TW201212105A - Organic vapor jet printing with a blanket gas - Google Patents

Abstract

A method of depositing organic material is provided. A chamber is provided having a substrate disposed therein. An organic material is deposited over the substrate by ejecting from a nozzle directed at the substrate: a first gas; and a vapor of the organic material carried by the first gas. During the depositing an organic material, a second gas is provided in the chamber. The flow rate of the second gas is at least 5% of the sum of the flow rates of all gases flowing into the vacuum chamber. The second gas has a molecular weight at least 20% greater than the molecular weight of the first gas. The second gas is provided in the chamber via an aperture remote from the nozzle.

Description

201212105 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an organic vapor jet printing (OVJP). The claimed invention is one or more of the following: and/or one or more of the following parties to reach a joint university company research agreement: Michigan State University Board of Directors, Princeton University Board of Directors, University of Southern California Board of Directors and Universal Display Corporati〇n. The agreement is effective on the day before and after the invention was made, and the claimed invention was made for the activities carried out within the scope of the agreement. [Prior Art] For a large number of reasons, photovoltaic devices using organic substances have become increasingly desirable. Many of the materials used to make such devices are relatively inexpensive, and therefore, organic optoelectronic devices have the cost advantage over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, make them well suited for particular applications such as manufacturing associated with flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (〇LEDs), organic optoelectronic crystals, organic photovoltaic cells, and organic photodetectors. For germanium LEDs, organic materials have performance advantages over those of the conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can generally be easily tuned by a suitable dopant. OLEDs utilize a thin organic film that emits light when a voltage is applied to the device. For applications such as flat panel displays, lighting and backlighting, OLEDs are becoming an increasingly interesting technology. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; J57726.doc 201212105 One method of depositing OLEDs and other organic devices is organic vapor nozzle printing (OVJP). The general principles of OVJP are described in U.S. Patent No. 7,404,862, issued July 29, 2008, U.S. Patent 7,744,957, issued on Jun. 29, 2010, and U.S. Patent No. 7, issued on October 7, 2008. , U.S. Patent No. 7,722,927 issued May 25, 2010, and U.S. Patent Application Serial No. 12/034,683, filed on Feb. 21, 2008. Such cases should be incorporated herein by reference. The term "organic" as used herein includes polymeric materials and small molecular organic materials that can be used to make organic optoelectronic devices. "Small molecule" means any organic material that is not a polymer, and "small molecules" can actually be quite large. In some cases, small molecules or the like may contain repeating units. For example, the long bond stimuli as a substituent system cannot remove molecules from the "small molecule" category. A small molecule or the like may also be used as a core portion of a dendrimer polymerization i, for example, as a side of a polymer backbone or as a part of the main chain. On the core part - a series of chemical shells. The core part of the dendrimer can be a fluorescent or phosphorescent small molecule emitter. The dendrimer can be a "small molecule" and we believe that it is currently used in the field of OLEDs. All dendrimers are small molecules. As used herein, "top" means the farthest from the substrate, and "bottom" refers to the closest to the substrate. The first layer describes the second layer of "located": Temple = the first layer is located far from the substrate. Unless the first layer is specified as ": contact", there may be other defects between the first and second layers. 7 ' Even if there are multiple layers of organic layers in between, the cathode can be described as being "on" the anode. 157726.doc 201212105 More OLED-related details and the above definitions can be found in U.S. Patent No. 7,279,704, the disclosure of which is incorporated herein by reference. SUMMARY OF THE INVENTION The present invention provides a method of depositing an organic substance. Provide a cavity with a built-in substrate to. The organic substance is sprayed through a nozzle directed to the substrate: a first gas; and a vapor of an organic substance carried by the first gas is deposited on the substrate. A second gas is supplied to the chamber during deposition of the organic material. The flow rate of the second gas of 5 hai is at least 5% of the sum of the flow rates of all the gases flowing into the vacuum chamber. The second gas has a molecular weight that is at least 20% greater than the molecular weight 1 of the first gas. The second gas system is provided in the chamber through a hole remote from the nozzle. Preferably, the flow rate of the second gas is at least 30% of the sum of the flow rates of all gases flowing into the vacuum chamber. More preferably, the flow rate of the second gas is at least 6 〇 0 / of the sum of the flow rates of all gases flowing into the vacuum chamber. . Preferably, the total pressure in the vacuum chamber is between 1 mTorr and 1 Torr during the deposition of the organic material. The first gas is preferably N2. Preferably, the second gas is selected from the group consisting of Ar, Kr, Freon, xe, C〇2, and WF6. The second gas can be a single substance. The second gas may be a mixture of different gases each having a molecular weight that is at least 20% greater than the molecular weight of the first gas. Preferably, the second gas has a molecular weight that is at least 100% greater than the molecular weight of the first gas. The second gas may be a mixture of materials each having a molecular weight greater than 100% greater than the molecular weight of the first gas.

