JP2008196023A - Film-forming method, film-forming apparatus and method for manufacturing organic electroluminescence device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce damage of the surface to be deposited, which is caused by a collision of charged particles produced when a film is formed by a magnetron sputtering technique. <P>SOLUTION: The film-forming method comprises: placing a first trap 15b having a principal plane made from an element contained in a sputtering target 16 and also having a through-hole therein which is opened on the principal plane, in between the sputtering target 16 and a substrate 17 so that the principal plane faces the sputtering target 16; and in this state, depositing a material contained in the sputtering target 16 on the substrate 17 by the magnetron sputtering technique. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a film forming technique using a magnetron sputtering method.

  The magnetron sputtering method has advantages such as film formation at a relatively low temperature and high sputtering efficiency per power consumption. Therefore, the magnetron sputtering method is used for manufacturing various articles. For example, as described in Patent Document 1, an electrode of an organic electroluminescent element may be formed by a magnetron sputtering method.

However, for example, when film formation is performed by the magnetron sputtering method, not only target particles but also recoil ions and γ electrons collide with the deposition surface of the substrate. Since recoil ions and γ electrons are high-energy particles, the surface to be deposited may be damaged due to the collision of these charged particles.
Japanese Patent Laid-Open No. 11-126691

  An object of the present invention is to reduce damage to a deposition surface due to collision of charged particles when a film is formed by a magnetron sputtering method.

  According to the first aspect of the present invention, a first trap having a main surface made of an element contained in the sputtering target and provided with a through hole opened in the main surface between the sputtering target and the substrate, A film forming method is provided, wherein the main surface is set to face the sputtering target, and in this state, a material contained in the sputtering target is deposited on the substrate by a magnetron sputtering method.

  According to a second aspect of the present invention, there is provided a method for manufacturing an organic electroluminescent device comprising a base material, and an organic electroluminescent element including a first electrode, an organic light emitting layer, and a second electrode sequentially formed thereon. And the manufacturing method characterized by including forming at least one of the said 1st and 2nd electrode with the film-forming method which concerns on a 1st side surface is provided.

  According to the third aspect of the present invention, a backing plate that supports the sputtering target, a cathode magnet that is installed facing the sputtering target across the backing plate, and a substrate holder that supports the substrate so as to face the sputtering target And a first trap having a main surface made of an element contained in the sputtering target and provided with a through hole opened in the main surface, wherein the first trap is positioned between the sputtering target and the substrate. In addition, a magnetron sputtering apparatus is provided that includes a trap holder that supports the main surface so as to face the sputtering target.

  According to the present invention, when a film is formed by the magnetron sputtering method, damage to the deposition surface due to collision of charged particles can be reduced.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, in each figure, the same referential mark is attached | subjected to the component which exhibits the same or similar function, and the overlapping description is abbreviate | omitted.

  FIG. 1 is a diagram schematically showing a magnetron sputtering apparatus according to an aspect of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a substrate holder that can be used in the magnetron sputtering apparatus of FIG. FIG. 3 is a cross-sectional view schematically showing an example of a Peltier element that can be used as a cooling element in the substrate holder of FIG. FIG. 4 is a plan view schematically showing an example of a magnet plate that can be used in the magnetron sputtering apparatus of FIG. FIG. 5 is a plan view schematically showing an example of a magnetic field trap that can be used in the magnetron sputtering apparatus of FIG. FIG. 6 is a plan view schematically showing an example of an electric field trap usable in the magnetron sputtering apparatus of FIG. In FIG. 1, reference symbol P indicates a plasma cloud.

  The magnetron sputtering apparatus shown in FIG. 1 includes a vacuum chamber 11. An exhaust system (not shown) is connected to the vacuum chamber 11. The exhaust system includes a vacuum pump and exhausts the inside of the vacuum chamber 11 to a vacuum.

  A gas supply source (not shown) is further connected to the vacuum chamber 11. The gas supply source supplies a rare gas such as argon or an inert gas as a plasma ion source in the vacuum chamber.

  In the vacuum chamber 11, a backing plate 12, a substrate holder 13, a magnet plate 14, a magnetic field trap 15a, and an electric field trap 15b are arranged.

  The backing plate 12 supports the sputtering target 16. The sputtering target 16 typically has a disk shape. The sputtering target 16 is bonded to the backing plate 12, for example.

  The substrate holder 13 detachably supports the substrate 17 and the mask 18. The substrate 17 is a plate-like body such as a glass plate, for example, and faces the sputtering target 16. The mask 18 covers the surface of the substrate 17 facing the sputtering target 16. When the substrate 17 is made of an insulator, a mask 18 having conductivity such as a metal mask is used, and this is used as an anode.

  In the example shown in FIG. 2, the substrate holder 13 includes a holder main body 131, a mask frame 132, and a cooling element 133. The holder body 131 and the mask frame 132 sandwich the substrate 17 and the mask 18. Typically, the holder main body 131 and the mask frame 132 are made of metal. For example, when a ferromagnetic material is used for one of the holder main body 131 and the mask frame 132 and a ferromagnetic material or a paramagnetic material is used for the other, the substrate 17 and the mask 18 are attached to the holder 13 using magnetic attraction. Can be supported.

  The cooling element 133 is disposed on the holder main body 131. The cooling element 133 cools the substrate 17 via the holder 131. When a Peltier element is used as the cooling element 133, the substrate 17 can be cooled without significantly modifying the apparatus.

  A Peltier element 133 shown in FIG. 3 includes a pair of ceramic substrates 1331 arranged to face each other. Metal electrodes 1334 are arranged on the facing surfaces of the ceramic substrate 1331. Both end portions of each metal electrode supported by one ceramic substrate 1331 are opposed to adjacent ends of two adjacent metal electrodes supported by the other ceramic substrate 1331. The pair of end portions facing each other sandwich the P-type semiconductor portion 1332 or the N-type semiconductor portion 1333. The P-type semiconductor portion 1332 and the N-type semiconductor portion 1333 are alternately arranged along the arrangement direction of the metal electrodes 1334.

  When the terminals 1335a and 1335b of the Peltier element 133 are connected to the anode and the cathode of the DC power source, respectively, one of the ceramic substrates 1331 generates heat and the other ceramic substrate 1332 generates heat. Therefore, the substrate 17 can be cooled if the ceramic substrate 1331 that generates heat is brought into contact with the holder main body 131 of FIG.

