Abstract:
Methods for preparing organic thin films on substrates, the method comprising the steps of providing a plurality of organic precursors in the vapor phase, and reacting the plurality or organic precursors at a sub-atmospheric pressure. Also included are thin films made by such a method and apparatuses used to conduct such a method. The method is well-suited to the formation of organic light emitting devices and other display-related technologies.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of U.S. application Ser. No. 09/736,090, filed on Dec. 13, 2000, now abandoned, which is a continuation of U.S. application Ser. No. 08/972,156, filed on Nov. 17, 1997, now U.S. Pat. No. 6,337,102, the subject matter of which is incorporated by reference herein. 
    
    
     GOVERNMENT RIGHTS 
     This invention was made with Government support under Contract No. F49620-92-J-05 24 (Princeton University), awarded by the U.S. Air Force OSR (Office of Scientific Research). The Government has certain rights in this invention. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to the fabrication of optical quality thin films, and more particularly to the low pressure fabrication of such thin films for application in non-linear optical devices and organic light emitting devices. 
     BACKGROUND OF THE INVENTION 
     The field of organic electroluminescence is a rapidly growing technology. Spurred by potential application to displays, organic light emitting devices (OLEDs) are capable of achieving external quantum efficiencies of over 30%, and operational lifetimes on the order of 10,000 hours at video brightness. Both small molecule and polymer-based OLEDs are known, but polymerbased devices have a general advantage of simple and inexpensive fabrication by spin-on deposition techniques. In contrast, small molecule devices are usually fabricated by thermal evaporation in vacuum, which is usually a more expensive process than spin-on deposition. Examples of OLED structures and processing techniques are provided in published PCT application WO 96/19792, incorporated herein by reference. 
     The use of organic vapor phase deposition (OVPD) has made progress towards the low cost, large scale deposition of small molecular weight organic layers with numerous potential photonic device applications such as displays. The OVPD process is described in U.S. Pat. No. 5,554,220 to Forrest et al.; S. R. Forrest et al., “Intense Second Harmonic Generation and Long-Range Structural Ordering in Thin Films of an Organic Salt Grown by Organic Vapor Phase Deposition,” 68 Appl. Phys. Lett. 1326 (1996); and P. E. Burrows et al., “Organic Vapor Phase Deposition: a New Method for the Growth of Organic Thin Films with Large Optical Non-linearities,” 156 J. of Crystal Growth 91(1995), each of which is incorporated herein by reference. 
     The OVPD process uses carrier gases to transport source materials to a substrate, where the gases condense to form a desired thin film. The OVPD technique has been used, for example, to deposit films of the optically non linear organic (NLO) salt, 4′-dimethylamino-N-methyl-4 stilbazolium tosylate (DAST), from volatile precursors 4′-dimethylamino-N-methyl-4-stilbazolium iodide (DASI) and methyl p-toluensulfonate (methyltosylate, MT), which are transported by carrier gases to a heated substrate. In this process, DASI thermally decomposes to form 4-dimethylamino-4-stilbazole (DAS), which subsequently reacts with MT to form DAST on the substrate. 
     Because of its capability for controlled codeposition of materials with radically different vapor pressures, OVPD is believed to be the only method for the precise stoichiometric growth of multi-component thin films. However, the OPVD process is conducted at atmospheric pressure, and films grown at or near atmospheric pressure are often rough and have non-uniform surface morphologies due to gas phase nucleation and a diffusion-limited growth process. 
     SUMMARY OF THE INVENTION 
     The present invention makes use of low pressure deposition techniques to produce organic thin films having superior surface properties. In one aspect, the present invention comprises a method for preparing an organic thin film on a substrate, the method comprising the steps of providing a plurality of organic precursors, the organic precursors being in the vapor phase; and reacting the plurality of organic precursors at a sub-atmospheric pressure in the presence of the substrate to form a thin film on the substrate. In another aspect, the present invention includes organic films made by such a method. In yet another aspect, the present invention includes an apparatus designed to facilitate the reaction of organic precursors at sub-atmospheric pressures to form an organic film on a substrate. 
     One advantage of the present invention is that it provides multi-component organic thin films wherein the amount of each component in such films can be controlled accurately and precisely. 
     Another advantage of the present invention is that it provides uniform organic thin films having smooth surfaces. 
     Another advantage of the invention is that it provides a low pressure organic vapor phase deposition method and apparatus for the growth of thin films of organic light emitting materials and optically non-linear organic salts. 
     Another advantage of the invention is that it provides a low pressure organic molecular beam deposition method and apparatus for the formation of thin films of organic light emitting materials and optically non-linear organic salts. 
     Yet another advantage of the invention is that it provides a method and apparatus for the uniform deposition of organic materials over large substrate areas. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 shows a LPOVPD reactor, in accordance with an embodiment of the present invention. 
     FIG. 2 shows an OMVD reactor, in accordance with an embodiment of the present invention. 
     FIG. 3 shows an apparatus for the continuous low pressure deposition of organic materials onto substrates, in accordance with an embodiment of the present invention. 
     FIGS. 4A and 4B are planar and cross-sectional views, respectively, of a reactant gas distributor, in accordance with an embodiment of the present invention. 
     FIG. 5 is a side view of a roll-to-roll substrate delivery mechanism, in accordance with an embodiment of the present invention. 
    