S 157726.doc . 201212105 S-chamber can be vacuum chamber β The present invention provides a method of depositing organic matter. Provide a chamber with a built-in substrate. The organic substance is ejected through a nozzle directed to the substrate: a first gas; and a vapor of an organic substance carried by the first gas is deposited on the substrate. A second gas is supplied to the chamber during deposition of the organic material. The second gas has a molecular weight that is at least 20% greater than the molecular weight of the first gas. The second gas system is provided in the chamber through a hole remote from the nozzle. The mouth has a hole of the smallest size. The organic material is deposited on a 5 liter substrate to form a patterned feature having a shape defined by the shape of the hole. Relative to the other identical deposition performed without the second gas, the partial pressure of the second gas in the chamber during the accumulation of the organic material is sufficient to provide a minimum size distance from the edge of the patterned feature The amount of organic matter deposited is reduced by a factor of two. [Embodiment] A general 'OLED' includes at least one organic layer between an anode and a cathode and electrically connected to an anode and a cathode. When a current is applied, the anode is injected into the cavity and the cathode injects electrons into the (or other) organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, they are formed as "excitons" of localized electron-hole pairs with excited states. When an exciton generates relaxation according to a light emission mechanism, it emits light. In some instances, an exciton can be localized to a exciton or an excitation complex. Non-radiative mechanisms such as thermal relaxation may also be present, but are generally considered undesirable. FIG. 1 shows an organic light emitting device 100. These figures are not necessarily drawn to scale. The device 100 includes a substrate u, an anode 115, a hole injection layer 157726.doc 201212105, a hole transfer layer 125, an electron blocking layer 13A, an emission layer 135, a hole barrier layer 14 The electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 16A. The cathode 16 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Apparatus 100 can be made by sequentially depositing the layers. The nature and function of the various layers and the example materials are described in more detail in US Pat. No. 6,279,704, the disclosure of which is incorporated herein by reference. Further examples of the various layers can be used. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, the disclosure of which is incorporated herein in its entirety by reference. An example of a p-doped type of hole-transporting layer is m-MTDATA in which a 50:1 molar ratio doping F is substituted for 4-TCNQ as disclosed in US Patent Application Publication No. 2003/0230980, the patent application. The full text is incorporated by reference. Examples of emissions and host materials are disclosed in

The entire disclosure of U.S. Patent No. 6,303,238 to T.S. An example of an η-doped electron-transporting layer is BPhen, which is doped with Li in a molar ratio of 1:1 as disclosed in U.S. Patent Application Publication No. 2003/0230980, the entire disclosure of which is incorporated herein by reference. An example of a cathode comprising a composite cathode having a thin layer of a metal such as Mg: Ag and an overlying transparent conductive sputter-deposited ITO layer is disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, each incorporated by reference. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147, and U.S. Patent Application Publication No. 2003/0230980, the entire disclosure of which is incorporated herein by reference. An example of an injection layer is provided in U.S. Patent Application Publication No. 2004/0174, the entire disclosure of which is incorporated herein by reference. A description of the protective layer c 157726.doc 201212105 can be found in U.S. Patent Application Publication No. 2/4,174,116, the entire disclosure of which is incorporated herein by reference. Figure 2 shows a reverse 0LED 2〇〇. The apparatus includes a substrate 21, a cathode 215, an emissive layer 22, a hole transport layer, and an anode. Mounting = 200 can be made by sequentially depositing the layers described. Since most of the hanging OLED groups have a cathode on the anode and the device employs a cathode 215 located below the anode 230, the device 2 can be referred to as a "reverse" OLED. Materials similar to those described for device i (10) can be used in the corresponding layer of the shock 200. Figure 2 provides an example of how some layers can be omitted from the structure of the device. The simple layered structure illustrated in Figures 1 and 2 is by way of non-limiting example, and it should be understood that embodiments of the invention may be utilized in a variety of other configurations. The particular materials and structures described are exemplary in nature and other materials and structures may be used. The functional 