  As shown in FIG. 1, the magnet plate 14 faces the sputtering target 16 with the backing plate 12 interposed therebetween. As shown in FIGS. 1 and 4, the magnet plate 14 includes a support plate 141 provided with a plurality of through holes or recesses, and a pin-shaped magnet 142 fitted in these through holes or recesses. These magnets 142 constitute a cathode magnet. The cathode magnet may be configured by combining ring-shaped magnets in a nested manner instead of the pin-shaped magnet 142.

  The magnet plate 14 is rotatable relative to the sputtering target 16 around its normal. Typically, the rotational axis of this rotation passes through the approximate center of the sputtering target 16 shown in FIG. The center of the cathode magnet 141 is separated from the previous rotation shaft.

  As shown in FIG. 1, the magnet plate 14 is separated from the backing plate 12 with a slight gap. A cooling liquid can flow between the magnet plate 14 and the backing plate 12.

  The magnetic field trap 15 a is interposed between the sputtering target 16 and the mask 18. As shown in FIGS. 1 and 5, the trap 15 a includes a frame body 151 and a plurality of magnets 152 supported by the frame body 151.

  The frame 151 is typically made of metal. For example, the frame 151 is a metal plate provided with a substantially circular through hole. The magnets 152 are arranged radially so that each one of the magnetic poles faces the center of the through hole provided in the frame 151, and the magnetic poles facing the previous center have the same polarity.

  The frame 151 has, for example, a ring shape having an outer diameter of 500 mm to 800 mm, an inner diameter of 450 mm to 750 mm, and a thickness of 1 mm to 2 mm. Each of the magnets 152 has, for example, 20 to 30 magnet pins each having a cylindrical shape with a diameter of 5 mm to 10 mm and a height of 20 mm to 30 mm. It is bundled into one so that it becomes. The strength of the magnetic field formed by the magnetic field trap 15a is, for example, 100 Gs to 200 Gs.

  As a material of the frame 151, for example, a low thermal expansion material such as 42 Alloy, SUS316, SUS304, Invar, Kovar, and Super Amber may be used. When a low thermal expansion coefficient material is used as the material of the frame 151, it is possible to suppress the target material adhering to the material from dropping from the frame 151 due to thermal expansion and contraction of the frame 151.

  The trap 15a can be omitted. However, the magnetic field formed by the magnet 152 bends the traveling direction of the charged particles. Therefore, if the trap 15a is installed, damage caused by charged particles to the substrate 17 can be reduced.

  The magnetic field trap 15a is typically connected to a DC power supply terminal. For example, the magnetic field trap 15a is grounded. In this way, it is possible to prevent the electric field between the sputtering target 16 and the substrate 17 from being changed due to the charging of the magnetic field trap 15a, and therefore it is possible to prevent the film formation conditions from changing.

  The electric field trap 15 b is interposed between the magnetic field trap 15 a and the mask 18. One main surface of the trap 15 b is made of an element contained in the sputtering target 16. The trap 15 b is installed so that the main surface faces the sputtering target 16. As shown in FIG. 6, the trap 15 b is provided with a through-hole that opens at the previous main surface.

  The electric field trap has, for example, a right-sided quadrilateral shape having a side of 70 mm to 100 mm and a thickness of 5 mm to 10 mm. The trap 15b may have a single layer structure or a multilayer structure.

  The electric field trap 15b is typically connected to a DC power supply terminal. Thereby, an electric field is formed in the vicinity of the trap 15b, and charged particles are attracted to the electric field trap 15b.

  This magnetron sputtering apparatus further includes a drive mechanism and a controller (not shown). The drive mechanism rotates the magnet plate 14 relative to the sputtering target 16 during film formation. The controller controls the magnitude of a DC voltage applied between the sputtering target 16 and the mask 18 during film formation.

  A voltage may be applied to the sputtering target 16 via the backing plate 12. Further, instead of applying a voltage to the mask 18, a voltage may be applied to the holder 13. When the substrate 17 includes a conductor layer, the conductor of the substrate 17 may be applied instead of applying a voltage to the mask 18. A voltage may be applied to the layer.

Here, plasma will be described.
The atom or molecule constituting the gas is in a quasi-neutral state where electrons are constrained around the nucleus. When energy is applied to a gas atom or molecule by discharge or the like, electrons are freed by shaking off the attractive force of the nucleus, and positive ions and electrons are generated. Plasma is a state in which these charged particles are present, and is said to be a fourth state of substances arranged in solid, liquid, and gas.

  The charged particles in the plasma are accelerated in the presence of an electric field or Lorentz force (a force received when a particle having a charge q moves in the magnetic field B: −qv × B), a pressure gradient, a viscous force, and the like. . In addition, since the plasma satisfies the quasi-neutral condition, when the valence of the positive ions is monovalent, the electrons and the positive ions have the same number density. Therefore, in order to obtain the plasma density, the density of one of electrons and positive ions may be examined.

  Plasma, which is the fourth state of matter, has properties that are physically and chemically unique. First, since the plasma is hot, the kinetic energy of the particles is large. Second, because plasma is a group of charged particles, it is conductive and behaves like a metal. Third, plasma is chemically active and highly reactive. For example, when methane gas and hydrogen gas are mixed to cause discharge in the chamber and the chamber wall temperature is set appropriately, diamond is deposited on the wall surface. Fourthly, since plasma emits light, it can be used as a light source. For example, lighting that uses a neon sign or sodium / mercury discharge that colors the night city is often seen. Such plasma properties are derived from collisions between electrons in the plasma and gas molecules.

Next, the principle of film formation by sputtering will be described.
Sputtering is a phenomenon that occurs when high-speed particles collide with a target. In view of the historical background that this phenomenon was discovered in a discharge tube and the viewpoint of simplicity, positive ions generated by glow discharge are often used as high-speed particles. The DC bipolar sputtering method is the simplest sputtering method using glow discharge.

The direct current glow discharge is a cold cathode discharge that occurs when two electrodes are placed facing each other in a low-pressure gas of about 10 to 10 × 10 ⁻² Torr and a high voltage of several hundred volts or more is applied between them. The current density is, for example, in the range of 1 to 10 × 10 ² A / m ² . This direct current glow discharge will be described below.

