JP2015007263A - Organic device manufacturing device and organic device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize both of low damage and high-speed film deposition on an organic layer when a thick upper electrode is deposited on a large-area substrate on which the organic layer is formed.SOLUTION: An organic device manufacturing device comprises a vapor deposition device capable of depositing a metal evaporation film on an organic layer, and a sputtering device capable of depositing a film on the metal evaporation film. The sputtering device comprises plural cathodes having balance-type magnetrons. The plural cathodes are arranged at identical intervals in parallel to a substrate face. Preferably, plural magnetic fields formed in the sputtering device are coupled in a direction almost symmetrical to an axis vertical to a center of a substrate and in which the cathodes are communicated with each other.

Description

  The present invention relates to a sputtering apparatus, and is applicable to, for example, an organic device manufacturing apparatus and an organic device manufacturing method.

  In recent years, organic devices have attracted attention as a new industrial field. For example, organic EL (electroluminescence) has been developed as a display device or lighting device, an organic transistor as a driving element such as organic EL, electronic paper, or RFID, and an organic thin-film solar cell as a solar cell. In particular, organic EL is required to increase the size of the manufacturing substrate with the increase in size of display devices and lighting devices, and the manufacturing substrate size is from the current 4.5th generation manufacturing line (glass substrate dimensions: 730 mm × 920 mm). , The substrate size is expanded to 5.5th to 6th generation (glass substrate size is 1300mm × 1500mm-1500mm × 1800mm), which is more than 2.9 times, and further, the 8th generation line (glass substrate size: 2200mm × 2500mm) ).

  Increasing the size of display devices and lighting devices has created new demands for lowering the resistance of the upper electrode of organic EL. In particular, when manufacturing large televisions and large-area lighting, the upper electrode, which is a common electrode, needs to have a sheet resistance as low as 1Ω / □ or less in order to suppress a decrease in luminance due to a voltage drop at the center of the light emitting surface. is there. Therefore, in the bottom emission method, a magnesium-silver alloy (Mg-Ag), a laminated film of Mg-Ag and silver (Ag), or a metal electrode such as aluminum (Al) is used. In the top emission method, an indium-tin oxide (ITO) is used. ) And indium-zinc oxide (IZO) and other conductive oxide transparent electrodes are required to be formed to a thickness of several hundred nm or more.

  The metal electrode for bottom emission has been conventionally formed by rotary evaporation using a resistance heating evaporation source using a crucible, an induction heating evaporation source, or an electron beam (EB) evaporation source, but the manufacturing substrate size was small. A sufficient distance between the evaporation source and the substrate, and the position of the evaporation source is offset from the center of the substrate to the substrate edge side, and the gentle part of the evaporation film thickness distribution is used for film formation, and the substrate is rotated. Film thickness uniformity has been secured by utilizing the averaging effect. In addition, a sufficient distance between the evaporation source and the substrate suppresses the substrate temperature rise due to heat radiation from the evaporation source, prevents thermal damage to the organic device, and ensures patterning accuracy by suppressing the thermal expansion of the metal mask. I came. However, when the production substrate size is increased, it is necessary to further increase the distance between the evaporation source and the substrate in order to ensure film thickness uniformity by rotary evaporation, and the material utilization efficiency becomes too poor. It also becomes difficult to rotate a large substrate. These problems of film thickness distribution, material utilization efficiency, and substrate rotation can be solved by linearly arranging a linear evaporation source or a plurality of evaporation sources in a linear form and scanning the vapor deposition section or the substrate close to the substrate. However, Ag and Al require a high temperature of 1000 ° C. or higher for vapor deposition. Especially when a thick upper electrode of several hundred nm is formed as in the case of bottom emission, the vapor deposition time becomes longer and the heat from the evaporation source is increased. Thermal damage to the organic layer due to radiation and a decrease in patterning accuracy due to thermal expansion of the metal mask are still problematic.

  Also, in electron beam (EB) vapor deposition, which has a relatively high deposition rate compared to resistance heating vapor deposition, the threshold voltage is applied to the thin film transistor (TFT) element on the backplane by soft X-rays generated by accelerated electron beam impact. It has been pointed out that a shift occurs. Thus, it is very difficult to form thick Mg—Ag, Ag, and Al electrodes on a large substrate by vapor deposition.

  Therefore, it is desired to form a thick Mg—Ag electrode, Ag electrode, Al electrode or the like for bottom emission by sputtering. On the other hand, ITO and IZO, which are expected to be applied for top emission, are generally difficult to form by vapor deposition, and it is also desirable to form films by sputtering. However, it is generally known that the sputtering method causes a large plasma damage to the organic layer. For this reason, various types of sputtering apparatuses that suppress damage to the organic layer have been proposed.

  For example, Patent Document 1 uses a pair of opposed targets and magnetic field generating means, and an opposed target sputtering apparatus that arranges a substrate at a position facing a space between the targets. Patent Document 2 proposes an apparatus in which a grit electrode having a ground potential or a positive potential or an aperture having an opening smaller than the target is provided between the target and the substrate. By using these methods, it has been proposed to reduce the influence of high-energy ions and particles and secondary electron beams generated by the sputtering method.

  In Patent Document 3, a substrate is passed through a side of an opposed target type sputtering unit composed of a first target and a second target, and after a film is formed with little damage, the substrate is directly opposed to a parallel plate type sputtering unit composed of a third target. It has been proposed to deposit thin films at high deposition rates by passing the position. In Patent Document 4, a movable grid electrode is provided between a target and a substrate, a thin film is formed for a certain time in a state where the grid electrode is between the target and the substrate, and then a grid is formed between the target and the substrate. It has been proposed to achieve both low damage and high-speed film formation by further forming a thin film with no electrode interposed.

  In Patent Document 5, it is proposed that a protective electrode layer is formed on a light-emitting portion by a vacuum deposition method, and then a main electrode layer is formed on the protective electrode layer by an inductively coupled magnetron sputtering method.

  On the other hand, in sputtering equipment for large substrates such as for liquid crystals, multiple targets are arranged facing the substrate surface, high-speed film formation by batch film formation, film thickness uniformity, discharge stability, and electrode film quality. A single wafer type sputtering apparatus that can be improved is generally used (Patent Documents 6 and 7).

JP-A-10-255987 Japanese Patent Laid-Open No. 10-158821 JP 2007-39712 A JP 2007-46124 A JP 11-162652 A JP 2005-290550 A JP 2009-191363 A

  The methods of Patent Document 1 and Patent Document 2 have a problem that the film formation rate is inferior to that of a normal sputtering method.

  In the case of forming a film only by sputtering of Patent Document 3 and Patent Document 4, it is difficult to completely prevent plasma damage, and the use of a grid electrode as in Patent Document 4 is a foreign matter accompanying film adhesion to and peeling from the grit. Occurrence is unavoidable and is not suitable for manufacturing a device sensitive to foreign matter such as organic EL.

The inductively coupled magnetron sputtering method of Patent Document 5 uses a high-frequency induced current using a coil, and is not suitable for increasing the size of the apparatus or ensuring film thickness uniformity on a large substrate. Therefore, the film formation rate is slower than direct current (DC) discharge, and even in the example of Patent Document 5, the film formation rate remains at 0.1 to 0.2 nm / second. For this reason, the film formation of several hundreds of nanometers requires several thousand seconds and is not suitable for mass production. In general, inductively coupled plasma is high-density plasma, and the electron density in the plasma is as high as about 10 ¹⁷ / m ^3, and there is a concern about damage due to charge-up of the element.

  The sputtering devices of Patent Document 6 and Patent Document 7 are not devised to reduce damage so that they can be applied to the manufacture of organic devices such as organic EL elements.

  An object of the present invention is to provide a sputtering apparatus capable of forming a metal or conductive oxide electrode on a substrate on which a large-area organic device is formed at a high speed with low damage. It is another object of the present invention to provide an organic device manufacturing apparatus and an organic device manufacturing method capable of making an element damage-free using a sputtering apparatus and a metal vapor deposition apparatus.

The outline of typical ones of the present invention will be briefly described as follows.
That is, an organic device manufacturing apparatus includes a vapor deposition apparatus capable of forming a metal vapor deposition film on an organic layer and a sputtering apparatus capable of forming a film on the metal vapor deposition film, and the sputtering apparatus includes a plurality of cathodes having a balanced magnetron. The plurality of cathodes are arranged at equal intervals in parallel with the substrate surface.

  According to the above organic device apparatus, it is possible to perform film formation at a high speed with low damage and a large area on a device using a material that is easily damaged by plasma, such as an organic layer.

  Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.