    
     DETAILED DESCRIPTION 
     The present invention provides a method and apparatus for the growth of organic thin films on substrates while under sub-atmospheric pressures. The method of the invention is herein identified as low pressure organic vapor deposition (LPOVPD). The LPOVPD method of the present invention allows for the accurate and precise control of the deposition of multi-component organic thin films. In addition, the thin films of the present invention are characterized by superior surface properties such as low surface roughnesses. 
     A LPOVPD reactor  10  in accordance with an embodiment of the present invention is schematically shown in FIG.  1 . Reactor  10  includes a reaction chamber, such as a reactor tube, and tubing extending into the reaction chamber. Reactor tube  12  is a cylinder having a suitable dimension such as, for example, a diameter of 10 cm and an approximate length of 45 cm in an experimental apparatus. Reactor tube  12  is made of any suitable material such as glass or quartz. An open container such as crucible  14  contains a first organic precursor material and is placed within tube  36  near one end  20  of the reactor tube  12 . Alternatively, crucible  14  is placed directly on the reactor tube  12  or on shelves or tubes therein. Crucible  14  is heated or cooled by means of a multi-zone heater/cooler  18 , which substantially surrounds reactor tube  12 . The temperature control of crucible  14  results in the thermal decomposition or volatilization of the first organic precursor material within crucible  14 . A regulated stream  30  of inert carrier gas is passed through tube  36  and into the reaction chamber, thus causing vapor of the first organic precursor to flow along the reactor tube  12  toward its exhaust end  22 . The inert carrier gas is an inert gas such as nitrogen, helium, argon, krypton, xenon, neon and the like. Gases with a reducing character, such as hydrogen, ammonia and methane, are also inert for many organic materials. Use of these reducing gases often has the additional benefit of assisting in the burning of undesired excess reactants. 
     Inert gas is delivered from tank  24  through a regulator valve  26  and into tubing  28  for delivery through at least two flow paths,  30  and  38 , and into reactor tube  12 . One flow path  30  includes a series connected pressure regulator  32 , flow meter  34  and quick switching valve  35  from which the carrier gas is delivered into end  20  of reactor tube  12 . The second flow path  38  includes a series connected pressure regulator  40 , flow meter  42  and quick switching valve  39  from which the carrier gas flows into a bubbler  46 , which contains a second organic precursor material  48 . To facilitate the temperature control of second organic precursor material  48 , bubbler  46  is partially immersed in bath  50  within container  52 . Inert gas from tank  24  bubbles through the second organic precursor  48  and through tubing  54  to carry vapor of the second organic precursor  48  into reactor tube  12 . During this process, tube  54  must be maintained at a sufficiently high temperature to avoid recondensation of the volatilized second organic precursor  48  as it travels from the bubbler to the reactor. 
     The amount of any precursor entering reactor tube  12  is controlled by processing parameters such as the temperature and flow rate of the carrier gas and the temperature of the reactants. The LPOVPD method provides precise metering of the precursors or reactants independently of their vapor pressure or chemical nature using pressure mass flow controllers. The present method thus permits the combination of materials with widely different characteristics in ratios necessary for the production of desired films. 