  There are positive ions and electrons generated by cosmic rays in the gas. These charged particles are accelerated by the electric field and collide with the electrode. If the voltage between the electrodes is high, positive ions collide with the cathode, and the cathode emits secondary electrons. The secondary electrons are accelerated by the electric field and travel toward the anode. If the energy of the accelerated secondary electrons is sufficiently large and the density of the gas molecules is sufficiently high, the gas molecules ionize by collision with the secondary electrons, and the electrons generated by this ionization ionize another gas molecule. Let That is, an avalanche is generated. Note that positive ions and electrons recombine in the discharge space and the electrodes, so that the density of electrons and ions reaches a steady state. Thus, glow discharge is based on cold cathode emission of secondary electrons and is distinguished from arc discharge based on thermionic emission.

When the glow discharge is viewed macroscopically, the generated positive ions form a positive space charge layer around the cathode. Most of the voltage drop occurs in this layer. A negative space charge layer is interposed between the positive space charge layer and the anode. Each positive ion is accelerated toward the cathode and steadily collides with the cathode. Due to the collision, the cathode emits secondary materials and cathode materials such as secondary ions and neutral particles, that is, target materials. This is direct current bipolar sputtering. The neutral particles jumping out from the cathode are deposited on the substrate to form a thin film. The amount of secondary ions is about 10 × 10 ⁻² times that of neutral particles. Therefore, when only thin film formation is considered, the contribution of secondary ions is usually ignored.

  The establishment of a film deposition method using direct current bipolar sputtering expanded the range of thin film applications and spurred the development of new materials. The magnetron sputtering method is a sputtering method for further improvement.

  In a magnetron sputtering apparatus, electrodes are arranged in the same manner as in a DC bipolar sputtering apparatus, a high-frequency bipolar sputtering apparatus, or the like. However, in the magnetron sputtering apparatus, a plurality of magnets are arranged on the back side of the cathode, and a closed magnetic field line, at least part of which is parallel to the main surface of the cathode, is formed near the surface of the cathode. The magnetic field formed by these magnets creates a toroidal tunnel on the cathode. The discharge plasma is constrained in the vicinity of this tunnel. The magnetic flux density is often about 200 to 500 Gs. Moreover, Ba-ferrite, an alnico alloy, a Co-rare earth alloy, an Nd-based alloy, or the like is used as the magnet material.

According to the magnetron sputtering method, for example, when argon is used as the sputtering gas, the pressure is about 5 mTorr, and the acceleration voltage is about 600 V, a discharge with a high current density of about 20 mA / cm ² can be obtained. At this time, a donut-shaped high-density plasma (≈10 × 10 ¹⁸ m ⁻³ ) that shines brightly across a thin dark portion of several mm is generated on the cathode. The maximum radius R (≈4 cm) of the donut is almost determined by the shape of the magnetic field lines, but the thickness a of the donut depends on the Larmor radius (ρ _e ) of the electron depending on the magnetic field (≈200 Gs) at the position of the radius R and the acceleration voltage Vd. ≈0.5 cm). Since ions are heavy and have a large Larmor radius, it may be considered that a magnetic field does not act.

The reason why high-density plasma is generated even at such a low pressure is due to the effect of the orbital motion (magnetron effect) caused by the E × B drift of secondary electrons as follows. The positive ions in the plasma are accelerated by the voltage drop in the cathode dark portion, strike the cathode surface, and emit secondary electrons therefrom. The secondary electrons are accelerated by the electric field in the dark part to obtain energy as high as eV _d (for example, 600 eV). In the absence of a magnetic field, the high-energy electrons run for the distance between the electrodes and are absorbed by the anode and disappear. Therefore, the lifetime is short and the ionization efficiency is poor. However, in a magnetron discharge, since there is a magnetic field parallel to the cathode surface, secondary electrons draw a cycloid while drifting in the vicinity of the cathode, and circulate in the azimuth direction along the donut. As a result, the lifetime until the secondary electrons are absorbed by the anode and disappears becomes longer, and a large amount of ionization occurs, so that a donut-shaped high-density plasma can be formed.

  Since the anode only functions to collect electrons and flow current, a method of installing a ring-shaped anode on the same plane as the cathode is often used in addition to a method of making it a flat anode facing the cathode. It has been. Since this magnetron plasma has a high current density and ions hit electrons with a high energy of 600 eV, the cathode material is sputtered at a high speed. Because of the low pressure, the mean free path of the sputtered particles is long, and the thin film can be formed by depositing the sputtered particles on the substrate placed opposite to the cathode.

  For these reasons, magnetron discharge is widely used for forming various thin films by sputtering. For example, magnetron discharge is widely used for forming metal films such as aluminum, tungsten, and titanium, oxide films, and nitride films.

  The magnetron sputtering apparatus shown in FIG. 1 includes a magnetic field trap 15a and an electric field trap 15b. As will be described below, the traps 15a and 15b reduce damage to the deposition surface due to collision of charged particles.

  As described above, the magnetic field trap 15 a includes a plurality of magnets 152. The magnets 152 are arranged radially so that the magnetic poles facing the center have the same polarity. The magnetic field formed by the trap 15a bends the traveling direction of charged particles such as recoil ions and γ electrons. The trap 15a can be omitted. However, the magnetic field formed by the magnet 152 bends the traveling direction of the charged particles. Therefore, if the trap 15a is installed, damage caused by charged particles to the substrate 17 can be reduced.

  The electric field trap 15 b is interposed between the magnetic field trap 15 a and the mask 18. For example, the main surface of the electric field trap 15 b facing the sputtering target 16 is set to a lower potential than the substrate 17. In this case, typically, the main surface of the electric field trap 15b facing the sputtering target 16 is set to a lower potential than the magnetic field trap 15a. Thereby, an electric field is formed between the sputtering target 16 and the electric field trap 15b. This electric field attracts charged particles such as recoil ions to the electric field trap 15b. Therefore, if the trap 15b is installed, damage caused by charged particles to the substrate 17 can be reduced.

  Further, as described above, the surface of the electric field trap 15b facing the sputtering target 16 is made of an element contained in the sputtering target 16. For example, when the sputtering target 16 is composed of the elements A to C, whether the surface of the electric field trap 15b facing the sputtering target 16 is composed of the elements A to C, the elements A and B, or the elements B and C. , Elements C and A, element A, element B, or element C.

  When the charged particles collide with the electric field trap 15b, the electric field trap 15b releases the elements constituting the electric field trap 15b. Therefore, when the element that the sputtering target 16 does not contain is included in the surface of the electric field trap 15 b facing the sputtering target 16, this element may be contained as an impurity in the film formed on the substrate 17. .