〇 LEDs can be passed by combining the different layers in different ways, or the layers can be completely omitted based on the tenth, performance and cost factors. Other layers not explicitly described may also be included. Materials other than those already described may be used. Although many examples are provided to describe different layer packages, single materials, it should be understood that materials such as a mixture of a host and a dopant or, more generally, a mixture may be used. In addition, the material layer can have different sub-layers. The names of the different layers in the text are not intended to be strictly limited, for example, 'in the middle hole hole transfer layer 225, the hole is transferred and the same as the hair layer 22G. t, and can be described as a hole transfer layer or a hole injection layer. In one embodiment, the '〇 LED can be described as having an organic layer at the cathode and the anode gate. The organic layer may comprise a single layer or may further comprise a plurality of layers of different organic materials, as described, for example, in Figures [and 2]. Structures and materials that are not specifically described may also be used, such as oled (pled) comprising a polymeric material as disclosed in U.S. Patent No. 5,247, s. By way of another example, an OLED having a single organic layer can be used. The 0 LEDs can be stacked, for example, as described in U.S. Patent No. 5,7,7,745, the entire disclosure of which is incorporated herein by reference. The 0 LED structure can deviate from the simple layered structure illustrated in Figures 2 and 2. For example, the structure may include an improved externally coupled inclined reflective surface (such as the mesa structure described in U.S. Patent No. 6, s. 91,195 to Forrest et al.) and/or a U.S. patent to Bul〇vic et al. The pore structure of the case No. 5,834,893, the entire contents of which are hereby incorporated by reference. Any layer of the embodiment may be deposited by any suitable method unless otherwise indicated. For organic layers, preferred methods include hot steaming, ink jetting, such as those described in the U.S. Patent No. 6, 〇 13, tor. 6, 〇 87, 196, incorporated herein by reference in its entirety. U.S. Patent No. 6,337,1, 2, U.S. Patent No. 6,337, the disclosure of which is incorporated herein by reference. Organic air jet printing (OWP) deposition in 1〇/233,47 〇. Other suitable deposition methods include spin coating and other solution based methods. The solution based method is preferably carried out in a nitrogen atmosphere or in an emotional atmosphere. For other layers, preferred methods include thermal evaporation. Preferably, the method of patterning includes, by way of text, the mask deposition, ^ in the U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference.

S J57726.doc 201212105 Soldering and patterning associated with some deposition methods such as inkjet and OVJP. Other methods are also available. The material to be deposited can be modified such that it can be compatible with a particular deposition process. For example, a substituent such as a branched or unbranched alkyl group and an aryl group preferably having at least 3 carbons may be used in the small molecule to enhance its ability to undergo solution treatment. Substituents having 2 or more carbons may be used, and 3 to 20 carbons are preferred ranges. Materials having an asymmetric structure may have better solution treatability than symmetric structures. Because asymmetric materials can have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing. Devices made in accordance with embodiments of the present invention can be incorporated into a variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lamps for indoor or outdoor lighting and/or signal transmission, heads-up displays, fully transparent displays No, flexible display, laser printer, telephone, mobile phone, personal digital assistant (pDA), laptop, digital camera, camcorder viewfinder, micro display, vehicle, large Area wall, theater or open field screen or signal conductor. A variety of control mechanisms, including passive and active matrices, can be used to (4) devices made in accordance with the present invention. In these devices. Many of the materials are used in a comfortable temperature range (such as 1 to 30C, and better room temperature (2〇i25C&gt;c)). The materials, structures, and methods described in the text may be in addition to 〇(四) The application in the external device. For example, other optoelectronic devices such as organic solar cells and organic light smears may utilize such materials, structures, and methods. More generally, organic devices such as organic transistors can utilize such materials and junctions. 