JP2013062185A - Transparent conductive film forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film forming method, by which a transparent conductive film having higher light permeability and conductivity than conventional arts can be formed on an organic film.SOLUTION: A transparent conductive film forming method for forming a transparent conductive film on an organic film includes: a metal oxide film forming step of discharging metal oxide particles in an atmosphere including no oxygen gas, bringing the metal oxide particles on the organic film, and forming a metal oxide film 27 on the organic film; and a metal oxide film modification step of oxidizing or reducing the metal oxide film 27 to form a first transparent conductive film 27'. In the film formation, the organic film is not damaged by oxygen gas or oxygen ions/radicals. A transparent conductive film 27' having desired film quality can be obtained by oxidizing or reducing the metal oxide film 27 and increasing/decreasing the oxygen content thereof.

Description

  The present invention relates to a method for forming a transparent conductive film, and more particularly to a method for forming a transparent conductive film used for organic semiconductor elements such as organic EL display devices, organic EL lighting, organic image sensors, and organic solar cells.

FIG. 9 is an internal configuration diagram of the organic semiconductor element 102 formed by using a conventional transparent conductive film forming method.
The organic semiconductor element 102 includes a substrate 111, and an electrode layer 121, a hole injection layer 122, a hole transport layer 123, an organic light emitting layer 124, and an electron transport layer 125 are formed on the surface of the substrate 111. The electron injection layer 126 and the transparent conductive film 128 are stacked and arranged in this order.

  The hole injection layer 122, the hole transport layer 123, the organic light emitting layer 124, and the electron transport layer 125 are organic films, and the electron injection layer 126 is an organic film, a metal-doped organic film, or a thin film thickness of 15 nm or less. This is a translucent metal film.

  When a positive terminal and a negative terminal of a power source (not shown) are respectively connected to the electrode layer 121 and the transparent conductive film 128 and a voltage is applied between the electrode layer 121 and the transparent conductive film 128, holes are transferred from the hole injection layer 122. Holes are injected into the transport layer 123, and electrons are injected from the electron injection layer 126 into the electron transport layer 125. The holes are transported through the hole transport layer 123 and moved into the organic light emitting layer 124, and the electrons are transported through the electron transport layer 125 and moved into the organic light emitting layer 124. In the organic light emitting layer 124, holes and electrons recombine to emit light.

  The electron transport layer 125, the electron injection layer 126, and the transparent conductive film 128 are light transmissive, and emitted light generated in the organic light emitting layer 124 is emitted from the electron transport layer 125 and the electron injection layer 126. Then, the light passes through the transparent conductive film 128 in order and is emitted to the outside.

  In the conventional transparent conductive film forming method, in an oxygen gas atmosphere, the organic films 122 to 126 (in the case where the electron injection layer 126 is a metal-doped organic film or a metal film, the organic films 122 to 125 and the metal-doped organic film or A transparent conductive film 128 was directly formed on the metal film 126). When oxygen gas is added to the film formation atmosphere, oxygen gas, particularly oxygen ions and oxygen radicals generated during film formation by reactive sputtering, react with the electron injection layer 126 and the underlying organic films 122 to 125. There was a problem of damaging these films.

  Therefore, in the conventional transparent conductive film formation method, in order to reduce damage to the electron injection layer 126 and the underlying organic films 122 to 125, the film formation method and film formation conditions are limited, for example, the film formation power of sputtering is reduced. The transparent conductive film 128 was formed by reducing the energy of particles in the plasma. However, as a result, the required performance such as conductivity and transparency of the transparent conductive film 128 is lowered, and the performance of the organic semiconductor element 102 is affected.

  Further, in the conventional transparent conductive film forming method, after forming the transparent conductive film 128, the film quality of the entire transparent conductive film 128 is not changed, and the conductivity and light transmittance cannot be improved. Therefore, the transparent conductive film 128 formed on the organic semiconductor structure films 122 to 126 under the film formation conditions limited as described above has to be left as it is.

  Patent Document 1 discloses a method in which a barrier layer is previously formed on an organic layer in order to avoid damage to the organic layer when forming the upper transparent conductive film. There is a disadvantage that it decreases or affects the conductivity of the transparent conductive film.

  Patent Documents 2 and 3 disclose techniques for modifying the formed ITO substrate surface in order to improve the hole injection property (work function) of the transparent conductive film, but only the surface of the ITO film is modified. In other words, the overall performance of the ITO film, such as conductivity and light transmission, cannot be improved.

JP 2009-259628 A JP 2000-133304 A JP 2010-182737 A

  The present invention was created to solve the above-mentioned disadvantages of the prior art, and its object is to form a transparent conductive film forming method of forming a transparent conductive film having higher light transmission and conductivity on an organic film. Is to provide.