  When the surface of the electric field trap 15b facing the sputtering target 16 is composed of an element included in the sputtering target 16, the element formed by the electric field trap 15b due to collision of charged particles is included in a film formed on the substrate 17. Same as element or part thereof. Therefore, if the surface of the electric field trap 15b facing the sputtering target 16 is made of an element contained in the sputtering target 16, it is possible to prevent an undesirable element from being included in the film formed on the substrate 17.

  Thus, the electric field trap 15b emits the same element as the element included in the sputtering target 16 or a part thereof. The element emitted by the electric field trap 15b may form a thin film on the components of the magnetron sputtering apparatus. Therefore, when this thin film is conductive, the previous component and the electric field trap 15b may be short-circuited. When such a short circuit occurs, it may be difficult to set the electric potential of the electric field trap 15b to a desired value.

FIG. 7 is a cross-sectional view schematically showing an example of a trap holder that can be used in the magnetron sputtering apparatus of FIG.
The trap holder 19 includes a spacer 191, an insulator 192, and a shield 193.

  The spacer 191 has a cylindrical shape. The spacer 191 is made of, for example, a metal material. The spacer 191 is placed, for example, on the periphery of the backing plate 12 or the magnetic field trap 15a.

  The insulator 192 is attached to the upper end surface of the spacer 191. Although only one insulator 192 is illustrated in FIG. 7, usually, a plurality of insulators 192 are arranged on the upper end surface of the spacer 191.

  The shield 193 has a box shape. Each insulator 192 is covered with a shield 193. The electric field trap 15 b is supported by the spacer 191 through the shield 193 and the insulator 192.

  When the structure shown in FIG. 7 is adopted, the shield 193 prevents the element emitted by the electric field trap 15 b from being deposited on the upper side surface of the insulator 192. Therefore, a thin film is not formed on the upper side of the insulator 192. Therefore, the electric field trap 15b and the spacer 191 are not short-circuited via the thin film formed on the insulator 192. Therefore, when this structure is adopted, it is easy to set the potential of the electric field trap 15b to a desired value.

Another structure may be adopted for the trap holder 19.
FIG. 8 is a cross-sectional view schematically showing another example of a trap holder that can be used in the magnetron sputtering apparatus of FIG.
The trap holder 19 is a clamp, for example, and supports the electric field trap 15b sandwiched from above and below. Of the surface of the trap holder 19, the contact surface with the electric field trap 15b, the lower surface, and the end surface connecting them are made of an insulator.

  When this trap holder 19 is used, the element emitted from the electric field trap 15 b is not deposited on the lower surface of the trap holder 19. Therefore, the component to which the trap holder 19 is attached and the electric field trap 15 b are not short-circuited via the thin film formed on the trap holder 19. Therefore, even when this structure is adopted, it is easy to set the potential of the electric field trap 15b to a desired value.

  The magnetic field trap 15a may be omitted from this magnetron sputtering apparatus. However, when the magnetic field trap 15a is used, both the magnetic field and the electric field can be used in order to reduce the damage to the deposition surface due to the collision of the charged particles. Therefore, as compared with the case where the magnetic field trap 15a is omitted, damage to the deposition surface due to the collision of charged particles can be further reduced.

  When the magnetic field trap 15a is used, the electric field trap 15b can be installed between the sputtering target 16 and the magnetic field trap 15a. However, when the electric field trap 15b is installed between the sputtering target 16 and the magnetic field trap 15a, more charged particles are contained in the electric field trap than when the electric field trap 15b is installed between the magnetic field trap 15a and the substrate 17. It will collide with 15b. That is, the electric field trap 15b emits more particles in the former case than in the latter case. Therefore, when the magnetic field trap 15 a is used, it is advantageous to install the electric field trap 15 b between the magnetic field trap 15 a and the substrate 17.

  The diameter of the through hole provided in the electric field trap 15b is, for example, equal to or smaller than the diameter of the through hole provided in the frame 151 of the magnetic field trap 15a. In this way, compared to the case where the diameter of the through hole provided in the electric field trap 15b is larger than the diameter of the through hole provided in the frame 151 of the magnetic field trap 15a, the damage to the deposition surface due to the collision of charged particles Can be made smaller.

When the magnetic field trap 15a is installed between the electric field trap 15b and the sputtering target 16, the following configuration may be adopted for the magnetic field trap 15a.
FIG. 9 is a perspective view schematically showing an example of a structure that can be adopted in the magnetic field trap shown in FIG.

  The magnet 152 shown in FIG. 9 includes a nonmagnetic holder 1521 and a magnet pin 1522.

  The nonmagnetic holder 1521 is provided with one or more recesses or through holes. The nonmagnetic holder 1521 is made of a nonmagnetic material such as aluminum.

  The magnet pin 1522 is inserted in the nonmagnetic holder 1521. When a plurality of magnet pins 1522 are supported by the nonmagnetic holder 1521, typically, the magnet pins 1522 are inserted so that the magnetic poles located on one end side of the nonmagnetic holder 1521 have the same polarity.

  In the magnetic field trap 15a shown in FIGS. 1 and 5, when the magnet 152 shown in FIG. 9 is used instead of the magnet 152 made of only a ferromagnetic material, the element emitted from the electric field trap 15b may be deposited on the magnet 152. The magnetic field formed by the magnet 152 is hardly affected by this deposit. That is, it is possible to suppress changes in the film formation conditions.

  The magnetron sputtering apparatus described above can be used for forming various layers. This magnetron sputtering apparatus is suitable for forming a transparent conductive film, particularly for forming a transparent conductive film on an organic material layer. Here, first, the transparent conductive film will be described.

  Applications of transparent conductive films are diverse. For example, transparent conductive films are used in various articles such as light emitting diodes, semiconductor lasers, and flat panel displays.

When the transparent conductive film is used as an electrode of an optoelectronic device, it must satisfy the requirements according to the use conditions of each device. For example, the material for the transparent conductive film is required to be excellent in both electrical characteristics and optical characteristics in the visible light region. As such a material, for example, an indium oxide material such as indium tin oxide (ITO) obtained by adding Sn as a dopant to In ₂ O ₃ , a tin oxide material obtained by adding a dopant to SnO ₂ , Aluminum zinc oxide (AZO) formed by adding Al as a dopant to ZnO, gallium zinc oxide (GZO) formed by adding Ga as a dopant to ZnO, and indium zinc oxide formed by adding In to ZnO as a dopant Examples thereof include zinc oxide-based materials.

