TWI223840B - Method of fabricating an organic device - Google Patents

Abstract

A method of fabricating an organic device is provided. A first layer is deposited over a substrate through a mask by a first process that results in the first layer having a first area of coverage. A second layer is then deposited over the substrate through the mask by a second process that results in the second layer having a second area of coverage that is different from the first area of coverage.

Description

1223840

FIG. 18 shows the pixel shape factor P as a function of mfp. Figure 19 shows the use of iO6 Alq3 molecules in & background from Monte.Cad. The simulated deposition results obtained illustrate the effect of changing the thickness of the mask. Figure 1 shows the shape factor as a function of mask thickness. Sounds like Figure 2. The results of non-simulated deposition are shown to illustrate the effect of changing the mask-substrate spacing. Figure 2i shows the simulated deposition results, illustrating the effect of different mask sidewall geometries on various mask thicknesses. Figure 22 shows the form factor as a function of the thickness of the mask under the different sidewall geometries of Figure 21. Figure 23 shows the simulated normalized height as a function of position under different overall velocity assumptions. 'Figure 24 shows the results of a pseudo-OVD deposition, in which the carrier gas system has an overall flow rate. Figure 25 shows a schematic diagram of the experimental OVPD system. Figure 26 shows a photomicrograph of the aiu layer deposited on Si by 0VPD and the results of an interference microscope near the edge of the layer. -Figure 27 shows a light intensity map from an interference microscope along the thin layer radius of Figure 26 and the corresponding pixel height map calculated from the interference pattern. FIG. 28 shows an experimental measurement pattern of the thin layer of FIG. 26. Figure 29 shows a scanning electron micrograph of an Alq3 film on Si at w = 7.5 microns and s ~ 0 microns below 10.6 Torr through stencil patterning, and at 1 = 3 · 5 microns, w = 7.5 microns and s < 1 micron, A · q3 pattern deposited on Si by OVPD via nickel stencil under 0.1 Torr Scanning electron micrograph of standard (CNS) A4 specification (210X297 mm) 1223840 A7 B7 V. Description of invention 5). Figure 30 shows a schematic of mixed deposition. Details • The metal and organic layers of an organic device can be patterned using the same mask, with the same apertures. The organic layer deposited by organic vapor deposition (OVPD) is used for natural and controllable distribution, depending on method parameters such as vapor pressure and the geometry of the mask and substrate. Metal layers deposited by vacuum thermal evaporation (VTE) usually have much lower spreadability. As a result, different patterns can be deposited through the same mask gap holes, so that the patterned organic layer is larger than the patterned metal layer. The organic device may be an organic light emitting device (OLED), or a different type of organic device ^ Such as organic transistors or organic solar cells. Various devices can be manufactured, including organic passive array displays and organic active array displays. The organic layer and subsequent metal layers can be sequentially deposited through the same orifice plate. Because of the difference in deposition methods, the organic layer can have greater spreadability. 7 The metal layer can be completely deposited on the organic layer without the metal layer and the Any layer under the organic layer is in contact. Therefore, short circuits can be advantageously avoided. This method helps to make organic devices such as organic light emitting devices (OLED). OLED uses organic thin film that emits light when voltage is applied to both sides of the device. OLED is an increasingly common application technology, such as flat panel display Λ m 4 SW, and later $ \\\ light. OLED structures include dual heterostructures, single heterostructures, and single layers. A variety of organic materials can be used to make OLEDs. US Patent No. 5,707,745 describes several OLED materials and structures. This patent refers to Ways are fully incorporated into this article. -8- Applicable to China National Standard (CNS) A4 size (210 x 297 mm) 1223840 A7 ____________ B7 V. Invention (1 6 1) " ~ ''-Many modern organic electronics and nano-structured devices need Micron-sized lateral pattern resolution, but not compatible with conventional lithography. In situ patterning of organic thin films is often used instead.

Specific embodiments of the invention may include moving the orifice plate between depositing various material layers. The description of the move can be referred to the patent pending case of the agent's pending case No. 1002/1/1501, which is fully incorporated herein by reference. The device array can be manufactured by moving the mask (or substrate) as follows. After the first organic layer and the first metal layer are deposited using a mask disposed in the first position, the mask is moved to a second position determined relative to the first position. A second organic layer may be deposited through a mask located at the second position, followed by a second metal layer. Since the second position is determined relative to the first position, it is advantageous to avoid costly and time-consuming alignment steps. After the second organic layer and the second metal layer are deposited, the mask can be moved to a third position determined relative to the second position. A third organic layer and a subsequent third metal layer may be deposited through a mask located at the third position. Such a method may be advantageously used, for example, a tri-color OLED is shown as' wherein the first, second, and third organic layers are each used to emit light of different colors. Specific embodiments of the present invention can be used to make multi-color OLED arrays with well-defined resolutions of 5 microns or greater. In fact, not every material (metals and organics are the opposite) requires an individual alignment step, as do the colors, increasing effective resolution. Specific examples of the invention may include the use of organic vapor deposition (OVPD). For the description of organic vapor deposition, please refer to the pending patent applications of the agents No. 1 200/37, 1 0020/3 702, and 1 0020/3703. Applicable to China National Standard (CNS) A4 specification (210X297 mm) decoration line 1223840 f—τ -—- ~~ __ 5. Description of the invention (7) The formula element is incorporated herein. Vacuum Thermal Evaporation (VT) Figure 1 shows a vacuum thermal evaporation (VTE) system 100. The source electrode u is heated, so that the material is evaporated into the vacuum chamber 120. The material is vacuum diffused onto the substrate 130 and deposited there. FIG. 2 shows a more detailed illustration of the vte system 200 with a cover 22o. The source electrode 2 10 provides an organic material which diffuses into a vacuum and has a size of 10-6 to ι7 · 7 Torr. The organic material is diffused through a vacuum and through the orifice plate 320. The orifice plate 220 having the gap holes 222 is disposed at a distance of s from the substrate 23. After the organic material passes through the orifice plate, it is deposited on the substrate 23 to form a patterned organic layer 240. Due to the low voltage of VTE, the average molecular free path λ (also known as 冚 邙) may be quite large. For example, at 10-7 Torr, about again! Meter. As a result, a mask-to-substrate spacing of less than 50 microns will produce pixels with clearly defined edges up to ~ 100 microns, where the distance between the source and the substrate from the chamber t is between 10 and 100 cm. . The distance between the substrate 23o and the source electrode 21o is preferably smaller than the average free path of the molecules, so that the collision between the molecules in a vacuum reaches a minimum. The distance from the substrate 230 to the source 210 has a clear line of sight. The patterning layer 24 is deposited at the < 2 > Using, you can get a trapezoidal pixel contour with a clear base. To 10'13 Pascal series is a better range of VTE pressure. Because the source electrode 2 10 is not a single point, the patterning layer 24 may be slightly larger than the aperture 222. Referring to FIG. 2, the bottom length of the patterning layer 24o is represented by: η line • 10-

1223840 A7 B7 _ _ | ----V. Description of the invention (8) t 1 Ο + ί) · (/ 1 + / 2) 2 h (l) where s = cover screen-substrate spacing, t = cover screen Thickness, 11 = source width, h 2 slot width, and h = source-mask distance. This formula represents the value of d that is very close to the experimental observation. Organic Vapor Deposition Organic Vapor Deposition (0 V P D) is ideal for depositing amorphous and crystalline organic thin films for displays, transistors, and photovoltaics. It is completely different from vacuum thermal evaporation in that a carrier gas is used to transport organic vapor to the deposition. The molecules diffuse here through a boundary layer and are physically adsorbed on the substrate. The carrier gas is preferably inert. Controlling dopant concentration, purity, and crystallinity of the deposited film can greatly improve vacuum thermal evaporation (Vte). In this case, we have tested the deposition of thin film from the gas phase from the details of experiments and model tests, emphasizing the patterning of orifice plates, a key step in manufacturing full-color displays based on OLEDs. Although the average free path of the molecule is generally > 30 cm, it is relatively easy to use vacuum thermal evaporation at < 丨 〇-6 to reach clearly defined pixels, but this situation is more complicated under OVPD. Because OVPD is generally performed under a pressure of> 10 · 2 Torr and 0 μm (several centimeters), the increased frequency of intermolecular impact near the plane of the mask causes the pixels to have relatively more diffuse edges. The deposition pressure in the range of 丨 to 10 Pascal is also good, and the average molecular free path (mfp) is individually from 103 to 1 mm. Of course, in this study, we have shown that deposition with a pattern sharpness of about 1 micron can be achieved with the appropriate substrate temperature, reactor pressure, and hood geometry. Our results show the different material delivery processes at 0vpD

