The invention relates to a method for depositing layers onto a substrate, in which a gas flow consisting of previously evaporated organic molecules conveyed by a carrier gas and having a molar mass greater than 300 g/mol or 400 g/mol are supplied in one or several inlets of a gas mixing device, the molecules of the one or several gas flows are homogeneously mixed in the carrier gas through multiple diversion by means of gas diversion elements, the mixture generated in this way is guided as a gas flow from an outlet of the gas mixing device into a conveying pipe, conveyed through the conveying pipe into a gas distribution volume of a gas inlet element, discharged through gas outlet openings of the gas distribution volume in the direction toward a susceptor, and the molecules are deposited as an organic layer onto a substrate received by the substrate holder.
The invention further relates to an apparatus for implementing the method with a gas mixing device, which has one or several inlets, each for supplying a gas flow consisting of previously evaporated organic molecules conveyed by a carrier gas and having a molar mass greater than 300 g/mol or 400 g/mol, gas diversion elements, which homogeneously mix the gas flows with each other through multiple diversion, and an outlet, from which a homogeneous gas mixture discharges, with a conveying pipe that is connected to the outlet, and with a gas inlet element, which has a gas distribution volume, into which the conveying pipe leads, and which has a gas outlet face that has gas outlet openings and faces a substrate holder for receiving the substrate.
DE 102014106523 A1 shows an apparatus for depositing layers onto substrates, in which two different gases are mixed in a mixing device and transported through a conveying pipe to a gas inlet element in the form of a showerhead. Previously known from DE 102014109196 A1 is an apparatus for evaporating an aerosol, which together with a carrier gas is transported into a gas distribution volume of a showerhead.
WO 2012/175128 A1 describes an apparatus for generating a vapor, which is brought into a gas inlet element through a conveying pipe.
The large-area deposition of layers comprised in particular of organic material, in particular for OLED's, takes place with a gas inlet element in the form of a showerhead, which has a gas distribution volume that is supplied by a conveying pipe. A gas mixing system is used to mix a homogeneous mixture of a vapor of molecules having a molar mass greater than 300 g/mol or greater than 400 g/mol, in particular ALQ3 molecules, into a carrier gas. A gas flow of this mixture is supplied to the conveying pipe. The gas flow discharging from the conveying pipe is distributed within the gas distribution volume and enters into the process chamber through gas outlet openings of a gas outlet plate. The gas outlet openings are faced by the substrate, onto which the layer is deposited. In prior art, total pressures of about 1 mbar are used within the gas distribution chamber or the conveying pipe or the process chamber.
In experiments to diminish the total pressure within the gas distribution chamber, lateral irregularities in layer growth or in layer composition were observed.
The object of the invention is to indicate measures with which the total pressure within the process chamber and the gas distribution chamber can be reduced to under 1 mbar, without the observed lateral inhomogeneities in layer growth or layer composition arising.
The object is achieved by the invention indicated in the claims, wherein the subclaims are not just advantageous further developments of the invention indicated in the secondary claims, but are also independent solutions of the object.
The invention is based upon the knowledge that the lateral inhomogeneities can be traced back to a segregation of the mixture supplied to the conveying pipe. During passage through the conveying pipe, the concentration of vapor molecules in the area of the center increases. A concentration gradient of the large molecules forms from the center toward the edge. This concentration gradient is traced back to a diffusion directed transverse to the flow (cross diffusion), the cause of which lies in a temperature inhomogeneity in the cross sectional surface of the conveying pipe. The paraboloid flow forms within the conveying pipe, in particular in the area of the section of the conveying pipe that is connected to the gas mixing device. This takes place with local accelerations or delays of the gas. The concomitant local energy change in the gas flow takes place adiabatically, as a consequence of which the temperature decreases in areas in which the gas is accelerated. This is the case in particular in the center of the gas flow, so that a temperature gradient forms that drops from the edge of the conveying pipe to its center. The latter is responsible for a thermal diffusion (thermophoresis) of the large, organic molecules to the center. Another cause for the segregation toward the center can lie in the shear stress gradient of the flow, which decreases from the edge toward the middle of the conveying pipe.