It is a figure which shows the result of having simulated the penetration | invasion length of the ion which generate | occur | produces by sputtering, and recoil particle | grains to Al film | membrane. It is a figure which shows the result of having measured the resistivity of the metal vapor deposition film. It is a figure which shows the structure of the evaluation element of sputtering damage. It is a figure which shows the result of having measured the threshold voltage of the current-voltage characteristic of an evaluation element, and the film thickness dependence with respect to the buffer layer of a diode current. It is a figure which shows the result of having measured the threshold voltage of the current-voltage characteristic of an element, and the target-substrate distance dependence of a diode current. It is a figure which shows the result of having measured the target-substrate distance dependence of the plasma density of a board | substrate position. It is a figure which shows the result of having calculated the magnetic force line distribution between the target and substrate which have an unbalanced magnetic field. It is the structure schematic of the rotary magnetron cathode which concerns on embodiment. It is the structure schematic of the planar magnetron cathode which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a figure which shows the result of having calculated the magnetic force line distribution between the target and board | substrate which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a structural schematic diagram which shows the relationship between the cathode and the board | substrate in the sputtering device which concerns on embodiment. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering apparatus which concerns on Example 1, and a board | substrate. It is a figure which shows the change of the film thickness distribution with respect to the distance (TS distance) between the target of the sputtering apparatus which concerns on Example 1, and a board | substrate. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering device which concerns on the modification 1, and a board | substrate. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering device which concerns on the modification 2, and a board | substrate. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering device which concerns on the modification 3, and a board | substrate. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering device which concerns on the modification 4, and a board | substrate. It is a figure which shows the result of having calculated the magnetic force line distribution between the target of the sputtering device which concerns on the modification 5, and a board | substrate. FIG. 4 is a structural schematic diagram of a cluster-type electrode film forming apparatus according to Example 2. 6 is a schematic structural diagram of a metal vapor deposition chamber according to Embodiment 2. FIG. FIG. 5 is a structural schematic diagram of a sputtering chamber according to Example 2. FIG. 5 is a schematic structural diagram of an inline-type electrode film forming apparatus according to Example 3. 6 is a schematic structural diagram of an organic EL manufacturing apparatus according to Example 4. FIG. It is structure sectional drawing of an organic EL element. It is the figure which showed the voltage-current-luminance characteristic of the organic EL element.

  Hereinafter, embodiments, examples, and modifications will be described with reference to the drawings and the like. The following description shows specific examples of the contents of the present invention, and the present invention is not limited to these descriptions. Various modifications by those skilled in the art are within the scope of the technical idea disclosed in this specification. Changes and modifications are possible. Moreover, in all drawings for explaining the present embodiment, examples, and modified examples, the same reference numerals are given to components having the same function, and repeated description thereof may be omitted.

First, a technique studied prior to the present invention will be described. We have studied various methods for forming a thick metal or conductive oxide upper electrode with a film thickness of several hundreds of nanometers on organic devices, especially organic EL organic layers, and organic layers during electrode formation by sputtering. We have analyzed the damage factors. As a result, it was clarified that the following damage factors are related.
(A) Damage occurs due to implantation of ions and recoil particles generated during sputtering. In order to prevent this damage, it is necessary to provide a continuous metal deposition film on the organic layer that is longer than the intrusion length of ions and recoil particles and completely covers the organic layer.
(B) Damage to the organic layer occurs due to charge-up caused by the inflow of charged particles generated by plasma. This damage cannot be prevented only by providing the metal vapor deposition film. In order to prevent this damage, it is necessary to reduce the plasma density at the position of the substrate generated by sputtering and suppress the inflow of charged particles to the substrate.
(C) The organic layer is damaged by the stress of the sputtering film. This damage cannot be prevented only by providing the metal vapor deposition film. In order to prevent this damage, as in (b), the plasma density at the substrate position generated by sputtering is lowered, the charged particle inflow to the substrate is suppressed, and the film formation at low temperature and the ion assist effect are reduced. It is necessary to reduce the stress.

  First, a detailed description will be given of a result of a damage factor analysis performed when forming an electrode of an organic EL element by a sputtering method.

(1) Implanting high-energy ions and recoil particles into the organic layer As the first cause of damage caused by sputtering film formation, high-energy ions and recoil particles generated in the plasma are implanted into the organic layer. There is. Therefore, it is effective to form a buffer layer of a metal vapor deposition film that can prevent implantation of ions, recoil particles, and the like on the organic layer. Here, an example of the result of trial calculation of the film density and film thickness of the buffer layer necessary for preventing implantation will be shown. FIG. 1 is a diagram showing the results of simulating the penetration depth of ions of sputtering material generated by sputtering, argon (Ar) ions of a discharge gas, and recoil particles into a buffer layer (here, an Al film). . The thickness of the buffer layer is 20 nm. In addition, between the organic layer and the buffer layer, there is 0.5 nm-thick lithium fluoride (LiF) that serves as an electron injection layer. It is known that the kinetic energy of particles generated by sputtering and flowing into the substrate is 100 eV or less (generally about 15 to 50 eV) because most of the energy is dissipated by collision with the discharge gas. Then, assuming the worst case, the penetration depth into the buffer layer (metal vapor deposition film) of Al or Ar having a kinetic energy of 500 eV which is the maximum energy that can be generated by the discharge voltage of sputtering (about 500 V) is considered. As a precaution, the higher 1000 eV case is also performed. Fig. 1 (a) shows the calculation assuming that the bulk density of Al is 2.7g / cm ³ as the buffer layer. In the case of 500eV, the penetration length of these particles (Al and Ar) is at most about 5nm. I understand. Fig. 1 (b) shows a case where the deposited film density is lower than the bulk density and is compared with 2.0 g / cm ³ (film density 74%). Is at most 7 to 10 nm. This simulation shows an example in which Al is used as a buffer layer material. The bulk density of Ag is 10.49 g / cm ³ , and the bulk density of Mg—Ag (composition ratio 10: 1) is 2.39 g / cm ² . Since it is cm ³ and 2.0 g / cm ³ or more, the penetration depth is 7 to 10 nm at most even with other metal materials. Theoretically, if a buffer layer of a metal vapor deposition film of 7 to 10 nm is provided, the penetration depth is high. It was found that energy ions and recoil particles can be prevented from being injected into the organic layer. In this analysis, Al, Ag, and Mg-Ag, which are representative electrode materials used in the organic EL, have been described. However, even if the metal density is 2.0 g / cm ³ or more even with a metal other than the above, it is effective. Are the same.

  However, the simulation assumes a metal vapor deposition film buffer layer with a uniform film thickness and density, whereas the actual vapor deposition film grows in an island shape in a thin region of about 5 to 7 nm, and the organic layer In reality, a film thickness larger than that is necessary.

  FIG. 2 is a diagram showing the results of measuring the resistivity of the metal deposited film. With respect to the resistivity of the metal vapor deposition film shown in FIG. 2, it can be seen that the Al, Ag, and Mg—Ag (10: 1) films all have a resistivity that rapidly increases below 10 nm and are not continuous films. Therefore, if the metal vapor deposition film is a continuous film and has an average film thickness of 20 nm or more with a film thickness of 7 to 10 nm or more even in a thin place, high energy ions and recoil particles are implanted into the organic layer by subsequent sputtering film formation. It is considered to function as a buffer layer that can prevent the above.

  Next, a result of actually forming a buffer layer of a metal vapor deposition film on an organic layer and forming a sputtering film thereon and evaluating damage is shown.

  FIG. 3 is a diagram showing the structure of an element for evaluating sputtering damage. As shown in FIG. 3, the evaluation element 11 is an Al lower electrode 1 formed by vapor deposition with a film thickness of 70 nm on a substrate 10 such as glass, an Al film formed by a laminated film of a metal vapor deposition buffer layer 2 and a sputtering film 3. A capacitor diode structure in which an organic layer 6 was formed between the upper electrode 4 and the electron injection layer 5 was used. The electron injection layer 5 is formed of a lithium fluoride (LiF) layer having a thickness of 0.5 nm. The organic layer 6 is formed of Alq3 (tris (8-quinolinolato) aluminum) having a thickness of 150 nm. Alq3 is a typical material used as an electron transport layer and a light emitting layer of organic EL. When the evaluation element 11 is sputtered during the formation of the sputtering film 3, the organic layer 6 at the interface with the electron injection layer 5 on the upper electrode 4 side is altered, and the current injection characteristics from the upper electrode 4 deteriorate. When the voltage is applied, the threshold voltage of the current-voltage characteristics (diode characteristics) is increased, the diode current is decreased, and further, the organic layer 6 is dielectrically broken to generate a leak current. Therefore, the damage can be evaluated by comparing and measuring the current-voltage characteristics of the evaluation element 11 with an element in which the upper electrode 4 is formed only by vapor deposition.