157726.doc 201212105 In many cases, organic vapor jet printing (OVJP) is an ideal method for depositing organic materials. The OVJP can deposit organic molecules having a shape or pattern defined by the nozzles without the use of a mask, photoresist or similar patterning technique based on substrate blocking or landing portions that are not desired to be deposited thereon. The nozzle produces an injection. Typically, the nozzles or nozzles of the OVJP system are in fluid communication with a source of carrier gas and an organic molecular source. As used herein, a "nozzle" is a mechanism that directs, directs, or controls the flow of material after it leaves the mechanism. Some (though not all) 〇VJP systems include deposition in the chamber. Many OVJP systems also include a substrate support that is adapted to support the substrate under the nozzle and move relative to the nozzle. The nozzle, the substrate support or both can be moved. Where a chamber is used, the nozzle and substrate support can be located within the chamber. The use of chambers allows for better control of ambient conditions such as background pressure, gas settling and temperature. As used herein, "below" the nozzle means in the direction of the nozzle (i.e., the nozzle is directed toward the substrate). The nozzle can be oriented in any number of directions of the substrate. OVJP has in fact demonstrated the use of a single carrier gas (generally referred to as nitrogen) to deliver organic vapor to the nozzle, which is deposited on the pure close to the nozzle to obtain a transverse dimension defined by the size of the nozzle. The film. Although, in general, Jane, Lu, and Media have stated that the width of the deposited film is equal to the size of the nozzle, but using _ ', λ, and more complicated analysis to show that there is no physical mask on the substrate. Less than 100% of the organic molecules emitted from the mouth will be deposited below the nozzle itself. Materials that will be accumulated outside the nozzle area

S 157726.doc 201212105 "Overspray". It is assumed that organic devices are susceptible to contamination (specifically, organic light-emitting devices are prone to have luminescent molecules with lower excitation energies), and a small amount of over-spraying (&lt;〇.called may be problematic. Therefore, it is desirable to make overshoot Minimization. It has been revealed that the addition of a non-organic gas around the nozzle as a "protective flow" reduces excessive bleed, see u s. 7, 744, 957. However, this coaxial configuration increases the complexity of the 0VJP pout. It is disclosed in the text: - A method for reducing the (4) order of the material, which is simply implemented by introducing a "filling" gas having a substantially higher atomic mass than the carrier gas in the deposition chamber. Figure 3 shows the cross section of the different nozzle geometries taken in the direction perpendicular to the airflow. The arrows in each hole indicate the "minimum size" of the hole. In mathematical terms, in the case of the smallest dimension, the length of the arrow is at a local maximum (for circles, ellipses, and triangles) or constant relative to the translation of the entire arrow in a direction perpendicular to the arrow (for rectangles) ), and the "minimum" size is the minimum local maximum or is generated for this point. Systematic. Figure 3 shows cross sections of holes 31, 32, 33 and 34, respectively, having a circular, sugar circular, triangular and rectangular cross section. For the deposition line, the rectangular hole is the best shape, and it is also relatively easy to obtain the shape in the nozzle which utilizes the stone carving. However, other shapes can be used. This month ^ the method of seeding organic matter. Provide a cavity with a built-in substrate to. The organic substance is sprayed through a nozzle directed to the substrate: a first gas; and a vapor of the organic substance carried by the first gas is deposited on the substrate 157726.doc • 12-201212105. A second gas is provided in the chamber during deposition of the organic material. The flow rate of the second gas is at least 5% of the sum of the flow rates of all gases flowing into the vacuum chamber. The helium gas has a knives larger than the molecular weight of the first gas to 2 〇/〇. The second gas system is provided in the chamber via a hole remote from the nozzle. The flow rate of the gas is at least 3% of the sum of the flow rates of all the gases flowing into the vacuum chamber 19. Preferably, the flow rate of the second gas is the sum of the flows of all the gases flowing into the vacuum chamber. At least 6 〇〇/〇. It has been confirmed (see Figure 5 and related discussion) that the presence of a second gas that can be "filled" with gas reduces the over-injection relative to the method in which only the carrier gas is substituted for the heavier fill gas. One feature of the second gas is that the basin is introduced into the chamber via a hole remote from the nozzle. By "away from" the nozzle, it means that at least the "minimum ruler" of the nozzle hole through which the gas is filled is removed from the nozzle hole. In most embodiments, it is highly probable that the pores through which the fill gas is introduced are further apart. The filling gas is different from "Bao Xiongqi", in its most common embodiment, 'it enters the chamber through a circle (four) around the nozzle through which it is introduced: that is, the specific position at which the protective flow is introduced is related to the self-nozzle The fluid dynamics of the injected gas. In its purest sense, it is irrelevant to introduce a specific location of the "filler gas" because the presence of a filling gas in the surrounding gas in the chamber affects the hydrodynamics of the gas ejected from the nozzle, resulting in a narrower jet diffusion. . Therefore, the use of a heavy fill gas can be easier to implement than when using a guard stream. For "heavy", the text means filling ((or first) gas at least 20% of the molecule', parent carrier flow &lt; knife miles. At least 2〇% molecular weight

