JP2007075719A - Manufacturing method of membrane, manufacturing method of device, manufacturing method of fuel cell, device, electro-optic device, fueo cell and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a membrane which can form an inclined composition area by using a polymer material, a manufacturing method of a device, a manufacturing method of a fuel cell, a device, an electro-optic device, a fuel cell and electronic equipment. <P>SOLUTION: A material liquid 26 of a positive hole injecting layer, material liquids for luminescent layers 27R, 27G, 27B and an electron injecting layer 28 are overlapped and applied on an element forming layer 10. Thereafter, the above materials are left as they are for a predetermined time, and the adjacent material liquids are diffused and then dried to form a diffusion area. Since when the material of the positive injecting layer 15 and the material of luminescent layers 17R, 17G, 17B are applied and left as they are, the two liquid materials are diffused and entangled each other, first diffusion areas 16R, 16G, 16B, the inclined composition areas, can be formed. In a same manner, since when the materials of the luminescent layers 17R, 17G, 17B and the material of the electron injecting layer 19 are applied and left as they are, the two liquid materials are diffused and entangled each other, second diffusion areas 18R, 18G, 18B, the inclined composition area, can be formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film manufacturing method, a device manufacturing method, a fuel cell manufacturing method, a device, an electro-optical device, a fuel cell, and an electronic apparatus.

In recent years, flat panel displays used in electronic devices such as personal computers and mobile phones are increasingly required to have higher density, higher image quality, and longer life.
As a flat panel display, for example, in an organic EL display device, an organic EL element constituting the organic EL display has a structure in which an organic light emitting material is formed into a thin film between an anode and a cathode. Then, electrons and holes injected from both electrodes are recombined in the light emitting layer, and the excited energy is emitted and emitted. Since such an organic EL element has a high charge injection barrier between each electrode and the light emitting layer, a hole injection transport layer (referred to as a hole injection layer) serving as an anode buffer layer and an electron serving as a cathode buffer layer. It has a laminated structure in which an injection layer is provided.
Non-Patent Document 1 proposes one method for extending the life. According to this, when the material of each of the hole injection layer, the light emitting layer, and the electron injection / transport layer is a low molecular material, the layer is formed by co-evaporation and has a gradient composition, so that the organic EL element has a long lifetime. What can be done is introduced.
On the other hand, polymer materials having high luminous efficiency have been developed and reported as organic light emitting materials. In particular, polymer materials having good light emission characteristics in the long wavelength region have been introduced.

Proceedings of SPIE, Volume 4800 (2003), USA, Zakya H. Kafafi, Homer Antoniadis “Organic Light-Emitting Materials and Devices VI”, P.A. 55-61

However, the method by co-evaporation shown in Non-Patent Document 1 cannot be applied to the case where the material of each layer is a polymer material, and it is impossible to form each layer.
The present invention has been made in order to solve the above-described problems, and its object is to manufacture a film capable of forming a gradient composition region using a polymer material, a device manufacturing method, and a fuel cell manufacturing. To provide a method, a device, an electro-optical device, a fuel cell, and an electronic apparatus.

  In order to achieve the above-described object, a film manufacturing method of the present invention is a film manufacturing method in which a plurality of films are stacked on a substrate, wherein a first functional liquid is applied to the substrate, A first layer arranging step of arranging a layer, and a second functional liquid having compatibility with the first functional liquid is applied on the first layer, and a second layer is arranged. And the first functional liquid and the second functional liquid are diffused at the interface between the first layer and the second layer to form a first diffusion region between the two layers. And a first diffusion region forming step to be formed.

  According to this, after the first functional liquid is disposed to form the first layer, the second functional liquid is disposed to form the second layer, and then the first layer and the second layer are formed. At the boundary surface of the layers, the first functional liquid and the second functional liquid having compatibility with the first functional liquid diffuse to form a first diffusion region. Therefore, a gradient composition region can be formed in the first diffusion region.

For example, when the material of the first layer and the second layer includes a conductive polymer material, in the first diffusion region, the polymer material of the first layer and the polymer of the second layer The material is in a diffused state. Therefore, compared with the case where the first layer and the second layer are directly laminated, in the first diffusion region, the polymer material of the first layer and the polymer material of the second layer are in contact with each other. There are many places. As a result, electrons, holes, and ions can easily flow between the first layer and the second layer.
Similarly, for example, when the materials of the first layer and the second layer include conductive particles, the first mixed particle material and the second layer particle material are used in the first mixed layer. Is mixed. Accordingly, in the first diffusion region, there are many places where the material of the first layer and the polymer material of the second layer are in contact with each other, and therefore, between the first layer and the second layer. Electrons, holes and ions can be easily flowed.
When applying the second functional liquid, the first layer may be in a liquid or semi-dry state, and the second functional liquid may contain a solvent for re-dissolving the first layer. good.

  In the film manufacturing method of the present invention, the first diffusion region forming step includes a diffusion step of diffusing each material of the first functional liquid and the second functional liquid for a predetermined time after the application of the second layer, and a diffusion step. And a drying step of drying the first layer and the second layer.

  According to this, in the first diffusion region, since the first diffusion region forming step includes the diffusion step and the drying step, each material of the first functional liquid and the second functional liquid is added in the diffusion step. By diffusing for a predetermined time, it is reliably diffused and dried in a drying process. Therefore, in the first diffusion region, the first functional liquid and the second functional liquid can be reliably diffused.

  In the method for producing a film of the present invention, the third functional liquid is applied to the third functional liquid having compatibility with the second functional liquid on the second layer, and the third layer is disposed. A second diffusion region is formed between the two layers by diffusing the second functional fluid and the third functional fluid at the interface between the step and the second layer and the third layer; Two diffusion region forming steps may be provided.

