JP2008214724A - Sputtering system, transparent conductive film deposition method, and manufacturing method of organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sputtering system capable of suppressing degradation of the luminescent potential by capturing plasma charged particles made incident on a surface to be deposited of a substrate from the surface of a sputtering target when forming an upper transparent electrode, and a transparent conductive film deposition method. <P>SOLUTION: In the transparent conductive film deposition method for patterning a transparent conductive film on the substrate by using an opposing target type sputtering method, a pair of projecting parts 6A projecting in the mutually approaching direction are formed on upper end side parts of targets 6 opposing to a substrate 2 arranged oppositely to a side (an upper side) between the pair of targets 6, and plasma charged particles leaking from a funnel-shaped plasma cloud end are shielded by corner parts of inner walls of the targets without making the particles be incident on the substrate. Not only a cathode magnet 4a is provided to the back side of the target 6 but also a cathode magnet 4b is provided to the surface of the projecting part 6A facing the substrate 2. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a sputtering apparatus using a facing target sputtering method, a method for forming a transparent conductive film using the sputtering apparatus, and a method for manufacturing an organic electroluminescent element.

  Transparent conductive films have been applied to a wide variety of fields such as optical communications, semiconductor lasers, various displays, recording media, consumer devices (digital cameras, projectors, mobile phones, lenses, mirrors, lamps, etc.), and In the manufacturing technique of transparent conductive films, stability at the time of mass production such as improvement in yield or film performance at the time of forming a multilayer film has become an important requirement item.

  The organic electroluminescent element has a structure in which an organic light emitting layer is sandwiched between two electrodes, and causes the organic light emitting layer to emit light by passing a current between the electrodes. And in order to take out the light light-emitted by this organic electroluminescent element, either one of the electrodes is made transparent. Further, a technical idea using a transparent conductive film made of indium / tin oxide (ITO) as a transparent electrode is known (see, for example, Patent Documents 1, 2, 3, and 4).

The top light extraction (top emission) type organic electroluminescent element uses an electrode on the side opposite to the base as a transparent electrode. In this case, it has been proposed that a transparent conductive film is formed on the metal thin film to protect the cathode and reduce the wiring resistance.
It is also known to provide a buffer layer between the organic light emitting layer and the transparent conductive film for the purpose of protecting the underlying organic light emitting layer and reducing the electron injection barrier in order to use the transparent conductive film as a cathode.
For the formation of such a transparent conductive film, conventional vapor deposition methods and plasma / ion beam assisted vapor deposition methods, ion plating methods, ion beam sputtering methods, etc., which have been used in recent years for optical communication, are mainly used. In some cases, wet methods such as a sol / gel method and a spray method are used as other methods.

On the other hand, a sputtering method is used as a method used in mass production apparatuses in thin film manufacturing processes such as semiconductors, flat panel displays, and electronic components. This sputtering method is widely used as a method suitable for mass production because the film formation rate and film composition are stable and uniform film formation on a large area substrate is possible. Furthermore, it has become mainstream because of its high uniformity of film thickness, conductivity and transparency, and excellent fine etching characteristics.
JP 2003-901158 A JP 2001-250678 A Japanese Patent No. 2850906 JP 2005-68501 A JP 2006-188733 A "Realization of full color by color conversion organic EL" Industrial Materials Vol. 52 no. 4 (2004. 4) "Technology of transparent conductive film" Japan Society for the Promotion of Science Ohm (1999.3)

When patterning a conductive film on a substrate by vapor deposition, particles are deposited on the substrate with only thermal energy to deposit the conductive film, so the energy of particles incident on the substrate is about 0.1 eV. is there. In contrast, when a transparent conductive film is patterned on a substrate by sputtering, the energy of particles incident on the substrate is as high as about 600 eV.
In general, when the energy of particles incident on the substrate is about 50 eV or more, there are problems that particles enter the substrate, atoms constituting the substrate are knocked out, or defects are generated in the substrate.

There are various sputtering methods for forming a thin film on a substrate, and one example thereof is a magnetron sputtering method.
When a transparent conductive film is formed on an organic thin film by magnetron sputtering, the molecular structure of the organic thin film is destroyed (bond breakage) due to scattering and collision of high-energy particles such as recoil Ar plasma, γ electrons, and target particles. There is a problem that the original light emission potential of the organic light emitting material is lowered (see Non-Patent Documents 1 and 2).

In this respect, it is more preferable to use a counter-target sputtering method in which the substrate is hardly affected by plasma by confining the plasma in a magnetic field space formed between a pair of targets, that is, in a so-called plasma-free state. become.
However, even this facing target type sputtering method cannot completely prevent plasma charged particles flying toward the film formation surface of the substrate (see Patent Document 5).

  The present invention has been made to solve the conventional problems as described above, and the invention of claim 1 is directed to a sputtering chamber and a pair arranged to face each other with a space in the sputtering chamber. And a magnetic field forming means for forming a mirror magnetic field between the pair of targets, and is formed on a substrate disposed facing the side between the pair of targets using a sputtering phenomenon at the target. In the sputtering apparatus for forming a film, protrusions for suppressing incidence of leaked plasma charged particles on the substrate are respectively formed in a direction close to the substrate on the opposing surfaces of the pair of targets so as to approach each other. It is characterized by that.

According to a second aspect of the present invention, in the sputtering apparatus according to the first aspect, the magnetic field forming means includes a first cathode magnet provided on a surface opposite to the opposing surfaces of the pair of targets, and the protrusions. And a second cathode magnet provided on a surface facing the substrate.
According to a third aspect of the present invention, in the sputtering apparatus according to the second aspect, the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided on the protrusion via the backing plate. It is characterized by.
According to a fourth aspect of the present invention, in the sputtering apparatus according to any one of the first to third aspects, a trap for trapping plasma charged particles is disposed between the projections.

  The invention according to claim 5 is a transparent conductive film forming method in which a transparent conductive film is patterned on a substrate by a counter target sputtering method through a mask, and is disposed so as to face each other in the sputtering chamber with a gap. And a sputtering apparatus having a magnetic field forming means for forming a mirror magnetic field between the pair of targets, and leaked plasma charged particles at a location near the substrate on opposite surfaces of the pair of targets. Protrusions that suppress the incidence of the light on the substrate are formed so as to protrude in directions close to each other, the substrate is disposed facing the side between the pair of targets, and a mirror magnetic field is generated between the pair of targets. Then, a transparent conductive film is patterned on the substrate using a sputtering phenomenon at the target. .