  As a material for the transparent conductive film, a CdO-based material and a gallium oxide-based material can be used. However, CdO-based materials have a problem that Cd has toxicity. A transparent conductive film made of a gallium oxide-based material has a number of features such as having a wide band gap, but gallium is difficult to produce. Thus, some materials that can be used for the transparent conductive film are restricted in use from the viewpoint of environment and resources.

As described above, the mother crystal of ITO is In ₂ O ₃ . ITO containing 5 to 10% by mass of tin in terms of oxide is transparent like an insulator, but has high conductivity (10 ³ S / cm) and low absorption.

ITO with excellent transparency has high structural integrity of In ₂ O ₃ crystal and has very few electron capture levels in the band gap. That is, in the ITO having excellent transparency, atoms are positioned correctly and without excess or deficiency in the crystal.

In ₂ O ₃ reagent is yellowish white. When In ₂ O ₃ is deposited or formed by sputtering in an atmosphere containing slightly oxygen (partial pressure is 10 × 10 ⁻¹ Pa or less), a transparent conductive film is obtained. However, this compound easily releases oxygen, and is easily reduced, for example, by heating in a vacuum or in a reducing atmosphere containing several percent of hydrogen, and the color changes to blue-black, black, and brown in this order. To do. The conductivity of the In ₂ O ₃ -based material is manifested by substituting In atoms in the mother crystal with Sn atoms or by forming a film under conditions that cause oxygen vacancies.

The transparency of ITO is derived from the fact that the band gap of ITO is in the vicinity of 400 nm, which is the shortest wavelength in the visible light wavelength region. However, this is not sufficient, and in order to achieve high transparency, it is necessary that the level in which electrons reside in the band gap at room temperature is small or negligible. Such a level in the band gap is derived from an oxygen deficiency or a lattice defect caused by an indium atom, a tin atom, or an atomic group (cluster). Therefore, in order to achieve excellent transparency, the mother crystal itself must be easy to form a good crystal lattice. In ₂ O ₃ satisfies this requirement unless it is formed in an atmosphere having extremely weak oxidizing properties. In fact, In ₂ O ₃ shows an X-ray diffraction pattern with a narrow half-value width from the stage of several tens of nanometers even if the substrate temperature is set to about 300 ° C., even under atmospheric conditions where oxygen is slightly insufficient. This feature of easily crystallizing In ₂ O ₃ is not lost if the amount of Sn added is in the range of about several tens of percent or less. This is a feature that is greatly different from the SnO ₂ film and the ZnO film.

  For the formation of the transparent conductive film, vacuum deposition, plasma or ion beam assisted deposition, ion plating, sputtering, and the like are mainly used. A wet method such as a sol-gel method or a spray method may be used for forming the transparent conductive film.

  The sputtering method is widely used for forming a thin film included in a semiconductor device, a flat panel display, and other electronic components. According to the sputtering method, a stable film formation rate and film composition can be achieved, and uniform film formation on a large-area substrate is possible. And if a sputtering method is utilized for formation of a transparent conductive film, the transparent conductive film excellent in the film thickness, the electroconductivity, and the uniformity of transparency can be obtained. Therefore, the sputtering method is widely used as a method suitable for mass production.

  Next, the formation of the transparent conductive film on the organic material layer by the sputtering method will be described by taking the production of an organic electroluminescent device as an example.

  An organic electroluminescent element, which is a main part of an organic electroluminescent device, includes a pair of electrodes and an organic light emitting layer interposed therebetween. In order to extract the light emitted from the organic light emitting layer to the outside of the organic electroluminescent element by passing a current between these electrodes, at least one of the electrodes needs to be light transmissive. For example, a transparent conductive film is used as the light transmissive electrode or a part thereof.

  In a top emission type organic electroluminescence device, of the pair of electrodes included in the organic electroluminescence element, the electrode facing the substrate with the organic light emitting layer interposed therebetween, that is, the upper electrode is light transmissive. It has sex. As this upper electrode, a metal layer is often formed from the viewpoint of electron injection, but this metal layer has low chemical stability and is formed to be extremely thin in order to achieve sufficient light transmission. The Therefore, the previous metal layer may be covered with a transparent conductive film made of ITO or the like for the purpose of reducing the resistance of the electrode and protecting the metal layer. In the top emission type organic electroluminescence device, a transparent conductive film made of ITO or the like is used as the upper electrode, and a buffer layer may be interposed between the upper electrode and the organic light emitting layer. The buffer layer serves to reduce the electron injection barrier and prevent the organic light emitting layer from being damaged by forming the transparent conductive film.

  As described above, the transparent conductive film can be formed by a sputtering method. However, when a transparent conductive film is formed on a substrate by a sputtering method, 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, and defects are generated in the substrate.

  Therefore, when a transparent conductive film is formed on the organic layer by sputtering, high-energy charged particles such as recoil ions and γ electrons collide with the organic layer, thereby destroying the molecules in the organic layer. As a result, the performance of the organic electroluminescent element becomes insufficient. For example, the light emission efficiency decreases, the drive voltage increases, and the life characteristics deteriorate.

  In the magnetron sputtering apparatus shown in FIG. 1, the magnetic field formed by the cathode magnet can be adjusted by changing the number and / or direction of the magnets 142 fitted into the through holes or the recesses of the support plate 141 shown in FIG. Therefore, for example, the magnetic flux density of the toroidal magnetic field formed by the cathode magnet 142 in the vicinity of the sputtering target 16 can be increased, and more charged particles, particularly secondary electrons, can be confined in the toroidal magnetic field. The collision of charged particles to the substrate 17 can be suppressed.

  The magnetron sputtering apparatus includes the electric field trap 15b as described above. Therefore, charged particles can be captured by the electric field trap 15b using the electric field. Therefore, when this configuration is employed, collision of charged particles with the substrate 17 can be further suppressed.

  Furthermore, the magnetron sputtering apparatus shown in FIG. 1 includes the magnetic field trap 15a as described above. The magnetic field formed by the magnet 152 of the trap 15a bends the traveling direction of the charged particles. Therefore, according to this magnetron sputtering apparatus, compared with the case where the trap 15a is omitted, collision of charged particles to the substrate 17 can be suppressed.

  Next, an organic electroluminescent device that can be used for manufacturing the magnetron sputtering apparatus shown in FIG. 1 will be described.

  FIG. 10 is a cross-sectional view schematically showing an example of an organic electroluminescence device that can be used for manufacturing the magnetron sputtering device shown in FIG.