According to this, as in the case where the first diffusion region is formed between the first layer and the second layer, the second layer having a gradient composition between the second layer and the third layer is used. A diffusion region is formed. Therefore, the gradient composition in both the first diffusion region between the first layer and the second layer and the second diffusion region between the second layer and the third layer. It can be.
For example, if the second diffusion region has the same function as the first diffusion region and the material of the third layer includes a conductive material, the second diffusion region and the third layer In the meantime, electrons, holes and ions can easily flow.

  In the film manufacturing method of the present invention, the first diffusion region forming step and the second diffusion region forming step are preferably performed simultaneously.

  According to this, since the first diffusion region forming step and the second diffusion region forming step are performed at the same time, the drying step is performed once. Therefore, since the process is completed once, it can be manufactured with high productivity.

  In the film manufacturing method of the present invention, both the first functional liquid and the second functional liquid include the first main material and the second main material, and the first main material is the second functional liquid. More contained in the first functional liquid, and the second main material is contained more in the second functional liquid than in the first functional liquid. In the first diffusion region, the first functional liquid and the second functional liquid are contained. The functional liquid diffuses, the content of the first main material decreases in the order of the first layer, the first diffusion region, and the second layer, and the second layer, the first diffusion region, the first layer The layer is preferably formed so that the content of the second main material decreases in the order of the layers.

  According to this, the first main material is formed so as to decrease stepwise from the first layer to the second layer, and conversely, the second main material is changed from the first layer to the second layer. It is formed so as to increase. In the first diffusion region formed between the first layer and the second layer, there is no abrupt concentration change so that the contents of the first main material and the second main material gradually change. It is formed. Therefore, further ideal diffusion is performed, and an ideal gradient composition can be obtained over the first layer, the first diffusion region, and the second layer.

For example, the above-described method can be applied to a manufacturing method for forming a hole injection transport layer (referred to as a hole injection layer) of an organic EL element constituting a pixel of an organic EL display device. When the first main material is a hole transfer material in the material of the hole injection layer and the second main material is an insulating material in the material of the hole injection layer, the first layer is on the anode side. When the second layer is formed on the light emitting layer side, the hole injection layer is in the form of a layer with more hole transport material on the anode side and more insulating material on the light emitting side.
In the hole injection layer in this embodiment, the anode side has a lot of hole transfer materials, so that holes are easily generated. On the other hand, since there are many insulating materials on the light emitting layer side, the amount of holes flowing into the light emitting layer is restricted and the inflow of electrons from the light emitting layer is restricted. Further, since the hole transport material is formed so as to gradually decrease in the mixed layer, the generated holes can be sequentially flowed through the hole transport material. As a result, stagnation of holes can be prevented and the hole transport material can flow efficiently, so that an organic EL element with high light emission efficiency can be obtained.

In the film manufacturing method of the present invention, it is desirable that the functional liquid is applied by using a droplet discharge method.
According to this, by using the droplet discharge method, compared with other coating methods such as a spin coating method, the consumption of the functional liquid is not wasted, and a minute amount of the functional liquid can be applied onto the substrate. it can. Furthermore, position control can be performed with high precision.

  A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, wherein the device has a hole injection layer, a light emitting layer, and an electron injection layer, and the first layer has , A hole injection layer, and the second layer is a light emitting layer.

  According to this, in this device, the light emitting layer is disposed on the hole injection layer, and a first diffusion region is formed between the hole injection layer and the light emitting layer. The hole injection layer and the light emitting layer have a form made of a polymer or an oligomer, and in the first diffusion region, the long chain molecules of the light emitting layer and the hole injection layer are intertwined and contact each other. There are many places. When holes flow from the hole injection layer to the light emitting layer, holes flow from the long chain molecules of the plurality of hole injection layers to the long chain molecules of one light emitting layer. Therefore, in the case where the first diffusion region is formed, the positive diffusion region and the light emitting layer are more positive when the first diffusion region is formed than when the holes flow from the hole injection layer to the light emitting layer. Resistance when holes flow from the hole injection layer to the light emitting layer is reduced, and holes can be efficiently supplied to the light emitting layer.

  A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, wherein the device has a hole injection layer, a light emitting layer, and an electron injection layer, and the first layer has , A light emitting layer, and the second layer is an electron injection layer.

According to this, in this device, the electron injection layer is disposed on the light emitting layer, and the first diffusion region is formed between the light emitting layer and the electron injection layer. The light emitting layer and the electron injecting layer have a form composed of a polymer or an oligomer. In the first diffusion region, the long chain molecules of the light emitting layer and the electron injecting layer are intertwined, and there is a place where they are in contact with each other. There are many. When electrons flow from the electron injection layer to the light emitting layer, electrons flow from the long chain molecules of the plurality of electron injection layers with respect to the long chain molecules of one light emitting layer.
Therefore, when the electron injection layer and the light emitting layer are formed in two layers, the electron injection layer is formed when the first diffusion region is formed as compared with the case where electrons flow from the electron injection layer to the light emitting layer. The resistance when electrons flow from the light to the light emitting layer is reduced, and electrons can be efficiently supplied to the light emitting layer.

  A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, and the device includes an electron injection layer, a light emitting layer, and a hole injection layer, The layer is an electron injection layer, and the second layer is a light emitting layer.

According to this, in this device, a light emitting layer is disposed on the electron injection layer, and a first diffusion region is formed between the electron injection layer and the light emitting layer. The electron injection layer and the light emitting layer have a form made of a polymer or an oligomer. In the first diffusion region, the long chain molecules of the light emitting layer and the electron injection layer are intertwined, and there are places where they are in contact with each other. There are many. When electrons flow from the electron injection layer to the light emitting layer, electrons flow from the long chain molecules of the plurality of electron injection layers with respect to the long chain molecules of one light emitting layer.
Therefore, in the case where the first diffusion region is formed as compared with the case where electrons flow from the electron injection layer to the light emitting layer when the electron injection layer and the light emitting layer are formed in two layers, Resistance when electrons flow to the light emitting layer is reduced, and electrons can be efficiently supplied to the light emitting layer.