According to a sixth aspect of the present invention, in the method for forming a transparent conductive film according to the fifth aspect, the magnetic field forming means includes a first cathode magnet provided on a surface opposite to a surface facing the pair of targets, and the protrusion. And a second cathode magnet provided on a surface of the portion facing the substrate.
According to a seventh aspect of the present invention, in the transparent conductive film forming method according to the sixth aspect, the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided on the protrusion via the backing plate. It is provided in.
The invention of claim 8 is characterized in that, in the transparent conductive film forming method according to any one of claims 5 to 7, a trap for trapping plasma charged particles is disposed between the protrusions. To do.

  The invention according to claim 9 includes at least a substrate, a first electrode, an organic light emitting layer, and a second electrode that are sequentially formed on the base material, and an organic current is caused to flow between the first electrode and the second electrode. In the method of manufacturing an organic electroluminescent element that emits light from a light emitting layer, a pair of targets arranged to be opposed to each other with a gap in a sputtering chamber, and a magnetic field forming unit that forms a mirror magnetic field between the pair of targets. And a projection device that suppresses the incidence of leaked plasma charged particles on the substrate at a location close to the substrate on the opposing surfaces of the pair of targets, respectively, and protrudes in a direction approaching each other. The substrate is disposed facing the side between the pair of targets, and after generating a mirror magnetic field between the pair of targets, By utilizing a sputtering phenomenon, characterized in that at least one of the patterning of the first electrode or the second electrode on the substrate.

A tenth aspect of the present invention is the method of manufacturing an organic electroluminescent element according to the ninth aspect, wherein the magnetic field forming means includes a first cathode magnet provided on a surface opposite to a surface facing the pair of targets, It has the 2nd cathode magnet provided in the surface facing the substrate of the projection.
The invention of claim 11 is the method of manufacturing an organic electroluminescent element according to claim 10, wherein the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided via the backing plate. It is provided in the protrusion.
The invention of claim 12 is the method of manufacturing an organic electroluminescent element according to any one of claims 9 to 11, wherein a trap for trapping plasma charged particles is disposed between the protrusions. Features.
According to a thirteenth aspect of the present invention, in the method for manufacturing an organic electroluminescent element according to the ninth aspect, a top emission type organic light emitting device that emits light from the organic light emitting layer by supplying a current between the first electrode and the second electrode. It is an electroluminescent element.

The invention according to claim 14 is the method for producing an organic electroluminescent element according to claim 9, wherein the organic light-emitting layer forming material is dissolved or dispersed in a solvent to form ink, and relief printing using the ink ( And a step of forming an organic light emitting layer on the substrate by a relief printing method.
The invention according to claim 15 is the method for producing an organic electroluminescent element according to claim 14, wherein a base material in which CaO is formed on glass is formed on the base material on which the organic light emitting layer and the electrode are formed. As a characteristic, both are bonded together.

In the production of the top emission type organic electroluminescence device, the upper transparent electrode cannot be formed by a vapor deposition method generally used for the organic electroluminescence device, but is formed by a sputtering method. Sputtering methods generate organic electroluminescence formed on the substrate because the kinetic energy of the deposited particles is large (several tens to several hundreds times) and plasma (O, Ar) is generated compared to the vapor deposition method. It is easy to damage the layer. A damaged organic electroluminescent device has an increased driving voltage and causes various problems such as a decrease in luminous efficiency and a short lifetime. Therefore, in a top emission type organic electroluminescent element, how to produce a transparent conductive film without damaging the organic electroluminescent layer is one technical problem.
In the top emission type organic electroluminescence device, a reflective electrode (anode) must be formed before the organic layer is formed. For this reason, the reflective electrode not only has a high reflectance, but also it is important to ensure surface flatness.

  A general top emission type organic electroluminescence device is laminated in the order of a reflective electrode (anode) / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / transparent cathode. In this structure, since there are a hole injection layer and a hole transport layer between the light emitting layer and the reflective electrode, the distance between the light emitting layer and the reflective electrode is larger than that of the bottom emission type organic electroluminescence device. When the optical distance between the light emitting layer and the reflective layer is about half the wavelength of the emission wavelength (excitation light) of 460 nm (blue green), optical interference is strongly received. Therefore, unless the film thickness of each layer is optimized, the emission characteristics (spectrum And efficiency) cannot be controlled. Therefore, optical design is also very important.

When the damaged portion of the organic film was analyzed in the production of the upper transparent electrode, it was found that the damage was caused by the collision of high-energy particles during sputtering, irradiation of the substrate with plasma or ultraviolet rays. When Ar ions were irradiated on the surface of Alq3, it was confirmed that the C1s binding energy did not change, but the binding energy of N1s, O1s, and Al2p changed.
Therefore, it has been found that Ar ion irradiation damages Al—O bonds and Al—N bonds in Alq 3 (quinolinol Al complex). After exposing the Alq3 surface with 400 W Ar and O2 plasma for 10 seconds, the surface was measured by atmospheric photoelectron spectroscopy. The slope of the electron spectroscopic signal after O2 plasma irradiation was reduced, and a change in work function was further observed. These are presumed to be caused by oxidation of the Alq3 surface. It was also found that O2 plasma causes more damage to Alq3 than Ar (reference document 1).

  Industrial technology that mass-produces devices that are commercialized by multilayering and processing ultra-thin films has become the infrastructure of information society such as information, energy, and environment. In particular, the advent of magnetron-type sputtering (1974), which is easy to form and control the composition of thin films with excellent adhesion that cannot be achieved by conventional vapor deposition methods and can be mass-produced (1974) It greatly contributes to the promotion of IT revolution in the display field.

  When the PVD technique in which the target surface and the substrate surface are opposed to each other is used, the thin film structure grown on the substrate surface varies greatly depending on sputtering conditions such as gas pressure, substrate surface temperature, and bias voltage. That is, it has been clarified that a uniform morphology (morphology) change is exhibited regardless of the type of material with respect to the sputtering gas pressure, the material melting point, and the substrate temperature, which is called Thornton model. It has been pointed out that the microstructure shown in this Thornton model includes many lattice defects that make the crystal lattice arrangement discontinuous, such as vacancies, at the grain boundaries including the initial layer.

  When the relation between the width δ of the disorder of the crystal arrangement at the grain boundary and the diffusion rate D on the surface of the sputtered particles is examined, the product of δ and D is almost constant (minimum δ to 5Å). That is, the deterioration of physical properties caused by the generation of lattice defect regions at the grain boundaries exists in the conventional thin film production by sputtering. For this reason, a CVD method for depositing a thin film by plasma decomposition of a raw material gas is practically used in the early 1980s for the production of various functional films such as silicon thin films used in amorphous solar cells and TFT liquid crystal displays. It became.