FIG. 4 shows the film thickness dependence of the threshold voltage of the current-voltage characteristics of the evaluation element and the diode current on the deposition of the buffer layer 2. The threshold voltage was defined as the voltage at which the diode current density was 10 ⁻⁵ A / cm ² as the rise of the diode current, and the diode current density was defined as the current density flowing when the applied voltage was 10V. Moreover, the case where the upper electrode 4 is formed only by vapor deposition is also plotted as a reference. As a result, the threshold voltage is the highest when the buffer layer 2 of the Al vapor deposition film is not present (0 nm) and the diode current is the lowest. On the other hand, as the buffer layer 2 becomes thicker, the threshold voltage decreases and the diode current decreases. Was found to increase. As described above, this is an effect that high energy ions and recoil particles generated in the plasma are prevented from being implanted into the organic layer 6. However, when the average film thickness is 20 nm or more, the change is saturated, and even if the film thickness is increased further, it does not improve any further. The threshold voltage of the element in which the upper electrode 4 is formed only by vapor deposition and the performance of the diode current I knew it would not reach. Accordingly, high-energy ions and recoil particles can be prevented from being implanted into the organic layer 6 if the average film thickness of the buffer layer 2 is 20 nm or more. It has become clear that there are other factors than the injection of jumping particles into the organic layer 6.

  Under these conditions, damage due to peeling of the upper electrode 4 was also observed when the thickness of the sputtering film 3 was further increased to 300 nm or more. This is because the internal stress of the sputtering film 3 is higher than that of the deposited film, and as the film thickness increases, the influence of the compressive force becomes significant.

(2) Charge-up Thus, the damage factor which cannot be prevented only by forming the buffer layer 2 of a metal vapor deposition film was considered and analyzed. As a cause of element damage due to sputtering, charge-up (charging) damage reported for semiconductor elements and the like can be considered. That is, this is a model in which charged particles such as electrons generated by discharge flow into the upper electrode 4 of the element, and the element deteriorates due to electrical charge-up. In an organic device such as an organic EL, since the organic layer 6 is generally highly insulating and becomes a capacitor-type element, a high voltage is induced by charging up the upper electrode 4, and charges such as electrons are injected into the organic layer 6. Or the organic layer 6 may break down. That is, the electron injection characteristic is lowered by trap formation by electron injection, causing the above-mentioned threshold voltage to rise and the diode current density to be lowered, and further, due to the partial breakdown of the organic layer 6 due to the high voltage, the leakage current is reduced. It is thought that the outbreak will occur.

  Also, the inflow of electrons with kinetic energy causes an increase in the substrate temperature, and the ion sheath formation by negative charging also promotes the incidence of ions, so the generation of thermal stress when the substrate returns to room temperature after film formation and the ion assist effect It is likely to cause an increase in film stress due to the densification of the film due to the above.

Therefore, the plasma density of the sputtering apparatus used in the above experiment was measured by the Langmuir probe method. The sputtering apparatus used in the experiment is a magnetron sputtering apparatus having an unbalanced magnetron using a circular cathode having a diameter of 100 mm and a target. The unbalanced type is a method in which there is a large difference in the magnetic force of magnets having a pair of polarities, for example, a magnetron method in which the magnetic force of the surrounding ring magnet is stronger than the central magnet. In the case of high-speed film formation conditions (discharge power 25 W / cm ² , discharge gas pressure 0.4 Pa, target-substrate distance 132.5 mm) at a film formation rate of 5 nm / second, the electron density and ion density at the substrate position are 4 respectively. It was 2 × 10 ¹⁶ pieces / m ³ and 5.6 × 10 ¹⁶ pieces / m ³ . Therefore, to prevent sputtering damage, it is considered necessary to lower the electron density and ion density at the substrate position below these values.

Based on the above results, a method for preventing damage caused by charge-up of the organic device was next examined. First, the plasma density (electron and ion density) necessary to prevent damage was determined. In order to lower the plasma density at the substrate position, it is a simple method to increase the distance between the target and the substrate. FIG. 5 shows the threshold voltage of the current-voltage characteristic of the evaluation element in which the Al sputtering film 3 is formed to 300 nm on the element in which the buffer layer 2 of the Al deposited film having an average film thickness of 20 nm is formed, and the dependence of the diode current on the target-substrate distance. FIG. 6 shows the target-substrate distance dependence of the plasma density at the substrate position. The film forming conditions are a discharge power of 25 W / cm ² and a discharge gas pressure of 0.4 Pa as described above. The threshold voltage and the diode current were the same as those formed only by the deposited film with a target-substrate distance of 250 mm or more. The plasma density at that time was an electron density of 1 × 10 ¹⁶ ions / m ³ and an ion density of 0.6 × 10 ¹⁶ ions / m ³ , respectively. However, the deposition rate decreased with the target-substrate distance, and decreased to 1/5 of 1 nm / second at 250 mm. This is due to the scattering of sputtered particles by the discharge gas and the target-substrate distance being too long compared to the target size (diameter 100 mm). In this case, it takes 5 minutes or more to form the upper electrode having a thickness of 300 nm or more, which is not suitable for mass production. In addition, the circular target can be put to practical use up to a diameter of about 200 mm due to the limitation of the distance between magnets, and even if a plurality of circular targets are arranged side by side, the film thickness distribution increases, making it suitable for film formation on large substrates. Not.

  Further, in the unbalanced magnetron sputtering apparatus, the circular cathode becomes an unbalanced magnetron because the number of outer ring magnets is larger than the number of central magnets, and the outer magnetic force becomes stronger. .

  FIG. 7 is a diagram showing a result of calculating a magnetic field line distribution between a target and a substrate of an unbalanced magnetron sputtering apparatus. Since the circular cathode 21 and the target 20 are used, calculation is performed using cylindrical coordinates centered on an axis perpendicular to the target 20. FIG. 7 shows the distribution of magnetic lines of force on the right half of the target 20. From this, it can be seen that the lines of magnetic force extend from the periphery of the target 20 toward the substrate 10 with high density. Since electrons and ions in the plasma perform a cyclotron movement along the lines of magnetic force, in such a sputtering apparatus using the cathode 21 of an unbalanced magnetron, the plasma density at the substrate position tends to be high.

  Therefore, in the following embodiments, the plasma density at the substrate position can be reduced even under conditions where the target-substrate distance is closer and the deposition rate is faster, and sputtering damage is not caused, and a uniform film thickness can be obtained even on a large-area substrate. A sputtering apparatus capable of forming a film will be described.

  First, a method for reducing the plasma density at the substrate position will be examined. FIG. 8 is a schematic structural view of a rotary magnetron cathode according to the embodiment. FIG. 9 is a schematic structural diagram of a planar magnetron cathode according to an embodiment. In order to reduce the plasma density at the substrate position, it is preferable to use a cathode having a balanced magnetron in which the magnetic forces of the magnet array having a pair of polarities are aligned. Specifically, as shown in FIG. 8, the cathode 20 has an elongated cylindrical shape, an elongated balanced magnet array 24 is fixed in the cathode, and a rotary magnetron cathode in which the cathode 20 and a target (not shown) rotate is used. The sputtering apparatus used is preferable. In FIG. 8, “N” on the upper side and “S” on the lower side indicate “N pole” on the upper side and “S pole” on the lower side of the magnet. In addition, the description of “S” on the upper side and “N” on the lower side indicates “S pole” on the upper side of the magnet and “N pole” on the lower side. The same applies to FIGS. 9 to 11 and FIGS. 13 to 16. As shown in FIG. 9, sputtering is performed using a planar magnetron cathode in which the cathode 20 has an elongated substantially rectangular shape (rectangular shape or rectangular shape with four rounded corners), and an elongated balanced magnet array 24 is also fixed inside. An apparatus is preferred. Since these cathodes 20 can have the same magnetic force according to the type, number, and shape of the magnet array 24 to be paired, a balanced magnet arrangement can be easily realized. The magnetic force ratio of the magnet array 24 that forms a pair of balanced magnetrons is preferably as close to 1 as possible, but may be 1.5 or less.

  10 and 11 are schematic structural views showing the relationship between the cathode and the substrate in the sputtering apparatus according to the embodiment. The cathode 20 of the balanced magnetron shown in FIGS. 8 and 9 is disposed in parallel with the substrate 10 at equal intervals as shown in FIGS. 10 and 11, so that the plasma density at the substrate position can be increased even with the large substrate 10. A low sputtering apparatus can be realized. The plurality of cathodes 20 are arranged symmetrically with respect to an axis perpendicular to the center of the substrate 10 to be held. Here, “parallel” means to make them as parallel as possible, and to allow an error (hereinafter, the same applies to examples and the like). “Equally spaced” means to be as evenly spaced as possible and to allow an error (hereinafter, the same applies to the embodiments and the like). “Symmetrically arranged” means that they are arranged as symmetrically as possible and allow an error (the same applies to the following examples). FIG. 12 shows the magnetic field line distribution in the arrangement of FIG. Closed magnetic field lines are formed on the target 21, and the density of magnetic field lines extending in the direction of the substrate 10 is reduced, so that the plasma density near the substrate 10 can be reduced. Further, in the cathode 20 of FIGS. 8 and 9, the magnet array 24 in the cathode 20 is symmetric with respect to an axis perpendicular to the opposing substrate 10, so that it is substantially symmetric with respect to the axis perpendicular to the substrate 10. A magnetic field is formed, and a uniform film thickness distribution is easily obtained. Here, the “symmetrical structure” is a structure that is as symmetric as possible and allows an error (hereinafter, the same applies to the examples and the like).