     The precursor streams are capable of being turned on and off almost instantly by employing quick switching valves  35  and  39 . These valves direct the precursor streams into reactor  12  or into a by-pass line (not shown), so that at any given time, different precursor streams may be entering the reactor  12  for the deposition of films of different compositions and characteristics. Valve  39  also regulates the admittance of carrier gas into bubbler  46 . Valves  35  and  39  thus allow the rapid change of reactant streams entering the reactor  12 , for changing the nature and the composition of the grown films. It is thus possible, for example, to grow ABAB, ABCABC, ABABCAB, and ABCDABCD-type films, where each letter denotes a different molecular layer or composition. 
     A vacuum pump  66  and control throttle valve  68  are attached to reactor  10  at the exhaust  62 . Most of the organic vapors not deposited onto substrate  58  are condensed in a trap  64  placed upstream from pump  66 . Trap  64  contains liquid nitrogen or a neutral, fluorocarbon oil, for example. Throttle valve  68  regulates the pressure in reactor  10 . An appropriate pressure gauge is connected to the reactor (not shown) with electronic feedback to the control throttle valve  68  to maintain a desired pressure in the reactor. 
     Vacuum pump  66  provides a pressure of about 0.00.1-100 Torr in reactor tube  12 . The actual pressure for any combination of acceptor, donor, and single component layers is experimentally determined with reference to the temperatures required to volatilize the precursor materials, the wall temperature to prevent condensation of the precursor materials, and the reaction zone temperature gradient. The optimal choice of pressure is unique to the requirements of each deposited organic layer. For example, optimal pressures for the deposition of single component layers such as tris-(8-hydroxyquinoline) aluminum (Alq 3 ) or N-N′-diphenyl-N,N-bis(3-methylphenyl) 1,1′-biphenyl 4,4′diamine (TPD) are about 0.1-10 Torr. 
     The substrates on which the thin films of the present invention are deposited are typically selected from those materials that are commonly encountered in semiconductor and optics manufacturing. Such materials include, for example, glass, quartz, silicon, gallium arsenide and other III-V semiconductors, aluminum, gold and other precious and non-precious metals, polymer films, silicon dioxide and silicon nitride, indium-tin-oxide and the like. For high quality optical thin films, it is preferable to use substrates that provide crystalline interactions with the deposited organic film to induce epitaxial growth. To achieve such epitaxial growth, it is often necessary to coat substrates with non-polar organics having crystalline structures similar to the film to be deposited. 
     In addition, as an organic thin film is deposited onto substrate  58 , it is often desirable to control the temperature of the substrate. Independent control of substrate temperature is accomplished, for example, by contacting substrate  58  with temperature-control block  60 , which has channels therein for the circulation of materials such as water, gas, freon glycerin, liquid nitrogen, and the like. It can also be heated by the use of resistance or radiant heaters positioned on or near the block  60 . 
     Reactor  20  of FIG. 1 is expandable to include multiple bubblers  46 N to feed additional precursors into reactor  20 . Similarly, multiple carrier gas flow paths  30 N are used to deliver yet additional precursors from crucibles  14 N. As an alternative, crucibles  14 ,  14 N are vertically stackable on shelves or in tubes within reactor tube  12  for processing the additional precursors. Depending on the organic film to be deposited, one or more flow paths  30 ,  38  are used alone or in any combination to provide the necessary precursor materials. 
     The method of the present invention is used to deposit a wide variety of organic thin films from the reaction of vapor precursors. As used herein, “reaction” refers to a chemical reaction in which precursor reactants form a distinct reaction product, or alternatively, it merely refers to a combination or mixture of precursor materials, or where precursor materials form a donoracceptor or quest-host relationship. For example, in accordance with the present invention, the following NLO materials are formed as thin films by the reaction of the listed precursors: 
     