  In the thin film formation by the CVD method, the source gas is uniformly decomposed and transported to the substrate, and desired atoms are selectively deposited according to the substrate temperature and the substrate bias. In this process, since there is no elementary process that damages the film, there is no grain boundary defect observed in the PVD method, and an amorphous lattice-bonded thin film grows. However, the CVD method often uses a life-threatening gas, and the organic substance decomposed by gas adheres to the necessary vacuum vessel and piping system during the thin film formation process, so a wide space and environmental safety and maintenance are considered. Expensive capital investment is required.

In 1977, a research group of Tokyo Institute of Technology proposed an opposed target sputtering (hereinafter referred to as FTS) method. Although the morphology of the thin film formed by this FTS apparatus is a PVD method, it has been clarified that a film having a dense structure without grain boundary defects can be formed, unlike the Thornton model.
In the FTS method, high-density plasma is constrained in a space sandwiched between targets with the target surfaces facing each other, and sputter particle generation is realized by high-vacuum and low-voltage discharge comparable to the plasma confinement of magnetron sputtering. There is a principle feature that makes it possible to control the sputter plasma such that the surface of the deposition substrate can be separated from the plasma impact by constraining the plasma by forming a magnetic field.

The FTS generates plasma in a space sandwiched between opposing target surfaces, and has a structure that separates plasma from the space near the substrate surface by restraining high-energy electrons with magnetic lines of force (mirror magnetic field formation). .
In FTS, a magnet that is a source of magnetic lines of force is installed on the back surface of the target, so that the distribution of magnetic lines of force is affected by the target material and shape and the distance between the opposing target surfaces. Therefore, it is important to optimize the magnetic field design that restrains the high-density electron drift generated in the plasma space. In addition, since a uniform line of magnetic force cannot be applied in the magnetron sputtering method, the substrate during film formation cannot be completely protected from plasma and γ electrons, but complete damage-free film formation is possible with FTS. In the case of a magnetron sputtering structure, negative ions generated from sputtering gas are accelerated and damaged by the Coulomb force in the direction of the substrate. However, in the case of FTS, the magnetic field / electric field is parallel to the target, so the substrate Protected from collisions. Furthermore, there is no problem using a ferromagnetic material as a target.

The movement of particles in the plasma is such that secondary electrons (γ electrons) emitted from the target surface and electrons generated during discharge move along the plasma focusing magnetic field due to the Lorentz force and reciprocate between the targets. Repeat collisions with gas atoms (molecules) to promote ionization.
Cations are generated mainly by ionization by γ electrons confined between the targets, are accelerated by the cathode fall voltage, and enter the target surface to cause sputtering. Neutral atoms (molecules) move without being bound by convergent magnetization. As a result, plasma is formed in a columnar and high density in a narrow region between both targets. This realizes advantages such as improved power, discharge at a low gas pressure, the substrate is not exposed to plasma (plasma free), and high speed film formation.
As described above, the FTS method is a thin film deposition technology that can spatially separate the plasma generation space and the substrate surface. Film formation that does not easily generate lattice defects at grain boundaries and high-energy particles of negative ions are bombarded on the deposition surface. Therefore, ultra-thin film formation with excellent homogeneity can be realized with good reproducibility.

  The plasma confinement principle in the FTS is to distribute a mirror magnetic field of a spindle type magnetic field configuration in which the magnetic field is strengthened at both ends by a cathode magnet provided on the back surface opposite to the facing surface of each facing target. The region where the magnetic field lines converge in a funnel shape is called a mirror, and the magnetic field becomes stronger here. When ions collide with the target surface, they recombine with electrons received from the surface, and the ions disappear. Electrons having a negative charge receive a Coulomb attractive force from ions having a positive charge, and are extracted from the plasma generator together with the ions extracted as a beam. Therefore, it is necessary to confine the plasma in the rotation axis direction and the rotation radius direction. By confining electrons, the plasma can be confined by utilizing the following properties of plasma diffusion.

  Electrons have a much smaller mass than ions, and the speed of thermal motion in plasma is overwhelmingly higher than ions. For this reason, electrons try to diffuse first. Then, charge separation occurs and the neutral state of the plasma collapses. At the same time, the Coulomb force attracting between the electron population and the ion population works, so that the electron diffusion is suppressed and the ion diffusion is accelerated. Thus, the plasma diffuses at the same speed as the ions while the plasma remains neutral. Therefore, if electrons are confined, plasma can be confined.

Mirror magnetic field means that when two coils are arranged and current flows in the same direction, a magnetic field configuration is formed that is strong near the coil (increased magnetic flux density) and weakened between the coils (decreasing magnetic flux density). Called magnetic field. The charged particles in the plasma move while wrapping around the magnetic field lines, and if this wrapping is solid, the particles are confined because they are rebounded as if there is a mirror in a strong magnetic field. This is the principle of plasma confinement by the mirror magnetic field.
However, some particles are loosely wound, and they escape from the end without being rebounded by the magnetic field, resulting in plasma end loss. In addition, in a simple mirror magnetic field such as FTS, the magnetic field is weakened from the center toward the outside in the radial direction, so that it is difficult for plasma to escape to the outside as a lump and to be stably confined. This is called plasma macroscopic (MHD) instability.

  In the prior art, it has been impossible to completely avoid the edge loss of the plasma charged particles due to the formation of the mirror magnetic field. However, the pair of sputtering targets in the present invention has the leakage plasma charged particle at the part where the substrate is opposed. Since the protrusions for suppressing incidence on the substrate are formed so as to protrude toward each other, plasma charged particles leaking from the end of the funnel-shaped plasma cloud do not enter the substrate, and the corners of the target inner wall It becomes possible to shield with.

Moreover, in the present invention, the pair of sputtering targets arranged opposite to each other has a protrusion that protrudes in a direction approaching each other, and not only the back surface opposite to the opposite surface of each target, but also the protrusion. Since the cathode magnet is also provided on the surface facing the substrate, it is possible to capture electrons in the magnetic force lines formed by the cathode magnet and to make Ar ions efficiently enter the corners of the inner wall of the target by electrostatic induction. It becomes possible.
In addition, the target particles emitted by Ar ions entering the corners of the inner wall of the target do not interfere with the target particles incident in the direction of the substrate and have directivity in the bottom direction of the sputtering chamber. Does not affect the film thickness distribution.
Further, by enhancing the magnetic force of the cathode magnet provided on the surface of each protrusion facing the substrate, the ability to capture leaked plasma charged particles can be improved.

  A trap for trapping plasma charged particles is provided between the protrusions of a pair of targets arranged opposite to each other, and a molding material for the trap is made of the material shown in FIG. Each material is a low coefficient of thermal expansion material, and it is possible to reduce the sliding (particle generation) of attached target particles due to trap expansion / contraction due to sputtering radiant heat. As the shape of the trap, for example, a mesh shape can be used.