In order to solve the above problems, the present invention provides a transparent conductive film forming method for forming a transparent conductive film on an organic film, wherein metal oxide particles are released into an atmosphere containing no oxygen gas, and the particles A metal oxide film forming step of forming a metal oxide film on the organic film, and a metal oxide forming the first transparent conductive film by oxidizing the metal oxide film And a film reforming step.
The present invention is a method for forming a transparent conductive film, wherein in the metal oxide film modification step, the metal oxide film is oxygenated in a chemical structure while maintaining a state where the surface of the metal oxide film is exposed. It is a method for forming a transparent conductive film that is oxidized by exposure to plasma of an oxygen-containing gas containing oxygen.
The present invention is a method for forming a transparent conductive film, wherein the oxygen-containing gas is any one of O ₂ , H ₂ O, CO ₂ , CO, and N ₂ O, or two or more kinds thereof. It is a transparent conductive film formation method which is a mixed gas.
This invention is a transparent conductive film formation method, Comprising: At the said metal oxide film modification process, it is a transparent conductive film formation method which inject | pours and oxidizes oxygen ion to the said metal oxide film.
The present invention is a transparent conductive film forming method, wherein a transparent conductive film is formed on an organic film, wherein metal oxide particles are released in an atmosphere containing no oxygen gas, A metal oxide film forming step for causing particles to reach the organic film and forming a metal oxide film on the organic film; and a metal oxide for reducing the metal oxide film to form a first transparent conductive film And a physical film reforming step.
The present invention is a method for forming a transparent conductive film, wherein in the metal oxide film reforming step, the metal oxide film is treated with an inert gas or a reducing gas while maintaining a state where the surface of the metal oxide film is exposed. This is a method for forming a transparent conductive film that is reduced by being exposed to plasma of one of the gases.
This invention is a transparent conductive film formation method, Comprising: The said inert gas is a transparent conductive film formation method containing any one kind of gas among Ar, He, Ne, Kr, and Xe.
The present invention is a transparent conductive film forming method, the reducing gas, and H _2, and CO, which is a transparent conductive film forming method which contains any one kind of gas among the N _2.
The present invention is a transparent conductive film forming method, wherein in the metal oxide film modification step, Ar ion, He ion, Ne ion, Kr ion, Xe ion, and H ion are applied to the metal oxide film. And a transparent conductive film forming method in which any one kind of cations out of N ions is injected and reduced.
The present invention is a method for forming a transparent conductive film, wherein in the metal oxide film forming step, the metal oxide material is heated from the metal oxide material in an atmosphere containing no oxygen gas. In this method, the vapor is released, the vapor reaches the organic film, and the metal oxide film is formed on the organic film.
The present invention is a method for forming a transparent conductive film, wherein in the metal oxide film forming step, a metal oxide target is sputtered in an atmosphere of a sputtering gas not containing oxygen gas, and the metal oxide is formed from the target. It is a method for forming a transparent conductive film, wherein particles are discharged, the particles reach the organic film, and the metal oxide film is formed on the organic film.
The present invention is a transparent conductive film forming method, wherein the sputtering gas is any one of Ar, He, Ne, Kr, and Xe, or a mixed gas of two or more. It is a forming method.
The present invention is a method for forming a transparent conductive film, wherein the first transparent conductive film includes tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped indium oxide (AZO), and GZO. , ZnO, SnO ₂ , In ₂ O ₃ , titanium oxide, tungsten oxide, Ta oxide, and transparent oxide that is a film containing one or more metal oxides of Mo oxide This is a film forming method.
This invention is a transparent conductive film formation method, Comprising: In the said metal oxide film formation process, it is a transparent conductive film formation method which forms the said metal oxide film with a film thickness of 1 nm or more and 50 nm or less on the said organic film.
The present invention is a transparent conductive film forming method, wherein the metal oxide film forming step and the metal oxide film modifying step are alternately repeated a plurality of times.
The present invention is a method for forming a transparent conductive film, wherein after the metal oxide film modification step, metal oxide particles are released into an atmosphere containing oxygen gas, and the particles are transferred to the first transparent conductive film. It is a transparent conductive film formation method which has a 2nd transparent conductive film formation process which makes it reach | attain and forms a 2nd transparent conductive film on said 1st transparent conductive film.
The present invention is a method for forming a transparent conductive film, wherein the second transparent conductive film includes tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped indium oxide (AZO), and GZO. , ZnO, SnO ₂ , In ₂ O ₃ , Nb ₂ O ₅ , titanium oxide, tungsten oxide, Ta oxide, and Mo oxide contain one or more metal oxides This is a method for forming a transparent conductive film that is a film to be formed.
This invention is a transparent conductive film formation method, Comprising: The heating target temperature below the glass transition temperature of the said organic film is made into the process target in which said 1st transparent conductive film was formed after the said metal oxide film modification process. It is a transparent conductive film formation method which has the annealing process heat-processed by.
This invention is a transparent conductive film formation method, Comprising: After the said 2nd transparent conductive film formation process, the process target in which said 2nd transparent conductive film was formed is heated below the glass transition temperature of the said organic film. It is a transparent conductive film formation method which has an annealing process which heat-processes at temperature.
This invention is a transparent conductive film formation method, Comprising: The said heating temperature is a 50 degreeC or more and 200 degrees C or less transparent conductive film formation method.