1223840 A7 B7 V. Description of the invention (9) The kinetics of an organic film growing in a free molecule, diffusion, and the intermediate between them at once, helps to confirm the effective processing conditions, and guides the OVPD system design. Organic vapor deposition (OVPD) technology is increasingly used to deposit amorphous and crystalline organic thin films for use in displays, transistors, and photovoltaic devices. The manufacturing of molecular organic LEDs is particularly attractive because of their low operating costs and ease of amplification compared to vacuum thermal evaporation (VTE). Low-voltage OVPD (LP-OVPD) has been used in previous technologies to deposit optical non-linear salts, optically pumped organic lasers, effective organic light emitting diodes (OLEDs), and channel thin film transistors (TFTs). Because OVPD was originally different from VTE due to the use of carrier gas, its volume delivery mechanism was also completely different. An example is a thin film deposition with an intermediate (0.1-100) Knudsen number in OVPD, both of which were performed experimentally and simulated by a Monte-Carlo computer. In particular, we detect the patterning of organic thin films through an orifice plate, especially regarding the deposition of multi-color pixels on the same substrate, such as used in the manufacture of full-color OLED displays. OVPD simulation of organic thin film patterning can also detect the transition flow process. The Knudsen number Kn = mfp / d is divided by the molecular mean free path mpf divided by the critical device size d and the different transport processes included in the qualitative gas flow method. When Kη < 1, the molecular-molecular impact frequency is much higher than the molecular wall impact. Mass transfer is described by Poiseuille flow. Metal-organic chemical vapor deposition (MOCVD), which is the same as used to grow inorganic semiconductor films and heterostructures, usually takes place during a pseudo-potential process. For the deposition of unpatterned thin films, OVPD—generally -12—clothing and paper size common Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1223840 A7 __ B7 V. Description of the invention (1 〇) Kn < < 1 occurred. However, for the purpose of patterning a high-resolution film, other flow processes are preferred, depending on whether Pdep and d correspond to the size, resolution, or aperture width of the figure. Although the molecular flow through the small channel has previously used a variety of different technologies (molecular beam epitaxy, gas feed, membrane gas permeation, aerosol filtration, etc.) and for the Kn range adjustment, the variable aiming flux has shown in Figure 2 The general characteristics, the results cannot be easily and accurately applied to the micropatterning of organic thin films by 0VPD. Molecular beam research generally involves extremely thin streams of the same molecules or atoms. In contrast, gas feed experiments use dense gas and large channels (diameters> mfp). The fluid dynamics of the flow is described by the Navier-Stokes equation. Gas flow patterns are generally not affected by the presence of dense surfaces. Gas and gas-driven particle transport in porous media are often related to global variables. The technical literature includes several types of reactive ion etching in through-holes and trenches, and the diffusion of 'child products' under the same Kri value of 0VPD, and studies mainly based on Monte-Carlo, only sub-micron gap size. This study used a patterned deposition experiment and a composition simulated by Monte_Carl〇 to study micropatterning by 0VPD. The process is simplified by ignoring gas-phase and surface reactions and molecular or particle re-emissions-one that needs to be considered in reactive deposition or etching. In 0VPD, the carrier gas flow generates a hydrodynamic boundary layer on the substrate, with a depth of 1 mm to ~ 5 cm. In previous studies, the film deposition rate was obviously limited by diffusion across this boundary layer. The organics are usually a few species (< 1 mole percent), diffuse through the carrier gas background, and easily collide with the substrate on the way. -13- National standard for paper-like degree towels (C @ A4 specifications (21QX 297 € ---- 1223840 A7) only _______ Β7 V. Description of the invention '~ ---—— When the ring is a figure size The Monte-Cad of the OVPD is patterned. It seems that the sedimentary edges often become less clear. The control of the resolution of the figure is achieved by changing the mfp, the overall gas flow rate, and the geometry of the aperture. -Cado simulation and OVPD experiment proves that it is possible to obtain a pattern of Dida and dimi, the deposition profile is closely related to the pressure, the shape of the pores and the distance from the substrate. It is also found that the dependence on mfp and the overall flow rate is low. Operating conditions and aperture geometry are the same as those that achieve higher resolution. The program parameters that are important to OVPD include evaporation and reactor wall temperature (Tevap, Twan), carrier gas flow rate (v), and deposition pressure (Pdep ), Compared to thin film> The product condition is characterized by 1 pa < pdep < 103 Pa, 500K < Tevap, Twall < 700K, and 10 sccm < * v < 100 () sccm. The program content In the limit, the vapor pressure of organic molecules is from 〇〇-2 to 〇〇1 Pascal, so that organic matter It remains volatile and still chemically stable, and the molecular diffusion rate of the gas phase is the size of the overall carrier gas flow, which promotes the film deposition rate and uniformity. The thickness of the thin layer can be controlled by mechanical blocking or by adjusting * V or The combination of the two is achieved. The better OVPD program tolerance is as follows. The lower limit of the source pressure is ~ q Pascal. Below this value, the pressure drop from the source inlet to the substrate is not enough to drive the air flow, organic matter. The transport will become dominated by diffusion, which is difficult to control. The upper limit of pressure Pdep in the deposition zone is about ~ 丨 Pascal, limited by the diffusibility of organic vapor that decreases with pressure α from 1 to 103 psi The molecular transport within the pressure range of the card changes from the Knudsen number value included in the VTE to the diffusion value, and the characteristics of the deposition can be greatly changed. Figure 3 shows the organic vapor deposition (0VPD) system 300. The carrier gas passes through the source member 3 and 10, and the organic substances are evaporated into the carrier gas here. May-14-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love)-1223840 A7 B7 V. Invention description 12) '~~ — -— Use multiple source components (not shown) to provide a mixture of organic materials, and / or provide different organic materials f at the same time. The carrier gas then passes through the substrate 3 30 30 5 Stencil 320. The carrier gas then hits the substrate 33. Organic substances are physically adsorbed on the surface of the substrate. The substrate 33 can be cooled. The side wall 340 of the system 300 can be heated to Reduce or prevent deposition of organic matter on the side wall 340. The organic substance may be a small molecule substance, or it may be a polymer material. .

Spatially and temporarily separating evaporation and deposition in 0VPD allows individual and accurate control of deposition rate, dopant concentration, and coating uniformity of molecular organic thin films. The deposition pressure is preferably in the range of about 0.01 and 10 Torr. Can grow amorphous films (such as fNPD, Alq3), and crystalline films (such as ^, E), in OVPD 'absorptive organic molecules are evenly distributed on the entire substrate area, which can be regarded as a dot close to the curtain Quasi-infinite aggregates of evaporation source | Within the preferred pressure range of 0.0 1 to 10 Torr used by OVPD, the carrier gas molecules (eg nitrogen, argon); I are individually centimeters to 0.1 micron. Therefore, using a micron-sized orifice plate pattern, the frequency change of molecules hitting above and below the mask under different pressures will cause the pixel profile to change significantly, as shown in Figure 4. FIG. 4 shows the OVPD system 400. The carrier gas is used to transport organic molecules from the source (not shown in FIG. 4, see, for example, FIG. 3). The molecule has an average free path λ. The mask 4 10 is arranged at a distance s above the substrate 4 2 0. The organic layer 430 is deposited on the substrate 42 through the holes 412 in the mask 410. Because of the intermolecular collision in the carrier gas, the obvious deposition of organic substances may occur in the area that is not directly above the aperture 4 丨 2 at a distance d under the mask I__ This paper is suitable for King S Standard (CNS) A4 Specifications (⑽, Xiang Gongdong) --------- 1223840 A7 B7 V. Description of the invention (13 domains. The deposition is preferably performed at a lower value in the pressure range, so that the average free path is greater than under high pressure D is corresponding to a low value to achieve micron-level resolution that is conducive to full-color display applications. With regard to the limitation of the high molecular nature of OVPD, we can state the ratio of the carrier gas velocity to the average molecular velocity About 0 ^ to 丨 is better, that is, the flow system in the LP-0 VPD is lower than the sonic method or wider. Because the pressure used is low, the Reynoms number Re is completely within the laminar flow method range (Re & lt < 2000). The Grashof number near the substrate is also lower than i, meaning that natural convection is not important in the mixing of gases close to the substrate. , Transport to the substrate Surface diffusion and surface diffusion have the most correlation with immobilization. Because the effective deposition of amorphous thin films includes minimal surface diffusion and desorption, it is better to use the lowest substrate temperature that can be practically used. In this case two cases occur Results · kads > kdes, and the crystallization rate is extremely high, the organic molecules diffused on the surface of the finger are far more diffuse than the substrate ^ due to r, the surface diffusion and immobilization system is extremely fast, and is not considered = crystalline The rate limiting of the film. This rate limiting step is therefore a diffusion that reaches the surface and reaches the surface of the substrate. &Amp; As shown in previous studies, the overall deposition rate ~ "can be expressed as:

rdep-^ see RT

V ηνδ / Don (2) where P〇r & / RT is the concentration of organic matter, V point is the dynamic rate, ㈣ is the thickness of BL, and is ^ ten or less than the carrier gas I _-16-this paper size Applicable to China National Standard (CNS) A4 size ㈣X 297 Gongai Factory a 1223840