  The relief printing method is a simple and economical printing method. The mechanism of the relief printing method is a printing system in which ink is applied to the surface of a relief printing plate (resin plate) with a roller called an anilox roll, and then the plate is pressed against a substrate to be printed for transfer. The ink that has passed over the anilox roll surface is scraped off by a doctor blade, and a stable amount of ink is always supplied to the plate surface.

  Moreover, in the manufacturing method of an organic electroluminescent element, on the base material which formed the organic light emitting layer and electrode of this invention, the base material which formed CaO on glass is used as a sealing base material, and both are bonded together, It became possible to perform sealing without inserting a desiccant. In addition, since the glass is directly bonded to the upper part of the base material, optical loss such as light absorption in the sealing base material and change in optical path length that occurs when using glass with a cap structure is reduced, and light extraction efficiency is reduced. Was able to improve.

Embodiments of the present invention will be described below.
Applications of the transparent conductive film used in the present invention are various. In particular, when it is used as an electrode for an optoelectronic device, it must satisfy the requirements according to the usage conditions of various devices. In particular, the transparent conductive film-forming material must be a material that satisfies both the electrical characteristics and the optical characteristics in the visible light region.
As a material for forming the transparent conductive film in the present invention, indium oxide-based ITO (added Sn as a dopant to In ₂ O ₃ ), SnO ₂ (dopant added) in addition to tin oxide, and AZO (addition of dopant) in zinc oxide-based ZnO (Al added as a dopant), GZO (ZnO added Ga as a dopant), IZO (ZnO added In as a dopant), or the like can be used.

  Besides these, it is possible to use CdO-based and gallium oxide-based materials. However, the CdO system is difficult to put into practical use because Cd has toxicity. In addition, gallium oxide-based transparent conductive films have many features such as a wide band gap, but like In, Ga is hardly an abundant material from the viewpoint of resources. As described above, the transparent conductive film forming material has a social background in which the environmental aspect must be given top priority as a material design guideline.

ITO is called Indium Tin Oxide, but its mother crystal is In ₂ O ₃ . ITO (In ₂ O ₃ : Sn) having a composition in which Sn is added in an amount of 5 to 10 wt% in terms of oxide is transparent like an insulator, but has high conductivity (10e + 3 S / cm) and little absorption. Transparency and conductivity are related to each other, but there is no one-to-one correspondence. Transparency means that the structural integrity of the In ₂ O ₃ crystal is high and the number of electron trap levels in the band gap is very small, but the atoms in the crystal are coordinate points of the crystal system (lattice position). It is determined by whether or not it is correctly positioned. The In ₂ O ₃ reagent is yellowish white, and a transparent conductive film can be obtained by vapor deposition or sputtering in an atmosphere containing a slight amount of oxygen (partial pressure is 10e-1 Pa or less). However, as a compound, it is easy to let go of oxygen, and it is easily reduced by heating in a vacuum or in a reducing atmosphere containing several percent of hydrogen. As the reduction proceeds, the color changes from blue-black to black and further to brown. . Conductivity is manifested by substituting with In atoms or Sn atoms of the mother crystal, or by forming a film under conditions that do not give sufficient and sufficient oxygen atoms.

The physical meaning of transparency of ITO can be attributed to the fact that the band gap as a semiconductor is in the vicinity of the short wavelength limit of 400 nm in the visible region. However, this is not enough, and in order to ensure high transparency, there are few or negligible levels at which electrons are resident at room temperature in the band gap. Such a level in the band gap is derived from lattice defects due to In, Sn atoms or atomic groups (clusters) other than Sn atoms substituted at oxygen vacancies or In positions, and the mother crystal itself is a high-quality crystal. It must be easy to form a lattice. In ₂ O ₃ satisfies this requirement unless the film is formed in an atmosphere having extremely weak oxidizing properties. In fact, with In ₂ O _{3, if} the glass substrate temperature is set to about 300 ° C., a well-prepared X-ray diffraction pattern with a narrow half-value width from a thickness of several tens of nanometers, even under atmospheric conditions where oxygen is slightly insufficient Indicates. Even if Sn is added, this characteristic that is easily crystallized is not lost up to about several tens of percent. This is a feature that is greatly different from the SnO ₂ film and the ZnO film.

Next, it shows about the transparent conductive film formation method of this invention.
In the present invention, a transparent electrode is formed on a substrate by a sputtering method. As the sputtering method, an ion beam sputtering method, a direct current sputtering method, a high frequency sputtering method, a magnetron sputtering method, a facing target sputtering method, or the like is used. Is possible.

The feature of the opposed target sputtering method is that plasma charged particle incidence to the substrate can be greatly suppressed, so the deposited film is not affected by resputtering, and a film almost equivalent to the target composition can be obtained, and the film is almost damaged. The crystal orientation is not changed.
On the other hand, even with the facing target sputtering method, plasma charged particles flying toward the film formation surface of the substrate cannot be completely prevented.
In the present invention, it was impossible to completely avoid the edge loss of plasma charged particles due to the formation of the mirror magnetic field, which is derived from the principle of the opposed target type sputtering method, but a pair of sputtering targets arranged opposite to each other approach each other. By adopting a configuration that includes a projecting portion that protrudes in the direction of the plasma, the plasma charged particles that have leaked from the funnel-shaped plasma cloud edge can be shielded at the corner of the inner wall of the target without being incident on the substrate.

The schematic diagram of the facing target type sputtering apparatus used for the transparent conductive film formation of this invention was shown in FIG.
In FIG. 1, the facing target type sputtering apparatus includes a vacuum sputtering chamber 13, a pair of sputtering targets 6 disposed opposite to each other in the sputtering chamber 13, and a relative relationship between the pair of sputtering targets 6. A plurality of first cathode magnets 4a respectively disposed on the back surface opposite to the facing surface via a backing plate (OFC) 5a, and a pair of sputtering targets 6 facing each other at locations close to the substrate 2 Are provided on the upper end surfaces of the pair of sputtering targets 6 including the protrusions 6A for suppressing the incidence of the leaked plasma charged particles 9 on the substrate 2 and the protrusions 6A. Another backing plate (OFC) 5b and this other backing plate The second charged cathode magnet 4b provided on the surface of the projection 6A facing the substrate 2 through the projection 5b and the plasma charged particle trap disposed between both the projections 6A so as to pass between them And a trap 3 for use.
As the first and second cathode magnets 4a and 4b, known permanent magnets such as neodymium alloys can be used.