       
         
               
               
               
             
           
               
                   
               
               
                 Film Material 
                 First Precursor 
                 Second Precursor 
               
               
                   
               
             
             
               
                 4′-dimethylamino-N- 
                 4′-dimethylamino-4- 
                 methyl tosylate 
               
               
                 methyl-4-stilbazolium 
                 stilbazole (DAS) 
                 (MT) 
               
               
                 tosylate (DAST) 
               
               
                 4′-dimethylamino-4- 
                 methyl 
                 4′-dimethyl amino- 
               
               
                 methylstilbazolium 
                 methanesulfonate (MM) 
                 4-stilbazole (DAS) 
               
               
                 methanesulfonate 
               
               
                 (DASM) 
               
               
                 4′-dimethylamino-4- 
                 methyl 
                 4′-dimethylamino- 
               
               
                 methylstilbazolium 
                 trifluoromethanesulfonate 
                 4-stilbazole (DAS) 
               
               
                 trifluoromethanesulfonate 
                 (M, f  M) 
               
               
                 (DASM f ) 
               
               
                 4′-dimethylamino-N- 
                 methyl tosylate (MT) 
                 4′-dimethylamino- 
               
               
                 methyl-4-stilbazolium 
                   
                 4-methyl- 
               
               
                 tosylate (DAST) 
                   
                 stilbazolium 
               
               
                   
                   
                 thiophenoxide 
               
               
                   
                   
                 (DASTh) 
               
               
                 4′-methoxy-4- 
                 methyl tosylate (MT) 
                 4′-methoxy-4- 
               
               
                 methylstilbazolium 
                   
                 methylstilbazole 
               
               
                 tosylate (MeOST) 
                   
                 (MeOS) 
               
               
                 4′-dimethylamino-N- 
                 methyl tosylate (MT) 
                 4′-dimethylamino- 
               
               
                 methyl-4-stilbazolium 
                   
                 4-ethylstilbazolium 
               
               
                 tosylate (DAST) 
                   
                 iodide (DAS(Et)I) 
               
               
                 4′-dimethylamino-N- 
                 methyl tosylate (MT f ) 
                 4′-dimethylamino- 
               
               
                 methyl-4-stilbazolium 
                   
                 4-ethylstilbazolium 
               
               
                 tosylate (DAST f ) 
                   
                 hydroxide 
               
               
                   
                   
                 (DAS(Et)OH) 
               
               
                 4′-dimethylamino-4- 
                 acetyl 
                 4′-dimethylamino- 
               
               
                 acetylstilbazolium 
                 toluenesulfonate (AT) 
                 4-stilbazole (DAS) 
               
               
                 tosylate (DAAST) 
               
               
                 4′dimethylamino-4- 
                 methyl 
                 4′-dimethylamino- 
               
               
                 methylstilbazolium 
                 trifluoroacetate 
                 4-stilbazole (DAS) 
               
               
                 trifluoroacetate 
                 (MA) 
               
               
                 (DASA) 
               
               
                   
               
             
          
         
       
     