  The organic electroluminescent device shown in FIG. 10 is a top emission type display. This display includes a base material 21, an organic electroluminescent element 22, a partition insulating layer 23, a barrier layer 24, a resin layer 25, and a sealing base material 26. The organic electroluminescent element 22 includes a first electrode 221, a second electrode 222, organic light emitting layers 223 a to 223 c, a hole transport layer 224, and an electron injection layer 225.

  As the base material 21, for example, a glass substrate or a plastic film or sheet can be used. When a plastic film or sheet is used as the substrate 21, an organic electroluminescence device can be manufactured by a winding method, and the device can be provided at a low cost. As a material for the plastic film or sheet, for example, polyethylene terephthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, or the like can be used. The plastic film or sheet has a gas barrier film made of a ceramic vapor-deposited layer, polyvinylidene chloride, polyvinyl chloride, saponified ethylene-vinyl acetate copolymer or the like on the back surface of the surface on which the organic electroluminescent element 22 described later is formed. May be laminated. Further, when the active matrix driving method is adopted for this display, an array substrate having a thin film transistor (TFT) or the like is used as the base material 21.

  On the base material 21, the first electrodes 221 are arranged. When the passive matrix driving method is adopted for this display, the first electrode 221 is arranged so as to form a stripe pattern. When the active matrix driving method is adopted for this display, the first electrodes 221 are arranged so as to form a matrix pattern.

  The first electrode 221 is, for example, a reflective electrode. The first electrode 221 is, for example, an anode. The first electrode 221 may have a single layer structure or a multilayer structure. As the first electrode having a single layer structure, for example, a metal layer made of magnesium, aluminum, chromium, or the like can be used. As the first electrode 221 having a multilayer structure, for example, a laminated body of a transparent conductive film made of ITO or the like and the previous metal layer can be used. In this case, the metal layer is positioned between the transparent conductive film and the substrate 21.

  A partition insulating layer 23 is further formed on the substrate 21. The partition insulating layer 23 is provided with an opening corresponding to the first electrode 221. The partition insulating layer 23 covers the edge of the first electrode 221.

  The partition insulating layer 23 is obtained, for example, by forming a film made of a photosensitive material and subjecting this film to pattern exposure and development. This photosensitive material may be either a positive type or a negative type. As this photosensitive material, for example, a novolac resin or a polyimide resin can be used.

  A hole transport layer 224 is formed on the first electrode 221. As a material of the hole transport layer 224, for example, a mixture (PEDOT / PSS) of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid can be used. The hole transport layer 224 is obtained, for example, by applying a coating solution obtained by dissolving this material in water onto the base material 21 by a spin coating method or the like and drying the coating film.

  An organic light emitting layer is formed on the hole transport layer 224. When the display can display a full color image, organic light emitting layers having different emission colors, for example, a red organic light emitting layer 223a, a green organic light emitting layer 223b, and a blue organic light emitting layer 223c are disposed. As a material for the organic light emitting layer, for example, polyparaphenylene vinylene (PPV) or polyfluorene (PF) can be used. Each of the organic light emitting layers 223a to 223c can be obtained by, for example, preparing an ink by dissolving the above material in an aromatic organic solvent such as toluene and printing the ink. This printing method will be described later.

  An electron injection layer 225 is formed on each of the organic light emitting layers 223a to 223c. As a material of the electron injection layer 225, for example, a rare earth element which is a low work function material such as Ca or Ba can be used. The electron injection layer 225 can be formed by, for example, a vacuum evaporation method.

  The electron injection layer 225 and the partition insulating layer 23 are covered with the second electrode 222. When the passive matrix driving method is adopted for this display, the second electrode 222 is arranged so as to form a stripe pattern. When the active matrix driving method is adopted for this display, the second electrode 222 is a continuous film.

  The second electrode 222 is light transmissive and includes a transparent conductive film. This transparent electrode can be formed using, for example, the magnetron sputtering apparatus shown in FIG. When this magnetron sputtering apparatus is used, damage to the organic layer can be suppressed as described above. Moreover, when this magnetron sputtering apparatus is used, it can suppress that the temperature of the mask 18 rises during film-forming. Therefore, thermal expansion and thermal deformation of the mask 18 can be suppressed, and the transparent conductive film can be formed with high positional accuracy.

  The second electrode 222 is covered with the barrier layer 24. The barrier layer 24 is light transmissive. As the barrier layer 24, for example, a silicon nitride layer, a silicon oxide layer, or a silicon nitride oxide layer can be used. The barrier layer 24 can be formed by, for example, a chemical vapor deposition (CVD) method. In the CVD method, a gas obtained by vaporizing a compound containing an element contained in a film to be formed or a mixed gas of this gas and a carrier gas such as hydrogen and / or nitrogen is heated to a high temperature. In this method, a thin film is formed on a substrate by supplying a chemical reaction such as decomposition, reduction, oxidation, and substitution to the substrate surface.

  The base material 21 on which the barrier layer 24 and the like are formed is bonded to the sealing base material 26 via the resin layer 25. The resin layer 25 and the sealing substrate 26 are light transmissive.

  Examples of the material of the resin layer 25 include a photo-curing adhesive resin, a thermosetting adhesive resin, a two-part curable adhesive resin, and an ethylene ethyl acrylate (EEA) made of epoxy resin, acrylic resin, silicone resin, ) Acrylic resins such as polymers, 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 can be used. .

  As a material of the sealing substrate 26, for example, glass such as non-alkali glass and alkali glass, or a plastic material can be used. The sealing substrate 26 may have a multilayer structure including a layer made of glass or a plastic material and a CaO layer formed thereon. When the base material 21 and the sealing base material 26 are bonded so that the CaO layer and the organic electroluminescent element 22 face each other, the CaO layer can be used as a desiccant. Since the CaO layer is transparent, it does not hinder image display. Therefore, the CaO layer can be formed over the entire display area.

  For bonding the base material 21 and the sealing base material 26, for example, thermocompression bonding using a roll can be used. Moreover, when using a photocurable adhesive resin as a material of the resin layer 25, it can bond together by irradiating an ultraviolet light.

  In this display, the space between the barrier layer 222 and the sealing substrate 26 is filled with the resin layer 25. Therefore, unlike the case where hollow sealing (or can sealing) is performed using a sealing substrate with a cap structure, a change in the optical path length between the barrier layer 222 and the sealing substrate 26 hardly occurs. Therefore, high light extraction efficiency can be achieved.

  FIG. 11 is a cross-sectional view schematically showing another example of an organic electroluminescent device that can be used for manufacturing the magnetron sputtering device shown in FIG.