The first cathode magnet 4a and the second cathode magnet 4b, and the sputtering power supply 41 for supplying power to them, form a magnetic field line (mirror magnetic field) 8 between a pair of targets to generate a high-density plasma 7. The first cathode magnet 4 a and the second cathode magnet 4 b are connected to the negative electrode of the sputtering power supply 41 via the lead wire 18, and the positive electrode of the sputtering power supply 41 is connected to the mask 15 of the substrate 2. Connected to the lead wire.
The trap 3 can reduce the frequency of incidence of plasma charged particles on the surface on which the substrate 2 is formed, and acts as a carrier trap mechanism. Note that the inside of the sputtering chamber 13 is in a vacuum state during film formation.
In FIG. 1, reference numeral 12 denotes a power supply terminal flange from the positive electrode of the sputtering power supply 41 to the mask 15, and reference numeral 11 denotes a viewing window for confirming plasma ignition provided in the sputtering chamber 13.

  In the formation of the transparent conductive film, it has been impossible in the prior art to completely avoid the edge loss of the plasma charged particles due to the formation of the mirror magnetic field. However, in the upper end portion of the pair of sputtering targets 6 in the present embodiment, Since the projections 6A projecting in directions approaching each other are provided, the plasma charged particles (Ar ions) 9 leaking from the end of the funnel-shaped plasma cloud are not incident on the substrate 2 and are projected by the projection 6A. It is possible to shield at the corner A of the target inner wall to be formed.

  In the present embodiment, not only the cathode magnet 4a is provided on the back surface opposite to the opposing surface of the sputtering target 6, but also the cathode magnet 4b is provided on the surface of the protrusion 6A facing the substrate 2. In addition to trapping electrons in the lines of magnetic force formed by these cathode magnets, Ar ions can be efficiently incident on the corners 61 of the target inner wall by electrostatic induction.

  The target particles emitted when Ar ions enter the inner wall corner 61 of the target do not interfere with the target particles incident in the substrate direction and have directivity in the bottom direction of the sputtering chamber. This does not affect the film thickness distribution. Moreover, the capture capability of the leaked plasma charged particles 9 can be improved by strengthening the magnetic force of the cathode magnet 4b provided on the projection 6A of each target.

The magnetic field lines 8 in the present embodiment are magnetic field lines in the mirror magnetic field inside the funnel-shaped plasma cloud formed between the opposing targets, and are formed parallel to the substrate surface.
The plasma 7 in the present embodiment is in a quasi-neutral state in which electrons and atoms are captured around the nucleus of the atoms and molecules constituting the gas. In such a gas, energy is given from the outside by discharge or the like. Then, the electrons are free to swing off the attractive force of the nuclei, and the gas is in a state where the electrons and nuclei (positive ions) are separated. This is the plasma 7. Plasma 7 is said to be a fourth state of substances arranged in solid, liquid, and gas.

Ar ions 9 in the present embodiment are positive ions formed when Ar gas in a quasi-neutral state is turned into plasma by discharge or the like.
The γ electrons that are secondary electrons are high-energy electrons that are emitted when plasma electrons collide with Ar gas or target particles.

FIG. 2 is a diagram for explaining the peripheral portion of the substrate in the transparent conductive film forming method of the present invention.
In FIG. 2, the substrate 2 is sandwiched between a mask 15 and a mask frame 17 and the magnet holder 1 and has a close contact structure. In the substrate 2, a transparent conductive film is patterned on the surface in close contact with the mask 15 according to the shape of the opening 15 a of the mask 15.
In the transparent conductive film forming method of the present invention, the substrate 2 is cooled by the Peltier element 14 during the formation of the transparent conductive film. The Peltier element 14 is provided on the magnet holder 1.

The Peltier element 14 is a semiconductor element that allows the substrate 2 and the mask 15 to be easily cooled by being installed on the contact substrate 2 under vacuum. When the Peltier element 14 is provided, it is not necessary to greatly modify the apparatus, and the substrate 2 and the mask 15 can be easily cooled.
Moreover, if a temperature difference is given to both ends of a material, an electromotive force is always generated except for a superconductor. This phenomenon is called the Seebeck effect, and it is a thermocouple used for temperature measurement that makes use of this phenomenon. If an external circuit is connected to the high temperature end and low temperature end of the substance, current is generated by this thermoelectromotive force and can be taken out as electric power. On the contrary, when two kinds of substances are joined and current is passed, heat is reversibly generated or absorbed at the joining point depending on the direction of the current. This is called the Peltier effect, and the Seebeck effect described above is a thermoelectric phenomenon integrated with the front and back. Heating and cooling can be done reversibly simply by reversing the current, and the response speed is extremely slow. As thermoelectric cooling and electronic cooling, cooling of semiconductor lasers, highly sensitive infrared detectors, CCDs, etc. Widely used in medical equipment and other fields that require precise temperature control and local rapid cooling. The two thermo-electric conversion processes, the Seebeck effect and the Peltier effect, are collectively referred to as thermoelectric conversion.

When the Peltier element 14 uses a P-type semiconductor and an N-type semiconductor, the P-type thermoelectric power has a plus sign, the N-type thermoelectric power has a minus sign, and the relative thermoelectric power is very large. can get.
FIG. 3 is a sectional view for explaining the Peltier element. As shown in FIG. 3, the Peltier element 14 has a cooling or heat absorption capability by alternately arranging P-type semiconductors 21 a and N-type semiconductors 21 b between ceramic substrates 19 via metal electrodes 20. It becomes an element. This element utilizes the Peltier effect that causes a temperature difference by flowing current, and is called a Peltier element.

Next, the manufacturing method of the organic electroluminescent element of this invention is described.
In the organic electroluminescent element of the present invention, a first electrode, an organic light emitting layer, and a second electrode are provided in this order on a substrate. In addition, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a charge generation layer, and the like are provided as necessary between the first electrode and the second electrode as a light emission auxiliary layer. The first electrode, the organic light emitting layer, and the second electrode provided on the substrate are sealed for the purpose of protecting both the electrodes, the organic light emitting layer, and the like from moisture in the environment. As sealing, a method in which a glass cap or a metal cap is bonded to a base material, or a method in which a base material provided with a first electrode, an organic light emitting layer, or a second electrode is covered with a barrier layer or the like can be used. .

One of the first electrode and the second electrode is an anode, and the other is a cathode. An organic electroluminescent element is a device that emits light from an organic light emitting layer by passing an electric current between electrodes. A method of taking out emitted light from a substrate side is a bottom emission method, and a method of taking out light from a side opposite to a substrate. This is called the top emission method. In the bottom emission method, it is necessary to make the layer on the substrate side transparent with respect to the organic light emitting layer in order to transmit light emitted from the organic light emitting layer. That is, the base material and the first electrode need to have transparency.
On the other hand, in a top emission type organic electroluminescent device, the layer on the side opposite to the substrate with respect to the organic light emitting layer needs to be transparent in order to transmit light emitted from the organic light emitting layer. That is, the second electrode needs to have transparency, and it is necessary to prevent light from being blocked by sealing.

