink material 104 onto substrate 190. Substrate 190 is positioned proximal to discharge nozzle 180 for receiving the vaporized ink material to form thin film 105. Simultaneously, reservoir 130 is provided with a new quantity of liquid ink 101 for the next deposition cycle.
Micropores can extend through the discharge nozzle or they can define blind micropores.
In an exemplary printing process each discharge nozzle receives liquid ink from one or more reservoirs (not shown). The discharge nozzles are preferably aligned with a corresponding liquid ink reservoir (see, for example,
To address these and other problems, an embodiment of the disclosure is directed to a gas knife for providing a continuous gas stream over the proximal surface of the discharge array. The proximal surface of the discharge array receives ink from one or more reservoirs. Once a quantity of the liquid ink is delivered to the discharge nozzle, pressurized gas (or air) in the form of a gas knife is directed over a surface of the discharge nozzle. The gas knife distributes pressurized gas (or air) across a surface of the discharge nozzle driving the liquid ink into the micropores and away from the surfaces between adjacent micropores.
In the embodiment of
After liquid ink is deposited on the micropores and the array surface (300
Once the ink material is drawn into the micropores, pressurized gas can help further evaporate the carrier fluid and drive down the carrier-free ink material deeper into each micropore. Upon evaporation of the carrier fluid, substantially carrier-free ink material can be collected at each micropore and can be discharged onto the substrate in solid or vapor form. In one embodiment, substantially solid ink material is vaporized at the micropore and allowed to condense on the substrate surface as a substantially liquid-free film material. This process can be aided by a local heater proximal to, or integrated with, each discharge nozzle (see, for example,
In an exemplary embodiment, the gas knife further includes a width and a length, which the sweeps along the longitude of the discharge nozzle. In one embodiment, the length of the gas knife is less than one third to total sweep distance, and the width is long enough to ensure complete coverage of the surface throughout the sweep.
In another embodiment, the liquid ink is delivered to and discharged from the proximal face of the micropores. The gas knife drives the delivered liquid ink into the micropores while simultaneously helping in evaporating and removing the carrier fluid from the proximal surface. It should be noted that the quantity of delivered ink can exceed the sum total of all of the available micropores' volume. Once the delivered ink material is received by the micropores, additional carrier fluid is evaporated, leaving behind a substantially solid ink material within each micropore. The gas knife will then help drive the substantially solid ink material through the micropores toward the distal face of the micropore. The substantially dry ink material is then vaporized and or ejected from the distal end onto a substrate, forming a substantially solid film thereon.
For blind pores, the ink can also be delivered in larger volume to the surface and spread using a flow of nitrogen or other gases through the gas knife. The gas used in the gas knife can be air, one or more noble gases or any combination thereof. The ink can then flow into the pores as it is passing above them but will not stay on the surface and will drain into the pores. This provides improved uniformity versus inkjet loading of the pores and removes leftover ink from the surfaces spanning between adjacent discharge nozzles (non-discharge surfaces). It also provides an alternative ink distribution structure to the orifice 170 while still allowing control over the amount of ink that is loaded in the pores. Alternatively, the flow of gas can be used in conjunction with inkjet printing or other methods to deliver a small volume of ink. Here, the purpose would be to remove leftover ink from the non-discharge surfaces.
In another embodiment, the non-discharge surfaces are modified to further aid micropore ink loading. Particularly, the non-discharge surfaces and the micropores can be treated such that non-discharge surfaces repel liquid ink while the micropores attract the liquid ink. The treatment can be one of chemical treatments (i.e., chemical coating to increase/decrease surface tension or surface energy), a physical treatment (i.e., etching or other forms of solid surface treatment to improve flow), an electrochemical treatment (i.e., anodic treatment) or a combination of these treatments. In still another embodiment, the non-discharge surfaces can be modified geometrically by changing the roughness of the material or creating steps, recesses or other structures with different height (e.g., fabricating ink wells). Super-wetting structures such as a multitude of pillars (i.e., a pillar forest to enhance flow of liquid ink) can be utilized on top of a pattern of pores or instead of a pattern pores.
Containment structures can also be used to prevent liquid ink from spreading onto the non-discharge surfaces. This is useful for open micropores on the sides opposite to the ink delivery mechanism to limit the effect of ink leaking through the micropores. A containment structure can be formed by creating a discontinuity in the surface wetting properties, such as with an abrupt change in surface material or topography. One containment structure is an oxide containment ring. For exemplary micropores etched in a silicon surface, an oxide ring is realized by etching silicon dioxide around the micropores down to bare silicon, and simultaneously patterning a 2-5 μm wide silicon dioxide ring around the pores. The size of the silicon dioxide ring is a function of the area to be contained and is not limited to the range provided herein.
When liquid ink reaches the oxide ring, which is more hydrophilic as compared to silicon, the ink is prevented from further spreading due to the abrupt increase in contact angle and surface energy at the outer oxide-silicon interface of the ring. Ink spreading is therefore blocked by the ring. Liquid Ink can then retract back into the pores as it dries. A small volume of ink may remain on the ring.
It should be noted that the illustrated embodiments of
To increase uniformity for the liquid ink loading into the micropores, the pattern of micropores as well as the pitch and relative positions of the pores can be modified. The micropores may also be replaced by interconnected channels so that the ink will spread uniformly inside the channels. This can also help with robustness to misalignment, and loading efficiency, as the channels will be more effective at drawing in liquid from the neighboring surface areas than pores.
To get the ink to preferentially wet the micropores compared to the non-discharge surfaces, the micropore sidewall surface and profile can be modified. For example the sidewalls can be smooth or rough, with different microstructures. The sidewall profile may be straight, slanted, or curved. The contour of the pore can also be modified; a pore with corners (such as a square for example) will be easier to fill than a round one.
While the principles of the disclosure have been illustrated in relation to the exemplary embodiments shown herein, the principles of the disclosure are not limited thereto and include any modification, variation or permutation thereof.
The instant application claims priority to provisional application No. 61/453,098, filed Mar. 15, 2011 and to patent application Ser. No. 12/139,409, filed Jun. 13, 2008, which claims priority to provisional application No. 60/944,000, filed Jun. 14, 2007, the disclosure of the identified applications are incorporated herein in their entirety.
Number | Date | Country | |
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61453098 | Mar 2011 | US | |
60944000 | Jun 2007 | US |
Number | Date | Country | |
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Parent | 12139409 | Jun 2008 | US |
Child | 13218451 | US |