  13 and 14 are schematic structural views showing the relationship between the cathode and the substrate in the sputtering apparatus according to the embodiment. As a more effective method for reducing the plasma density at the substrate position, as shown in FIGS. 13 and 14, the magnet array 24 is arranged so that the polarities of the magnetic poles of the elongated cathodes 20 are alternately arranged, and within the sputtering apparatus. A plurality of magnetic fields to be formed are coupled substantially symmetrically with respect to an axis perpendicular to the substrate 10 and in a direction in which the cathodes 20 are connected. Thereby, electrons and ions leaking from the magnetic field trap on the target 21 can be trapped even in the magnetic field between the cathodes 20.

  15 and 16 are schematic structural views showing the relationship between the cathode and the substrate in the sputtering apparatus according to the embodiment. Further, as shown in FIGS. 15 and 16, an auxiliary magnet array 25 is disposed between the elongated cathodes 20, and a plurality of magnetic fields formed in the sputtering apparatus are substantially symmetric with respect to an axis perpendicular to the substrate 10. In addition, the magnet array 24 and the auxiliary magnet array 25 in the cathode 20 are coupled in a continuous direction. Thereby, electrons and ions leaking from the magnetic field trap on the target 20 can be trapped even in the magnetic field between the magnet array 24 of the cathode 20 and the auxiliary magnet array.

  A more specific embodiment used in a sputtering apparatus in which these magnetic fields are combined to reduce the plasma density at the position of the substrate 10 will be described below.

  FIG. 17 is a diagram illustrating a cross-sectional view of the sputtering apparatus according to Example 1 and a result of calculating a line of magnetic force between the target and the substrate. In the sputtering apparatus of this embodiment, a plurality of cathodes 20 and targets 21, a magnet array 24 inside the cathodes, and the opposing substrate 10 and metal member 26 are arranged. In the present embodiment, an example of a sputter-up method in which the cathodes 20 are arranged at equal intervals in the horizontal direction and a film is formed on the substrate 10 from below is shown. The cathode 20 has an elongated cylindrical shape with a diameter of 75 mm and a length of 1800 mm. In the cathode 20, two magnet arrays 24 having different polarities and uniform magnetic forces are fixed, and the cathode 20 and the target 21 are rotated. An example is shown. This figure is shown in an orthogonal coordinate system, and the cross-sectional shape is maintained in a range longer than the depth of the substrate 10 in the direction perpendicular to the paper surface. In this embodiment, the distance between the centers of the cathodes 20 is 220 mm, and therefore the closest distance between the targets is 145 mm. The plurality of cathodes 20 can be formed at a uniform film thickness over the entire surface of the substrate 10 so that the width of the substrate 10 becomes narrower than the interval between the perpendiculars extending from the centers of the cathodes 20 at both ends to the substrate 10 side. Are arranged at equal intervals in parallel. The number of cathodes 20 used was eight so that the distance between the vertical lines extending from the centers of the cathodes 20 at both ends to the substrate 10 side from the long side or short side of the 5.5th to sixth generation substrates 10 was widened. Further, the two magnet arrays 24 in the cathode 20 have a symmetric structure with respect to an axis perpendicular to the opposing substrate 10, and a magnetic field symmetric with respect to an axis perpendicular to the substrate 10 on the cylindrical target 21. By forming traps, the film thickness uniformity is improved. The longer the distance between the target 21 and the substrate 10, the easier it is to ensure film thickness uniformity. However, if the distance is too long, the film formation rate tends to decrease due to scattering of the discharge gas.

  FIG. 18 is a diagram illustrating a change in the film thickness distribution with respect to the distance (TS distance) between the target and the substrate of the sputtering apparatus according to Example 1. FIG. 18 shows a change in the film thickness distribution with respect to the distance between the target 21 and the substrate 10 (TS distance) with reference to the interval between the adjacent targets 21 under the condition of the discharge gas pressure of 0.4 Pa. When the TS distance is closer than 145 mm between the targets 21, the film thickness distribution having a valley at the position of the center axis of the target 21 (the position of the center axis of the substrate 10 and the position of the substrate 0 in FIG. 18). However, if the TS distance is the same or long, a film thickness uniformity of ± 5% can be secured. Therefore, in this embodiment, 150 to 200 mm is appropriate as the TS distance. When the discharge gas pressure is increased above 0.4 Pa, the scattering of sputtered particles by the discharge gas increases and is more averaged, so that the film thickness uniformity is further improved.

  In the case of forming a metal or conductive oxide film, it is preferable to perform direct current (DC) discharge, which has the fastest film formation speed, in sputtering. In this embodiment, Al was used for high-speed film formation at 5 nm / second. Electrons in the plasma generated by the discharge are trapped by a cyclotron movement along the magnetic field lines of this magnetic field, and the ionization of the discharge gas is promoted to generate high-density ions and the sputtering of the target 21 on the cathode 20 is promoted. To do. In the rotary magnetron cathode, since the target 21 is rotating, the sputtering surface of the target 21 is continuously changed and uniformly cut, so that the occurrence of arcing is suppressed.

  In this embodiment, these magnet arrays 24 also couple the magnetic field with the magnet array 24 of the adjacent rotary magnetron cathode, and continuously couple the magnetic field in front of the substrate 10 in the direction in which the cathodes 20 are connected. As a result, electrons leaking from the magnetic field trap on the target 21 are also trapped in the magnetic field between the cathodes 20, further suppressing the inflow of electrons to the substrate 10.

  A chamber (not shown) mainly plays the role of the anode in this embodiment. However, when the cathode 20 is opposed to a large glass substrate or film substrate having high insulation, the anode is effectively used. There is a possibility that the anode disappears, which disappears and the discharge stops. However, since it is difficult to perform photolithography or etching on an organic material in an organic device, generally, a metal member 26 such as a metal mask or a metal frame is disposed for patterning an electrode. Therefore, in order to prevent the anode from disappearing and the discharge from becoming unstable, a metal member 26 such as a metal mask or a metal frame is connected to the anode potential of the chamber directly or via a resistor as shown in FIG. It is possible to stabilize the discharge.

<Modification 1>
FIG. 19 is a diagram showing the result of calculating the magnetic force line distribution between the target and the substrate of the sputtering apparatus according to the first modification. FIG. 19 shows a case where the number of the magnet arrays 24 in the cathode 20 is three (corresponding to FIG. 13). In order to make the film thickness distribution in the substrate 10 uniform, the three magnet arrays 24 in the cathode 20 have a symmetric structure with respect to an axis perpendicular to the opposing substrate 10, and the substrate is placed on the cylindrical target 21. Two magnetic field traps are formed that are generally symmetric about an axis perpendicular to 10. By increasing the number of magnet arrays 24, the area of the portion contributing to sputtering on the target 21 can be increased, and the film formation rate and the film thickness uniformity can be further improved. In addition, these magnet arrays 24 invert the polarity at the adjacent rotary magnetron cathode, thereby coupling the magnetic field with the magnet array 24 of the adjacent rotary magnetron cathode, and continuing the magnetic field in front of the substrate 10 in the direction in which the cathode 20 continues. Can be combined. As a result, the electrons leaking from the magnetic field trap on the target 21 are also trapped in the magnetic field between the cathodes 20, thereby suppressing the inflow of electrons into the substrate 10.

  The number of the magnetic pole arrays 24 in the cathode 20 can be four or more. As can be seen from FIGS. 17 and 19, when the number of the magnetic pole arrays 24 is an even number, the polarities of the magnetic pole arrays 24 in all the rotary magnetron cathodes are arranged in the same arrangement. A magnetic field can also be coupled to the magnet array 24 of adjacent rotary magnetron cathodes, and the magnetic field in front of the substrate 10 can be continuously coupled in the direction in which the cathodes 20 are connected.