FIG. 4 shows a sectional view for explanation of a top emission type organic electroluminescence device.
In FIG. 4, a reflective electrode 24 is patterned as a first electrode on a substrate 23, a partition wall 25 is formed between the reflective electrodes 24, a hole transport layer 26, an organic light emitting layer on the reflective electrode 24. 27a, 27b, and 27c are provided in this order, and the electron injecting protective layer 30 and the transparent electrode 31 as the second electrode are provided on the organic light emitting layers 27a, 27b, and 27c. The substrate 23 provided with the reflective electrode 24, the partition wall 25, the hole transport layer 26, the organic light emitting layers 27 a, 27 b, 27 c, the electron injecting protective layer 30, and the transparent electrode 31 includes the barrier layer 32 and the resin layer 33. The sealing substrate 34 is sealed. In addition, a substrate provided with a reflective electrode, a partition wall, a hole transport layer, an organic light emitting layer, an electron injecting protective layer, and a transparent electrode is directly bonded to a glass substrate on which CaO is formed as a desiccant and sealed. May be.

In the top emission type organic electroluminescent element in the embodiment of the present invention, the base material 23 may be a glass base material or a plastic film or sheet. If a plastic film is used, an organic electroluminescent element can be manufactured by winding, and the element can be provided at low cost.
As the plastic film material in this case, for example, polyethylene terephthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate or the like can be used.
Moreover, you may laminate | stack other gas-barrier films, such as a ceramic vapor deposition film, a polyvinylidene chloride, a polyvinyl chloride, and an ethylene-vinyl acetate copolymer saponified material, on the side which does not form an electrode. Further, when the organic electroluminescent element is an active matrix organic electroluminescent element, it is necessary to use a TFT substrate having a thin film transistor (TFT) as a substrate.

There are a passive matrix type and an active matrix type as a driving method of the organic electroluminescent element. The organic electroluminescent element of the present invention is either a passive matrix type organic electroluminescent element or an active matrix type organic electroluminescent element. Applicable.
The passive matrix method is a method in which stripe-shaped electrodes are opposed to each other so as to be orthogonal to each other with an organic light emitting layer interposed therebetween, and light is emitted at the intersection, whereas the active matrix method is a so-called thin film transistor substrate in which a transistor is formed for each pixel. Is used to emit light L independently for each pixel.

In the passive matrix organic electroluminescence device, the lighting time in each pixel is shortened as the number of stripe-shaped electrodes to be scanned increases, so that it is necessary to increase the instantaneous light emission luminance in the ON state. When the instantaneous light emission luminance is increased, the lifetime of the element is reduced, so that it is not suitable for a large-capacity display that requires hundreds to thousands of electrodes on the stripe to be scanned.
The display area of the passive matrix system is composed of a simple matrix composed of an anode and a cathode, and can emit light at the intersection of the cathode and the anode. It is duty drive that lights only when the Row line, that is, the cathode is selected, and the driver IC for driving needs to be externally mounted. Since the organic electroluminescence device has a fast response and no afterglow characteristics, it can be driven in a passive manner.

  In an active matrix organic electroluminescent element, since a switching element and a memory element (active element) are provided for each pixel, the operation state can be maintained for one scanning cycle, so that the display is enlarged. However, the instantaneous light emission luminance may be small and the durability is excellent. Further, since it is driven at a lower voltage than the passive matrix method, power consumption can be reduced. Therefore, it can be said that the active matrix system is superior in increasing the display area and definition.

Since the organic electroluminescent element is current-driven, a TFT capable of flowing a relatively large current is required. For this reason, a low temperature p-Si TFT substrate with high mobility is employed for the active matrix method. The low-temperature p-Si TFT can be manufactured using an inexpensive glass substrate, and a peripheral driver circuit can be incorporated, so that a compact display can be manufactured.
The application field of the active matrix type organic electroluminescence display overlaps with the application field of the active matrix type liquid crystal display using TFT. Accordingly, the market scale is huge, and in the future, the replacement of liquid crystal displays and the development of new markets specific to organic electroluminescent elements can be made, and the growth potential is greatly expected.

The reflective electrode 24, which is the first electrode, can be formed as a positive electrode by using a metal material such as Mg, Al, or Cr by a vacuum film forming method such as a vapor deposition method or a sputtering method. Further, the reflective electrode may have a two-layer structure of a reflective electrode such as Mg, Al, and Cr and a transparent electrode such as ITO. At this time, ITO is provided as an anode interface layer.
After the formation of the reflective electrode 24, the partition wall 25 is formed between the reflective electrodes so as to cover the edge of the reflective electrode. The partition wall needs to have insulating properties, and a photosensitive material or the like can be used. The photosensitive material may be a positive type or a negative type, and a novolac resin, a polyimide resin, or the like can be used, and a partition wall is formed through an exposure process and a development process by a photolithography method.

A hole transport layer 26 is provided on the reflective electrode 24. As the hole transport layer forming material, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) or the like can be used. PEDOT / PSS is dissolved in water to form a coating solution, which is coated on a substrate by a spin coating method or the like and dried.
On the hole transport layer 26, organic light emitting layers 27a, 27b, and 27c are provided. When organic electroluminescent elements are displayed in full color, it is necessary to pattern organic light emitting layers having red (R), green (G), and blue (B) emission colors for each pixel. In FIG. , A red organic light emitting layer 27a, a green organic light emitting layer 27b, and a blue organic light emitting layer 27c. Polyparaphenylene vinylene (PPV), polyfluorene (PF), etc. can be used as the organic light emitting layer forming material. These organic light-emitting materials are dissolved in an aromatic organic solvent such as toluene to form ink, and are patterned into three colors by using a printing method.

  As a printing method, an ink jet printing method, an offset printing method, a relief printing method, or the like can be used, and among them, a relief printing method can be preferably used. FIG. 6 shows a schematic diagram of the printing process in the relief printing method.

  In FIG. 6 (a), the surface of the relief printing plate 38 provided on the impression cylinder 37 is coated with ink obtained by dissolving or dispersing the organic light emitting layer forming material in a solvent by the anilox roll 36, and the relief printing plate. 38 is pressed against the transfer substrate 39 through the impression cylinder 37 as shown in FIG. Ink that has excessively adhered to the surface of the anilox roll 36 is scraped off by the doctor blade 35, and a stable amount of ink is always supplied to the surface of the relief printing plate 38.