  The organic electroluminescent device shown in FIG. 11 is a double-sided light emitting display. This display has substantially the same structure as that of the display shown in FIG. 10 except that the first electrode 221 has optical transparency. This display can display images on both the upper and lower surfaces.

  In the manufacture of this display, the magnetron sputtering apparatus shown in FIG. 1 can be used to form the transparent conductive film included in the first electrode 221 and / or the second electrode 222.

  As described above, the use of the magnetron sputtering apparatus shown in FIG. 1 is described for the formation of the transparent conductive film included in the top emission display. This magnetron sputtering apparatus is used for forming the transparent conductive film included in other optoelectronic devices. Can also be used. For example, this magnetron sputtering apparatus may be used for forming a transparent conductive film included in a bottom emission display.

  In the display shown in FIGS. 10 and 11, the hole transport layer, the organic light emitting layer, and the electron injection layer are interposed between the first electrode 221 and the second electrode 222. One or both of the layers may be omitted. The organic electroluminescent element 22 may further include a light emission auxiliary layer such as a hole injection layer, an electron transport layer, and a charge generation layer.

  In the display shown in FIGS. 10 and 11, a flexible plastic substrate may be used as the substrate 21 and the sealing substrate 26. In this way, a flexible organic electroluminescent display is obtained.

  Either the passive matrix driving method or the active matrix driving method may be employed for the display shown in FIGS. The passive matrix driving method is a driving method in which striped 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. On the other hand, the active matrix driving method is a driving method in which an array substrate provided with a transistor for each pixel is used to electrically separate a pixel for writing a video signal and a pixel for performing a display operation from each other.

  In the passive matrix driving method, as the number of stripe-shaped electrodes to be scanned increases, the lighting time in each pixel becomes shorter. Therefore, in the ON state, it is necessary to increase the instantaneous light emission luminance. When the instantaneous light emission luminance is increased, the device life is shortened, so that it is not suitable for a high-definition display in which the number of striped electrodes to be scanned exceeds several hundreds. The display area of the passive matrix driving system is composed of a simple matrix composed of an anode and a cathode, and can emit light at a portion where the cathode and the anode intersect. The passive matrix driving method is duty driving that lights only when the Row line, that is, the cathode, is selected, and the driver IC for driving needs to be externally mounted.

  In the active matrix driving type organic electroluminescence device, each pixel includes a switching element and a memory element. According to the active matrix driving method, each pixel stores a video signal in the writing period, and continues to emit light at a luminance corresponding to the magnitude of the previous video signal in the display period following the writing period. Even when the display is enlarged, the instantaneous light emission luminance may be small, which is advantageous from the viewpoint of life. In addition, since low voltage driving is possible as compared with the passive matrix driving method, power consumption can be reduced. Therefore, it can be said that the active matrix driving method is more excellent from the viewpoint of increasing the display area and the definition.

  Since the organic electroluminescent element is driven by current, when the active matrix driving method is adopted for the organic electroluminescent display, a TFT capable of flowing a relatively large current is required. For this reason, in many cases, a low-temperature polysilicon TFT having high mobility is used as the TFT. The low-temperature polysilicon TFT can be formed on an inexpensive glass substrate, and a peripheral driver circuit including the low-temperature polysilicon TFT can be formed on the glass substrate. Therefore, a compact display can be realized. 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 enormous, and in the future, replacement of liquid crystal displays and development of new markets peculiar to organic electroluminescent elements are highly expected.

  Next, a printing method that can be used for forming the organic light emitting layers 223a to 223c will be described.

  When the organic light emitting layers 223a to 223c are formed by a printing method, an inkjet printing method, an offset printing method, a relief printing method, or the like can be used as the printing method.

12 and 13 are cross-sectional views schematically showing an example of the relief printing method.
In the relief printing method, as shown in FIG. 12, the anilox roll 43 is rotated and the ink 41 accommodated in the ink reservoir 42 is adhered to the surface thereof. After an excessive amount of ink 41 adhering to the surface of the anix roll 43 is scraped off by the doctor blade 44, the ink 41 is supplied onto the resin relief plate 46 wound around the plate cylinder 45 from the surface of the anix roll 43. Thereafter, as shown in FIG. 13, the ink 41 is transferred from the resin relief plate 46 onto the transfer substrate 48.

  In this relief printing method, a water-based ink or UV ink 41 is attached to a thick and highly elastic resin relief plate 46 by an anilox roll 43, and the ink 41 is directly transferred from the resin relief plate 46 to a printing medium 48. Therefore, according to this relief printing method, it is possible to print on a surface with low smoothness or a flexible substrate such as a film and cloth. 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 small.

Examples of the present invention will be described below.
(Example)
In this example, the organic electroluminescent display shown in FIG. 10 was manufactured by the following method. However, in this example, all of the organic light emitting layers 223a to 223c are organic light emitting layers whose emission color is green.

  First, a chromium layer and an ITO layer were sequentially formed on the glass substrate 21 by sputtering. Subsequently, the laminated body of the chromium layer and the ITO layer was patterned into a stripe shape using a photolithography technique. Thereby, an anode 221 made of a laminate of a chromium layer and an ITO layer was obtained.

  Next, a partition insulating layer 23 made of polyimide was formed at a position corresponding to the opening of the previous stripe pattern by using a photolithography technique.

  Next, PEDOT and PSS were dissolved in water to prepare a coating solution. This coating solution was applied to the main surface of the substrate 21 on the partition insulating layer 23 side by a spin coating method to obtain a hole transport layer 224.

  Thereafter, polyfluorene (PF), which is a green organic light emitting material, was dissolved in toluene to prepare an ink. This ink was printed on the hole transport layer 224 by a relief printing method to obtain organic light emitting layers 223a to 223c.

  Next, an electron injection layer 225 made of barium and aluminum was formed in a stripe shape on the organic light emitting layers 223a to 223c by an evaporation method using a mask. The electron injection layer 225 was formed so that the stripe pattern was orthogonal to the stripe pattern of the anode 221.

  Next, a cathode 222 having a thickness of 150 nm made of ITO was formed on the electron injection layer 225 and the partition insulating layer 23 under the following conditions using the DC magnetron sputtering apparatus shown in FIG.