     In another example relating more specifically to light emitting materials used to make OLEDs, the precursors consist of, for example, tetrathisferlvalene (TFF) and 7,7,8,8-tetracyanoquinodimethane (TCNQ). The mixing step results in the charge transfer complex TTF-TCNQ which deposits onto a substrate. In another example relating to OLEDs, 4-(dicyanomethylene)-2-methyl-6-(p-dimethyl-aminostyryl)-4H-pyran (DCM) is added into a high flow rate carrier gas stream while Alq 3  is added into a lower flow rate carrier gas stream. These streams are then mixed in a central reactor tube, thus providing the desired dilution of the guest molecule in the host matrix film to form a single luminescent layer. Other guest molecule examples in Alq 3 , hosts are 5, 10, 15, 20-tetraphenyl-21H, 23H-porphine (TPP), Rubrene, DCM2, Coumarin, etc. As a variation, multiple dopants can be added into a single host to achieve efficient broad color conversion. 
     In another example, a bilayer light emitting device consisting of a hole transporting layer (“HTL”) such as TPD; α-4,4′-bis[N-(1-naphthyl)-N-Phenyl-amino] biphenyl (α-NPD); or MTDATA, layered onto the surface of a light emitting layer (“EL”) such as Alq 3 , bis-(8 hydroxyquinoline) aluminum oxyphenyl ((Alq 3 )′-OPh) or doped combinations of these layers, is grown by sequentially growing the HTL and EL to desired thicknesses. This is followed by growing additional layers onto the organics, or by growth on metallic contact layers using organometallic sources such as trimethyl-indium, trimethyl-gallium, and the like. 
     In addition to the apparatus and method described with reference to FIG. 1, the present invention includes a low pressure reactor 70 and method as shown in FIG.  2 . Reactor  70  includes a modified ultra-high vacuum chamber  71  and a vacuum pump such as a turbomolecular pump (not shown) connected to valve  72 . Typical chamber base pressures in chamber  71  are 10 −8 -10 −11  Torr. The process of depositing organic layers with the use of reactor  70  is called organic molecular beam vapor deposition (OMVD). Although both LPOVPD and OMVD make use of sub-atmospheric pressures for the deposition of organic layers, the principle difference between these processes is that in the latter, the molecular mean free path is comparable to or larger than the dimensions of the chamber  70 . In comparison, the mean free path in LPOVPD is significantly shorter than the gas reactor dimensions. OMVD thus allows for the formation of highly directed molecular “beams” from the injectors to the substrate, allowing for precise kinetic control of the grown film thickness, purity and morphology. 
     Bubbler  74  is included for containing a first precursor material  75 . The bubbler  74  is placed into, container  76  and immersed in a temperature controlled bath  80 . A high purity inert carrier gas  78  bubbles through first precursor  75 , and carries respective vapors through heated tubing  79  and into vacuum chamber  71  by way of injector  82 . Once inside chamber  71 , the precursor vapors form a molecular beam  83  that impinges on substrate  85 . Substrate  85  is provided with a means for providing temperature control such as coolant port  81 , for example. 
     Vacuum chamber  71  optionally is provided with at least one Knudsen or K-cell  86 , which contains a second precursor material  88 . K-cell  86  is a uniformly heated and controlled oven for the effusion of evaporants under vacuum. For example, K-cell  86  is heated to crack DASI or other precursor and sublime the resulting DAS, such that it is injected into reactor  70  as a molecular beam  89 . Alternatively, K-cell  86  simply sublimes a single component substance such as Alq 3 . Alternatively, K-cell  86  is fitted with a carrier gas inlet used to dilute the concentration of the molecular species being sublimed or evaporated into the gas stream by thermalization. This dilution process is particularly useful in achieving precise doping levels of guest-host systems such as DCM-Alq 3  by controlling the temperatures of bath  80  and Knudsen cell  86  as well as the flow of carrier gas  78  to bubbler  74 . 
     Molecular beams  83  and  89  impinge on substrate  85  to deposit an organic thin film, the thickness of which is monitored by quartz crystal  93 . Sample holder  90  rotates to ensure a uniform deposition and reaction of precursor materials. The deposition of precursor materials is further controlled by shutters  87 , which are used to interrupt molecular beams  83  and  89 . 