<Modifications 2 and 3>
FIG. 20 is a diagram illustrating a result of calculating the magnetic force line distribution between the target and the substrate of the sputtering apparatus according to the second modification. FIG. 21 is a diagram illustrating a calculation result of a magnetic force line distribution between a target and a substrate of a sputtering apparatus according to Modification 3. Sputtering apparatuses according to FIG. 20 (Modification 2) and FIG. 21 (Modification 3) are outside the rows of the plurality of cathodes 20 of the sputtering apparatus according to FIG. 17 (Example 1) and FIG. 19 (Modification 1), respectively. Further, an elongated auxiliary magnet array 25 is arranged in the depth direction of the drawing with the polarity reversed with respect to the outer magnet of the adjacent cathode 20, and is magnetically coupled. This corrects the entire magnetic field, further suppresses the spread of the magnetic field, traps electrons leaked from the magnetic field trap on the target 21 even in the magnetic field between the cathode 20 and between the cathode 20 and the auxiliary magnet array 25, and thereby the substrate 10. It is possible to further suppress the inflow of electrons. The auxiliary magnet array 25 is usually connected to a chamber (not shown), and can function as an anode.

<Modifications 4 and 5>
FIG. 22 is a diagram showing the result of calculating the magnetic force line distribution between the target and the substrate of the sputtering apparatus according to Modification 4. FIG. 23 is a diagram showing the result of calculating the magnetic force line distribution between the target and the substrate of the sputtering apparatus according to Modification 5. The sputtering apparatus according to FIG. 22 (Modification 4) and FIG. 23 (Modification 5) are adjacent to the cathode rows of the sputtering apparatus according to FIG. 20 (Modification 2) and FIG. 21 (Modification 3), respectively. In this example, the magnet array 24 at both ends of the cathode 20 and the auxiliary magnet array 25 whose polarity is reversed are arranged so that the magnet array 24 of the cathode 20 and the auxiliary magnet array 25 are alternately magnetically coupled. . Electrons leaking from the magnetic field trap on the target 21 are also trapped in the magnetic field between the cathode 20 and the auxiliary magnet array 25, and the inflow of electrons to the substrate 10 can be further suppressed. Since these auxiliary magnet arrays 24 are usually connected to a chamber (not shown), they can function as anodes.

  In all of the first embodiment, the first modified example, the second modified example, the third modified example, the fourth modified example, and the fifth modified example, the rotary magnetron cathodes are arranged at equal intervals in the horizontal direction. Although an example of the sputter-up method in which film formation is performed is shown, the rotary magnetron cathode can be held in any direction. For example, film formation is performed by holding the substrate 10 in a vertical direction while holding it in the vertical direction. It is also possible to employ a side sputtering method.

  In the first embodiment, the first modified example, the second modified example, the third modified example, the fourth modified example, and the fifth modified example, the rotary magnetron cathode is illustrated as an example. Thus, the same effect can be obtained.

  Examples in which the sputtering apparatus according to Example 1, Modification 1, Modification 2, Modification 3, Modification 4 and Modification 5 are applied to a cluster type film forming apparatus will be described.

  FIG. 24 is a top view schematically showing the structure of the cluster electrode film forming apparatus according to the second embodiment. The cluster type electrode film forming apparatus 30 includes a vapor deposition apparatus and a sputtering apparatus. The cluster-type electrode film forming apparatus 30 is centered around a robot chamber 31 having a transfer robot 36, and has a substrate relay chamber 32-1, a metal vapor deposition chamber 33 (33-1, 33-2), and a sputtering chamber 34 (34). -1, 34-2), and the substrate relay chamber 32-2 and the gate valve 35 (35-1, 35-2, 35-3, 35-4, 35-5, 35-6) separating them. . The substrate relay chamber 32-1 is a relay chamber connected to a device in the previous process (a cluster type vapor deposition device (vapor deposition cluster) for depositing an organic layer). The substrate relay chamber 32-2 is a relay chamber connected to an apparatus in a later process (such as a sealing process). In this embodiment, the substrate relay chamber 32 has two chambers (32-1, 32-2), the metal deposition chamber 33 has two chambers (33-1, 33-2), and a sputtering chamber, centered on a hexagonal robot chamber 31. In the example, two chambers (34-1, 34-2) are provided. However, the robot chamber is further diversified, for example, in an octagonal shape, so that three metal deposition chambers 33 and three sputtering chambers 34 are provided. It may be increased as follows. A metal evaporation source 43 is disposed in the metal evaporation chamber 33, and a rotary magnetron cathode 44 is disposed in the sputtering chamber 34. Although the metal deposition chamber 33 and the sputtering chamber 34 depend on the shape of the cluster, usually two or more film formation chambers are provided, and continuous production can be achieved by performing film formation in the other film formation chambers while one chamber is in maintenance. It is preferable to do so.

  FIG. 25 is a schematic view of the metal vapor deposition chamber 33. In this embodiment, an example of a side deposition method in which a film is formed with the substrate 10 standing substantially vertically will be described. The metal vapor deposition chamber 33 includes a processing vacuum chamber 40, a gate valve 35 for maintaining a vacuum between the robot chamber (not shown), a substrate transfer unit 41, and a drive unit 42 for raising the substrate 10 substantially vertically. It comprises a metal member 26 for patterning, a metal evaporation source 43 arranged in the horizontal direction, and the like. As the metal evaporation source 43, a linear evaporation source made of a high melting point metal such as titanium or molybdenum, or a plurality of point evaporation sources (5 in this embodiment) using a ceramic crucible as shown in FIG. This is a scanning method in which a film is formed on the entire surface of the substrate 10 by being arranged in series longer than the horizontal side of the substrate and scanning in the height direction of the substrate 10. In some cases, the metal evaporation source 43 may be a combination of upper and lower stages so that co-evaporation or stacked vapor deposition can be performed.

  FIG. 26 is a schematic view of the sputtering chamber 34. In this embodiment, an example of a side sputtering method in which a film is formed with the substrate 10 standing substantially vertically will be described. The sputtering chamber 34 includes a processing vacuum chamber 40, a gate valve 35 for maintaining a vacuum with a robot chamber (not shown), a substrate transfer unit 41, a drive unit 42 for standing the substrate 10 substantially vertically, and patterning. And a plurality of (eight in the present embodiment) rotary magnetron cathodes 44 fixed to the chamber wall surface at regular intervals in the horizontal direction. In the rotary magnetron cathode 44, the magnetic poles in the cathode 20 are arranged as in the first embodiment, the first modification, the second modification, the third modification, the fourth modification, and the fifth modification. The cathode 20 is magnetically coupled in the direction in which the cathodes 20 are connected via the auxiliary magnet array 25, and the electrons in the plasma are trapped by the magnetic field, so that the inflow of electrons to the substrate 10 can be suppressed.

  In each of the present embodiments, an example of a method in which deposition or sputtering is performed from the side surface on the substrate 10 standing substantially vertically is shown. However, the deposition surface of the substrate 10 is transported while keeping the bottom surface, and deposition or sputtering is performed upward. May be performed.

  Next, a method for manufacturing an organic EL panel using the cluster electrode deposition apparatus 30 having the metal vapor deposition chamber 33 and the sputtering chamber 34 will be described below.

  First, the organic layer 6 is formed on the substrate 10 by a cluster type vapor deposition apparatus (vapor deposition cluster) for vapor-depositing an organic EL organic layer (not shown). The gate valve 35-1 of the substrate relay chamber 32-1 with the vapor deposition cluster shown in FIG. 24 is opened, the substrate 10 is loaded into the robot chamber 31, and then 35-1 is closed. Next, the gate valve 35-6 between the metal vapor deposition chamber 33-1 is opened, and the substrate 10 is carried into the substrate transfer section 41 by the upper surface conveyance by the conveyance robot 36 in the robot chamber 31. The transfer robot 36 has two comb-shaped hands in two upper and lower stages. For example, the upper part is used for carrying in and the lower part is used for carrying out, and the carrying-in / out process can be performed simultaneously by one operation. After loading the substrate 10, the gate valve 35-6 is closed.