Since the metal oxide film is formed on the organic film in an atmosphere not containing oxygen gas, the organic film is not damaged by oxygen gas, oxygen ions, or oxygen radicals, and the performance of the organic film is not deteriorated.
After the metal oxide film is formed, the metal oxide film can be oxidized or reduced to increase or decrease its oxygen content to a predetermined reference value. A transparent conductive film is obtained.

(A) (b): The figure for demonstrating the transparent conductive film formation method of this invention Schematic diagram of the first example of organic semiconductor device manufacturing equipment (A)-(d): The figure for demonstrating the organic film formation process The figure for demonstrating a 2nd transparent conductive film formation process The internal block diagram of the organic-semiconductor element formed using the transparent conductive film formation method of this invention Internal configuration diagram of the first example of the reforming chamber Internal configuration diagram of the second example of the reforming chamber Schematic diagram of the second example of organic semiconductor device manufacturing equipment Internal configuration diagram of organic semiconductor element formed using conventional transparent conductive film formation method

The transparent conductive film forming method of the present invention will be described by taking an example of a method for manufacturing an organic semiconductor element.
(Organic film formation process)
Reference numeral 30 in FIG. 2 indicates an example of an organic semiconductor element manufacturing apparatus.

The organic semiconductor element manufacturing apparatus 30 has a transfer chamber 31, which includes a carry-in / carry-out chamber 32, first and second organic film forming chambers 33 and 34, and a vapor deposition chamber 35. The first PVD chamber 36, the reforming chamber 37, the second PVD chamber 38, and the sealing chamber 39 are connected to each other through a gate valve 40.
The chambers 31 to 39 and the gate valve 40 are shielded from the atmosphere and evacuated by a vacuum evacuation device (not shown).

A transfer device 41 is disposed in the transfer chamber 31, and is configured so that substrates can be carried in and out between the transfer chamber 31 and the other chambers 32 to 39 via the gate valve 40. .
A plurality of processing objects 10 before the film forming process are carried into the carry-in / carry-out chamber 32 in advance. Referring to FIG. 3A, here, the processing object 10 includes a substrate 11 and an electrode layer 21 formed on the surface of the substrate 11.

With reference to FIG. 2, the processing object 10 in the loading / unloading chamber 32 is unloaded from the loading / unloading chamber 32 by the transfer device 41 and loaded into the first organic film forming chamber 33.
Two evaporation sources (not shown) are disposed in the first organic film forming chamber 33, the organic material of the hole injection layer is disposed in one evaporation source, and the hole transport layer is disposed in the other evaporation source. Organic materials are arranged.

  The vapor of the organic material of the hole injection layer is discharged from the evaporation source in which the organic material of the hole injection layer is disposed, and the vapor reaches the surface of the electrode layer 21 with reference to FIG. The hole injection layer 22 is formed on the surface, and then the vapor of the organic material of the hole transport layer is discharged from the evaporation source in which the organic material of the hole transport layer is disposed, and arrives at the surface of the hole injection layer 22 Thus, the hole transport layer 23 is formed on the surface of the hole injection layer 22.

After the hole transport layer 23 is formed, the processing object 10 on which the hole injection layer 22 and the hole transport layer 23 are formed is transferred to the first organic film forming chamber by the transport device 41 with reference to FIG. It is carried out from the inside 33 and carried into the second organic film forming chamber 34.
An evaporation source (not shown) is disposed in the second organic film forming chamber 34, and an organic material for the organic light emitting layer is disposed in the evaporation source.

The vapor of the organic material of the organic light emitting layer is released from this evaporation source, and with reference to FIG. 3C, the organic light emitting layer 24 is formed on the surface of the hole transport layer 23 by reaching the surface of the hole transport layer 23 To do.
After forming the organic light emitting layer 24, the processing target 10 on which the organic light emitting layer 24 is formed is carried out from the second organic film forming chamber 34 by the transfer device 41 with reference to FIG. Carry in.
Two evaporation sources (not shown) are arranged in the vapor deposition chamber 35, the organic material of the electron transport layer is arranged in one evaporation source, and the organic material of the electron injection layer is arranged in the other evaporation source. Yes.

  The vapor of the organic material of the electron transport layer is discharged from the evaporation source in which the organic material of the electron transport layer is disposed, and the surface of the organic light emitting layer 24 is reached by referring to FIG. The electron transport layer 25 is formed on the surface, and then the vapor of the organic material of the electron injection layer is emitted from the evaporation source in which the organic material of the electron injection layer is arranged to reach the surface of the electron transport layer 25 to transport the electron. An electron injection layer 26 is formed on the surface of the layer 25.