  In relief printing, an anilox roll 36 is used to apply water-based ink or UV ink to a thick, highly elastic resin relief printing plate, and print directly on the substrate. Therefore, flexographic printing is also applicable to flexible substrates such as surfaces with poor smoothness, films and cloths. It is also good at very thin and uniform solid printing, and it is possible to further improve the accuracy by applying various resins and chemicals repeatedly. In recent years, technological innovation in relief printing has enabled highly precise and sophisticated multicolor expression. In addition, since water-based ink is suitable for relief printing, it is considered to be highly environmentally friendly and is widely used particularly in the food and pharmaceutical packaging fields. Furthermore, since the amount of ink applied is small, the residual solvent is also small.

Next, the electron injecting protective layer 30 is provided on the organic light emitting layers 27a, 27b, and 27c. As a material for forming an electron injecting protective layer, rare earth elements having a low work function such as Ca and Ba can be used, and these rare earth elements are formed by vacuum deposition to form an electron injecting protective layer.
Next, a transparent electrode 31 is provided as a cathode on the electron injecting protective layer 30. In forming the transparent electrode, the above-described transparent conductive film forming method of the present invention can be used.
In the top emission type organic electroluminescent device, the transparent conductive film forming method of the present invention can be suitably used when forming a transparent electrode. Since the transparent conductive film forming method of the present invention can reduce damage to an organic thin film such as an organic light emitting layer when forming a film by sputtering, an organic electroluminescent device having excellent light emitting characteristics can be obtained. . Further, the transparent conductive film forming method of the present invention can suppress the temperature rise of the patterning mask during film formation. Therefore, thermal expansion and thermal deformation of the mask can be suppressed, and the transparent electrode can be accurately patterned. In the organic electroluminescent element of the present invention, the reflective electrode may be a cathode and the transparent electrode may be an anode.

Next, sealing is performed on the base material 23 on which the reflective electrode 24, the partition wall 25, the hole transport layer 26, the organic light emitting layers 27a, 27b, and 27c, the electron injecting protective layer 30, and the transparent electrode 31 are formed. First, the barrier layer 32 is formed on the entire base material 23.
As the barrier layer 32, a silicon nitride film, a silicon oxide film, a silicon nitride oxide film, or the like can be used. The barrier film is formed by a CVD method. In the CVD method, a vaporized compound (source gas) containing the element to be filmed is mixed as it is or mixed with a carrier gas such as hydrogen or nitrogen, and is sent as uniformly as possible to the substrate surface heated at high temperature. In this method, a thin film is formed on a substrate by causing a chemical reaction such as reduction, oxidation, or substitution.

Furthermore, the base material 23 provided with the barrier layer 32 is bonded to the sealing base material 34 via the resin layer 33. As the sealing base material 34, what is necessary is just to have transparency, and glass and plastic materials, such as alkali free glass and alkali glass, can be used. Alternatively, the base material in which CaO is formed on the glass may be used as the sealing base material 34 to bond them together. Thereby, it is possible to perform sealing without inserting a desiccant. In addition, since the glass is directly bonded to the upper part of the base material, the light absorption at the sealing base material and the change in the optical path length that occurs when using a glass with a cap structure do not occur, and the light extraction efficiency is improved. You can also.
Examples of the resin layer 33 include a photo-curing adhesive resin made of an epoxy resin, an acrylic resin, a silicon resin, a thermosetting adhesive resin, a two-component curable adhesive resin, an ethylene ethyl acrylate (EEA) polymer, and the like. Acrylic resins, vinyl resins such as ethylene vinyl acetate (EVA), thermoplastic resins such as polyamide and synthetic rubber, and thermoplastic adhesive resins such as acid-modified products of polyethylene and polypropylene.

  As a bonding method, a method by pressure bonding with a heated roll can be used. Moreover, when using a photocurable adhesive resin as a resin layer, it can bond together by irradiating with ultraviolet light.

Moreover, in the organic electroluminescent element of this invention, it can be set as a flexible organic electroluminescent element by using a flexible plastic base material for a base material and a sealing base material.
Moreover, in the organic electroluminescent element of this invention, it can be set as a transparent organic electroluminescent element by making both electrodes into a transparent electrode, making a base material into a transparent base material, and sealing with a transparent material.

FIG. 5 is a sectional view for explaining the transparent organic electroluminescent device.
In FIG. 5, a transparent electrode 24 is formed as a first electrode on the transparent base material 23, and as in the case shown in FIG. 4, the partition wall 25, the hole transport layer 26, the organic light emitting layers 27a, 27b, 27c, An electron injecting protective layer 30 and a transparent electrode 31 are formed. Furthermore, it is sealed by a transparent barrier layer 32, a resin layer 33, and a sealing substrate 34. In a transparent organic electroluminescent element, it becomes possible to display an image from both sides of the substrate side and the opposite side of the substrate.

  A glass substrate was used as a substrate, Cr was formed on the substrate as a reflective electrode as an anode, and ITO was laminated as an anode interface layer by a sputtering method. The laminated film of Cr and ITO on the obtained substrate was patterned by a photolithographic method to obtain a stripe pattern. Next, a partition wall was formed by a photolithography method using a polyimide material so as to cover the end portion of the striped Cr. Next, PEDOT / PSS was used as a hole transport material, which was dissolved in water to form a coating solution, and a hole transport layer was formed by a spin coating method.

  Next, using a green organic light emitting material made of polyfluorene (PF), this green organic light emitting material was dissolved in toluene to form an ink, and an organic light emitting layer was formed in stripes by a relief printing method. Next, an electron injecting protective layer made of Ba and Al was formed on the organic light emitting layer by vapor deposition using a mask so as to be orthogonal to the Cr stripe pattern of the anode.

  Next, a transparent electrode was formed using the facing target sputtering apparatus of the present invention. Further, a trap for trapping plasma charged particles was provided between steps on the short side of each target arranged oppositely. Further, a mask was provided so as to come into contact with the substrate, and the mask was fixed by a magnet holder. A Peltier element was provided on the side opposite to the transparent electrode film-forming surface of the substrate.

  FIG. 8 shows sputtering conditions of the opposed target sputtering apparatus of the present invention.

Next, sealing was performed by providing a silicon oxide film over the entire light emitting region of the organic electroluminescent element by a CVD method and further bonding it to a glass substrate through a CaO film to obtain a top emission type organic electroluminescent element.
As for the element characteristics of the obtained organic electroluminescent element, the maximum luminance is 5000 cdm-2, and the maximum current efficiency is 2.6 cdA-1.