  Next, the substrate 10 carried into the metal vapor deposition chamber 33-1 is erected substantially vertically by the drive unit 42 shown in FIG. 25, and then aligned with the metal member 26 for patterning. The metal member 26 for patterning is a grid-like metal frame of an organic EL panel unit, is a metal structure having a thickness of about 0.1 to several mm, and is used for patterning the upper electrode 4 of the organic EL. It is done. Subsequently, the metal evaporation source 43 is scanned in parallel with the surface of the substrate 10 to form the thin buffer layer 2 of the upper electrode 4 on the entire surface of the substrate 10. The metal material to be formed is Mg—Ag alloy, Ag, Al or the like. In the case of an Mg—Ag alloy, co-evaporation is performed using a linear evaporation source for Mg and a plurality of point evaporation sources for Ag. The ratio of Mg and Ag is preferably about 10: 1. When Al is used, a plurality of point evaporation sources using a plurality of ceramic crucibles or the like are used. Especially in the case of Al with a relatively high work function, and even when Mg—Ag with a low work function is used, LiF, Liq (lithium 8-quinolinolato), etc. are further deposited as an electron injection layer 5 using a linear evaporation source. In addition, when a buffer layer is laminated and deposited thereon, the characteristics are improved. In that case, in the metal vapor deposition chamber 33-1, the evaporation source for the electron injection layer 5 and the evaporation source for the buffer layer 2 are arranged one above the other to perform continuous film formation. Or although not demonstrated in a present Example, the metal vapor deposition chamber 33-1 may be used for the film-forming of LiF or Liq, and Mg-Ag alloy, Ag, and Al may be formed in another metal vapor deposition chamber 33-2 grade | etc.,. Film formation is performed by scanning the surface of the substrate 10 at least once, or by scanning up and down twice. For example, Mg-Ag alloy, Ag, and Al that serve as a buffer layer are formed twice by up and down reciprocation, and the electron injection layer LiF and Liq that are formed as thin as about 0.5 nm are formed only in the scanning forward path, On the return path, the shutter is closed and no film is formed.

  The deposited film thickness of the Mg—Ag alloy, Ag, and Al can be set to an average film thickness of 20 nm that can prevent ion implantation during the subsequent sputtering film formation and can be formed in about 1 minute by the metal evaporation source 44. . Thereby, the buffer layer 2 of the continuous metal vapor deposition film which is longer than the penetration depth of ions or recoil particles and completely covers the organic layer 6 can be provided on the organic layer 6.

  When the deposition is completed, the substrate 10 is separated from the patterning metal member 26 by the driving unit 42, and is tilted by the substrate transfer unit 41 and held horizontally. Next, the gate valve 35-6 between the robot chamber 31 and the robot chamber 31 is opened, and the substrate 10 is carried out to the robot chamber 31 by upper surface transfer by the transfer robot in the robot chamber 31.

  After unloading the substrate 10, the gate valve 35-6 to the metal vapor deposition chamber 33-1 is closed, and the gate valve 35-2 to the sputtering chamber 34-1 is opened instead. The substrate 10 is carried into the substrate transfer section 41 of the sputtering chamber 34-1 by the upper surface conveyance by the robot. After loading the substrate 10, the gate valve 35-2 is closed.

  Next, after the substrate 10 that has been loaded is set up substantially vertically by the drive unit 42, alignment with the metal member 26 for patterning is performed. The metal member 26 for patterning is connected to the processing vacuum chamber 40 directly or via a resistor, and also functions as an anode during sputtering. By making the metal member 26 for patterning a part of the anode, it is possible to avoid the possibility of the disappearance of the anode.

  During the alignment, Ar is introduced into the sputtering chamber as a discharge gas. The discharge gas pressure is set to a range of about 0.4 to 1 Pa where the discharge is stabilized. Subsequently, a negative DC voltage is applied to the rotary magnetron cathode 44 to start sputtering discharge. A sputtering film 3 of a metal such as Mg—Ag alloy, Ag, Al, or a conductive oxide such as ITO or IZO is formed. In the rotary magnetron cathode 44 of this embodiment, it is possible to form a plurality of cathodes 20 on the entire surface of the substrate 10 by arranging a plurality of cathodes 20 at equal intervals parallel to the surface of the substrate 10. It is possible to form a thick sputtering film 3 of 300 nm in 1 minute at a film formation rate of 5 nm / second. A plurality of magnetic fields formed in the sputtering apparatus 34 are coupled symmetrically with respect to an axis perpendicular to the center of the substrate and in a direction in which the cathodes 20 are connected, and trap the electrons in the plasma by the magnetic field, Suppresses inflow of electrons. Thereby, it is possible to prevent the charge-up damage of the organic EL element. Moreover, since it is difficult to form an ion sheath by suppressing electron inflow, ion inflow can also be suppressed, and the ion assist effect can be reduced, and the sputtering film 3 having a low film stress can be formed.

  In the above-described embodiment, the case where the metal vapor deposition chamber 33-2 and the sputtering 34-2 are not used is described. However, it is possible to double the tact by using the metal vapor deposition chamber 33-2 and the sputtering 34-2. -1 and sputtering 34-1 may be used for continuous production by film formation and maintenance alternately.

  Thus, by clustering the metal vapor deposition chamber 33 and the sputtering chamber 34, it is possible to form the thick upper electrode 4 having a film thickness of about 300 nm in a short time of about 1 minute.

  In the sputtering apparatus of the present embodiment, the rotary magnetron cathode is shown as an example, but a planar magnetron cathode having a substantially rectangular shape may be used.

  In the display device, alignment with a mask or the like is necessary, and the cluster type film forming apparatus 30 of the second embodiment is suitable. However, the illumination does not require fine patterning, and an inline type film forming apparatus is also suitable. Therefore, here, an embodiment in which the sputtering apparatus according to the first embodiment, the first modification, the second modification, the third modification, the fourth modification, and the fifth modification is applied to an in-line type film forming apparatus will be described.

  FIG. 27 is a side view schematically showing the structure of the inline-type electrode film forming apparatus according to the third embodiment. The inline-type electrode film forming apparatus 50 includes a vapor deposition apparatus and a sputtering apparatus. In the in-line type electrode film forming apparatus 50, the in-line metal deposition chamber 51 is connected to the in-line sputtering chamber 53 via the substrate relay chamber / gas replacement chamber 52, and gate valves 54 (54-1, 54-2) separating them. , 54-3, 54-4). The gate valve 54-1 is connected to an apparatus (organic layer deposition apparatus) in the previous process (not shown) or a substrate relay chamber that receives a substrate therefrom. The gate valve 54-4 is connected to a device for the next process (not shown) or a substrate relay chamber for delivering the substrate thereto.

  In the present embodiment, an example of a deposition-up method is shown in which the substrate 10 is held horizontally and passed over the metal evaporation source 43 at a constant speed. In the in-line metal vapor deposition chamber 51, the metal evaporation source 43 is a linear evaporation source made of a high melting point metal such as titanium or molybdenum, or a plurality of point evaporation sources using a ceramic crucible or the like in the direction in which the substrate 10 is conveyed. Arrange at right angles. The substrate 10 is a scanning method in which a film is formed on the entire surface of the substrate 10 by being transported horizontally on rails and pulleys 55 and scanned on the metal evaporation source 43 at a constant speed. In some cases, the metal evaporation source 43 may be combined in multiple stages in the traveling direction of the substrate 10 so that co-evaporation or stacked vapor deposition can be performed.

  In the in-line sputtering chamber 53, the cathode is composed of a plurality of rotary magnetron cathodes 44 fixed at equal intervals in the horizontal direction at right angles to the traveling direction of the substrate 10. In the rotary magnetron cathode 44, the magnetic poles in the cathodes are arranged as in the first embodiment, the first modification, the second modification, the third modification, the fourth modification, and the fifth modification. Through an array, the cathodes are magnetically coupled in the direction in which the cathodes are connected, and the electrons in the plasma are trapped by the magnetic field, so that the inflow of electrons to the substrate can be suppressed.

  In each of the present embodiments, an example of a method of performing vapor deposition or sputtering from below on the substrate 10 that is held horizontally and transported at a constant speed has been shown. It is also easy to carry and vapor deposition or sputtering from the side.

  Next, a method for manufacturing an organic EL panel using the inline-type electrode film forming apparatus 50 having the inline metal deposition chamber 51 and the inline sputtering chamber 53 will be described.

  First, the organic layer 6 is formed on the substrate 10 by a vapor deposition apparatus (organic layer vapor deposition apparatus) for vapor-depositing an organic EL organic layer (not shown). The gate valve 54-1 of the in-line metal vapor deposition chamber 51 is opened, and the substrate 10 is carried in. Next, the substrate 10 is scanned on the metal evaporation source 43 along the pulley 55 and the like in the in-line metal vapor deposition chamber 51 at a constant speed, and the buffer layer 2 of the thin upper electrode 4 is formed on the entire surface of the substrate 10. The metal material to be formed is Mg—Ag alloy, Ag, Al or the like. In the case of an Mg—Ag alloy, co-evaporation is performed using a linear evaporation source for Mg and a plurality of point evaporation sources for Ag. The ratio of Mg and Ag is preferably about 10: 1. When Al is used, a plurality of point evaporation sources using a plurality of ceramic crucibles or the like are used. As the electron injection layer 5, LiF, Liq, or the like is pre-deposited using a linear evaporation source, and an Mg—Ag alloy, Ag, or Al buffer layer 2 is stacked thereon. Film formation is performed only by passing in front of the substrate 10 surface.

  The deposited film thickness of the Mg—Ag alloy, Ag, and Al was set to an average film thickness of 20 nm that can prevent ion implantation during the subsequent sputtering film formation and that can be formed by scanning on the metal evaporation source 43. As a result, a continuous metal vapor deposition film 2 that is longer than the penetration depth of ions or recoil particles and completely covers the organic layer 6 can be provided on the organic layer 6.