157726.doc -13. S 201212105 is expected to have an effect as demonstrated with respect to Figure 5 and related experiments, since Ar has a molecular weight of 18 compared to the molecular weight 14 of Nz. From the viewpoint of narrow injection diffusion, it is understood that the heavier the filling gas is, the better the carrier gas is. Preferably, the molecular weight of the filling gas is at least 1% greater than the molecular weight of the carrier gas. Preferably, the filling gas is inert depending on the performance of the device. The filling gas should not react with the material of the device being manufactured. Suitable gases which are inert and heavy include Ar, Κι·, Freon, Xe, c〇2 and wf6. N2 is preferably used as the first gas because it is inert and extremely light. He can also be used as a carrier gas, which shows a new possibility of "heavy" filling gas. For example, A is heavier than ^, and when He is a carrier gas, n2 can be used as a filling gas. The filling gas may be a single gas that meets the weight standard, or whether it is 20% or 100% larger than the molecular weight of the carrier gas, and may be a mixture of gases each meeting the weight standard. However, for the sake of simplicity, it is preferred to use a single gas which has its intended effect because it consists of molecules that are heavier relative to the carrier gas and should be generated regardless of whether all of the filling gas molecules are the same or not. This effect. In most embodiments, the carrier gas is desirably a single gas, preferably helium. However, embodiments of the present invention may utilize a carrier gas implementation having multiple gas components. Under the 5th brother, the "molecular weight" of the carrier gas should be regarded as the molar average molecular weight. Preferably, during deposition of the organic material, the total pressure in the vacuum chamber is between 1 mTorr and 1 Torr. Generally, it is a preferred pressure range for 〇VJp. Similarly, 0VJP (including VJP using a fill gas) can be implemented at high pressure and low pressure. However, the pressure below the lower limit of the range is not better than 157726.doc 201212105, because 〇vjp introduces gas into the chamber according to its nature, so that it is compared with the method such as hot evaporation. Similar to the degree of vacuum, the lower vacuum may require a vacuum device that is extremely expensive. Higher pressures can be easily exploited, but in general, Yan Ming is willing to remove the carrier gas so that the deposition can take place within the chamber for a controlled period of time, and it is extremely easy to obtain 1 Torr of waste. The use of an atmospheric or high pressure sub-corpore is applicable to the chamber, preferably a vacuum chamber, however, an embodiment of the OVJP is applied, and a gas encapsulating embodiment is employed. The method of filling the amount of milk into the inner cavity is based on the flow rate. The relative flow rate of the different gases introduced into the chamber during equilibrium may correspond to the gas located at a location remote from any of the holes in the incoming gas (i.e., the "surrounding" gas within the chamber). Lack of;, *, ± Knife..., and the control and measurement of the speed is much easier than the partial pressure. Another method of quantifying the amount of gas filled in the chamber is the determination of the overspray effect. One object of embodiments of the present invention in the context of OLEDs is to reduce the amount of impure molecules in adjacent devices having different structures and generally emitting light of different colors. Impure molecule. In the case of emissivity in a device that treats it as an impurity, it is easy to quantify the enthalpy of impurities contained by measuring the emitter of the device. The experiment of Figure 5 shows that a suitable amount of fill gas can easily reduce the amount of impurities relative to the atmosphere in which the fill gas is present, but the same total pressure is the same (and is due to the presence of carrier gas). Generally, the nozzles that are suitable for use may have a "minimum dimension" as described with respect to Figure 3. One method of quantifying whether the filling gas has a partial pressure sufficient to have the desired effect is to perform a simple leg, such as the experiment of 201212105, at the same total pressure, using a filling gas to carry out the 〇vjp and carrying only the carrier gas therein. 