  That is, as the magnetic field trap 15a, a frame 151 made of austenitic stainless steel (SUS304) was used. The outer diameter of the frame 151 was 700 mm, and the inner diameter was 600 mm. As the electric field trap 15b, the one formed by forming an ITO layer on a metal plate provided with a circular through hole was used. The diameter of the through hole provided in the electric field trap 15b was 600 mm. The electric field trap 15b was installed so that the ITO layer faced the sputtering target 16 with the magnetic field trap 15a interposed therebetween. A sputtering target 16 having a disk shape with a diameter of 600 mm was used.

  While keeping the pressure in the vacuum chamber 11 at 1.0 Pa, argon gas and oxygen gas were supplied into the vacuum chamber 11 at flow rates of 150 sccm and 0.2 sccm, respectively. The discharge power was 1.5 kW, and the distance between the sputtering target 16 and the substrate 17 was 200 mm. Moreover, the temperature of the mask 18 was maintained at 50 ° C. or lower by cooling the mask 18 with the Peltier element 133.

  Next, a barrier layer 24 made of silicon oxide was formed on the partition insulating layer 23, the organic light emitting layers 223a to 223c, and the cathode 222 by a CVD method. Furthermore, the glass substrate 26 with the CaO layer formed on one main surface was bonded through the resin layer 25 so that the CaO layer faced the partition insulating layer 23 and the like. As described above, the organic electroluminescent display shown in FIG. 10 was completed.

Next, the characteristics of this display were examined. As a result, the maximum luminance was 5000 cd / m ² and the maximum current efficiency was 2.6 cd / A.

(Comparative example)
In this example, the organic electroluminescent display shown in FIG. 13 was manufactured by the same method as described in Example 1. However, in this example, as in Example 1, all of the organic light emitting layers 223a to 223c are organic light emitting layers having a green emission color. Further, in this example, the traps 15a and 15b and the Peltier element 133 are omitted.

Next, the characteristics of this display were examined. As a result, the maximum luminance was 200 cd / m ² and the maximum current efficiency was 0.05 cd / A.

The figure which shows schematically the magnetron sputtering apparatus which concerns on 1 aspect of this invention. Sectional drawing which shows schematically an example of the substrate holder which can be used with the magnetron sputtering apparatus of FIG. Sectional drawing which shows roughly an example of the Peltier device which can be used as a cooling element with the board | substrate holder of FIG. The top view which shows roughly an example of the magnet plate which can be used with the magnetron sputtering apparatus of FIG. The top view which shows roughly an example of the magnetic field trap which can be used with the magnetron sputtering apparatus of FIG. The top view which shows roughly an example of the electric field trap which can be used with the magnetron sputtering apparatus of FIG. Sectional drawing which shows roughly an example of the trap holder which can be used with the magnetron sputtering apparatus of FIG. Sectional drawing which shows schematically the other example of the trap holder which can be used with the magnetron sputtering apparatus of FIG. FIG. 6 is a perspective view schematically showing an example of a structure that can be adopted in the magnetic field trap shown in FIG. 5. Sectional drawing which shows schematically an example of the organic electroluminescent apparatus which can utilize the magnetron sputtering apparatus shown in FIG. 1 for manufacture. Sectional drawing which shows schematically the other example of the organic electroluminescent apparatus which can utilize the magnetron sputtering apparatus shown in FIG. 1 for manufacture. Sectional drawing which shows an example of the relief printing method roughly. Sectional drawing which shows an example of the relief printing method roughly.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Vacuum chamber, 12 ... Backing plate, 13 ... Substrate holder, 14 ... Magnet plate, 15a ... Magnetic field trap, 15b ... Electric field trap, 16 ... Sputtering target, 17 ... Substrate, 18 ... Mask, 19 ... Trap holder, 21 ... Base material 22 ... Organic electroluminescence element 23 ... Partition insulating layer 24 ... Barrier layer 25 ... Resin layer 26 ... Sealing base material 41 ... Ink 42 ... Ink reservoir 43 ... Anilox roll 44 ... Doctor Blade: 45 ... Plate cylinder, 46 ... Resin relief plate, 48 ... Transfer substrate, 131 ... Holder body, 132 ... Mask frame, 133 ... Cooling element, 141 ... Support plate, 142 ... Magnet, 151 ... Frame, 152 ... Magnet , 191 ... spacer, 192 ... insulator, 193 ... shield, 221 ... first electrode, 222 ... second electrode, 223 ... Organic light emitting layer, 223b ... Organic light emitting layer, 223c ... Organic light emitting layer, 224 ... Hole transport layer, 225 ... Electron injection layer, 1331 ... Ceramic substrate, 1332 ... P-type semiconductor part, 1333 ... N-type semiconductor part, 1334 ... Metal electrode, 1335a ... Terminal, 1335b ... Terminal, 1521 ... Non-magnetic holder, 1522 ... Magnet pin.

Claims (8)

  A first trap having a main surface made of an element contained in the sputtering target and provided with a through hole opened in the main surface is disposed between the sputtering target and the substrate, and the main surface faces the sputtering target. In this state, the material contained in the sputtering target is deposited on the substrate by magnetron sputtering.   The film forming method according to claim 1, wherein the material is deposited on the substrate by setting the main surface to a lower potential compared to the substrate.   The second trap including a plurality of magnets arranged in a radial pattern is installed between the sputtering target and the first trap, and the material is deposited on the substrate. 2. The film forming method according to 2.   A method of manufacturing an organic electroluminescent device, comprising: a base material; and an organic electroluminescent element including a first electrode, an organic light emitting layer, and a second electrode sequentially formed thereon, wherein the first and first A manufacturing method comprising forming at least one of the two electrodes by the film forming method according to claim 1.   The manufacturing method according to claim 4, wherein the organic electroluminescent device is a top emission type, and the second electrode is formed by the film forming method.   5. The method according to claim 4, further comprising forming the organic light emitting layer on the first electrode by a relief printing method using an ink obtained by dissolving or dispersing the material of the organic light emitting layer in a solvent. 5. The production method according to 5.   5. The method according to claim 4, further comprising bonding the base material and a base material having a CaO layer formed on one main surface so that the organic electroluminescent element and the CaO layer face each other. The manufacturing method of any one of thru | or 6. A backing plate for supporting the sputtering target;
A cathode magnet installed facing the sputtering target across the backing plate;
A substrate holder that supports the substrate so as to face the sputtering target;
A first trap having a main surface made of an element contained in the sputtering target and provided with a through-hole opened in the main surface; wherein the first trap is located between the sputtering target and the substrate; A magnetron sputtering apparatus comprising a trap holder that supports the main surface so as to face the sputtering target.

Images