  When the deposition is completed, the gate valve 54-2 of the in-line metal deposition chamber 51 and the substrate relay chamber / gas replacement chamber 52 is opened, and the substrate 10 is carried into the substrate relay chamber / gas replacement chamber 52 and temporarily stops. After carrying in, the gate valve 54-2 on the inline metal deposition chamber 51 side is closed, and the gate valve 54-3 on the inline sputtering chamber 53 side is opened instead. Next, Ar is introduced as a discharge gas into the in-line sputtering chamber 53 and the substrate relay chamber / gas replacement chamber 52. The discharge gas pressure is set to a range of about 0.4 to 1 Pa where the discharge is stabilized. Subsequently, a negative DC voltage is applied to the rotary magnetron cathode 44 to start sputtering discharge. A sputtering film 3 of a metal such as Mg—Ag alloy, Ag, Al, or a conductive oxide such as ITO or IZO is formed. In the rotary magnetron cathode 44 of the present embodiment, three cathodes can be arranged at equal intervals in parallel with the substrate surface, and film formation can be performed at a high speed on a part of the substrate passing therethrough. The film formation rate is 6 nm / second in terms of dynamic rate and 9 nm / second in terms of static rate. It is possible to form a film thickness of about 300 nm on a large substrate having a substrate transfer speed of 2 cm / second and 1 m or more in about 1 minute on the entire surface of the substrate 10. A plurality of magnetic fields formed in the sputtering apparatus 53 are coupled symmetrically with respect to an axis perpendicular to the center of the substrate 10 and in a direction in which the cathodes 44 are connected, and trap the electrons in the plasma by the magnetic field. Suppresses the flow of electrons into the. Thereby, it is possible to prevent the charge-up damage of the organic EL element. Further, since it is difficult to form an ion sheath due to suppression of electron inflow, it is possible to suppress inflow of ions, thereby reducing the ion assist effect and forming a metal film with low film stress. Finally, the gate valve 54-4 is opened, and the substrate 10 is sent to the apparatus for the next process or the substrate relay chamber.

  Thus, by connecting the in-line metal vapor deposition chamber 51 and the in-line sputtering chamber 53, it is possible to form a thick upper electrode having a thickness of about 300 nm in a short time of about 1 minute.

  In the sputtering apparatus of the present embodiment, the rotary magnetron cathode is shown as an example, but a planar magnetron cathode having a substantially rectangular shape may be used.

  FIG. 28 is a schematic structural diagram of an organic EL manufacturing apparatus according to Example 4. The organic EL manufacturing apparatus of the present embodiment uses the cluster type electrode film forming apparatus of the second embodiment. The organic EL manufacturing apparatus of the present embodiment is generally configured by connecting an organic cluster 60 for forming various organic layers and a cluster electrode film forming apparatus 30. The organic cluster 60 is composed of organic cluster robot chambers 63 (63-1, 63-2, 63-3, 63-3) connected by organic cluster substrate relay chambers 62 (62-1, 62-2, 62-3, 62-4). The vapor deposition chamber is arranged on both sides centering on 63-4). More specifically, a hole injection layer deposition chamber 64 and a hole transport layer deposition chamber 65 are provided on both sides of the organic cluster substrate relay chamber 63-1, and a red light emitting layer deposition chamber is provided on both sides of the organic cluster substrate relay chamber 63-2. 66 and a green light emitting layer deposition chamber 67 are provided on both sides of the organic cluster substrate relay chamber 63-3, and a blue light emitting deposition chamber 68 and a hole blocking layer deposition chamber 69 are provided on both sides of the organic cluster substrate relay chamber 63-4. The layer deposition chamber 70 and the electron injection layer deposition chamber 71 are arranged. The cassette 73 and the load chamber 61, the load chamber 61 and the organic cluster substrate relay chamber 62, the organic cluster substrate relay chamber 62 and the organic cluster robot chamber 63, the organic cluster robot chamber 63 and each deposition chamber are partitioned by a gate valve 75 and transferred. The substrate is transferred by the robot 76. Each organic vapor deposition chamber has two substrate transfer portions 77, and an organic linear evaporation source 74 capable of scanning left and right and up and down allows one to align the mask while depositing the other, thereby improving the tact time. Can be doubled. In the organic cluster 60, the substrate formed up to the injection layer on the TFT substrate is sent to the substrate relay chamber 32-1, and Mg is deposited in the metal vapor deposition chamber 33-1 or 33-2 of the cluster type electrode film forming apparatus 30. -A buffer layer 2 such as an Ag alloy or Al is formed thick in a sputtering film 3 such as Al in the sputtering chamber 34-1 or 34-2. Thereafter, the substrate is transferred from the substrate relay chamber 32-2 to the unload chamber 72 and transferred to the sealing step.

  FIG. 29 is a schematic diagram of a cross-sectional structure of a green light emitting layer portion of an organic EL element. The organic EL element 91 includes a transparent electrode 80 such as IZO, a hole injection layer 81, a hole transport layer 82, a green light emitting layer 83, a hole blocking layer 84, an electron transport layer 85, an electron on a substrate 90 on which a TFT circuit is formed. The injection layer 95, the buffer layer 92 of a metal vapor deposition film, and the sputtering film 93 are laminated. The thicknesses of each of the transparent electrode 80 are 110 nm, the hole injection layer 81 is 40 nm, the hole transport layer 82 is 15 nm, the green light emitting layer 83 is 10 nm, the hole blocking layer 84 is 10 nm, the electron transport layer 85 is 50 nm, and the electron injection layer. 95 is 0.5 nm, the metal deposited film buffer layer 92 is 20 nm, and the sputtering film 93 is 300 nm. The organic EL element 91 can be produced by, for example, the organic EL manufacturing apparatus of Example 4.

FIG. 30 shows voltage-current-luminance characteristics of the organic EL element of FIG. The left curve in FIG. 30 represents current density, and the right curve represents luminance. In the organic EL element 91, no electrode peeling was observed, and there was no problem of stress. The current-voltage characteristics were good without the occurrence of leakage current, the luminance was 1000 cd / m ^{2 at} 5 V, and there was no influence of charge-up damage due to sputtering. As described above, when the organic EL manufacturing apparatus using the cluster type electrode film forming apparatus of this embodiment is used, a bottom emission type organic EL element having good characteristics is formed using high-speed film formation by a sputtering apparatus. I was able to.

  In addition, although the present Example showed the example of preparation of the bottom emission type element which used the sputtering film 93 of Al for the upper electrode, if conductive oxides, such as ITO, are used for the sputtering film 93, a top emission type element will also be used. Can be created.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiments, examples, and modifications. However, the present invention is not limited to the above-described embodiments, examples, and modifications. It goes without saying that various changes can be made.