  A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, and the device includes an electron injection layer, a light emitting layer, and a hole injection layer, The layer is a light emitting layer, and the second layer is a hole injection layer.

According to this, in this device, the hole injection layer is disposed on the light emitting layer, and a first diffusion region is formed between the light emitting layer and the hole injection layer. The light emitting layer and the hole injection layer are formed of a polymer or an oligomer, and in the first diffusion region, the long chain molecules of the light emitting layer and the hole injection layer are intertwined and contact each other. There are many places. When holes flow from the hole injection layer to the light emitting layer, holes flow from the long chain molecules of the plurality of hole injection layers to the long chain molecules of one light emitting layer.
Therefore, when the hole injection layer and the light-emitting layer are formed in two layers, the positive diffusion region is formed more positively when the first diffusion region is formed than when holes flow from the hole injection layer to the light-emitting layer. Resistance when holes flow from the hole injection layer to the light emitting layer is reduced, and holes can be efficiently supplied to the light emitting layer.

  A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, wherein the device has a hole injection layer, a light emitting layer, and an electron injection layer, and the first layer has , A hole injection layer, the second layer is a light emitting layer, and the third layer is an electron injection layer.

  According to this, the device is arranged in the order of a hole injection layer, a light emitting layer, and an electron injection layer. A first diffusion region is formed between the hole injection layer and the light emitting layer. A second diffusion region is formed between the light emitting layer and the electron injection layer. The hole injection layer, the light emitting layer, and the electron injection layer have a form composed of a polymer or an oligomer, and in the first diffusion region, the long chain molecules of the light emitting layer and the hole injection layer are intertwined, There are many places that are in contact. When holes flow from the hole injection layer to the light emitting layer, holes flow from the long chain molecules of the plurality of hole injection layers with respect to the molecular arrangement of one light emitting layer.

Therefore, when the hole injection layer and the light-emitting layer are formed in two layers, the positive diffusion region is formed more positively when the first diffusion region is formed than when holes flow from the hole injection layer to the light-emitting layer. Resistance when holes flow from the hole injection layer to the light emitting layer is reduced, and holes can be efficiently supplied to the light emitting layer.
In the second diffusion region, the long chain molecules of the light emitting layer and the electron injection layer are intertwined, and there are many portions in contact with each other. When electrons flow from the electron injection layer to the light emitting layer, electrons flow from the long chain molecules of the plurality of electron injection layers to the long chain molecules of one light emitting layer.

Therefore, when the electron injection layer and the light emitting layer are formed in two layers, the first diffusion region is formed when the first diffusion region is formed as compared with the case where electrons flow from the electron injection layer to the light emitting layer. Resistance when electrons flow to the light emitting layer is reduced, and electrons can be efficiently supplied to the light emitting layer.
Since both holes and electrons are efficiently supplied to the light emitting layer, the light emitting layer can emit light efficiently.

A device manufacturing method of the present invention is a device manufacturing method using the above-described film manufacturing method, and the device includes an electron injection layer, a light emitting layer, and a hole injection layer, The layer is an electron injection layer, the second layer is a light emitting layer, and the third layer is a hole injection layer.
According to this, the device is arranged in the order of an electron injection layer, a light emitting layer, and a hole injection layer. A first diffusion region is formed between the electron injection layer and the light emitting layer, and a second diffusion region is formed between the light emitting layer and the hole injection layer.
In the first diffusion region, the long chain molecules of the electron injection layer and the light emitting layer are intertwined, and there are many portions in contact with each other. Similarly, in the second diffusion region, the long chain molecules of the light emitting layer and the hole injection layer are intertwined, and there are many portions that are in contact with each other.
Therefore, in the case where the first diffusion region is formed as compared with the case where electrons flow from the electron injection layer to the light emitting layer when the electron injection layer and the light emitting layer are formed in two layers, Resistance when electrons flow to the light emitting layer is reduced, and electrons can be efficiently supplied to the light emitting layer.
Similarly, in the case where the second diffusion region is formed as compared with the case where holes flow from the hole injection layer to the light emitting layer when the hole injection layer and the light emitting layer are formed in two layers, Resistance when holes flow from the hole injection layer to the light emitting layer is reduced, and holes can be efficiently supplied to the light emitting layer.
As a result, since both holes and electrons are efficiently supplied to the light emitting layer, the light emitting layer can emit light efficiently.

The device of the present invention is manufactured using the device manufacturing method described above.
According to this, since at least one of an electron and a hole is efficiently supplied to the light emitting layer, this device can be a device capable of emitting light with high luminous efficiency and high luminance.

  The fuel cell manufacturing method of the present invention is a fuel cell manufacturing method using the above-described membrane manufacturing method, wherein the first layer and the second layer are a first electrode layer and a first fluid diffusion. It corresponds to two layers adjacent in the stacking order among the layer, the first reaction layer, the electrolyte layer, the second reaction layer, the second fluid diffusion layer, and the second electrode layer.