Examinations, in particular model calculations, have shown that the observed segregation can be avoided if the flow rate does not exceed an upper value and/or a quotient of the diameter of the conveying pipe and the average speed of the flow therein lies above a lower limit. If possible, the Mach number of the average flow rate should be less than 0.1. In particular, the average flow rate should thus be less than 40 m/s, 30 m/s, 20 m/s or 10 m/s. The value of a function with the arguments gas flow through the conveying pipe, pressure in the conveying pipe, temperature of the conveying pipe and diameter of the conveying pipe should lie below a limit that depends on a maximum permissible inhomogeneity of the deposited layer. For example, the maximum inhomogeneity of the layer (also the quotient of the maximum deviation from an average value and the average value of the layer thickness) should be no greater than 0.5 percent or no greater than 1 percent. Proposed in particular to achieve this are means with which the pressure within the conveying pipe is increased, for example to pressures within a range of 0.5 mbar or 1 mbar. The pressure barrier used to achieve this is preferably arranged at the end of the conveying pipe, and is located in particular within the gas distribution volume. The pressure barrier can have a plate with gas passage openings formed into a ring, which envelops a volume into which the gas mixture transported through the conveying pipe is supplied. The gas mixture passes through the gas passage openings into the gas distribution chamber. The pressure barrier can have an annular body provided with gas passage openings, which envelops a volume sealed by a floor, wherein the floor preferably has no gas passage openings, and lies opposite the mouth of the conveying pipe. Due to the pressure barrier, the pressure in the gas distribution chamber can measure less than one half, one fourth or one eighth of the pressure in the conveying pipe, but preferably no less than 1/10 or 1/20 of the pressure in the conveying pipe, which can preferably be greater than 1 mbar or 0.5 mbar. However, in order to adjust the flow rate or the aforementioned quotient, it is also possible to lay out the diameter of the conveying pipe accordingly. Diffusion influencing means can further be provided, which reduce, inhibit, or prevent the diffusion of large molecules directed transverse to the flow. The diffusion influencing means can be physical barriers, which divide the flow through the conveying pipe into several parallel partial flows, for example coaxial flows. The diffusion influencing means can be nested tubes, and/or extend over the entire length of the conveying pipe. The gas mixing device has at least one inlet, into which a mixture of an organic vapor in a carrier gas is supplied. The gas mixing device has a plurality of gas diversion elements, which repeatedly divert the gas flow, so that as perfect a mixture as possible forms at the outlet of the gas mixing device. In particular, it is provided that the gas mixing device has two or more inlets, through which mixtures of organic molecules that differ from each other are supplied. The differing organic molecules can be brought into vapor form by evaporating a solid or a liquid. To this end, a respective aerosol generator is preferably used, which generates an aerosol that is transported to an evaporator with a carrier gas supplied to the aerosol generator with a supply line, where the aerosol particles come into contact with heat transfer surfaces and evaporate. The differing vapors are mixed in the gas mixing device.
Examinations, in particular model calculations, have yielded the following correlation for ALQ3 between inhomogeneity and average speed in the conveying pipe:
The following functional correlation arises for the average value for the speed of the gas flow in the conveying pipe:
This yields the following inequality:
The invention will be explained below based upon exemplary embodiments. Shown on:
The gas mixing device 1 has a mixing chamber, which is kept by a heating device 26 at a temperature lying above the condensation temperature of the organic molecules. An at least once-diverted path extends within the mixing chamber, and carries the flow of mixture inhomogeneously supplied to the inlets 2, 2′. The flow of this mixture is repeatedly diverted by means of gas diversion elements 7, and diverted in such a way as to achieve as homogeneous a distribution of organic molecules as possible in the carrier gas in the area of the outlet 8.
As shown schematically on
The outlet 8 of the gas mixing device 1 empties into a conveying pipe 9, which can be designed as a tube with a circular cross section. The conveying pipe 9 can have a cross sectional surface of 10-20 cm2. The conveying pipe 9 is heated by a heating device 27 to a temperature, which can be the same temperature to which the gas mixing device 1 is also heated. However, the two temperatures can also differ from each other. Within the conveying pipe 9, the gas mixture has a pressure P3. In the exemplary embodiment, the conveying pipe 9 is located in the same housing 17 in which a gas inlet element 10 is also located.
The conveying pipe 9 empties into a gas distribution volume 11 of the gas inlet element 10. To this end, the gas inlet element 10 has a gas inlet opening 14, through which the gas mixture transported through the conveying pipe 9 can enter into the gas distribution volume 11. A floor of the gas distribution volume 11 forms a gas outlet plate 13 with a gas outlet face 13′. Gas outlet openings 12 are located in the gas outlet plate 13. The gas outlet openings 12 are evenly distributed across the gas outlet face 13′. The gas outlet openings 12 are directed toward a substrate 16, which is carried by a substrate holder 15 that is cooled by means of a coolant flowing through the coolant channels 18, such that the organic molecules can condense on the substrate 16. A heating device 19 is provided, with which in particular the gas outlet plate 13 or the walls of the gas inlet element 10 are heated to a temperature lying above the condensation temperature of the organic molecules.
In order to avoid this irregularity, one aspect of the invention provides that the flow rate within the conveying pipe 9 be less than 40 m/s, less than 30 m/s, less than 20 m/s or less than 10 m/s.
v
m=0,00261×v1.572em
The nonuniformity of the layer thickness (δg/gm) can be kept in a permissible range through a selection of process parameters if the process parameters Q: gas flow through the conveying pipe (sccm under standard pressure P0 and at standard temperature T0), T: temperature of the gas in the conveying pipe, P: pressure of the gas in the conveying pipe and d: diameter of the conveying pipe are selected in such a way that the following inequality applies:
wherein a measures 49.62 for ALQ3, but can be larger or smaller for other molecules, and wherein c measures 1.5·107·π.