  The electron injection layer 26 is not limited to an organic film, and the electron injection layer 26 made of a metal-doped organic film is formed by causing the organic material of the electron injection layer and the vapor of the metal material to reach the surface of the electron transport layer 25 together. Alternatively, the electron injection layer 26 made of a metal film may be formed by allowing the vapor of the metal material of the electron injection layer to reach the surface of the electron transport layer 25. When the electron injection layer 26 made of a metal film is formed, the thickness of the electron injection layer 26 is preferably 15 nm or less. This is because if it is thicker than 15 nm, light transmittance cannot be obtained.

(Metal oxide film formation process)
After forming the electron injection layer 26, the processing object 10 with the electron injection layer 26 exposed on the surface is unloaded from the vapor deposition chamber 35 by the transfer device 41 and is loaded into the first PVD chamber 36.
In the present embodiment, a first sputtering gas supply device 42 is connected to the first PVD chamber 36, and a first target (not shown) is disposed in the first PVD chamber 36.

The first target is tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped indium oxide (AZO), GZO, ZnO, SnO ₂ , In ₂ O ₃ , oxidation It is composed of one or more metal oxides of titanium, tungsten oxide, Ta oxide, and Mo oxide.

  There is a correspondence between the deposition conditions of the metal oxide film and the oxygen content of the metal oxide film formed under the deposition conditions. In this embodiment, the film formation conditions of the metal oxide film are determined in advance, and the oxygen content of the metal oxide film formed under the film formation conditions is determined in advance by a measurement test or simulation using an analyzer such as EPMA. Seek and remember.

  After carrying the film formation target 10 into the first PVD chamber 36, the surface of the electron injection layer 26 exposed on the surface of the film formation target 10 is made to face the surface of the first target, and the first sputtering gas A sputtering gas is supplied from the supply device 42 into the first PVD chamber 36.

The sputtering gas is any one of Ar, He, Ne, Kr, and Xe, or a mixed gas of two or more, and does not include oxygen gas.
Plasma is generated in an atmosphere of a sputtering gas that does not contain oxygen gas, a first target is sputtered under predetermined film-forming conditions, and sputtered particles are released from the first target. ), The sputtered particles reach the surface of the electron injection layer 26 to form a metal oxide film 27 on the surface of the electron injection layer 26.

The metal oxide film 27 is made of the same metal oxide as the first target. Since the first target contains oxygen atoms, the formed metal oxide film 27 contains oxygen atoms. .
In this embodiment, the film is formed under a predetermined film formation condition, and the oxygen content of the formed metal oxide film 27 is the same as the oxygen content stored in advance. That is, the oxygen content of the formed metal oxide film 27 is known.
Since the sputtering gas does not contain oxygen gas, the electron injection layer 26 and the underlying organic films 22 to 25 are not damaged by reaction with oxygen ions or oxygen radicals during the formation of the metal oxide film 27.

  When the film thickness of the metal oxide film 27 reaches a desired film thickness of 1 nm or more and 50 nm or less, sputtering is stopped. The thinner the metal oxide film 27 is, the easier it is to oxidize or reduce the entire metal oxide film 27 in the metal oxide film modification step described later. However, when the film thickness is less than 1 nm, the metal oxide film 27 Each of the underlying layers 22 to 26 also undergoes an oxidation or reduction reaction. If the metal oxide film 27 is thicker than 50 nm, it is difficult to oxidize or reduce the entire metal oxide film 27.

(Metal oxide film modification process)
After the metal oxide film 27 is formed, the processing object 10 with the metal oxide film 27 exposed on the surface is unloaded from the first PVD chamber 36 and loaded into the reforming chamber 37 by the transfer device 41. .

Reference numeral 37 a in FIG. 6 shows an example of the reforming chamber 37.
Reforming chamber 37a includes a vacuum chamber 61, an oxygen-containing gas source 62 _1, the inert gas source 62 _2, and a reducing gas source 62 _3, the first, second, third flow controller 63 _1, 63 ₂ , 63 ₃ and a plasma generation source 64.

A vacuum exhaust device 66 and a vacuum gauge 67 are connected to the vacuum chamber 61, and the vacuum chamber 61 is in a vacuum atmosphere at a desired pressure.
The plasma generation source 64 is hermetically inserted into the wall surface of the vacuum chamber 61, and a part of the plasma generation source 64 is disposed inside the vacuum chamber 61 and the other part is disposed outside the vacuum chamber 61 to generate plasma of the supplied gas. And is configured to be discharged into the vacuum chamber 61.