Diffusion. The dynamic viscosity itself depends on the pressure: V: " / P, where PP / RT plus moonscape gas pressure pdeP may cause the deposition rate rdep to decrease sub-linearly (subHnear) due to two opposite factors. Diffusion D. ^ The decrease makes rdep lower, and the decrease makes it improve the delivery rate. This formula can be used to predict the overall deposition rate under specific program conditions, combined with the surface molecular diffusion model, to predict the crystallization reagent and grain size of polycrystalline thin films. The system near the substrate can be subjected to engineering processing and model experiments when the vertical jet of gas impinges on the plate, close to the plate and becomes a stagnant uniform flow, or resists the flow on the rotating disk (improves the coating uniformity); in all cases , 5 all take the following forms:

Where V is the kinematic viscosity of the gas, and a is the amount that decreases linearly with the V point and / or the rotation rate, so that this formula can be directly used to estimate 5, when v is cm2 / s, the unit is cm, and a is the overall axial flow velocity in centimeters per second. In terms of the better conditions used for OVPD and this study, such as T-275 C 'Pdep = 0.2 Torr and V point = 15 seem nitrogen, 5 is approximately equal to 1 to 10 cm. However, because 5 is not much smaller than the axial size (1 to 30 cm) of a general sedimentation tank, the term boundary layer should be used with caution.

The 0 VPD antecedent theory conducted through the orifice plate is based on continuity and is based on the reliability caused by the use of uniform overall diffusivity DQr & and the thickness of the boundary layer δ. This paragraph tests the validity of the continuity hypothesis when applying orifice covers in 0 vPD. -17- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1223840

Description of the invention / Organic molecules maintain their original whole_flow rate when reaching the plane of the mask Bi is a factor affecting OVPD. First of all, * person assumes the existence of a boundary layer bl, which is defined here as the memory that the molecule loses its overall transport, and its velocity distribution is completely thermalized. In this case, T qualitatively finds that the decrease in DQrg due to higher p will not make the pattern less clear. Because ο ”is isotropic, it takes longer for the knife to diffuse vertically to the substrate.] It takes longer (same amount) to diffuse. These rates cancel each other out and produce the same pattern under different pressures. This is not an observed experimental tendency. (See, for example, the following formula (8)): The cartilage is slightly reduced in the orientation of the substrate along a decreasing temperature gradient. However, the decrease is isotropic. The pattern should be kept unaffected. The z-component that loosens the isotropic velocity in the boundary layer and keeps the molecule at the original velocity can be expressed as: line where dmax is the pixel edge dispersion, as shown in the figure As shown in Figure 4, and u is the velocity of the carrier gas in the deposition chamber. In this case, it is assumed that ^ is sufficient to model the program as a point-type source diffusion model located along the gap hole of the mask. The The pixel edge dispersion increases with the square root of pressure through Dorg and the mask_substrate spacing 3. This model towel 'increases the overall flow rate naturally to improve sharpness. However, this formula will be appropriate for the pressure (such as Q "Tor) Pixel edges are scattered Estimated at least - the number of bits, not because of this discussion about the size and pressure are strictly in line with the transport diffusion hypothesis. The experimental deposition pattern suggested that the mechanism is located between two diffusion modes. In this case, 1223840 A7 B7 should be noted. V. Description of the Invention (16) The continuity and the diffusion assumptions caused by it are not correct for most VPD conditions. As mentioned earlier, the Knudsen ^ (λ / L, where L = characteristic length) based on the size of the orifice plate is large, and its quantity and energy equations no longer form a closed combination. Organic molecules close to the substrate Arbitrary collision causes the pixels to spread sideways. Because the complete randomization of the molecular velocity occurs in BL, the expected size affects the sharpness of the pattern. In addition, the latter is limited by the following factors: average molecular free path; ^, Mask _ to · substrate spacing s, and the shape of the pores in the mask. In terms of program parameters, these factors are determined by the deposition pressure, the carrier gas flow rate, the type of carrier gas used, and the orifice plate. Also. Ten controls. Because D.rg and people are closely related, we then detect how λ changes with Pdep and its effect on the sharpness of the pattern. Monte-Carlo simulation can be used to perform model experiments of deposition through orifice plates. Reference Figure 4. A larger person will reduce the number of intermolecular collisions in the BL. With the lateral uniform concentration distribution on the orifice plate, the pattern on the substrate will have less lateral dispersion. The low pressure of a single component Non-polar gas In terms of,; 1 has the following form: ^ __ / eg · Γ 4l ·; τ · σ21 pdep (5) Therefore, by reducing the gas pressure, the average free path is increased, and a pixel of good luck is obtained. However, the pressure Can not be reduced indefinitely; the inflow of carrier gas used to transport organic steam will inevitably generate background gas pressure. The limit of the extremely low / child product pressure pdep indicates the free molecular transport method, in which a large 'carrier gas velocity V point limit material Conveying. Increasing the v-point yields more than -19- The paper size is suitable for the national material of the country (CNS) A4 size (Ca χ tear public love) ------ Decoration line 1223840 A7 B7 V. Description of the invention (17)

Pdep is large, and when λ becomes smaller, the transportation becomes a diffusion-restricted body gas flow rate and maximizes the vapor phase diffusion of organic matter. The optimal pressure range of 0.01 to 10 Torr used in OVPD. . The use of fully loaded coordination arises from the fact that although formula (5) can be used positively against non-dilute gases such as lactate and argon, 0vPD uses complex molecules such as Alqs and carrier gases such as ^ from or lice. The impact profile person and loosely modified representations are determined by the following relationships: Mixture. Can be expanded by Equation 5

⑹ In this case, the Chapman-Enskog notation for the diffusivity of molecules with dipoles or induced dipoles can be used:

Dab = 1.835. 1〇8.7 ^ 丄 + ---- ^ ΜαΡσ2Μ〇.ΑΒ \ 0.5

Mb) Installation line where Mi is the mass of the diffusive substance I, T is the gas temperature, and σ ΑB is the average impact profile, cr ΑΒ = [ΐ / 2 (σ Α + cr Β) 2] 1/2. The quantity Ω D ab is a two-dimensional function of Lennard-Jones intermolecular potential and temperature. As far as the general materials used by Oled are concerned, the reliable Lennard-Jones parameter is often invalid, and the Fuller correlation can be replaced afterwards:

(8) Where Σ v is the effective volume of the individual structural components of the molecules in the diffusion -20- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1223840 A7 B7 V. Description of the invention ( π) distribution. Calculate constants specific to various molecules using standard group distribution methods described elsewhere. As shown in Table 1, the value of DAB varies between different theories by as much as half a digit, and more detailed experiments and / or molecular dynamics simulations may be required to determine the binary diffusion more accurately. However, the estimates of ^ and σ should be sufficient to determine the propensity to stress, which can be used to control the desired deposition properties. Simulation binding

The Monte-Carlo simulation was performed as follows. The calculation space is divided into three-dimensional grids with varying component sizes. Particles representing organic molecules are assigned to any original position on the boundary layer and the mask, and satisfy the Maxwell-Boltzmann distribution. After a period of time and a travel distance of no more than 1/10 of the average free path, the molecule collided with a locally generated carrier molecule with an arbitrary velocity from the Maxwell-Boltzmann distribution. Use the collision acceptance calculated as:

PccU FNCFfUrAt

Vc (9) where FN is the number of actual molecules represented by a simulated molecule, ^ τ is the total cross-sectional area of the collision molecule, u is its relative speed, △ is the time interval allowed for collision, where VG is Is the volume of the component that collided. The value of ^ can be calculated from deff and effective collision diameter ~ using relative particle velocity 乂 "estimate-calculation: (10) repeat the overall method 'to track millions of molecules in space. With the plane of the substrate -21-This paper scale applies to China Standard (CNS) A4 specification (210 X 297 ^ 7 1223840 A7 _ ___B7 V. Description of the invention (~~) '~' —- Or when any other side of the curtain collides, the organic particles are fixed there. Period of lateral placement The boundary conditions are used to fix a fixed concentration of organics and carrier gas on the edge of the boundary layer. The simulation is performed until the desired film thickness is formed on the substrate. Tracking of millions of molecules composed of several individual molecules, In order to save the calculation cost. Simulation results and discussion Figure 5 shows the simulation results of deposition through the orifice plate in the expansion of the government. When the nominal s = 10 microns and the thickness of the mask is 8 microns, the figure $ shows again = 8 25, 82.5, and 825 microns (Pdep ~ 〇.〇1, 〇 ·; [″ · 〇tor)) deposition pattern. Molecules are emitted at an arbitrary angle of 2000 microns from the mask, with an average molecular thermal velocity, And can diffuse through the mold The volume of space. It has been found that the / Chen degree curve near the substrate is linear 'indicates that the transport is simply diffusion. This is the reason why there is no difference in the d value found for different lambda values in Figure 5. It is also like the continuity model molecule The ratio of deposition on the substrate and the mask, that is, the deposition efficiency, is lower when λ is smaller, corresponding to a low value Dorg. This simulation uses a mask opening of 30 microns wide, a mask thickness of 18 microns, and s = 10 micron mask pitch. Figures 510, 520 and 520 show the deposition thickness curves of the mask (higher) and substrate (lower) at λ = 8 · 25, 82.5, 825, Pdep = 1.0, 〇l 〇〇1 Torr. There is no significant difference in the pixel shape between points 510, 520, and 53 0, indicating that the pressure of the simple diffusion method has little effect on the edge dispersion; as predicted, the deposition efficiency follows the λ value. Decrease and decrease. Figure 6 shows the simulation results of deposition through the orifice plate in the diffusion method. The mask ** has a curtain opening of 30 microns wide, t = 18 microns and long = 82.5 microns, and Figures 610, 620, and 63 0 individual s = 3, 10, and 20 microns. Smaller s values produce sharper -22- this paper Of the applicable Chinese National Standard (CNS) A4 size (210 X 297 mm)

AT

1223840 A7 _____ B7 V. Description of the invention (21 1Γ ^ ~ Ί Product curve becomes sharp. When the overall flow rate Ubuik is close to the molecular thermal capture u, its! Is close to the trapezoidal characteristic of vacuum > This point suggests a deposition mode, Among them, the ultra-fast carrier gas spray is used to spray organic materials on the substrate, as if sprayed | black print. An example of this type of vapor spray deposition mode is illustrated in Figure 9 The drawing, in which the overall velocity is superimposed on the arbitrary heat of the molecule 丨 moves' produces a jet of molecular flow passing through the pores of the mask curtain. I Fig. 10 shows the measured drawing of the village material, which shows the ejection characteristics such as deposition: and super Fast carrier flow. The overall deposition efficiency of this method can be close to 100%. The ratio is' because the pixels are patterned by guided gas spray, no material is wasted when coating the | orifice plate. Should be used Individual nozzles for pixels of each color | The / pair product system is engineered to obtain an effective, accurate, and easier to carry zero deposition system. The deposition curve in Figure 10 shows the same as the vacuum deposition box. Clear trapezoidal pixel boundaries; experimental seal

Alqs' organic thin film deposition is performed using a multi-barrel glass reactor system with in-situ temperature and thickness measurement equipment. In short, the reactor was a 1 × 1 m diameter by 150 cm length pyrex® cylinder. B is heated by a three-section stove to control the source electrode by placing components along the temperature gradient in the tube: 丨 temperature. Each source is individually packaged in a 2.5 cm diameter by 7 5 cm length | glass tube. The carrier gas flow is adjusted by its flow controller, and deposition 丨: The pressure is maintained within the range of 0.1 and 10 Torr by adjusting the pump throttle valve, and the total carrier flow rate is maintained between 10 and 50 sccm. Use a liquid nitrogen cooling morphine: 40 lpm vacuum pump to discharge uncondensed carrier and organic matter. Organic steam cooling. 丨 Condensed on a rotating water-cooled substrate behind the mechanically operated shutter. Film Thickness 丨 -24- ： This paper size applies to China National Standard (CNS) Α4 specification (210 X 297 mm) 1223840

The degree and growth rate are detected by a quartz crystal microbalance calibrated using polarized light to measure the thickness of the organic thin film. In addition to using OVPD to deposit organic thin films, a conventional vacuum thermal evaporator was used. The source-to-substrate distance is 30 cm; the deposition pressure is maintained at 10-6 Torr. The arrangement of the orifice cover is illustrated in FIG. 11. A mask 1110 including a screen 112 and a plate 1130 is used. A clamp 114o was used to keep the mask m0 at a fixed distance above the substrate 1150. The stencil 1120 includes a 5 micron-thick nickel mesh composed of ⑺ micron interlaced wires to form a 15 micron square opening. This stencil was placed directly on top of a 1 mm-thick silver-coated glass sheet, covering a 50-micron-thick nickel plate 113 including circular holes having a diameter of 1 and 0.3 mm. This configuration allows simultaneous measurement of two s-value deposits. Because of the non-square shape of the metal mesh including the nickel mesh, as shown in Fig. 11, the minimum value of s is ~ 2 m. In this case, the dispersion value d at s = 2 microns means the fuzziness of the square pixels 7 to 10 microns on the side. The value corresponding to s = 5 micrometers means the fluffiness of the circular deposition edge formed. The 50 micrometers at the top of the stencil and the 1 mm and 0.3 mm holes of the thick mask are located at the top of the stencil. The subsequent maximum spacing of 50 micrometers was achieved using a double-layer nickel mask as illustrated in FIG. Additional orifice manufacturing can be integrated on this substrate to provide the most accurate mask-to-substrate spacing. The mask is formed using a photoresist / chrome / photoresist (Pr1 / Ci > / PR2) sandwich structure and lithography. After depositing Alqs, the formed pixel pattern was detected using a scanning electron microscope. Test results and discussion -25- Applicable to Chinese National Standard (CNS) A4 size (210 X 297 mm) for binding paper size binding line 1223840 A7 B7 V. Description of the invention (23) Figure 12 shows from 0VPD through the orifice plate at 2 ) d (scanning electron micrograph of the pattern formed below the range of 6 to 2 Torr. When the deposition pressure is increased, both the simulation and experimental data show the loss of edge sharpness. Images 1210, 1220, and 1230 individual Show the results of pdep = 2 · UT6, Pde wide 0 2 Torr and ρ_ = 2 Torr. The distance between the left column and the right block is s = 5 and 2.5 micrometers respectively. As predicted by the model, the pixel is under pressure And the mask-substrate distance becomes more diffuse as the pitch increases. It has been found that a pressure of 0.2 Torr and a pixel resolution of up to 15 microns can reach a few micron size resolution, which is sufficient for full-color display devices. Degree, I define the dispersion parameter d as the distance along the X-axis, where the pixel thickness is between 90 and 10 percent of its center maximum. This value is approximated by the mask-substrate spacing s, Generate dimensionless pixel dispersion, for experiments and The simulated value is relative to the deposition pressure edge map. The mixed deposition Figure 13 shows the simulation results of the eighth / eighth micropattern formed by the mixed 0VPD-VTE deposition. Both use the same orifice plate. Automatically ensure the metal layer The superior alignment between 1310 and the underlying organic layer 132 ° prevents potential short-circuits around the edge. The simulation results show that, as in the experiments within the pressure-dried surroundings, the dispersion increases with pressure. Because at present The deposition system cannot easily reach a pressure between i (r6 and 101 Torr), so the simulation results will fill the gap. Under the limitation of extremely low deposition pressure, the pixel edge dispersion can gradually approach a Non-zero constant, this is the characteristics of the geometry of the vacuum chamber and the curtain. When manufacturing full-color OLED displays, the thin layers of various patterned materials are -26-