The invention further provides that the reduction in flow rate be achieved by a pressure barrier 20. The pressure barrier 20 shown on
The exemplary embodiment depicted on
The diffusion influencing means 25 can extend over the entire length of the conveying pipe 9, the diameter of which in particular is less than an average diameter of a flow path within the gas mixing device 1 and/or is less than a cross sectional surface of the gas distribution volume 11.
In particular, it is provided and/or tolerable that the gas flow being discharged from the gas mixing device 1 be accelerated while entering into the conveying pipe 9 in such a way that the gas temperature in the center of the gas flow decreases. According to the invention, however, the temperature difference of the gas flow at the edge of the conveying pipe 9 is so low that inhomogeneous layer growth is avoided, or confined to a tolerable minimum.
While the measures described above do not enable a 100% reduction in the temperature gradient or a gradient of shear forces in the flow, the gradient can be limited to a magnitude at which its technological relevance is eliminated, i.e., layers are deposited whose irregularity lies below a predefined limit, so that the result is technologically acceptable.
The above statements serve to explain the inventions covered by the application as a whole, which each also independently advance the prior art at least by the following feature combinations, wherein two, several or all of these feature combinations can also be combined, specifically:
A method, characterized in that the average flow rate vm in the conveying pipe 9 is selected in such a way, the conveying pipe 9 has diffusion influencing means 25 that are designed in such a way, or a pressure barrier 20 at the end of the conveying pipe 9 facing the gas inlet element 10 is provided in such a way as to at least inhibit, preferably prevent, a segregating diffusion of organic molecules, which is directed in the center of the cross section of the conveying pipe 9 and causes a lateral, inhomogeneous layer growth.
An apparatus, characterized in that the conveying pipe 9 has a cross sectional surface, diffusion influencing means 25, or that a pressure barrier 20 is provided at its end facing the gas inlet element 1, so as to at least inhibit, preferably prevent, a segregating diffusion of the organic molecules, which is directed toward the center of the cross section of the conveying pipe 9 and causes a lateral, inhomogeneous layer growth.
A method or an apparatus, characterized in that the pressure barrier 20 is an in particular annular throttle within the gas distribution volume 11 and/or is a plate provided with gas passage openings 22 and extending in particular on a cylindrical shell surface and/or has an open-pored foam body 24.
A method or an apparatus, characterized in that the diffusion influencing means 25 have a barrier that acts at least in the radial direction, and extends in the axial direction of the conveying pipe 9.
A method or an apparatus, characterized in that the total pressure P3 in the conveying pipe 9, the mass flow of the mixture through the conveying pipe 9 and the diameter D of the conveying pipe 9 are selected in such a way that the average flow rate vm is less than 40 m/s, 30 m/s, 20 m/s or preferably less than 10 m/s and/or that the total pressure
P0 in the gas distribution volume 11 is preferably less than 0.9 mbar, 0.6 mbar, 0.3 mbar or 0.1 mbar.
A method or an apparatus, characterized by the following parameters:
wherein a is a molecule-dependent value that measures 49.62 M/s for ALQ3,
A method or an apparatus, characterized by at least two evaporation apparatuses 6 for respectively evaporating aerosol particles that consist of the organic molecules and were brought into the carrier gas flow, wherein it is provided in particular that the aerosol particles of the organic molecules differing from each other are evaporated at differing temperatures and/or at differing total pressures and/or are supplied to the gas mixing device in inlets 2, 2′ differing from each other.
A method or an apparatus, characterized by a first temperature control unit 26, with which the gas mixing device is heated to a first temperature, and by a second temperature control unit 27, with which the conveying pipe is heated to a second temperature.
All disclosed features (whether taken separately or in combination with each other) are essential to the invention. The disclosure of the application hereby also incorporates the disclosure content of the accompanying/attached priority documents (copy of the prior application) in its entirety, also for the purpose of including features of these documents in claims of the present application. Even without the features of a referenced claim, the subclaims characterize standalone inventive further developments of prior art with their features, in particular so as to submit partial applications based upon these claims. The invention indicated in each claim can additionally have one or several of the features indicated in the above description, in particular those provided with reference numbers and/or indicated on the reference list. The invention also relates to design forms in which individual features specified in the above description are not realized, in particular if they are recognizably superfluous with regard to the respective intended use, or can be replaced by other technically equivalent means.
Number | Date | Country | Kind |
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10 2019 129 176.3 | Oct 2019 | DE | national |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2020/080278 | 10/28/2020 | WO |