     Reactor  70  also optionally includes a cooled shroud  91  to help keep the pressure of vacuum chamber  71  to a minimum for re-evaporated precursor materials. Also preferably included is a partition  92  to keep precursor materials from migrating and thus contaminating each other. 
     Reactor  70  is embellished with many of the same attributes of the LPOVPD reactor shown in FIG. 1, such as quick switching valves, bypass lines and the like. Reactor  70  is able to be fitted with multiple Knudsen cells and bubblers for the deposition of multiple precursor materials onto substrate  85 . Reactor  70  also preferably includes a “load-lock”  94  for sample introduction. Load-lock  94  includes door  95  and vacuum pump  96 , and provides for the exchange of samples without compromising the pressure of chamber  71 . 
     The apparatus of FIG. 1 is optionally modified for the continuous deposition of organic layers on large area substrates, as shown by the example illustrated in FIG.  3 . The apparatus of FIG. 3 includes a plurality of vacuum chambers such as loading chamber  146 , organic layer deposition chambers  150  and  152 , contact deposition chamber  154 , and unload chamber  156 . As an example, each deposition chamber is a LPOVPD reactor  10  of FIG.  1 . The substrates  137  are transported on a conveyor belt  148  through each of chambers  150 ,  152 ,  154  and  156 . In the embodiment shown in FIG. 3, chambers  150 ,  152  and  154  include sources  158 ,  160  and  162 , respectively, of radiant heat to prevent the condensation of organic vapors. Although only two organic layer deposition chambers  150  and  152  are shown in FIG. 3, additional chambers are included as desired. In passing from the loading chamber  146  to the organic layer deposition chambers  150  and  152 , and from the contact deposition chamber  154  to the unload chamber  156 , the substrate  137  passes through air locks (not shown) so as not to compromise the vacuum in the chambers  150 ,  152 , and  154 . As an example relating to OLEDs, chambers  150  and  152  are used for the deposition of TPD and Alq 3 , respectively, and chamber  154  is used for the deposition of an Mg:Ag contact layer. 
     Each of the chambers  150 ,  152 , an  154  in the example of FIG. 3 includes a reactant gas distributor (RGD)  108  for the deposition of organic precursor materials, as shown in detail in FIGS. 4A and 4B RGD&#39;s  108  are used as an alternative to the organic precursor delivery mechanisms of FIGS. 1 and 2, and are used to provide gas curtains,  120 ,  120 ′,  120 ″ and  120 ′″. RGD  108  ensures that where multiple organic precursors are deposited, the precursors remain separated until deposited on a substrate, whereupon reaction of the precursors is permitted to take place. RGD  108  includes heater  122 , second carrier gas inlet  112  and gas manifold  132 . Heater  122  prevents the premature condensation of organic precursor materials. Over RGD  108  is a first carrier gas inlet  114  and distributor plate  110 . First carrier gas inlet  114  supplies gas which usually carries a first organic precursor of generally low volatility such as, for example, MT. The first carrier gas enters a reaction chamber though distributor plate  110 , which is a wire mesh, a glass filter material, or a porous stainless steel plate, for example. The column of carrier gas flowing through distributor plate  110  is shadowed by the RGD  108 . RGD  108  provides a planar gas curtain  120  of a second organic precursor of generally low vapor pressure such as, for example, DAS. A second carrier gas containing a second organic precursor enters at inlet  112  and is directed into gas manifold  132 . Manifold  132  is a hollow tube having a line of holes  134  for feeding the second carrier has into an annular cavity  126 , which surrounds manifold  132 . Second carrier gas exits RGD  108  through slit  136 , thus giving it the shape of a planar curtain. 
     As an example, curtain  120  is comprised of TPD vapors, curtain  120 ′ is comprised of Alq 3  vapors and curtain  120 ″ is comprised of vapors such as a polypyrole or metallorganic compounds that produce a conductive surface. If desired, control or tuning of the color of light emitted by an OLED can be effected by suitable doping of the Alq 3  layer with an additional RGD device  108  in the chamber  152  that produces a curtain  120 ′″ of dopant vapor. 