According to this, when the two layers are the first electrode layer and the first fluid diffusion layer, a diffusion region in which the materials of the two layers are mixed is formed between the two layers. Electrons easily flow between one electrode layer and the first fluid diffusion layer. Therefore, the electrical resistance between the first electrode layer and the first fluid diffusion layer can be reduced as compared with the case where the diffusion region is not formed. Similarly, when a diffusion region is formed between the first fluid diffusion layer and the first reaction layer, the diffusion region is not formed between the first fluid diffusion layer and the first reaction layer as compared with the case where no diffusion region is formed. The electrical resistance can be lowered.
When a diffusion region is formed between the first reaction layer and the electrolyte layer, the ionic substance generated from the fuel by the catalytic action in the first reaction layer is likely to come into contact with the material of the electrolyte layer. It becomes easy to flow in. Therefore, compared with the case where the diffusion region is not formed, in the first reaction layer, the fuel is efficiently separated into the ionic substance and the electrons, so that the power generation efficiency is improved.
When a diffusion region is formed between the electrolyte layer and the second reaction layer, the ionic material that has passed through the electrolyte layer and the catalyst constituting the second reaction layer are likely to come into contact with each other, so that no diffusion region is formed. Compared with the case, it becomes easier for the ionic substance and the electrons to be combined, and the power generation efficiency is improved.
When the diffusion region is formed between the second reaction layer and the second fluid diffusion layer, the region between the second reaction layer and the second fluid diffusion layer is smaller than when the diffusion region is not formed. Electric resistance can be lowered. Similarly, when the diffusion region is formed between the second fluid diffusion layer and the second electrode layer, the second fluid diffusion layer and the second electrode layer are compared with the case where the diffusion region is not formed. It is possible to reduce the electrical resistance between the two.

An electro-optical device according to the present invention includes the above-described device.
According to this, since the device has high luminous efficiency and can emit light with high luminance, the electro-optical device including this device can be an electro-optical device having bright display performance.

According to another aspect of the present invention, there is provided an electronic apparatus including the electro-optical device as a display unit.
According to this, since the electro-optical device is an electro-optical device having a bright display performance, an electronic device including the electro-optical device as a display unit is an electronic device including a bright display unit. Can do.

The fuel cell of the present invention is manufactured by the above-described fuel cell manufacturing method.
According to this, the fuel cell is manufactured so that the electric resistance of each layer is low and the fluidity of the ionic substance is improved. Therefore, this fuel cell can be a high output fuel cell.

The electronic apparatus according to the present invention includes the fuel cell as a power supply source.
According to this, since the fuel cell is a high output fuel cell, an electronic device equipped with the fuel cell as a power supply source can be an electronic device capable of consuming a large amount of power.

(First embodiment)
Hereinafter, a first embodiment of an organic electroluminescence display (hereinafter referred to as “organic EL display”) as an electro-optical device embodying the present invention will be described with reference to FIGS.
FIG. 1 is a planar schematic circuit layout diagram of the organic EL display of the present invention, and FIG. 2 is a cross-sectional view of the organic EL display taken along the line aa in FIG. FIG. 3 is an enlarged view of the main part of FIG.

  As shown in FIG. 1, the organic EL display 1 includes a display unit 2 and a flexible circuit board 3 connected to the lower side of the display unit 2.

  The display unit 2 includes a substrate 4. In this embodiment, the substrate 4 is made of a glass plate. As shown in FIGS. 1 and 2, the substrate 4 includes a substantially quadrangular display region 5 at the approximate center thereof. In the display area 5, as shown in FIG. 1, m × n pixels 6 are formed in a matrix. A pair of scanning line drive circuits 8 and an inspection circuit 9 are formed on the substrate 4 in an area other than the display area 5 (hereinafter referred to as a non-display area 7).

  In the display area 5, n pixels 6 groups per row are formed in m rows. Each pixel 6 includes a red organic EL element 10R as a light emitting element that emits red light as a device, a green organic EL element 10G as a light emitting element that emits green light, and a light emitting element that emits blue light. Together with the blue organic EL element 10B as a single pixel. The organic EL elements for color 10R, 10G, and 10B are arranged in the order of the organic EL element for red 10R, the organic EL element for green 10G, and the organic EL element for blue 10B along the X direction (column direction) in FIG. ing.

  That is, the organic EL elements 10R, 10G, and 10B for each color are red organic EL element 10R, green organic EL element 10G, blue organic EL element 10B, and red organic EL along the X arrow direction in FIG. The element 10R, the green organic EL element 10G,... Are repeatedly arranged in this order. In addition, organic EL elements 10R, 10G, and 10B of the same color are arranged along the direction of the arrow Y (row direction) in FIG. The organic EL elements for color 10R, 10G, and 10B are arranged at equal intervals with the adjacent organic EL elements for color 10R, 10G, and 10B.

  As shown in FIG. 2, each color organic EL element 10 </ b> R, 10 </ b> G, 10 </ b> B is formed on a circuit forming layer 4 b formed on the substrate 4. This circuit formation layer 4b constitutes a circuit element such as a thin film transistor 11 for driving each pixel 6 formed in the display area 5, and a scanning line driving circuit 8 and an inspection circuit 9 formed in the non-display area 7. This is a layer in which a circuit element portion is formed. In addition, in a region corresponding to the display region 5 on the circuit forming layer 4b, a bank 12 that partitions each organic EL element 10R, 10G, 10B in a matrix is formed.

The surface of the bank 12 has liquid repellency. The bank 12 may be made of a material having liquid repellency, for example, a fluorine resin. Further, those having no liquid repellency, for example, an organic resin such as an acrylic resin or a polyimide resin formed into a pattern and the surface made liquid repellant by CF ₄ plasma treatment or the like may be used.

  As shown in FIG. 3, pixel electrodes 13 are formed on the bottoms of concave regions (hereinafter referred to as element formation regions 10) on the circuit formation layer 4 b and partitioned by the banks 12. Each pixel electrode 13 is electrically connected to the corresponding thin film transistor 11 through a contact hole 14. On each pixel electrode 13, in the present embodiment, a hole injection / transport layer (hereinafter referred to as a hole injection layer 15) as a first layer, first diffusion regions 16R, 16G, 16B, a second layer Light emitting layers 17R, 17G, and 17B as layers, second diffusion regions 18R, 18G, and 18B, and an electron injecting and transporting layer (hereinafter referred to as an electron injecting layer 19) as a third layer in order of layers and regions A functional layer 20 is formed by laminating layers.