The oxygen-containing gas source 62 ₁ , the inert gas source 62 _2, and the reducing gas source 62 ₃ are disposed outside the vacuum chamber 61 and connected to the plasma generation source 64 through the gas introduction pipe 65. From the oxygen-containing gas source 62 ₁ , the inert gas source 62 _2, and the reducing gas source 62 ₃ , an oxygen-containing gas containing oxygen in the chemical structure, an inert gas, and a reducing gas, respectively. The gas is supplied to the plasma generation source 64 through the gas introduction pipe 65.

The first, second, and third flow control devices 63 ₁ , 63 ₂ , and 63 ₃ are respectively attached in the middle of the gas introduction pipes 65 through which the oxygen-containing gas, the inert gas, and the reducing gas pass. Yes. The first flow rate control device 63 ₁ can adjust the flow rate of the oxygen-containing gas supplied from the oxygen-containing gas source 62 ₁ to the plasma generation source 64, and the second flow rate control device 63 ₂ is an inert gas. The flow rate of the inert gas supplied from the source 62 ₂ to the plasma generation source 64 can be adjusted, and the third flow rate control device 63 ₃ reduces the reduction gas supplied from the reducing gas source 62 ₃ to the plasma generation source 64. The flow rate of the sex gas can be adjusted.

Valves 69 that can be opened and closed are respectively installed in the middle of the gas introduction pipes 65 through which the oxygen-containing gas, the inert gas, and the reducing gas pass.
A substrate holder 68 is disposed at a position facing the plasma generation source 64.
After the film formation target 10 is carried into the vacuum chamber 61, the film formation target 10 is held by the substrate holder 68 with the surface of the metal oxide film 27 facing the plasma generation source 64.

The oxygen content (hereinafter referred to as the reference value) of the transparent conductive film formed on the organic film is determined in advance according to the purpose (desired film quality) of the transparent conductive film.
The oxygen content contained in the metal oxide film 27 after the metal oxide film formation step is known from the film formation conditions of the metal oxide film formation step, and this oxygen content is compared with a predetermined reference value. If it is less than the reference value, the plasma of the oxygen-containing gas is emitted from the plasma generation source 64, and if it is more than the reference value, either one of the inert gas and the reducing gas or both of the inert gas and the reducing gas is emitted from the plasma generation source 64. A mixed gas plasma is emitted.

Here, the oxygen-containing gas is any one kind of gas among O ₂ , H ₂ O, CO ₂ , CO, and N ₂ O, or a mixed gas of two or more kinds.
Here, the inert gas contains one kind of gas or two or more kinds of mixed gases of Ar, He, Ne, Kr, and Xe, and the reducing gas is H ₂ , CO, and the like. , N ₂ contains any one kind of gas or two or more kinds of mixed gas.

  The surface of the metal oxide film 27 of the film formation target 10 is directed to the plasma generation source 64, and the metal oxide film 27 was released from the plasma generation source 64 while maintaining the exposed state of the surface. Exposure to plasma.

  When the metal oxide film 27 is exposed to the plasma of the oxygen-containing gas, it undergoes an oxidation reaction to increase the oxygen content, and is exposed to the plasma of one of the inert gas and the reducing gas or a mixed gas of both. Then, the oxygen content is reduced due to a reduction reaction, and referring to FIG. 1B, the metal oxide film 27 is a first transparent conductive film 27 ′ having the same oxygen content as a predetermined reference value. become.

  A standard in which the oxygen content of the metal oxide film 27 containing oxygen atoms is determined in advance in a shorter time than the method of oxidizing the metal film containing no oxygen atoms by oxidation or reduction reaction. Can be changed to a value.

  In addition, by performing an oxidation or reduction reaction while maintaining the state where the surface of the metal oxide film 27 is exposed, deposits do not adhere to the surface of the metal oxide film 27 to create a shadow on the plasma. Unevenness of oxidation or reduction reaction hardly occurs.

In the present embodiment, by exposing the metal oxide film 27 to plasma, the reaction rate is faster and the productivity is better than the method of exposing to the oxidizing or reducing gas.
The metal oxide film forming step and the metal oxide film modifying step may be alternately repeated a plurality of times to laminate a plurality of first transparent conductive films 27 ′.

(Second transparent conductive film forming step)
After forming the first transparent conductive film 27 ′, the object 10 on which the first transparent conductive film 27 ′ is formed is unloaded from the reforming chamber 37 by the transfer device 41 with reference to FIG. Then, it is carried into the second PVD chamber 38.
A second sputtering gas supply device 45 and a reactive gas supply device 46 are connected to the second PVD chamber 38, and a second target (not shown) is disposed in the second PVD chamber 38. .

The second target is the ITO, and IZO, and AZO, and GZO, and ZnO, and SnO _2, and an In ₂ O _3, and Nb ₂ O _5, titanium oxide, and tungsten oxide, and oxide Ta, oxide It is comprised from any 1 type or 2 types or more of metal oxides among Mo.