〇 ν; ρ for comparison. This can be achieved as shown in Figure 5. The effect of overspray can be measured at a minimum size from the edge of the patterned feature. The partial pressure of the second gas in the chamber during deposition of the organic material is sufficient to deposit at a distance from a margin of the patterned feature edge relative to other identical deposits performed without the second gas The amount of organic matter is reduced by a factor of two, and it can be said that the filling gas has a remarkable effect. As illustrated in Figure 5, this effect is easily achieved by a suitable filling gas. Preferably, the OVJP is carried out at a relatively low vacuum (generally, j millitorr to chin), however, embodiments with higher vacuum to atmospheric pressure or higher are highly desirable. Thus, the evaluable partial pressure of the residual gas in the vacuum chamber can be observed by the organic molecules after they have been carried by the carrier gas through the nozzle. Within this limit, some combination of pressure and carrier gas flow rate results in a minimum amount of over-injection. Embodiments of the present invention include further reducing the excessive mouth spray by intentionally introducing a gas having a partial pressure within the deposition chamber that is heavier than the carrier gas. This heavier gas can be referred to as a "filler" gas. The heavier gas is more restrictive to the expansion of the carrier gas and organic vapor exiting the nozzle than the carrier gas. In a particular exemplary embodiment, the carrier gas is nitrogen and the chamber is filled with a portion of the pressure of argon. The over-injection in the case from the chamber to the argon-containing example is less than measurable to the extent of over-injection to the case where only nitrogen introduced via the carrier gas is included. There may be an optimum total pressure 'which may be different from the Ar fill gas using only the optimum pressure of N2 and it may be desirable to measure the optimum total pressure. Can be determined by different total pressure 157726.doc 201212105 force, 歹, j deposition and determination of the knot easily measured the best total force. This is customary for the regular 〇vjp without the filling gas and should be the equivalent of the OVJP with the filling gas. Only the reduction in over-injection is taken to the right, and it is desirable to use the heaviest possible filling gas. However, in selecting a fill gas, other factors should be considered, such as cost and toxicity. The filling gas should also be inert, T: it should react adversely with any part of the organic device. As for the gas which is desired to be used as the filling gas due to the high knives, the preferred choices include the composite gas molecules of Kr, CF4, C2F6, and the gas, the heart, and the like in the order of high to low. It is expected that over-injection can be desirably reduced when there is a heavy fill gas in the same total p-field when only the carrier gas is present. However, it is contemplated that each of the packed/carrier gas combinations can have different partial pressures that minimize over-injection, which can be determined by relatively simple experiments. One consideration for filling OVJp deposits with specialty gases is very likely to be cost. It is preferred to continuously introduce a new fill gas to compensate for the carrier gas exiting the nozzle, otherwise the deposition chamber will eventually be filled with only the carrier gas. This point means that a large volume of fill gas can be used over time&apos; and cost and/or disposal should be considered. Embodiments of the invention can be implemented in a multi-dimensional range. It is desirable to use heavy ambient gas for any size of the OVJP system. Figure 4 shows a simple single nozzle embodiment of an embodiment of the invention. Figure 4 shows systems 410 and 450. The system 41 includes a chamber 420 having a 〇Vjp nozzle 422, a hole 424 for introducing a fill gas, and a hole 426 for removing gas from the chamber 420. A vacuum system can be coupled to the aperture 426. In the case where the gas originates from a source outside the chamber, the nozzle 422 is abstractly illustrated as

- S 157726.doc 201212105 Jet stream of gas 430. It should be understood that any of a variety of known systems including nozzles for jp can be used. System 410 illustrates a wider spray spread in the presence of a light ambient gas. System 450 includes a chamber 46 having an OVJP nozzle 462, a bore 464 for introducing a fill gas, and a bore 466 for removing gas from chamber 460. A vacuum system can be coupled to the aperture 466. In the case where the gas originates from a source outside the chamber, the nozzle 426 is abstractly illustrated as a jet of gas introduced into the chamber. It should be understood that any of a variety of known systems including nozzles for OVJP can be used. System 450 illustrates a narrower jet spread with heavy ambient gas. One dimensional array of nozzles (i.e., nozzle lines) is a preferred embodiment of the nozzle block. Such arrays enable