The hole injection layer 15 has a function of generating and propagating holes upon receiving the voltage of the pixel electrode 13. The forming material is preferably a polymer material having triphenylamine as a skeleton, and in this embodiment, a material containing ADS254BE manufactured by ADS is used.
The light emitting layer 17R is a layer made of an organic light emitting material that emits red light. In this embodiment, MEHPPV (poly (3-methoxy, 6- (3-ethylhexyl) paraphenylenevinylene) is used as a material for forming the light emitting layer 17R. The light emitting layer 17G is a layer composed of an organic light emitting material that emits green light, and in this embodiment, the light emitting layer 17G is formed of polydioctylfluorene and F8BT (dioctylfluorene and benzoic acid). The light-emitting layer 17B is a layer composed of an organic light-emitting material that emits blue light, and in the present embodiment, the light-emitting layer 17B is a layer composed of an organic light-emitting material that emits blue light. The material containing polydioctylfluorene is adopted.

The first diffusion region 16R is located between the hole injection layer 15 and the light emitting layer 17R, and is a region where the materials constituting the hole injection layer 15 and the light emitting layer 17R are mixed. Similarly, the first diffusion region 16G is located between the hole injection layer 15 and the light emitting layer 17G, and is a region where the materials constituting each of the hole injection layer 15 and the light emitting layer 17G are mixed. The first diffusion region 16B is located between the hole injection layer 15 and the light emitting layer 17B, and is a region where the materials constituting the hole injection layer 15 and the light emitting layer 17B are mixed.
The electron injection layer 19 has a function of transmitting electrons to the light emitting layers 17R, 17G, and 17B. A material containing a bisacetylacetonate / calcium complex (Ca (acac) 2) was used as a material for forming the layer. Between the light emitting layers 17R, 17G, and 17B and the electron injection layer 19, second diffusion regions 18R, 18G, and 18B are formed. This region is a region where the material of the light emitting layers 17R, 17G, and 17B and the material of the electron injection layer 19 are mixed.

  A cathode 21 is formed over the entire surface of the functional layer 20 and the bank 12, and electrons are caused to flow through the electron injection layer 19. A part of the cathode 21 is formed so as to cover the non-display area 7. The cathode 21 is made of a light-transmitting conductive material. In the present embodiment, the cathode 21 has an aluminum thin film formed by a vapor deposition method.

  Then, the pixel electrode 13, the hole injection layer 15, the first diffusion region 16R, the light emitting layer 17R, the second diffusion region 18R, the electron injection layer 19 and the cathode 21 are stacked to form the red organic EL element 10R. Composed. The pixel electrode 13, the hole injection layer 15, the first diffusion region 16G, the light emitting layer 17G, the second diffusion region 18G, the electron injection layer 19, and the cathode 21 are laminated to constitute the green organic EL element 10G. The Similarly, the pixel electrode 13, the hole injection layer 15, the first diffusion region 16B, the light emitting layer 17B, the second diffusion region 18B, the electron injection layer 19 and the cathode 21 are laminated to constitute the blue organic EL element 10B. Is done.

In the red organic EL element 10R, when the thin film transistor 11 is switched on, a voltage is applied between the pixel electrode 13 and the cathode 21, and the holes generated in the hole injection layer 15 move to the light emitting layer 17R. The electrons move from the cathode 21 to the electron injection layer 19 and move to the light emitting layer 17R via the electron injection layer 19. In the light emitting layer 17R, the combination of holes and electrons excites the material of the light emitting layer 17R, temporarily enters an excited state, emits light, and shifts to the ground state.
In a non-patent document (Proceedings of SPIE vol.4800 (2003) P.55-61), a first diffusion region 16R is formed between the hole injection layer 15 and the light emitting layer 17R, and the electron injection layer 19 emits light. It is introduced that when the second diffusion region 18R is formed between the layers 17R, the luminous efficiency of the light emitting layer 17R as the red organic EL element 10R is improved and the lifetime is extended.

The following can be considered as the reason. The forming material of each layer of the hole injection layer 15 and the light emitting layer 17R is a thread-like long chain molecule. By forming the first diffusion region 16R, the material of the hole injection layer 15 and the material of the light emitting layer 17R are changed. A region having many portions that are in contact with each other is formed. Accordingly, a large number of paths through which holes generated from the material of the hole injection layer 15 move from the long chain molecules of the hole injection layer 15 to the long chain molecules of the light emitting layer 17R are formed.
Similarly, in the second diffusion region 18R, many paths through which electrons move from the long chain molecules of the electron injection layer 19 to the long chain molecules of the light emitting layer 17R are formed. As a result, it is considered that holes and electrons have a reduced resistance to movement to the light emitting layer 17R, increase the opportunity for the holes and electrons to merge, and increase the light emission efficiency.

Further, since there are many paths through which holes move from the hole injection layer 15 to the long chain molecules of the light emitting layer 17R and electrons move from the electron injection layer 19 to the long chain molecules of the light emitting layer 17R, there are many positive paths. The holes and electrons reach various points of the long chain molecules of the light emitting layer 17R and coalesce. Therefore, in the long chain molecules of the light emitting layer 17R, the molecules are excited, the light emitting points are dispersed, and the deterioration of the long chain molecules is delayed.
The same applies to the green organic EL element 10G and the blue organic EL element 10B.