  The surface of the first transparent conductive film 27 ′ of the film formation target 10 is opposed to the surface of the second target, and a sputtering gas is supplied from the second sputtering gas supply device 45 into the second PVD chamber 38. Oxygen gas is supplied from the reaction gas supply device 46.

  Plasma is generated in an atmosphere of a mixed gas of sputtering gas and oxygen gas, the second target is sputtered, and sputtered particles are released from the second target. With reference to FIG. Sputtered particles reach the surface of 27 ', and a second transparent conductive film 28 is formed on the surface of the first transparent conductive film 27'. The second transparent conductive film 28 is made of the same metal oxide as the second target.

By performing sputtering in an atmosphere containing oxygen gas, it is possible to form a transparent conductive film having a higher oxygen content than in sputtering in an atmosphere not containing oxygen gas, and in an atmosphere containing no oxygen gas. A transparent conductive film can be formed at a higher speed than oxidation after sputtering.
The electron injection layer 26 is covered with the first transparent conductive film 27 ′, and the electron injection layer 26 and the underlying organic films 22 to 25 are not damaged by reacting with oxygen ions or oxygen radicals in the plasma. Absent.

(Sealing film deposition process)
The processing object 10 on which the second transparent conductive film 28 is formed is unloaded from the second PVD chamber 38 and loaded into the sealing chamber 39 by the transfer device 41 with reference to FIG.
In the sealing chamber 39, referring to FIG. 5, a light-transmitting sealing film 29 is formed on the surface of the second transparent conductive film 28 to obtain the organic semiconductor element 2.

  With reference to FIG. 2, the obtained organic semiconductor element 2 is unloaded from the sealing chamber 39 and loaded into the loading / unloading chamber 32 by the transfer device 41. Next, it is carried out from the carry-in / carry-out chamber 32 to the atmosphere. Referring to FIG. 5, the sealing film 29 prevents the layers 22 to 28 underlying the sealing film 29 from reacting with moisture and reaction gas in the atmosphere and deteriorating, and the performance of the organic semiconductor element 2 is maintained. Is done.

(Heating process)
In addition, after the above-mentioned metal oxide film modification | reformation process, before the 2nd transparent conductive film formation process, the film-forming target object 10 in which 1st transparent conductive film 27 'was formed is each organic film 22 ~. The heat treatment may be performed at a heating temperature equal to or lower than the glass transition temperature of 26, or the processing object 10 on which the second transparent conductive film 28 is formed after the second transparent conductive film forming step is applied to each organic film 22. You may heat-process at the heating temperature below the glass transition temperature of -26.

By heat treatment, the film quality of the first transparent conductive film 27 ′ can be made uniform.
The heating temperature is preferably 50 ° C. or higher and 200 ° C. or lower. If it is lower than 50 ° C., the film quality of the first transparent conductive film 27 ′ cannot be made uniform due to insufficient heating, and if it is higher than 200 ° C., the organic films 22 to 26 may be damaged by heat.

(Another example of metal oxide film formation process)
The metal oxide film forming step of the present invention is not limited to the above-described metal oxide film forming step as long as it is a PVD method in an atmosphere not containing oxygen.

Another example of the metal oxide film forming step will be described.
After forming the electron injection layer 26, the processing object 10 with the electron injection layer 26 exposed on the surface is unloaded from the vapor deposition chamber 35 by the transfer device 41 and is loaded into the first PVD chamber 36.
In the present embodiment, a vapor deposition source (not shown) is disposed in the first PVD chamber 36, and a metal oxide material of a metal oxide film is disposed in the vapor deposition source.

The metal oxide material is any one of ITO, IZO, AZO, GZO, ZnO, SnO ₂ , In ₂ O ₃ , titanium oxide, tungsten oxide, Ta oxide, and Mo oxide. Or it is comprised from 2 or more types of metal oxides.

  There is a correspondence between the deposition conditions of the metal oxide film and the oxygen content of the metal oxide film formed under the deposition conditions. The film forming conditions for the metal oxide film are determined in advance, and the oxygen content of the metal oxide film formed under the film forming conditions is obtained in advance through tests and simulations and stored.

  In a vacuum atmosphere not containing oxygen gas, vapor of the metal oxide material is released from the vapor deposition source under a predetermined film formation condition, and the vapor is deposited on the surface of the electron injection layer 26 with reference to FIG. And a metal oxide film 27 is formed on the surface of the electron injection layer 26.

The metal oxide film 27 is made of the same metal oxide as the metal oxide material. Since the metal oxide material contains oxygen atoms, the formed metal oxide film 27 contains oxygen atoms. .
In this embodiment, the film is formed under a predetermined film formation condition, and the oxygen content of the formed metal oxide film 27 is the same as the oxygen content stored in advance. That is, the oxygen content of the formed metal oxide film 27 is known.
Since the oxygen atmosphere is not contained in the vacuum atmosphere, the electron injection layer 26 and the underlying organic films 22 to 25 are not damaged by reacting with the oxygen gas during the formation of the metal oxide film 27.