high throughput patterning by moving the nozzles relative to the substrate (and vice versa, in the direction perpendicular to the nozzle line). Other configurations of multiple nozzles, such as a two-dimensional array, can also be used. A variety of nozzle shapes are available. For example, preferably, the heels may be elongated (e.g., rectangular) depending on the long axis in the direction of the translational array relative to the substrate. Embodiments of the invention may generally be practiced in conjunction with other techniques for 〇VJp or modified 〇v JP. For example, embodiments of the present invention may be implemented in conjunction with an ejector in a nozzle block that causes localized vacuum, as disclosed herein. U.S. Patent Application Serial No. 11/643,795, the disclosure of which is incorporated herein by reference. Figure 5 shows a plot of the emission versus distance from the deposition edge, which provides a measure of how much over-spray occurs during deposition. Different deposition conditions exemplify the effect of heavy fill gas on OVJP deposition and, in particular, reduce over-injection by using a heavy fill gas. The NPD/TPBi double layer device was obtained by vacuum thermal deposition (VTE) on a 6&quot;glass substrate patterned with a 1 mm wide ITO anode having a line spacing of 157726.doc 201212105 0.5 mm. The device's charge injection and transfer characteristics are highly asymmetric such that all excitons generated are closely constrained to the NPD/TPBi interface. The resulting device showed a blue light EL from NPD in the absence of contamination. A fine red dopant line is deposited using 0VJP along one of the ITO lines between the filled VTE deposition of NPD and TPBi. Since the effective exciton is transferred to the red dye, the deposition line shows red electric excitation light. Any overspray of the red dye at the far end of the deposited ITO strip may also exhibit some degree of red light emission depending on the amount of red dye deposited at that location. The peaks in the electroluminescence spectrum are significantly independent of the red dye and the preset NPD emission and the ratio of the red and blue peaks quantitatively defines the amount of red dye present; this ratio is the controlled VTE of the test structure Deposition is performed for calibration. Due to the effective limitation of excitons at the organic heterointerface and the high efficiency of energy transfer over time, these structures are highly prone to overspray and have been used to detect &lt;0.25 A material or about 1/1 inch. Floor. The experimental configuration is somewhat embarrassing. Illustratively, the fabrication of the device OVJP portion is accomplished in a chamber such as the chamber illustrated in Figure 4. The chamber is a vacuum chamber, but the vacuum does not have a variable value - that is, the vacuum is opened or closed without setting conditions therein. Assuming that the vacuum system is open, the total pressure in the chamber is measured by the flow rate of the carrier gas and the filling gas. The chamber has a single pressure measuring device that measures the total pressure within the chamber. The different maps of Fig. 5 are expressed as follows: N1 托 N2 indicates a calibration operation to determine the total pressure (〇1 Torr) in the case where the carrier gas flow rate is set to a specific amount, and

S 157726.doc -19- 201212105 The only gas entering the chamber is the carrier gas passing through the nozzle. The plot shows that the over-injection is less because the total pressure is smaller, but it is not similar to other plots used to determine whether the surrounding gas is the same as the carrier gas or includes the effect of a heavier fill gas. For the two edge maps of &amp; 0.3 Torr, the Ar experiment is the same experiment. The flow rate of the Ns carrier gas is the same as the flow rate of the 〇" but the Ar gas enters the chamber through the hole away from the nozzle. . The flow rate of αγ is sufficient to reach a total pressure of 0,3 Torr. For the two plots of 乂.3 托, N2 was filled for the same experiment, which was carried out in the same way as the Ar filling experiment, except that A gas was introduced into the chamber instead of Ar gas via a hole away from the nozzle to achieve up to 〇. · Outside the total pressure of 3 Torr. The data is shown at the same pressure, compared to the use of the preset Ν2 fill, using a 〇3 Torr fill to make the over-spray less. The minimum amount of overspray shown in Figure 5 is suitable for calibration operations where no fill gas is present. The two results for the fill gas show that the overspray is more than the deposition using the preset A fill to the crucible. However, due to the limited nature of experimental instruments, 丨. 