  A sealing member 23 made of a light transmissive material is formed so as to cover the entire surface of the cathode 21. As shown in FIG. 1, a pair of scanning line driving circuits 8 is arranged in the non-display area 7 on the substrate 4 so as to sandwich the display area 5. Each scanning line driving circuit 8 outputs a scanning signal for selecting a desired group of pixels 6 in the m-row pixels 6 group described above. Further, as shown in FIG. 1, an inspection circuit 9 is formed in the non-display area 7 in the vertical direction of the display area 5 on the substrate 4. The inspection circuit 9 is a circuit for inspecting whether or not each color organic EL element 10R, 10G, 10B is normally driven, and the organic EL display 1 is driven and inspected before shipping.

  As shown in FIG. 1, a data line driving circuit 24 and a control circuit 25 are formed on the flexible circuit board 3. The data line driving circuit 24 outputs driving signals for the respective color organic EL elements 10R, 10G, and 10B to the group of pixels 6 selected by the scanning line signal output from the scanning line driving circuit 8. The light emission luminance of each color organic EL element 10R, 10G, 10B is determined by this drive signal. Thereby, the color and light emission luminance of each pixel 6 are determined.

  The control circuit 25 is a circuit for comprehensively controlling the driving of the scanning line driving circuit 8 and the data line driving circuit 24, generates various control signals, and uses the generated control signals as the scanning line driving circuit 8 and the data line driving. Each is output to the circuit 24.

  In the organic EL display 1 configured as described above, the scanning line driving circuit 8 and the data line driving circuit 24 are driven and controlled by various control signals output from the control circuit 25, and the organic EL elements 10R, 10G, and The light emission luminance of 10B is controlled. As a result, a desired image is displayed on the display area 5.

Next, a droplet discharge device 30 for forming the functional layer 20 by a droplet discharge method in the manufacture of the organic EL display 1 will be described with reference to FIGS. FIG. 4 is a schematic perspective view of the droplet discharge device. FIG. 5 is a schematic perspective view showing a portion of the head portion of the droplet discharge device, and FIG. 6 is a cross-sectional view of a main portion of the head portion.
In the organic EL display 1, the material of the hole injection layer 15, the light emitting layers 17 R, 17 G, and 17 B and the electron injection layer 19 is formed by a droplet discharge device 30. The formation of each layer other than the hole injection layer 15, the first diffusion regions 16R, 16G, and 16B, the light emitting layers 17R, 17G, and 17B, the second diffusion regions 18R, 18G, and 18B, and the electron injection layer 19 is publicly known. Since it is formed by an apparatus and a method, description of the manufacturing method is omitted.

4 shows a hole injection layer material liquid 26 as a first functional liquid, which is a liquid composition for forming the hole injection layer 15, the light emitting layers 17 R, 17 G, and 17 B and the electron injection layer 19. It is a perspective view which shows the structure of the droplet discharge apparatus 30 which apply | coats the material liquid 27R, 27G, 27B of the light emitting layer as a functional liquid, and the material liquid 28 of the electron injection layer as a 3rd functional liquid.
As shown in FIG. 4, the droplet discharge device 30 includes a base 31 formed in a rectangular parallelepiped shape. In the present embodiment, the longitudinal direction of the base 31 is the Y direction, and the direction orthogonal to the Y direction is the X direction.

  On the upper surface 31a of the base 31, a pair of guide rails 32a and 32b extending in the Y direction are provided so as to protrude over the entire width in the Y direction. On the upper side of the base 31, a stage 33 constituting a scanning means provided with a linear motion mechanism (not shown) corresponding to the pair of guide rails 32a and 32b is attached. The linear movement mechanism of the stage 33 is, for example, a screw type linear movement mechanism including a screw shaft (drive shaft) extending in the Y direction along the guide rails 32a and 32b and a ball nut screwed to the screw shaft. The drive shaft is connected to a Y-axis motor (not shown) that receives a predetermined pulse signal and rotates forward and backward in units of steps. When a drive signal corresponding to a predetermined number of steps is input to the Y-axis motor, the Y-axis motor rotates normally or reversely, and the stage 33 corresponds to the same number of steps along the Y-axis direction. The robot moves forward or backward (scans in the Y direction) at a predetermined speed.

  A mounting surface 34 is formed on the upper surface of the stage 33, and a suction-type substrate chuck mechanism (not shown) is provided on the mounting surface 34. When the substrate 4 is placed on the placement surface 34, the substrate 4 is positioned and fixed at a predetermined position on the placement surface 34 by the substrate chuck mechanism.

  A pair of support bases 35a and 35b are erected on both sides in the X direction of the base 31, and a guide member 36 extending in the X direction is installed on the pair of support bases 35a and 35b. The guide member 36 is formed so that the width in the longitudinal direction is longer than the X direction of the stage 33, and one end of the guide member 36 projects to the support base 35 a side.

  On the upper side of the guide member 36, a storage tank 37 for storing the liquid to be discharged is provided. On the other hand, below the guide member 36, a guide rail 38 extending in the X direction is provided so as to protrude over the entire width in the X direction.

  The carriage 39 arranged so as to be movable along the guide rail 38 is formed in a substantially rectangular parallelepiped shape. The linear movement mechanism of the carriage 39 is, for example, a screw type linear movement mechanism having a screw shaft (drive shaft) extending in the X direction along the guide rail 38 and a ball nut screwed to the screw shaft. The drive shaft is connected to an X-axis motor (not shown) that receives a predetermined pulse signal and rotates forward and backward in steps. When a drive signal corresponding to a predetermined number of steps is input to the X-axis motor, the X-axis motor rotates forward or reversely, and the carriage 39 moves forward or backward along the X direction by the amount corresponding to the same number of steps. Move (scan in X direction).

  Further, as shown in FIG. 5, the first to fifth droplet discharge heads 45 to 49 protrude in parallel to each other in the X direction on the lower surface of the carriage 39 (the surface on the stage 33 side: the head arrangement surface 39a). It is installed. Nozzle plates P1 to P5 are provided on the lower surfaces of the first to fifth droplet discharge heads 45 to 49, respectively. In the nozzle plates P1 to P5, a plurality of nozzles N1 to N5 are arranged at predetermined intervals in the X direction.