(Comparative example)
As in the example, a transparent electrode was formed on the glass substrate on which the reflective electrode, the partition, the hole transport layer, the organic light emitting layer, and the electron injecting protective layer were formed using the counter target type sputtering apparatus in the same manner as in the example. Went. However, in the opposed target sputtering apparatus, a step-shaped opposed sputtering target was not used, and a trap for trapping plasma charged particles was not provided between the steps on the short side of each of the opposed targets. Further, no Peltier element was provided on the substrate. In the sputtering, other sputtering conditions are the same as in Table 2.
At this time, the mask temperature during sputtering was 60 ° C., which was higher by about 10 ° C. than the example. Moreover, sealing was performed on the substrate on which the transparent electrode was formed in the same manner as in the example to obtain an organic electroluminescent element. The maximum luminance of the obtained organic electroluminescent element was 100 cdm-2, and the maximum current efficiency was 0.05 cdA-1.

It is a schematic diagram of the opposing target type | mold sputtering apparatus used for transparent conductive film formation of this invention. It is explanatory drawing of the board | substrate periphery part in the transparent conductive film formation method of this invention. It is sectional drawing for description of a Peltier device. It is sectional drawing for description of a top emission type organic electroluminescent element. It is sectional drawing for description of a transparent organic electroluminescent element. It is a schematic diagram of the printing process by the relief printing (relief printing) method of this invention. It is a figure which shows the molding material of the trap for plasma charged particle trap arrange | positioned so that it may face between the protrusions of a pair of target of this invention. It is a figure which shows the sputtering conditions of the facing target type | mold sputtering device of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Magnet holder, 2 ... Glass substrate, 3 ... Sputtering trap, 4a ... 1st cathode magnet, 4a ... 2nd cathode magnet, 5a, 5b ... Backing plate, 6 ... Sputtering target, 6A ...... Projections, 7 ... Plasma, 8 ... Magnetic lines (mirror magnetic field), 9 ... Leaked plasma charged particles, 10 ... Target particles, 11 ... Peeping window, 12 ... Power supply terminal flange, 13 ... ... Sputtering chamber, 14 ... Peltier element, 15 ... Mask, 15a ... Mask opening, 17 ... Mask frame, 18 ... Lead wire, 19 ... Ceramic substrate, 20 ... Metal electrode, 21a ... P-type semiconductor, 21b ... N-type semiconductor, 23 ... base material, 24 ... reflecting electrode (first electrode), 25 ... partition wall, 26 ... hole transport layer, 7a: red (R) organic light emitting layer, 27b: green (G) organic light emitting layer, 27c: blue (B) organic light emitting layer, 30: electron injecting protective layer, 31: transparent electrode (second electrode) Electrode), 32 ... Barrier layer, 33 ... Resin layer, 34 ... Sealing substrate, 35 ... Doctor blade, 36 ... Anilox roll, 37 ... Plate cylinder, 38 ... Relief printing plate, 39 ... ... substrate to be transferred, L ... light emission.

Claims (15)

A sputtering chamber, a pair of targets arranged to be opposed to each other at an interval in the sputtering chamber, and magnetic field forming means for forming a mirror magnetic field between the pair of targets, In a sputtering apparatus for forming a film on a substrate arranged facing the side between the pair of targets by utilizing a sputtering phenomenon,
Protrusions for suppressing the incidence of leaked plasma charged particles on the substrate on the opposite surfaces of the pair of targets are formed so as to approach each other.
A sputtering apparatus characterized by that.   The magnetic field forming means includes a first cathode magnet provided on a surface opposite to the opposing surfaces of the pair of targets, and a second cathode magnet provided on a surface of the protrusion facing the substrate. The sputtering apparatus according to claim 1.   The sputtering apparatus according to claim 2, wherein the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided on the projection via a backing plate.   The sputtering apparatus according to any one of claims 1 to 3, wherein a trap for capturing plasma charged particles is disposed between the protrusions. A transparent conductive film forming method for patterning a transparent conductive film on a substrate by a facing target sputtering method through a mask,
A pair of targets arranged in the sputtering chamber so as to face each other at an interval, and a sputtering apparatus having a magnetic field forming means for forming a mirror magnetic field between the pair of targets,
Protrusions that suppress the incidence of leaked plasma charged particles on the substrate at the locations near the substrate on the opposing surfaces of the pair of targets are formed so as to protrude from each other, respectively.
The substrate is arranged facing the side between the pair of targets,
After generating a mirror magnetic field between the pair of targets, patterning a transparent conductive film on the substrate using a sputtering phenomenon in the pair of targets,
A method for forming a transparent conductive film.   The magnetic field forming means includes a first cathode magnet provided on a surface opposite to the opposing surfaces of the pair of targets, and a second cathode magnet provided on a surface of the protrusion facing the substrate. The method for forming a transparent conductive film according to claim 5.   The transparent conductive film formation according to claim 6, wherein the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided on the protrusion via a backing plate. Method.   The method for forming a transparent conductive film according to any one of claims 5 to 7, wherein a trap for trapping plasma charged particles is provided between the protrusions. An organic electric field comprising at least a substrate, a first electrode, an organic light emitting layer and a second electrode sequentially formed on the base material, and causing the organic light emitting layer to emit light by passing a current between the first electrode and the second electrode. In the method for manufacturing a light emitting device,
A pair of targets arranged in the sputtering chamber so as to face each other at an interval, and a sputtering apparatus having a magnetic field forming means for forming a mirror magnetic field between the pair of targets,
Protrusions that suppress the incidence of leaked plasma charged particles on the substrate at the locations near the substrate on the opposing surfaces of the pair of targets are formed so as to protrude from each other, respectively.
The substrate is arranged facing the side between the pair of targets,
After generating a mirror magnetic field between the pair of targets, patterning at least one of the first electrode or the second electrode on the substrate using a sputtering phenomenon in the pair of targets,
A method for producing an organic electroluminescent device, comprising:   The magnetic field forming means includes a first cathode magnet provided on a surface opposite to the opposing surfaces of the pair of targets, and a second cathode magnet provided on a surface of the protrusion facing the substrate. The method for producing an organic electroluminescent element according to claim 9.   11. The organic electroluminescent device according to claim 10, wherein the first cathode magnet is provided on the target via a backing plate, and the second cathode magnet is provided on the protrusion via the backing plate. Manufacturing method.   The method for manufacturing an organic electroluminescent element according to claim 9, wherein a trap for capturing plasma charged particles is disposed between the protrusions.   The organic electroluminescent device according to claim 9, wherein the organic electroluminescent device is a top emission type organic electroluminescent device that emits light from the organic luminescent layer by supplying a current between the first electrode and the second electrode. Method.   A step of dissolving or dispersing the material for forming the organic light emitting layer in a solvent to form an ink, and a step of forming the organic light emitting layer on the substrate by a relief printing method using the ink. The method for producing an organic electroluminescent element according to claim 9.   The organic electroluminescent element according to claim 14, wherein both of the organic light emitting layer and the electrode are bonded to each other on the base material on which CaO is formed on glass as a sealing base material. Manufacturing method.

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