In addition, a part of the contents described in the embodiment will be described below.
(1) The sputtering apparatus includes a plurality of cathodes having a balanced magnetron, and the plurality of cathodes are arranged at equal intervals in parallel to a surface (substrate surface) on which a substrate is held. Arranged symmetrically with respect to an axis perpendicular to the center of the substrate to be held, a target is mounted on the plurality of cathodes, and a plurality of magnetic fields formed in the sputtering apparatus are coupled in the direction in which the cathodes are connected. Then, the sputtering apparatus is subjected to direct current discharge.
(2) The sputtering apparatus according to (1) further includes an auxiliary magnet array disposed between the cathodes, and the auxiliary magnet array is disposed symmetrically with respect to an axis perpendicular to the center of the substrate to be held. A plurality of magnetic fields formed in the sputtering apparatus are coupled in a direction in which the cathode and the auxiliary magnet array are connected.
(3) In the sputtering apparatus according to any one of the above (1) and (2), the magnet array set in the cathode has a symmetrical structure with respect to an axis perpendicular to the substrate surface.
(4) In the sputtering apparatus according to any one of (1) to (3) above, the cathode has an elongated cylindrical shape, and a set of balanced magnet arrays is fixed therein, and the target attached to the cathode and the cathode is A rotating rotary magnetron cathode.
(5) In the sputtering apparatus according to any one of the above (1) to (3), the cathode is a planar magnetron cathode having a long and narrow rectangular shape and a set of balanced magnet arrays fixed therein.
(6) In the sputtering apparatus of (2), the auxiliary magnet array outside the cathode also functions as an anode.
(7) In the sputtering apparatus according to any one of (1) to (6), the electron and ion density of plasma at the position of the substrate to be held is 1 × 10 ¹⁶ ions / m ³ or less.
(8) In the sputtering apparatus according to any one of (1) to (7) above, the distance between the target on the plurality of cathodes and the substrate to be held is the same or longer than the target interval.
(9) In the sputtering apparatus according to any one of (1) to (8), a metal member such as a metal mask or a metal frame is disposed on the front surface of the substrate to be disposed, and the metal member is formed. Functions as part of the anode.
(10) In any one of the sputtering apparatuses (1) to (9), a film is formed on the substrate to be disposed from below.
(11) In the sputtering apparatus according to any one of (1) to (9) above, the substrate to be arranged is vertically formed to form a film from the lateral side.
(12) An organic device manufacturing apparatus comprising: the sputtering apparatus according to any one of (1) to (11) above; and a vapor deposition apparatus that forms a metal vapor deposition film on the organic layer.
(13) In the organic device manufacturing apparatus according to (12), the vapor deposition apparatus forms a film from below on the substrate to be disposed.
(14) In the organic device manufacturing apparatus of the above (12), the vapor deposition apparatus is configured to form a film from the lateral side with the substrate to be disposed standing vertically.
(15) In the organic device manufacturing apparatus according to any one of (12) to (14), the vapor deposition apparatus has a linear evaporation source or an evaporation source in which a plurality of crucibles are arranged in series, and scans the evaporation source or the substrate. To form a film.
(16) In the organic device manufacturing apparatus according to any one of (12) to (14), the vapor deposition apparatus and the sputtering apparatus are clustered through a robot chamber.
(17) In the organic device manufacturing apparatus according to any one of (12) to (14), the vapor deposition apparatus and the sputtering apparatus are inlined.
(18) An organic device manufacturing method using the organic device manufacturing apparatus according to any one of (12) to (14) above, wherein a thin film of a metal vapor deposition film is formed by a vapor deposition apparatus, and then sputtering is performed. A metal or conductive oxide is thickly formed by sputtering with an apparatus, and an electrode film is formed on the organic layer.
(19) In the method for producing an organic device according to (18), the continuous film of the metal vapor deposition film on the organic layer is Al, Ag, Mg-Ag alloy, or a metal having a density equal to or higher than the metal, The thickness is 20 nm or more, and is thinner than the sputtering film formed thereon.
(20) An organic device manufacturing method includes: (a) a step of preparing a substrate on which an organic layer is formed; and (b) an Al, Ag, Mg—Ag alloy, or the metal on the organic layer by a vapor deposition apparatus. And (c) a step of depositing a metal or a conductive oxide by a balanced magnetron sputtering apparatus after the step (b). In the step (b), a deposited film having a thickness of 20 nm or more is formed, and in the step (c), a sputtering film having a thickness of 300 nm is formed.

DESCRIPTION OF SYMBOLS 1 ... Lower electrode, 2, 92 ... Buffer layer of metal vapor deposition film, 3, 93 ... Sputtering film, 4 ... Upper electrode, 5, 95 ... Electron injection layer, 6 ... Organic layer 10, 90 ... substrate, 11 ... evaluation element, 20 ... cathode, 21 ... target, 22 ... center magnet, 23 ... ring magnet, 24 ... magnet array 25 ... auxiliary magnet array, 26 ... metal member, 30 ... cluster-type electrode film forming apparatus, robot chamber ... 31, substrate relay chamber ... 32, metal deposition chamber ... 33 , Sputtering chamber ... 34, gate valve ... 35, transfer robot ... 36, processing vacuum chamber ... 40, substrate transfer unit ... 41, drive unit ... 42, metal evaporation source ... 43, rotary magnetron cathode ... 44, in-line type Electrode deposition apparatus ... 50, Inline metal deposition chamber ... 51, Substrate relay chamber / gas replacement chamber ... 52, Inline sputtering chamber ... 53, Gate valve ... 54, Organic cluster ... 60, load chamber ... 61, organic cluster substrate relay chamber ... 62, organic cluster robot chamber ... 63, hole injection layer deposition chamber ... 64, hole transport layer deposition chamber ... 65, red Light-emitting layer deposition chamber ... 66, Green light-emitting layer deposition chamber ... 67, Blue light-emitting deposition chamber ... 68, Hole blocking layer deposition chamber ... 69, Electron transport layer deposition chamber ... 70, Electron injection Layer deposition chamber 71, unload chamber ... 72, cassette ... 73, organic linear evaporation source ... 74, gate valve ... 75, transfer robot ... 76, substrate transfer unit ... 77, Transparent electrode ... 80, hole injection ... 81, a hole transport layer.. 82, green light-emitting layer.. 83, a hole blocking layer.. 84, the electron transport layer.. 85, the organic EL ... 91

Claims (20)

A deposition apparatus capable of forming a metal deposition film on the organic layer;
A sputtering apparatus capable of forming a film on a metal vapor deposition film;
With
The sputtering apparatus includes a plurality of cathodes having a balanced magnetron,
The organic device manufacturing apparatus, wherein the plurality of cathodes are arranged in parallel with the substrate surface at equal intervals.   The organic device manufacturing apparatus according to claim 1, wherein a plurality of magnetic fields formed in the sputtering apparatus are coupled in a direction that is substantially symmetrical with respect to an axis perpendicular to a center of the substrate and that the plurality of cathodes are connected.   The organic device manufacturing apparatus according to claim 1, wherein the sputtering apparatus includes a first auxiliary magnet array disposed outside the plurality of cathodes.   A plurality of magnetic fields formed in the sputtering apparatus are coupled substantially symmetrically with respect to an axis perpendicular to the center of the substrate and coupled in a direction in which the plurality of cathodes and the first auxiliary magnet array are connected. Item 3. The organic device manufacturing apparatus according to Item 3.   The sputtering apparatus includes a second auxiliary magnet array disposed between the plurality of cathodes, and the plurality of cathodes and the second auxiliary magnet array are disposed at equal intervals in parallel to the substrate surface. The organic device manufacturing apparatus according to claim 1.   A plurality of magnetic fields formed in the sputtering apparatus are coupled substantially symmetrically with respect to an axis perpendicular to the center of the substrate and coupled in a direction in which the plurality of cathodes and the second auxiliary magnet array are connected. Item 5. The organic device manufacturing apparatus according to Item 5.   The organic device manufacturing apparatus according to claim 1, further comprising a magnet array set in the cathode, wherein the magnet array set has a symmetrical structure with respect to an axis perpendicular to an opposing substrate.   The organic device manufacturing apparatus according to any one of claims 1 to 7, wherein the cathode is an elongated cylindrical shape, and a set of a balanced magnet array is fixed in the cathode, and the cathode rotates.   The organic material according to any one of claims 1 to 7, wherein the cathode is a planar magnetron cathode in which an elongated rectangular shape or a rectangular shape with rounded four corners is rounded and a set of balanced magnet arrays is fixed therein. Device manufacturing equipment.   The organic device manufacturing apparatus according to claim 3 or 4, wherein the first auxiliary magnet array also functions as an anode. The organic device manufacturing apparatus according to any one of claims 1 to 10, wherein an electron and ion density of plasma at a held substrate position is 1 × 10 ¹⁶ ions / m ³ or less.   The organic device manufacturing apparatus according to any one of claims 1 to 11, wherein a distance between the target on the plurality of cathodes and a substrate to be held is equal to or longer than a target interval.   The organic device according to any one of claims 1 to 12, wherein a metal member such as a metal mask or a metal frame is disposed on a front surface of the substrate held by the sputtering apparatus, and the metal member functions as a part of an anode. manufacturing device.   The organic device manufacturing apparatus according to claim 1, wherein the substrate held by the sputtering apparatus is formed from below the substrate.   The organic device manufacturing apparatus according to claim 1, wherein the substrate held by the sputtering apparatus is vertically set to form a film from a lateral side of the substrate.   The metal deposition apparatus according to any one of claims 1 to 15, wherein the metal deposition apparatus includes a linear evaporation source or an evaporation source in which a plurality of crucibles are arranged in series, and the deposition source or the substrate is scanned to form a film. Organic device manufacturing equipment.   The organic device manufacturing apparatus according to claim 1, wherein the vapor deposition apparatus and the sputtering apparatus are clustered through a robot chamber.   The organic device manufacturing apparatus according to claim 1, wherein the vapor deposition apparatus and the sputtering apparatus are inlined. A thin film of a metal vapor deposition film is formed thinly on the organic layer by the vapor deposition device,
The organic device using the organic device manufacturing apparatus according to any one of claims 1 to 18, wherein a sputtering film is formed by thickening a metal or a conductive oxide on the continuous film of the metal vapor deposition film by the sputtering apparatus. Device manufacturing method.   The continuous film of the metal vapor-deposited film is Al, Ag, Mg-Ag alloy, or a metal having a density equal to or higher than that of the metal, and has an average film thickness of 20 nm or more and a sputtering film formed thereon. The method of manufacturing an organic device according to claim 19 which is thin.

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