     The apparatus of FIG. 1, FIG. 2 or FIG. 3 is optionally modified by using a “roll-to-roll” substrate delivery system, as shown in FIG.  5 . The delivery system shown in FIG. 5 is suitable for the deposition of organic thin films onto large area, flexible substrates. Substrate  180  is made of a polymer sheet or metal foil, for example, and is delivered from roll  181  to roll  182 . The deposition of organic precursors onto substrate  180  occurs when substrate  180  is unrolled from roll  181  and is therefore exposed to the reaction chamber of FIG. 1, or when exposed to the molecular beam or curtains of FIGS. 2 and 3, respectively. Rolls  181  and  182  are driven by any suitable means, such as a variable speed motor. The speed at which substrate  180  is passed from roll  181  to roll  182  dictates the thickness of the organic film that forms on substrate  180 . 
     The present invention is further described with reference to the following non-limiting examples. 
     EXAMPLE 1 
     Using the apparatus of FIG. 1, layers of organic light emitting materials were grown using glass and flexible polyester substrates precoated with transparent layers of indium tin oxide (ITO). The ITO forms the anode of the device with a thickness of 1700 A and 1200 A for the glass and polyester substrates, respectively, yielding anode resistances of 10Ω and 60Ω, respectively. Glass substrates were cleaned by rinsing in a solution of detergent and deionized water in an ultrasonic bath, and then boiling in 1,1,1-tri.chloroethane, rinsing in acetone and finally rinsing in 2-propanol. To avoid damage due to exposure to organic solvents, the flexible substrates were cleaned by rinsing only in the detergent and 2-propanol solutions. 
     Glass substrates were placed within the reactor tube  12  at a location where the temperature was approximately 220° C. The first layer deposited on the ITO surface was TPD, a hole transporting material. Specifically, TPD vapor was carried from crucible  14  to substrate  28  via nitrogen carrier gas. The TPD growth conditions included a source temperature of 200±5° C., a nitrogen carrier gas flow rate of 100 sccm, a reactor pressure of 0.50 Torr and a growth time of 20 minutes. At a nitrogen flow rate of 100 sccm, the Reynolds number of the system was −500, indicating operation well within the laminar flow regime. The TPD layer was grown to a thickness of between 100-300 Å. 
     After deposition, the temperature near the TPD crucible was reduced, and the corresponding nitrogen flow was shut off. Next, an electron transporting layer of Alq 3  was grown by turning on a separate nitrogen line to carry Alq 3  vapor from crucible  14 N into chamber  12 . The Alq 3  growth conditions included a source temperature of 247±8° C., a nitrogen flow rate of 50 sccm, a pressure of 0.65 Torr and a growth time of 10 minutes. During the deposition of both the TDP and Alq 3 , the substrate was maintained at 15° C. using a water cooled stainless steel substrate holder. The TPD layer was grown to a thickness of between 700-1100 Å. 
     After deposition of the Alq 3  layer, the substrate was removed from the reactor and a Mg:Ag top contact was applied by thermal evaporation. The contact was completed with the evaporation of a 1000 Å thick protective Ag layer. 
     The use of low pressures during deposition resulted in organic layers having smooth and uniform surfaces. For example, the TPD and Alq 3  layers were measured via atomic force microscopy to have RMS roughnesses of 6-8 Å and 9-11 Å, respectively. The resulting OLED devices exhibited current-voltage characteristics wherein I∝V at low voltages and I∝V9 at higher voltages. The turn-on voltage, V T , at which the power law dependence of I on V changed, was about 6V. 
     EXAMPLE 2 
     An NLO film was prepared using the apparatus shown in FIG.  1 . MT  48  was loaded into a 30 cm 3  bubbler  46 , the temperature of which was maintained at approximately 80°-100° C. by silicone oil bath  50 . Nitrogen gas was used to bubble through the MT  48 , thereby carrying MT vapor through glass tube  54  and into reactor tube  12  at a location approximately 5 cm beyond crucible  14 , which contained was placed on the floor of reactor tube  12  and DASI. The pressure within reactor tube  12  was maintained at about 10 −2  torr. DAS vapor reacted with the MT vapor to form a solid film of DAST on substrates  58 , which were supported on substrate block  60 . Excess unreacted MT vapor and any volatile side-reaction products were exhausted from exhaust tube  62 . DAST films thus formed are useful as optical switches, for example. 
     The present invention makes use of low pressure deposition techniques to produce organic thin films having superior surface properties and accurate and precise compositions. Although various embodiments of the invention are shown and described herein, they are not meant to be limiting. For example, those of skill in the art may recognize certain modifications to these embodiments, which modifications are meant to be covered by the spirit and scope of the appended claims. 