FIG. 6 is a cross-sectional view of a main part for explaining the structure of the first to fifth droplet discharge heads 45 to 49. As shown in FIG. 6, a cavity 54 is formed at a position above the nozzle plates P1 to P5 and facing the nozzles N1 to N5. The hole injection layer material liquid 26 stored in the storage tank 37 is supplied to the cavity 54 of the first droplet discharge head 45. Further, the material liquids 27R, 27G, and 27B of the light emitting layer stored in the storage tank 37 are supplied to the cavities 54 of the second to fourth droplet discharge heads 46, 47, and 48. Similarly, the material liquid 28 of the electron injection layer stored in the storage tank 37 is supplied to the cavity 54 of the fifth droplet discharge head 49.
On the upper side of the cavity 54, a vibration plate 55 that vibrates in the vertical direction and expands and contracts the volume in the cavity 54 and a piezoelectric element 56 that expands and contracts in the vertical direction and vibrates the vibration plate 55 are disposed.
The piezoelectric element 56 expands and contracts in the vertical direction to vibrate the diaphragm 55, and the diaphragm 55 enlarges and reduces the volume in the cavity 54. Thereby, the material liquid of the functional layer 20 supplied into the cavity 54 is discharged through the nozzles N1 to N5.

  The first droplet discharge head 45 discharges micro droplets 50 of the material liquid 26 of the hole injection layer. Similarly, the second droplet discharge head 46 discharges the minute droplet 51R of the material liquid 27R of the light emitting layer, and the third droplet discharge head 47 discharges the minute droplet 51G of the material liquid 27G of the light emitting layer. The fourth droplet discharge head 48 discharges the minute droplet 51B of the material liquid 27B of the light emitting layer. The fifth droplet discharge head 49 discharges micro droplets 52 of the material liquid 28 of the electron injection layer.

  When the first to fifth droplet discharge heads 45 to 49 receive the nozzle drive signal for driving and controlling the piezoelectric element 56, the piezoelectric element 56 expands and the diaphragm 55 increases the volume in the cavity 54. to shrink. As a result, the material liquid 26 of the hole injection layer corresponding to the reduced volume is ejected from the nozzle N1 of the first droplet ejection head 45 as the micro droplet 50. Further, from the nozzles N2, N3, and N4 of the second to fourth droplet discharge heads 46, 47, and 48, the material liquids 27R, 27G, and 27B of the light emitting layer corresponding to the reduced volume are microdroplets 51R, 51G, and 51B. Are discharged. Similarly, the material liquid 28 of the electron injection layer is discharged as the fine droplets 52 from the nozzle N5 of the fifth droplet discharge head 49.

  Next, a method for manufacturing the hole injection layer 15, the light emitting layers 17R, 17G, and 17B and the electron injection layer 19 using the above-described droplet discharge device 30 will be described with reference to FIGS. FIG. 7 is a flowchart of a manufacturing method of the hole injection layer 15, the light emitting layers 17R, 17G, and 17B and the electron injection layer 19, and FIGS. 8 to 10 illustrate a droplet discharge operation of the droplet discharge device 30. FIG. FIG.

  In the flowchart of FIG. 7, steps S1 to S4 are manufactured by the same droplet discharge device 30. In step S1, a material liquid 26 for a hole injection layer is applied to a certain element formation region 10 on the substrate 4 as a first layer arranging step. In step S2, the light emitting layer material liquids 27R, 27G, and 27B are applied as a second layer arrangement process, and in step S3, the electron injection layer material liquid 28 is applied as a third layer arrangement process. In step S4, it is determined whether or not all functional layer material liquids have been applied. When not applied, steps S1 to S3 are repeated for the element forming region 10 that has not been applied. When all the functional layer material liquids are applied, the process proceeds to step S5.

  Specifically, the substrate 4 on which the bank 12 is formed and the pixel electrode 13 is formed in the bank 12 (element formation region 10) is arranged and fixed on the mounting surface 34 of the stage 33. Then, after setting the carriage 39 (first to fifth droplet discharge heads 45 to 49) at a predetermined position in the X direction, the stage 33 (substrate 4) is moved in the Y direction. Then, minute droplets 50, 51R, 51G, 51B, and 52 are ejected to the element formation region 10 of the substrate 4 that passes in the Y direction directly below the first to fifth droplet ejection heads 45 to 49.

  At this time, the red element formation region 10 formed on the substrate 4 first passes directly under the first droplet discharge head 45 and is applied with the micro droplet 50, and then the second droplet discharge head. The minute droplet 51R is applied by passing directly under 46, and the minute droplet 52 is applied by passing directly under the fifth droplet discharge head 49.

  In step S5, the hole injection layer material liquid 26 and the light emitting layer material liquids 27R, 27G, and 27B are diffused, and the light emitting layer material liquids 27R, 27G, and 27B and the electron injection layer material liquid 28 are diffused. . Next, in step S6, the hole injection layer material liquid 26, the light emitting layer material liquids 27R, 27G, and 27B and the electron injection layer material liquid 28 are dried to form a functional layer.

That is, as shown in FIG. 8A, first, the micro droplet 50 of the material liquid 26 of the hole injection layer is first ejected from each nozzle N1 of the first droplet ejection head 45 into each element forming region 10. And applied (step S1). As a result, as shown in FIG. 8B, the material liquid 26 for the hole injection layer is applied in the element formation region 10.
Subsequently, as shown in FIG. 9A, the light emitting layer material liquid 27 </ b> R is transferred from the nozzle N <b> 2 of the second droplet discharge head 46 to the element forming region 10 where the hole injection layer material liquid 26 is applied. The minute droplet 51R is discharged and applied (step S2). As a result, as shown in FIG. 9B, in each element formation region 10, a liquid reservoir is formed in which the material liquid 26 for the hole injection layer and the material liquid 27 </ b> R for the light emitting layer are applied in an overlapping manner.