1223840 A7 B7 5. Description of the invention (24) It is better to align with each other. An actual flowchart consists of combining OVPD through an orifice plate at an appropriate pressure, as shown in Figure 4, and then depositing metal contacts under low pressure, as shown in Figure 2, without removing the mask between the two steps. Controlled dispersion of the organic coating prevents short circuits around the edges of the organic film. This concept is illustrated by the simulation illustrated in FIG. FIG. 14 shows a scanning electron micrograph of a structure experimentally manufactured based on the simulation of FIG. 13. The Alq3 organic layer 1410 is deposited by OVPD, and then the Ag metal layer 1420 is deposited by VTE. Because different parameters are used to deposit this layer, the organic layer is fixed and reliably larger than the metal layer, even if it is deposited through the same orifice plate, and remains fixed in the same location through the deposition of organics and metals. The second set of pixels can be deposited by simply laterally transforming the mask (perhaps in situ), without the need to align the mask with the previously deposited pattern, and then deposit a second organic layer (perhaps emitting a different color), It is followed by a metal layer. This method can be repeated once for a tri-color display. Table 1: Gas diffusion coefficients in mixtures of Alq3, N2, and Alq3KN2 τ (κ) Dorg (dynamic theory) (cm2 / s) Dorg (FuU et al.) (Cm2 / s) Dorg (Chapman-Enskog) ( Cm2 / s) 273 0.0355 (N2) 0.68 (N2) 0.105 (Alq3) 0.0629 (N2) 548 0.101 (N2) 2.30 (N2) 0.356 (Alq3) 0.179 (N2) The transport method included in OVPD is not very accurate, but it can be used to understand the patterning of OVPD by considering the simple diffusion in limiting the geometric shape. FIG. 15 illustrates a bell-shaped outline of a pixel deposited through an orifice plate by OVPD. Base-27- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 1223840 A7 B7 V. Description of the invention (25 Packing materials 15 丨 0 are arranged under the cover 1520. The shape of the gap wall The feature is the angle j (or α '). The mask 1520 has a thickness t, and the gap 1525 having a width of ~ is separated from the substrate by s. The material layer 1530 is deposited on the substrate 1510 via the mask 1520. The incident on the substrate The molecular flow on the wood originates from an infinitely evenly distributed point source surrounded by -w / 2 < x < w / 2 in space, producing a deposit with the bell-shaped shape shown. Each of the continuous methods For isotropic diffusion, the base of the sediment widens directly in proportion to s. Therefore, a smaller number 3 should produce a larger pattern resolution. If S remains constant, but the deposition pressure increases, the Diffusion is reduced. However, because the diffusion system is isotropic, the longer it takes for molecules to diffuse vertically to the substrate, and the longer it takes for lateral diffusion (same amount). These rates cancel each other out, resulting in different pressures. The same pattern is not an experimental tendency found. Also, In the continuity hypothesis, pattern formation is independent of the shape of the pores located above the edge closest to the substrate. Conversely, the simulation of deposition-observation of speculative scattering of molecules located near the substrate-predicts the pattern deposited The shape is not only related to s, but also to mfp and the shape of the gaps. Because of the discontinuous transport properties of the wire at low numerical density, several parallel correction effects on the organic molecular flow passing through the gaps of the mask also need to be considered. First The parallel correction of molecular flow can be proportional to the aspect ratio t / w of the gap (sacrifice deposition efficiency). Second, if the heavier organic molecules retain the important fraction of their original overall flow rate U, then when they reach the plane of the mask At this time, a partial parallel correction occurs, and its prerequisite is u < U (we assume that the sedimentation tank is a fully developed flow, so at the edge of the boundary layer, it is assumed that U of the organic molecules is equal to U of the carrier gas molecules). Considered here In the OVPD method, the overall flow is related to the flux -28- this paper size suitable financial S ® household materials (CNS) A4 ^ (21G X 297 public director) " '1223840 A7

It is not important that the flat / horizontal is right, because u ~ 100 to 400 meters / second, and u ~ i to 10 meters / second ', therefore, the simple diffusion near the substrate is dominant. However, the effect of the overall flow momentum of the carrier gas can still be evaluated using a Monte_Cari simulation. For example, if U / U> (U, then a change of 11 will affect the deposition profile. Finally, because natural convection rates are not meaningful compared to diffusion at low number densities, it is estimated that the thermal driving force near the substrate is relatively small Therefore, no further consideration is given. 'The discussion of the shape of the pattern is based on the definition of the shape factor ^ equal to the thin layer 1530 area 1535-surrounded by _w / 2 < x < w / 2 (diagonal area)-divided by the total deposition profile Packing is carried out. When? Is equal to-, it is " perfect, " The rectangular sediments decrease with increasing p, t / w, and 5. One of the purposes of this simulation is to understand the organic molecules in The method of restricting the transport in the geometric shape is that the size of the xuan device is the size of the average free path of the molecule, and the description based on continuity is not used. The model proposes the patterning of organic deposition on the substrate, which has limited The thickness of the interstitial surface is limited by condensation. This simulation shows the random nature of the diffusion method in the intermediate Kn. Therefore, the model vertical organic molecules hit the lighter carrier gas molecules near the substrate and are deposited on the cooled The surface is the path of the substrate and the edge of the gap. In short, it is assumed that the retention probability is one. The preferred vapor pressure of the organic substance is about 10-2 towels of white ska, and the preferred background carrier gas pressure is 丨To the size of Pascal, organic-organic collisions rarely occur. The overall diffusion and transport of gas is an average free path phenomenon, and its velocity has the characteristic of diffusivity D. The theory of dynamics of pure gas makes the overall parameters 0 and The molecule-based quantity is related. If a single component is a low-pressure non-polar gas -29- this paper size is suitable for towels S @ 家 料 (CNS) Α4 size (⑽X 诺 公 爱) ---- 1223840 A7 ______ B7 V. Description of the invention (27) Under the low pressure mfp, the average free path mfp is: ϋ = -ΪΙ ^ φ 3. (Π) Because the organic vapor system used by 〇 VPD is a large molecule, geometrically and dynamically, it is more dynamic theory The hard spherical atoms are complex, so there may be some differences between simulation and experimental results.

The Monte-Carlo simulation was performed as follows. The calculation space is divided into x-z grids that extend indefinitely in the y_ direction. The purpose is to position the substrate and the surface of the mask and track the changes in the thickness of the sediment. Particles representing organic molecules are assigned to any original location (XQ, h, ZG) in the boundary layer and above the mask. Select any original direction ’particle travels a distance r = [(XrXQ) + (yi,) + (Zi_z.)] 1/2, where Oi, yi, Zi) is the new position of the particle. The distance Γ is the minimum value of the grid size or mfP / l0. Probability of collision with carrier gas molecules pe.丨 1 is expressed as Pconon = r / mfp, and is detected relative to a random number rand between 0 and 1. If Peon < rand, the molecule can still advance a distance r in the same direction. If PCDH > rand ', the particles collide with a carrier gas molecule that is locally generated with a velocity selected arbitrarily from the MaxweU-B0Uzmann distribution. The speed and angle of the molecular turn caused by this collision are consistent with the conservation of momentum and energy of the elastic collision of two hard balls. If the path of the particles traverses the plane of the substrate or the wall of the gap, it is assumed that the particles stay on the surface with a single efficiency, and the thickness of the sediment is updated. A single slot is simulated to place periodic boundary conditions in the X · direction. The simulation time increases with the number of molecules used to perform the deposition, and decreases with larger m fp. The influence of the gap geometry on the pattern formation is based on model experiments by assigning different angles of the gap sidewalls. Α = 45, 90, -30. This paper is applicable to China National Beech Standard (cn ^ 7I ^ (210 χ 297 public directors) 1223840 A7 B7 V. Description of the invention (28) 135 'and α' = 270. As shown in Figure 5. Let us consider the archetypal molecule three (8-hydroxyjunline) (Alq3) Thin film growth, d ~ 10 angstroms. The collision profile of the mixture of Alch in% carrier gas is taken as the average value of the individual profiles of two substances in their own diffusion, ¢ 1 ^ / 2 (^ 43 + (^ 2), and the formula ( 1) ρρ. Figure 16 shows a simulation curve of the concentration of organic matter at the end of the simulation of 105 particles, S = 7 microns, t = 3 microns, and αM35., And _ = 100 microns, corresponding to the T = Total deposition pressure of ~ 37 Pascal at 500K. The organic layer 1630 (simulation) is deposited on the substrate 1620 through the mask 1610, which is arranged at a distance s above the mask 1610. The particle velocity at the beginning of production is from arbitrary The heat distribution is distributed, superimposed on the z-direction velocity vector, and the size is 1 / 10m / s. The size is enlarged to show the outline of the thickness of the deposited film. The η line in FIG. 17 shows the same simulation curve as in FIG. 16, in which the organic layer 1730 (simulation) is deposited on the substrate 1720 via the mask 1710 and is disposed on the mask The distance s from the top of the screen is 17. The mfp used to generate the result of FIG. 17 is 10 times smaller than the user of FIG. 16. By reducing the mfp by 10 times, a more diffuse pattern is obtained. The film shown may be thicker than practically larger devices, but the figure also shows the increase in parasitic deposition on the inside of the mask and the wall of the aperture when the mfp decreases. The thickness of the film of 1000 Angstroms is more practical. The simulation results only provide thickness curves. For clarity, the wells are not overlapped. Unless otherwise stated, the following OVPD simulations use 106 Alq3 molecules in a specific carrier gas. The effect of deposition pressure on pattern resolution is by Change mfp to evaluate 'proportional to reactor pressure. Consider growth via voids of w = 830 μm, P70 μm, distance between substrate and edge of lower layer curtain -31-