(Another example of metal oxide film modification process)
If the metal oxide film modification step of the present invention can form the first transparent conductive film 27 ′ having a desired film quality by oxidizing or reducing the metal oxide film 27, the above-described metal oxide film is used. It is not limited to the reforming process.

Another example of the metal oxide film modification step will be described.
After the metal oxide film 27 is formed, the processing object 10 with the metal oxide film 27 exposed on the surface is unloaded from the first PVD chamber 36 and loaded into the reforming chamber 37 by the transfer device 41. .

Reference numeral 37 b in FIG. 7 shows an example of the reforming chamber 37.
Of the structure of the reforming chamber indicated by reference numeral 37b, the same portions as those of the reforming chamber indicated by reference numeral 37a described above are denoted by the same reference numerals and description thereof is omitted.

The reforming chamber 37b includes an ion gun 74 and a substrate bias power source 79 instead of the plasma generation source 64 of the reforming chamber 37a.
The ion gun 74 is hermetically inserted through the wall surface of the vacuum chamber 61, a part thereof is disposed in the vacuum chamber 61 and faces the substrate holding unit 68, and the other part is disposed outside the vacuum chamber 61. The plasma of the supplied gas is generated, and the ions in the plasma are discharged into the vacuum chamber 61.

The oxygen-containing gas source 62 ₁ , the inert gas source 62 _2, and the reducing gas source 62 ₃ are connected to the ion gun 74 via the gas introduction pipe 65. From the oxygen-containing gas source 62 ₁ , the inert gas source 62 _2, and the reducing gas source 62 ₃ , oxygen-containing gas, inert gas, and reducing gas are each ionized through the gas introduction pipe 65. The gun 74 is supplied.

The vacuum chamber 61 is placed at the ground potential.
The substrate bias power source 79 is electrically connected to the substrate holding unit 68 so that a positive voltage or a negative voltage can be applied to the substrate holding unit 68 with respect to the ground potential.

After the processing object 10 is carried into the vacuum chamber 61, the processing object 10 is held by the substrate holder 68 with the surface of the metal oxide film 27 facing the ion gun 74.
The oxygen content (reference value) of the transparent conductive film formed on the organic film is determined in advance according to the purpose (desired film quality) of the transparent conductive film.

  The oxygen content contained in the metal oxide film 27 after the metal oxide film formation step is known from the film formation conditions of the metal oxide film formation step, and this oxygen content is compared with a predetermined reference value. If it is less than the reference value, an oxygen-containing gas is supplied to the ion gun 74 to release oxygen ions. If it is greater than the reference value, the ion gun 74 is supplied with either an inert gas or a reducing gas. Both gas mixtures are supplied to release cations.

Here, the cation is one kind or two or more kinds of cations among Ar ion, He ion, Ne ion, Kr ion, Xe ion, H ion, and N ion.
In this embodiment, a positive voltage and a negative voltage are alternately applied from the substrate bias power supply 79 to the substrate holding unit 68.

  When a voltage having a polarity opposite to the charge of the emitted ions is applied to the substrate holding unit 68, the released ions are attracted to the substrate holding unit 68 and exposed to the surface of the processing object 10. 27 enters the metal oxide film 27.

  When oxygen ions are implanted, the metal oxide film 27 is oxidized to increase the oxygen content, and when cations are implanted, the metal oxide film 27 is reduced to decrease the oxygen content. The first transparent conductive film 27 ′ has the same oxygen content as the determined reference value.

The reaction rate or reaction depth of the metal oxide film 27 may be increased or decreased by increasing or decreasing the amount of ions emitted from the ion gun 74 or the absolute value of the voltage applied to the substrate holding unit 68.
Further, a voltage having a value different from that of the other part may be applied to a part of the substrate holding part 68 so that a part of the first transparent conductive film 27 ′ has a film quality different from that of the other part.
In the present embodiment, a positive voltage and a negative voltage are alternately applied to the substrate holder 68, and the surface of the first transparent conductive film 27 ′ is prevented from being scraped by incident ions.

In addition, the apparatus used for the transparent conductive film formation method of this invention is not limited to the structure of the above-mentioned single-wafer | sheet-fed organic-semiconductor-element manufacturing apparatus 30 with reference to FIG. 2, but with reference to FIG. 39 may be an in-line type organic semiconductor device manufacturing apparatus 30 ′ connected in series via the gate valve 40 in this order.
In the above description, the organic semiconductor element 2 that emits light is formed using the transparent conductive film forming method of the present invention. However, even if an organic semiconductor element that receives incident light such as an image sensor or a solar cell is formed. Good.