     The subject invention as disclosed herein may be used in conjunction with co-pending applications: “High Reliability, High Efficiency, Integratable Organic Light Emitting Devices and Methods of Producing Same”, Ser. No. 08/774,119 (filed Dec. 23, 1996), now U.S. Pat. No. 6,046,543; “Novel Materials for Multicolor LED&#39;s”, Ser. No. 08/850,264 (filed May 2, 1997), now U.S. Pat. No. 6,045,930; “Electron Transporting and Light Emitting Layers Based on Organic Free Radicals”, Ser. No. 08/774,120 (filed Dec. 23, 1996), now U.S. Pat. No. 5,811,833; “Multicolor Display Devices”, Ser. No. 08/772,333 (filed Dec. 23, 1996), now U.S. Pat. No. 6,013,982; “Red-Emitting Organic Light Emitting Devices (LED&#39;s)”, Ser. No. 08/774,087 (filed Dec. 23, 1996), now U.S. Pat. No. 6,048,630; “Driving Circuit For Stacked Organic Light Emitting Devices”, Ser. No. 08/792,050 (filed Feb. 3, 1997), now U.S. Pat. No. 5,757,139; “High Efficiency Organic Light Emitting Device Structures”, Ser. No. 08/772,332 (filed Dec. 23, 1996), now U.S. Pat. No. 5,834,893; “Vacuum Deposited, Non-Polymeric Flexible Organic Light Emitting Devices”, Ser. No. 08/789,319 (filed Jan. 23, 1997), now U.S. Pat. No. 5,844,363; “Displays Having Mesa Pixel Configuration”, Ser. No. 08/794,595 (filed Feb. 3, 1997), now U.S. Pat. No. 6,091,195; “Stacked Organic Light Emitting Devices”, Ser. No. 08/792,046 (filed Feb. 3, 1997), now U.S. Pat. No. 5,917,280; “High Contrast Transparent Organic Light Emitting Device Display”, Ser. No. 08/821,380 (filed Mar. 20, 1997), now U.S. Pat. No. 5,986,401; “Organic Light Emitting Devices Containing A Metal Complex of 5-Hydroxy-Quinoxaline as a Host Material”, Ser. No. 08/838,099 (filed Apr. 15, 1997), now U.S. Pat. No. 5,861,219; “Light Emitting Devices Having High Brightness”, Ser. No. 08/844,353 (filed Apr. 18, 1997), now U.S. Pat. No. 6,125,226; “Organic Semiconductor Laser”, Ser. No. 60/046,061 (filed May 9, 1997), “Organic Semiconductor Laser”, Ser. No. 08/859,468 (filed May 19, 1997), now U.S. Pat. No. 6,111,902; “Saturated Full Color Stacked Organic Light Emitting Devices”, Ser. No. 08/858,994 (filed May 20, 1997), now U.S. Pat. No. 5,932,895 ; “An Organic Light Emitting Device Containing a Hole Injection Enhancement Layer”, Ser. No. 08/865,491 (filed May 29, 1997), now U.S. Pat. No. 5,998,803; “Plasma Treatment of Conductive Layers”, Serial No. PCT/US97/10252; (filed Jun. 12, 1997), now U.S. national phase application number 09/202,152, filed May 5, 1999; Patterning of Thin Films for the Fabrication of Organic Multi-Color Displays”, Serial No. PCT/US97/10289 (filed Jun. 12, 1997), now U.S. national phase application number 09/202,152, filed Jun. 14, 1999; “Double Heterostructure Infrared and Vertical Cavity Surface Emitting Organic Lasers”, Ser. No. 60/053,176 (filed Jul. 18, 1997), now U.S. Pat. No. 5,874,803; “Oleds Containing Thermally Stable Asymmetric Charge Carrier Materials”, Ser. No. 08/929,029 filed (Sep. 8, 1997), “Light Emitting Device with Stack of Oleds and Phosphor Downconverter”, Ser. No. 08/925,403 (filed Sep. 9, 1997), now U.S. Pat. No. 5,874,803, “An Improved Method for Depositing Indium Tin Oxide Layers in Organic Light Emitting Devices”, Ser. No. 08/928,800 (filed Sep. 12, 1997), now U.S. Pat. No. 5,981,306, “Azlactone-Related Dopants in the Emissive Layer of an Oled” (filed Oct. 9, 1997), Ser. No. 08/948,130, “A Highly Transparent Organic Light Emitting Device Employing A Non-Metallic Cathode”, (filed Nov. 3, 1997), now U.S. Pat. No. 6,030,715, (Provisional), now U.S. Provisional Application No. 60/064,005, and “A Highly Transparent Organic Light Emitting Device Employing a Non Metallic Cathode”, (filed Nov. 5, 1997), now U.S. Ser. No. 08/964,863, each co-pending application being incorporated herein by reference in its entirety. The subject invention may also be used in conjunction with the subject matter of each of co-pending U.S. patent application Ser. No. 08/354,674, now U.S. Pat. No. 5,707,745, Ser. No. 08/613,207, now U.S Pat. No. 5,703,436, Ser. No. 08/632,322, now U.S. Pat. No. 5,757,026 and Ser. No. 08/693,359 and provisional patent application Serial No. 60/010,013, to which non-provisional U.S. application Ser. No. 08/779,141 filed Jan. 6, 1997 claimed benefit, now U.S. Pat. No. 5,986,268; No. 60/024,001, to which non-provisional U.S. application No. 08/789,319 filed Jan. 23, 1997 claimed benefit, now U.S. Pat. No. 5,844,363 and No. 60/025,501, to which non-provisional U.S. application Ser. No. 08/844,353 filed Apr. 18, 1997 claimed benefit, now U.S. Pat. No. 6,125,226, each of which is also incorporated herein by reference in its entirety.