1223840 A7 B7

V. Description of the invention (S-20 microns. The selection of S and t is the same for high-resolution display (pixels) of P, P, K, and VTE, in which the substrate with the evaporation geometry facing downward leads to the cover. The curtain is bent from the substrate under gravity such that s ~ 20 microns. To harden the mask and minimize s', t &gt; 70 microns is commonly used. Figure M shows a graph of the shape factor versus the average free path. Shape The factor "Coriolis increases slightly with the increase of m fp in the four digits (1 material and a half of &lt; · mf, Λ M is the knife made of water $ mpfg 1000 microns, which corresponds to about 103 Pa ^ Pdep ^ Pa), As predicted by the Knudsen transport system, J: ,, <, and 77 cannot be reached due to parasitic deposition on the side wall of the square gap hole. As expected, the highest pattern edge resolution is at the maximum mfp When it is achieved, the low Pdep is taken. However, the profile of the pattern has a hemispherical shape because of the relatively large t / w ratio. Figure 19 shows the same simulated organic layer profile as the thin layer 630 of Figure 16, but using different parameters Generation. Increasing the thickness of the pores will improve the leveling of molecular flow towards the substrate Corrected because it is condensed on the gap wall. Figures 1910, 1920, 1 930, and 1940 individually show the contours of the gap thickness of 50, 20, 10, and 5 microns, s = mfp = 20 microns. W = = 300 microns should not affect the spread on the contour edges. However, as t / w increases, the deposited pattern becomes greatly expanded, because the upper edge of the pores sweeps the organic molecules Q shape factor at} microns &lt; The t &lt; 丨 ⑽ micron range is reduced to less than 5%. The pixel deposition efficiency decreases as t increases due to the parasitic deposition on the side wall of the gap. Figure 2 0 M Figure 16 The same simulated organic layer The contour of the wheel, but generated using different parameters. The mask interval s can change due to bending under gravity (VTE), or may be heated during the deposition process. Figures 2010, 2020, 2003 〇 and 2040 show the outline of the deposit, with individual s = 2, 10, 22, and 50 microns -32- This paper size is suitable for financial standards (CNS) A4 specifications (210 X 297) &quot; '— ----- 1223840 A7 B7 V. Description of the invention (30) For each figure, the words' t = 20 micrometers, w = 30 micrometers, and mfp = 20 micrometers. The apparent edge widening may be caused by the collision in the mask_substrate gap during s &gt; mfp. In addition, the expansion in the middle of the deposition is also increased, contrary to the high value t / w, it is accompanied by the pixel edge widening The 2050 insets in Figure 20 are plotted relative to s for this series of deposits, showing that "they decrease rapidly with s. The resolution of the graph of the moment / child product is reached at the minimum s and ○. Because 0vp 〇 Basically, it can be performed by using a mask located above the substrate, so a thin mask can be used without sacrificing low s value due to the bending of the mask, which occurs in VTE. One disadvantage of thin hoods is that they are more susceptible to thermal and mechanical stress. FIG. 21 shows the contour of a simulated organic layer that is the same as the thin layer 1630 of FIG. 16, but generated using different parameters. The contour in Figure 21 illustrates the effect of different side wall angles. Figure 2 11 shows the contour generated using a 45-degree side wall angle. The $ system is 10 micrometers, the mfp system is 20 micrometers, and the mask thickness t is cultured between 5 and 80 micrometers to generate different contours of FIG. 2110. Figures 2120, 2130, and 2140 were generated using the same parameters as in Figure 2 with the difference that the "fixed system is 135, 270, and 45 degrees. Figure 21 shows that it can be minimized at the edge of the gap, and the other Keep the thickness in place. Figure 22 shows the figure of the shape factor relative to the thickness of the mask, based on the outline. Figures 2210, 2220 '2230, and 2240 are based on Figures 2ιom, 2120, 2130, and 2140. Please shape the hole shape. The change is evaluated by changing the angles of the side walls of the apertures α = 45, 90, 135 and α, = 27 °. The apertures called ^ produce the most diffusive pixels because of the lack of close angle of physical adsorption molecules Parallel correction. Double taper apertures (α, = 27〇.) Are slight, but at "40. And ^ 45. The sharpest pattern is achieved under geometric shapes. Except deposition

Installation line 1223840 V. Description of the invention (in addition to 3L sharp picture 3L, 'these aperture angles get the maximum under a specific deposition shape &quot; product efficiency &quot; and the structure is stronger than the other shape of the specific shield. When the mfp increases (corresponding to the lowered dagger ^), the molecule enters and penetrates the boundary 3 T to stay closer to its original overall flow velocity. In this case, the parallel / redundant contour of the tracked flat sentence Aide car becomes sharper. Figure 23 shows the normalized relative degree with respect to the position in the three cases. Figure 2310 shows the contour generated under the pure diffusion &quot; L product. Figure 2320 shows the overall conveying speed (set at the average thermal speed). One tenth) is added to the Z component of the heating velocity vector of the carrier gas molecule. Figure 2330 is the case of the intermediate, in which the two-direction velocity of the carrier molecule decreases inversely as it approaches the substrate. The pure diffusion mud A narrow and clear sedimentary edge is generated, and Figure 232 produces the sharpest pattern. The actual deposition mechanism is also limited by these two limits, which proves that the complex gas flow of the carrier gas 2 'heavier organic molecules retain the whole One of the ratio z-direction components of the body gas flow. Consider a carrier gas jet delivered on a cooled substrate via a small-diameter capillary. In the Monte-Carlo simulation, the z-direction carrier gas velocity Uz can be increased to simulate a jet, which Widened only by overlapping isotropic arbitrary molecular velocities over this flow range. Figure 24 shows the spatial concentration curve of the simulated jet with Aiqs, mfp = 10 microns, t = 50 microns, and Uz is 0 m / s. , And the average thermal velocity ΰ = 500 m / s. Because the flow range in this flow method is unknown, for simplicity, the simulation maintains dUz / dz = 〇. The figure shows that a parallel-corrected jet will result in a clear edge. Deposits, even s &gt; &gt; mfP. With careful selection of U, Pdep, ^, and 3 can be printed using molecular organic thin films' as inkjet printing for polymers 34-gutter 1223840 A7 ______ B7 V. Description of the invention (a-'The liquid solvent in different places is replaced by a jet of highly volatile inert carrier gas. The carrier gas system containing organic molecules in Figure 24 is from the gap in the cover 2410 The hole 2415 sprays and hits the substrate 2420. Figures 2430, 2440, and 2450 illustrate different simulation results, in which the nozzle system is at a different distance from the substrate, showing that the steaming stream is widened away from the nozzle. Additional experiments