27 …… Metal oxide film 27 ′ …… First transparent conductive film 28 …… Second transparent conductive film

Claims (20)

A transparent conductive film forming method for forming a transparent conductive film on an organic film,
A metal oxide film forming step of releasing metal oxide particles in an atmosphere containing no oxygen gas, allowing the particles to reach the organic film, and forming a metal oxide film on the organic film;
A metal oxide film modification step of oxidizing the metal oxide film to form a first transparent conductive film;
A method for forming a transparent conductive film.   In the metal oxide film modification step, the metal oxide film is oxidized by exposing the metal oxide film to a plasma of an oxygen-containing gas containing oxygen in the chemical structure while maintaining a state where the surface of the metal oxide film is exposed. The method for forming a transparent conductive film according to claim 1. 3. The transparent conductive film according to claim 2, wherein the oxygen-containing gas is any one of O ₂ , H ₂ O, CO ₂ , CO, and N ₂ O, or a mixed gas of two or more. Forming method.   The transparent conductive film forming method according to claim 1, wherein in the metal oxide film modification step, oxygen ions are implanted into the metal oxide film to be oxidized. A transparent conductive film forming method for forming a transparent conductive film on an organic film,
A metal oxide film forming step of releasing metal oxide particles in an atmosphere containing no oxygen gas, allowing the particles to reach the organic film, and forming a metal oxide film on the organic film;
A metal oxide film reforming step of reducing the metal oxide film to form a first transparent conductive film;
A method for forming a transparent conductive film.   In the metal oxide film modification step, the metal oxide film is turned into plasma of one of an inert gas and a reducing gas while maintaining a state where the surface of the metal oxide film is exposed. The method of forming a transparent conductive film according to claim 5, wherein the transparent conductive film is reduced by exposure.   The transparent conductive film forming method according to claim 6, wherein the inert gas contains any one of Ar, He, Ne, Kr, and Xe. The transparent conductive film forming method according to claim 6, wherein the reducing gas contains any one of H ₂ , CO, and N ₂ .   In the metal oxide film modification step, any one of positive ions of Ar ions, He ions, Ne ions, Kr ions, Xe ions, H ions, and N ions is applied to the metal oxide film. The transparent conductive film forming method according to claim 5, wherein ions are implanted and reduced.   In the metal oxide film forming step, the metal oxide material is heated to release vapor of the metal oxide from the metal oxide material in an atmosphere not containing oxygen gas, and the vapor is deposited on the organic film. The transparent conductive film forming method according to claim 1, wherein the metal oxide film is formed on the organic film.   In the metal oxide film forming step, a metal oxide target is sputtered in an atmosphere of a sputtering gas not containing oxygen gas, the metal oxide particles are released from the target, and the particles are placed on the organic film. The transparent conductive film forming method according to claim 1, wherein the metal oxide film is formed on the organic film.   The method for forming a transparent conductive film according to claim 11, wherein the sputtering gas is one kind of gas or a mixture of two or more kinds of Ar, He, Ne, Kr, and Xe. The first transparent conductive film includes tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped indium oxide (AZO), GZO, ZnO, SnO ₂ , and In ₂ O _3. 13. The film according to claim 1, wherein the film contains one or more metal oxides of titanium oxide, tungsten oxide, Ta oxide, and Mo oxide. A transparent conductive film forming method.   The transparent conductive film forming method according to claim 1, wherein, in the metal oxide film forming step, the metal oxide film is formed on the organic film with a thickness of 1 nm to 50 nm.   The transparent conductive film forming method according to claim 1, wherein the metal oxide film forming step and the metal oxide film modifying step are alternately repeated a plurality of times.   After the metal oxide film reforming step, metal oxide particles are released into an atmosphere containing oxygen gas, and the particles reach the first transparent conductive film, and the first transparent conductive film The transparent conductive film formation method of any one of Claims 1 thru | or 15 which has a 2nd transparent conductive film formation process which forms a 2nd transparent conductive film on it. The second transparent conductive film includes tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped indium oxide (AZO), GZO, ZnO, SnO ₂ , and In ₂ O _3. The transparent conductive film according to claim 16, which is a film containing one or more metal oxides of Nb ₂ O ₅ , titanium oxide, tungsten oxide, Ta oxide, and Mo oxide. Forming method.   The process according to claim 1, further comprising an annealing step in which the object to be processed on which the first transparent conductive film is formed is heat-treated at a heating temperature lower than a glass transition temperature of the organic film after the metal oxide film reforming step. The method for forming a transparent conductive film according to claim 15.   The annealing process which heat-processes the process target object in which the said 2nd transparent conductive film was formed at the heating temperature below the glass transition temperature of the said organic film after a said 2nd transparent conductive film formation process. Or the transparent conductive film formation method of any one of Claim 17.   The method for forming a transparent conductive film according to claim 18, wherein the heating temperature is 50 ° C. or higher and 200 ° C. or lower.

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