丨 为 is the minimum achievable pressure to increase the pressure through the nozzle and any filling gas, so the limited instrument can be used to test the Ar filling at a total pressure of 1 Torr. . Compared to the N2 (Ar-filled) of the 〇3 tray, the control associated with the NAN is filled with 〇3 Torr, which is shown at the same pressure, with respect to the lighter ambient gas, the heavier ambient gas (or Specifically, the excessive gas is reduced due to the generation of at least a significant partial pressure of the gas by the heavy gas. This is accurate even in the case where heavy gas is introduced into the cavity through the hole away from the nozzle. It is to be understood that the various embodiments described herein are by way of example only, and the 157726.doc -20-201212105 heat is not intended to limit the scope of the invention. For example, many of the materials and alternatives may be made without departing from the spirit of the invention. Thus, the present invention is intended to include variations of the specific examples and preferred embodiments described herein. It should be understood that the different theories of why the invention operates are not intended to be limiting. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an organic light-emitting device. Figure 2 shows a reverse organic light-emitting device without different electron-transport layers. Figure 3 shows the cross-face of a different nozzle geometry taken in a direction perpendicular to the airflow. Figure 4 shows two chambers for material deposition, one with light ambient gas and the other with heavy ambient gas. Figure 5 shows a plot of the emission versus distance from the deposition edge, which provides a measure of how much over-spray occurs during deposition. [Main component symbol description] 100 Organic light-emitting device 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transfer layer 130 Electron barrier layer 135 Emissive layer 140 Hole barrier layer 145 Electron transfer layer

S 157726.doc -21 _ 201212105 150 electron injection layer 155 protective layer 160 cathode 162 first conductive layer 164 second conductive layer 200 reverse OLED 210 substrate 215 cathode 220 emission layer 225 hole transfer layer 230 anode 310 sub L 320 sub L 330 hole 340 hole 410 system 420 chamber 422 nozzle 424 sub L 426 sub L 430 gas 450 糸 460 chamber 462 nozzle 157726.doc -22 201212105 464 sub L 466 sub L 470 gas s 157726.doc -23-

Claims (1)

201212105 VII. Patent application scope: 1. A method comprising: a chamber for a built-in substrate; a nozzle sprayed from the substrate: a first gas; and an organic material carried by the first gas The vapor of the substance 'deposits the organic substance on the substrate; during the accumulation of the organic substance, a second gas is supplied in the chamber. wherein" the flow rate of the second gas is the flow rate of all the gas flowing into the vacuum chamber At least 5% of the sum; the second oxygen body has a molecular weight that is at least 2% greater than the molecular weight of the first gas; and the second gas system is provided in the chamber through a hole away from the nozzle. The method of claim π, wherein the flow rate of the second gas is at least 30 〇 / 〇 of the sum of the flow rates of all the gases flowing into the true two chambers. 3. = the method of the present invention, wherein the second gas The flow rate is at least 60% of the sum of the flow rates of all the gases flowing into the true February. 4' i is the method of claim 1, wherein during the deposition of the organic matter, the total pressure in the vacuum chamber is introduced. Yu Yutuo to the care 5. The method of claim 1 wherein the first gas is Ν 2. 6 ^ The method of claim 1 wherein the second gas system is selected from the group consisting of Ar, Kr, freons, Xe a group consisting of c〇2 and WF0. 7 · If JE 1 is requested, the method of drinking 1, wherein the second gas is a single substance. 8. If the method of claim 1 is requested, wherein the second gas has a comparison The first gas s 157726.doc 201212105 has a knife amount of at least 1 〇〇〇 / 0. The method of claim 1 wherein the second gas has a molecular weight greater than the first gas. A mixture of materials having a molecular weight of 20%. 10. The method of claim </ RTI> wherein the second gas is a mixture of materials each having a molecular weight greater than 100% greater than the molecular weight of the first gas. The method of claim 1, wherein the chamber is a vacuum chamber. 12. A method comprising: providing a chamber having a built-in substrate; k spraying from a nozzle directed to the substrate: a first gas; and by the first a vapor of an organic substance carried by the gas to deposit an organic substance on the substrate; Providing a second gas in the chamber during deposition of the organic substance; wherein the second gas has a molecular weight that is at least 2% greater than a molecular weight of the first gas; the nozzle has a pore having a minimum size; the organic substance is Deposited on the substrate to form a patterned feature having a shape defined by the shape of the hole; the second gas in the chamber during deposition of the organic substance relative to other identical depositions performed without the second gas The partial pressure is sufficient to reduce the amount of organic material deposited at a distance from the edge of the patterned feature by a factor of two. 157726.doc