The Alqa organic thin film is deposited using a multi-barrel quartz deposition system 'using in-situ temperature and thickness measurement equipment. Figure 25 shows a description of the deposition system. An 11 cm diameter by 150 long quartz cylinder 25 10 is used as the bulkhead. This cylinder system is installed at the upstream end and has 4 evaporation source barrels 2520 (only 2 are seen in FIG. 25). It is composed of 2.5 cm diameter by 100 cm quartz cylinders equipped with quartz evaporation components. . The main pipe is heated by a three-section stove 2530 to control the source temperature by placing each component along the temperature gradient in the tube. The carrier gas flows on the inside of the cylinder 25 10 and the source barrel 2520, and is adjusted by mass flow control, while the deposition pressure is maintained by adjusting the pump throttle and the overall carrier flow rate from 10 to 100 seem Between 0 and 10 Torr. Use a 40 lpm vacuum pump with a liquid nitrogen cold trap to discharge uncondensed carriers and organics. Organic molecules from the gas phase are physically adsorbed on a rotating substrate 2540 that is water-cooled and located behind a mechanically operated shutter 255. The film thickness and growth rate were detected using quartz crystal microbalances corrected for polarizing the organic film thickness. The system of Figure 25 was also used to generate the experimental results discussed previously. The deposition profile of the organic thin film obtained using OVPD was compared with those obtained from a conventional vacuum heat generator. The source-to-substrate distance is about 30 cm; and Shen-35- this paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 public ^ ------- 1223840 A7 B7 V. Invention Explanation (33 product pressure is maintained at 10-6 Torr. Three types of orifice plates are used.-60 micron thick, i cm x cm cm square block, with circular openings with diameters of 000, 500, and 00 microns. The profile of the apertures in this mask is cylindrical (α = 9 (Γ). The other type of mask used is a ^ millimeter thickness with circular apertures with nominal diameters of 300 and 100 microns. Molybdenum plate. The opening in this hood has double-inclined edges to form a double-tapered gap (^ 27 (Γ). The third type of military curtain is a criminal screen, 3 5+ 〇5 microns thick, with a nominal 7.5 and 12.5 micron square openings, separated by "wide lines." The military curtain is fixed to the base material by using a retaining ring. The material substrate distance is placed on the base material of the Si substrate and the bottom of the Mo cover. The multi-layer Ni screen slabs between the faces are controlled. When depositing through the Nl screens, they are clamped between the substrate and the first or second type of screen by the centimeter x ΐ cm screen. Then, it is clamped on the bracket by the retaining ring and fixed to the substrate. Because the minimum effective distance between the rims of the Ni screen is 1 · 0.5 ± 0.5 microns, but because of the burnability of the screen itself, it has It can be larger. The analysis of the deposition pattern profile is performed using a scanning electron microscope (SEM) and atomic force microscope (AFM) for the smallest image anomaly size, and an interference microscope for larger pixels. Post-methods include Monochromatic light (U 540 ± 100mm) was used to shoot the substrate, and the fringe pattern formed by the inclined edges of the bell-shaped pixels was observed. An example of the obtained image is shown in FIG. 26. The image 26m0 shows the circle deposited by 〇 卿SEM microscopy results of shaped pixels (αzan). The cylindrical gap mask used for this deposition includes pixel diameters of w = 100, 300, and 1000 microns. Image 2630 shows image 2610. The results of interference microscopy in this area. -36- The paper size is suitable for financial use (CNS) A4 size (21GX ^^ 1223840 A7 ________B7 V. Description of the invention (~-~ ---) Figure 27 shows the results from Figure 26 The thickness profile of the image is 2710, by counting from the edge (Figure 2720) The number of lines is derived from the digitized pixel image using the following formula: 2 n (12) where Η is the pixel thickness, m = 0, i, 2, 3, etc., is the fringe level, λ = 540 nanometers M, and η = 1.74, which is a refractive index of eight ... Fig. 28 shows the measurement pattern outline of the deposited layer of Fig. 26. Figs. 2810, 2820, and 2830 each show 10, 3, and 1 The outlines of the 00 micron diameter layers each have s = 0 micron and 50 micron. Figures 285, 2860, and 2870 show the contours of the 100, 300, and 1000 micron diameter layers, 5 each = 40 microns and ^ microns. Figure 2820 corresponds to a nominal 2 micron thick film, and Figure 2880 corresponds to a nominal 1.6 micron thick film. Figure 2840 shows Figure 2860, which is nominally reduced to Figure 2820 by multiplying by 2 / 1.6 and superimposed on Figure 2820. These figures show that the pixel deposition efficiency (meaning the area under each contour) decreases with the aspect ratio t / w. The expansion of the middle portion of each pixel at a large t / w is the same as that found in the simulation (see Figure 19). By comparing the nominalized s = 0 micron and s = 40 micron curves, obviously increasing s reduces the efficiency of pattern deposition (because it condenses on the back of the mask) and edge sharpness, as expected from simulation experiments ( (See Figure 20 and related discussions). The highest resolution pattern obtained by OVPD can therefore be achieved using a capping device made by placing a N 丨 net clip between the substrate surface and one of the thicker masks. A patterned Alq3 thin film deposited by OVPD at Pdep = 0.1 Torr was imaged using an atomic force microscope (AFM). Use nominal t ~ 3 microns -37- This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public love) Description of the invention (36) This situation is particularly expected. The sequence can also be reversed, with a wider layer being deposited a second time. Although various specific examples describe 0 VPD and VTE as specific methods in which the coverage area of the deposited layer can be controlled using basic pressure and other parameters, the concept can be extended to other deposition techniques such as sputtering, electron beam, or general physics Vapor deposition. The coverage area can also be controlled in specific methods. For example, ’can deposit a wide organic layer (or vice versa) on a narrower organic layer, both using OVPD, but using different OVPD parameters. Obviously OVPD can be used for patterned deposition of organic thin films with micron-sized resolution. I found that because the carrier gas and organic molecules used in 0VPD have a low degree of bifurcation, the molecular free path is often the size of the mask. This method should be modeled using Monte-Carlo direct simulation experiments. Although deposition is mostly carried out in diffusion mode, experimental evidence shows that organic molecules are transported by the carrier gas as a whole, so their velocity has been kept in a considerable proportion. As the deposition pressure decreases, the average free path increases, resulting in sharper pixel edges. The use of a heavier carrier gas does not have a first-order effect on the pixel shape in the diffusion method, but improves the edge sharpness in the vapor-jet deposition mode. Smaller than the average free path mask of this system, the substrate spacing often produces trapezoidal pixel profiles found in line-of-sight vacuum deposition. A thicker mask helps increase the sharpness of the pixel edges, but only at the expense of the mask-to-substrate deposition efficiency. The simulated steam jet deposition method shows that organic matter can be directly patterned by ultrafast gas jets, where the flow rate matches or exceeds the thermal velocity of the molecules. This method can produce organic vapour depositions with nearly 100% effective patterning. Sub-micron pattern resolution can be achieved by depositing at the bottom of the pressure range (&lt; 10pa) and using an appropriate void shape (e.g., &lt; 90). -39-1223840 A7 B7 Fifth invention description (37 ) Degrees. Although the present invention has been described with respect to specific embodiments and preferred specific examples, it is known that the present invention is not limited to these embodiments and specific examples. The invention therefore includes variations of the specific embodiments and preferred embodiments described herein, as is known to those skilled in the art. Although some specific examples can be individually described and applied, it is known that various specific examples described and applied herein can be used in combination. -40- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297mm) A port / j 乂 Application date ______ Case No. J 9L 091120149 Category A4 C4 Chinese manual replacement page (April 1993)

2. Weng 1 Name Order Invention φ — 新 金 寻 # ^ Instructions 1223840 METHOD OF FABRICATING AN ORGANIC DEVICEf, NAME 1. Maxitan

2. STEVE R · FRED STEPHEN R. FORREST Nationality 1.-2. USA USA Name of residence and residence (name) Nationality 1 · 7-ζMacchi Building, Feichutti Road, Princeton, New Jersey, USA I ^! 1AGIE FACULTY ROAD, PRINCETON, NEW JERSEY 08540, USA 2. 4 8 148 HUNT DRIVE PRINCETON, NEW JERSEY 08540, USA The United States of America Princeton University Trust The TRUSTEES OF PRINCETON UNIVERSITY PO BOX 36, PRINCETON, NEW JERSEY 08544, USA Michelle D. Kristin, Princeton, NJ

MICHELLE D · CHRISTY This paper size is applicable to China National Standard (CNS) Α4 size (21〇 χ 邠 7mm) 1223840

Nl 5 ^ 091120149 Patent Application g Invention Description (1) Priority of the following U.S. patent applications with reference to related patent applications: 60,3 1 7,2 1 5 (September 2001 4th application), 60/31, 6,264 (filed on September 4, 2001), 60/3 1 6,968 (filed on September 5, 2001), and 60 / 332,009 ( (2001, January 21, 2001). These patent applications are fully incorporated herein by reference. Statement on Government Rights This invention is sponsored by the government under contract number P4962〇_92 _; _ 〇5 24 (Princeton University), u.s. Air Force 0SR (Office of Scientific Research) ^. The government has certain rights in the invention ^ FIELD OF THE INVENTION The invention relates to a method for manufacturing an organic semiconductor device such as an organic light emitting device. More particularly, the present invention relates to a method of manufacturing a device for depositing organic materials through a mask. SUMMARY OF THE INVENTION The present invention provides a method of manufacturing a device. This method can be referred to as the "mixed method" because different deposition methods are used to deposit the organic layer and the metal layer, and the difference between these methods helps the method. The orifice plate is placed at a specific distance from the fish substrate, followed by organic vapor deposition (0VPD; deposition via a mask. Then vacuum thermal evaporation (VTE) is used to deposit metal (or conductivity) through the same mask Metal oxide) layer 1 is the difference between 0 ° C and VTE 'The organic layer can be in the metal layer under credible and controllable conditions, even if both the organic and metal layers are deposited through the same mask The present invention provides a method for manufacturing an organic device. By making ^ -4- Yiwangmu paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1223840 Patent Application No. 09U20149

Replacement page of the Chinese manual (May 1993) 丨 7 months on the fifth day 5. Description of the invention (2) ^ The first layer is deposited through the mask to form the first layer with the first coverage area. Two layers are deposited on the substrate, and then a second layer having a second coverage area that is attached to the first coverage area is formed through the mask through a process. The present invention also provides another method for manufacturing a device. The aforementioned hybrid method is used to deposit a first organic layer through a mask, followed by a first metal layer, wherein the mask is disposed at a first position. The mask then moves to a second position, which can be determined relative to the first position. After that, a second organic layer is deposited via the mask using the mixing method, and then a second metal layer is formed. The mask can then be moved to a second position, which is determined relative to the second position. A hybrid method is then used to deposit a third organic layer through the mask, followed by a third metal layer. The substrate can be moved outside or instead of the veil. In each of the methods provided, the substrate may be cooled during the deposition of the organic layer. An object of the present invention is to provide an improved method for manufacturing an organic semiconductor device, which uses fewer steps than the previous method. Another step of the present invention is to provide an improved method for manufacturing an organic semiconductor device, which uses the OVPD method. Brief description of the drawings Figure 1 shows a vacuum thermal evaporation system. Figure 2 shows a vacuum thermal evaporation system. FIG. 3 shows an organic vapor deposition system. Figure 4 shows an organic vapor deposition system. Fig. 5, including Figs. 5a, 5b and 5c, showing the deposition process through the orifice plate;

This paper is scaled by Shicai® National Standard No. f 091120149 (April 1993) 3 V. Description of the invention (Proposed results, showing the effect of different deposition pressures. Figure 6 'Contains Figures 6a, 6bA6c, showing through the orifice plate The simulation results of the deposition did not change the effect of the gap between the mask and the substrate. Fig. 7 'includes Fig. 7a' 7b & 7e, showing the simulation results of deposition through the orifice plate, showing the effect of changing the thickness of the mask Fig. 8, including Figs. 8a and 8b, shows the results of the simulation of deposition through a perforated plate 'shows the effect of changing the effective boundary layer thickness. Fig. 9 and Fig. 10 show the effect of deposition through a perforated plate relative to the carrier gas flow rate Simulation results. Figure 11 shows a general schematic diagram of the substrate_orifice assembly used in the experiment. The illustration shows a scanning electron micrograph detailing the top mask and nickel mesh directly placed on the substrate. Figure 12 shows Scanning electron micrograph of a representative Alq3 pattern formed on a silver-coated glass substrate after deposition without an orifice. Figure 13 shows A formed by mixing 0VPD_VTE deposition lq3 / Ag micropattern simulation results, where both use the same orifice plate. Figure 14 shows a scanning electron micrograph of the experimental results of Alq3 / Ag micropattern formed by mixing 0VPD_VTE deposition. The same orifice plate. Figure 15 shows the bell-shaped outline of the pixel deposited by OVPD through the orifice plate. Figure 16 shows the use of 105 particles without mfp = i00 microns, s = 7 microns, t = 3 microns, and α = 135 ° simulated deposition results from Monte-Carlo simulation. Figure 17 shows the use of 105 particles, mfp = 10 μm, s = 7 μm, 3 μm, and 35. Simulated deposition results from Monte-Carlo simulation The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 1223840 A7 B7 $ 091120149 Patent application Chinese manual replacement page (April 1993) V. Description of the invention () and ^ ~ &amp; 〇 微The m screen serves as the mask 'S &lt; 1 micron. The edge sharpness is about 3 micron, which is derived from the thickness profile. The experimental pattern profile is adapted by: sword knife, using w = 6.0 micron, t = 3.5 micron, s = 〇5 microns, mf: -20 microns and the core 27 (). The simulation and experimental dimensions are close Similarly, it should be shown that the random simulation can accurately describe the patterned deposition mechanism. I obtain the same pattern for deposition under a pressure of 0.1 to 2 Torr, and lower pressure is more conducive to sharper pixels The two extreme cases are explained by the SEM of the deposited thin film shown in Figure ^. Image 3110 shows the Ah deposited on the Si by VTE through Ni screen at pdep = i0_6 Torr and s ~ 0.5 microns] Image 3120 shows a similar pattern deposited in 0vpD under Pdep = 2 Torr. The pattern of vacuum deposition shows the aforementioned trapezoidal profile, ΐ2 &lt; m = m, and OVPD_ has edge dispersion of ⑴micron size. Simulations show that submicron resolution can be achieved with the smallest gap hole. Figure 30 shows hybrid deposition through a single mask. The mask 3220 is arranged on the bottom layer of the substrate 3210. First, the organic layer 3230 is deposited on the substrate side through the VPD via the mask 3220. Thereafter, a metal or hafnium oxide layer 3240 is deposited on the organic layer 3230 by VTE through the mask 3220. Because of differences in methods such as basic pressure, the organic layer is wider than the metal or metal oxide layer, even if it is deposited at the same location through the same mask. During or between the two deposition processes, the mask has no relative to the substrate. Any move. This phenomenon can be advantageously used to deposit a second layer on a wider first layer, so that the second layer is not in contact with any layer located on the bottom layer of the first layer—for example, when the first layer is a light-emitting layer and the second layer System, is an electrode, and S _ electrode system is located at the bottom of the organic layer -38-1223840 No. 091120149 Patent Application Chinese Specification Replacement Page (April, 1993) V. Description of the Invention (38) A7 B7 Symbol Description of Schematic Elements 100,200 Vacuum thermal evaporation system 110, 210 Source 120 Vacuum chamber 130, 230, 330, 420, 1150, 1510, 1620, 1720, 2420, 3210 Substrate 220, 320, 410, 1110, 1520, 1610, 1710, 2410, 3220 Cover 222,412, 1525 Slot 240 Patterned organic layer 300, 400 Organic vapor deposition system 310 Source component 340 Wall 430, 1320, 1630, 1730, 3230 Organic layer 1120 Screen plate 1130 Plate 1140 Fixture 1210, 1220, 1230, 2610 , 2630, 3110, 3120 image 1310 metal layer 1410 Alq3 organic layer 1420 Ag metal layer 1530 layer 1535 area 2510 quartz cylinder 2520 evaporation source barrel 2530 furnace 2550 shutter 2620 area 2710 thickness profile 3240 metal / metal oxidation Material layer η line -41-This paper size applies to China National Standard (CNS) Α4 size (210 X 297 mm)

Claims (1)

Shen M. Patent Fanyuan · A method of manufacturing an organic device, including a) depositing a first layer on a substrate through a mask under a first basic pressure; b) passing the same mask under a second basic pressure The second layer is deposited by the curtain; wherein the basic pressure is used to control the size of the first and second layers. 2. A method of manufacturing an organic device, comprising: a) using organic vapor deposition to deposit a first layer on a substrate through a mask, wherein the first layer is an organic substance; b) by a method through the same mask A second layer is deposited on the first layer, resulting in a second layer with a smaller coverage area than the first layer. 3. The method according to item 2 of the scope of patent application, wherein step b) is steam thermal evaporation (VTE). 4. A method of manufacturing an organic device, comprising: a) depositing a first layer on a substrate through a mask over a sheep by a process to produce a first layer having a first coverage area; b) by -The process deposits a second layer on the substrate through the mask to produce a second layer having a second coverage area different from the first coverage area. 5. If the method of item 4 of the scope of patent application, i +, 隹 &gt; θ, the basic pressures of steps a) and b) are different, and the difference is a value of 1 糸 to control the Relative coverage of the first and second layers. 6 · According to the method in the fourth item of the patent application, the first layer of the farmer includes metal or conductive metal oxide, and this step is ^ steam evaporation, and the second layer includes 3 organic materials, After this step (b), ^ is from organic vapor deposition, and the second overlying area is larger than the — ## replenishment area. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 1223840 For example, the method of applying for item 4 of the patent scope, wherein the _ layer system material 枓, the step a) feeder vapor deposition, the genus oxide, the step coverage area in this step is larger than the 2 € cover region. 8. The lighting device of the unit such as the item 4 in the scope of patent application. In the middle feeder device, there is the organic device, there is the organic device, and the metal or the metal is oxidized. 9 The method such as the scope of the patent application No. 4 electromechanical crystal. 10. Method of applying for patent No. 4 in the Fan Garden. 11. If the method of claim 7 is applied, the material layer is completely arranged on the right side. I is placed on the organic layer so that the metal or metal oxide layer is 12. The basic pressure of the method of claim 7 0.1 to 10 Torr. 13. Method as claimed in item 4 of the patent application Passive array display. 14. The method according to item 4 of the patent application. Active Array Display. Does not come into contact with any material located on the bottom of the organic layer. During the deposition of the first layer, where the method is used for manufacturing, where the method is used for manufacturing, -2-