Subsequently, as shown in FIG. 9C, the material liquid 28 for the electron injection layer is supplied from the nozzle N5 of the fifth droplet discharge head 49 to the element formation region 10 where the material liquid 27R for the light emitting layer is applied. A micro droplet 52 is discharged and applied (step S3). As a result, as shown in FIG. 10A, the hole injection layer material liquid 26, the light emitting layer material liquid 27 </ b> R, and the electron injection layer material liquid 28 were applied to each element formation region 10 in an overlapping manner. A liquid pool is formed.
Similarly, in the green element formation regions 10, minute droplets 50 of the material liquid 26 of the hole injection layer are ejected and applied to each element formation region 10 from the nozzle N 1 of the first droplet ejection head 45. (Step S1) The material liquid 26 for the hole injection layer is applied. Next, the micro droplet 51G of the green light emitting layer material liquid 27G is ejected and applied from the nozzle N3 of the third droplet ejection head 47 (step S2), and hole injection is performed in each element formation region 10. A liquid reservoir is formed by applying the material liquid 26 for the layer and the material liquid 27G for the light emitting layer on top of each other. Subsequently, the minute droplets 52 of the material liquid 28 of the electron injection layer are ejected and applied from the nozzle N5 of the fifth droplet ejection head 49 (step S3), and hole injection is performed in each element formation region 10. A liquid reservoir is formed in which the material liquid 26 for the layer, the material liquid 27G for the light emitting layer, and the material liquid 28 for the electron injection layer are applied in layers.

In the blue element formation regions 10, minute droplets 50 of the material liquid 26 of the hole injection layer are discharged and applied to each element formation region 10 from the nozzle N <b> 1 of the first droplet discharge head 45 (step S <b> 1). ), The hole injection layer material liquid 26 is applied. Next, the micro droplet 51B of the material liquid 27B of the blue light emitting layer is ejected and applied from the nozzle N4 of the fourth droplet ejection head 48 (step S2), and hole injection is performed in each element formation region 10. A liquid reservoir is formed by applying the material liquid 26 for the layer and the material liquid 27B for the light emitting layer in an overlapping manner. Subsequently, a fine droplet 52 of the material liquid 28 of the electron injection layer is discharged and applied from the nozzle N5 of the fifth droplet discharge head 49 (step S3), and the hole injection layer is formed in each element formation region 10. A liquid reservoir is formed in which the material liquid 26, the light emitting layer material liquid 27B, and the electron injection layer material liquid 28 are applied in layers.
It is confirmed that the material liquid of each functional layer has been applied to all the element forming regions 10 that are to be applied, and if it has been applied, the application is terminated (step S4).

Next, as shown in FIG. 10B, in the diffusion process, the material liquid 26 for the hole injection layer, the material liquids 27R, 27G, and 27B for the light emitting layer and the electron injection layer formed in each element formation region 10. The liquid reservoir with the material liquid 28 is left for a predetermined time and diffused (step S5). In addition, the same xylene as the material liquids 27R, 27G, and 27B of the light emitting layer and the material liquid 28 of the electron injection layer is commonly used as the solvent or dispersion medium of the material liquid 26 of the hole injection layer of the present embodiment. . Accordingly, the material liquid 26 for the hole injection layer, the material liquids 27R, 27G, and 27B for the light emitting layer and the material liquid 28 for the electron injection layer are compatible functional liquids.
As a result, in the red element formation region 10, the hole injection layer material liquid 26 and the light emitting layer material liquid 27R diffuse at the boundary surface between the hole injection layer material liquid 26 and the light emitting layer material liquid 27R. A combined first diffusion liquid 57R is formed. Further, a second diffusion liquid 58R in which the light emitting layer material liquid 27R and the electron injection layer material liquid 28 diffuse together is formed at the interface between the light emitting layer material liquid 27R and the electron injection layer material liquid 28. The

Similarly, in the green element formation region 10, the hole injection layer material liquid 26 and the light emitting layer material liquid 27G diffuse at the boundary surface between the hole injection layer material liquid 26 and the light emitting layer material liquid 27G. A combined first diffusion liquid 57G is formed. Further, a second diffusion liquid 58G in which the material liquid 27G of the light emitting layer and the material liquid 28 of the electron injection layer are diffused is formed at the interface between the material liquid 27G of the light emitting layer and the material liquid 28 of the electron injection layer. The
In the blue element formation region 10, the hole injection layer material liquid 26 and the light emitting layer material liquid 27 </ b> B diffuse at the boundary surface between the hole injection layer material liquid 26 and the light emitting layer material liquid 27 </ b> B. 1 diffusion liquid 57B is formed. Further, a second diffusion liquid 58B in which the material liquid 27B of the light emitting layer and the material liquid 28 of the electron injection layer diffuse together is formed at the boundary surface between the material liquid 27B of the light emitting layer and the material liquid 28 of the electron injection layer. The

Next, in the drying step, the substrate 4 is dried. In this embodiment, drying is performed under vacuum (1 torr (133.3 Pa)) at room temperature for 20 minutes, whereby the solvent or the dispersion medium is removed. At this time, in the element formation region 10, the material liquid 26 for the hole injection layer, the first diffusion liquids 57R, 57G, 57B, the material liquids 27R, 27G, 27B for the light emitting layer, and the second diffusion liquids 58R, 58G, 58B. The material liquid 28 for the electron injection layer is solidified. As shown in FIG. 10C, the hole injection layer 15, the first diffusion regions 16R, 16G, and 16B, the light emitting layers 17R, 17G, and 17B, and the second diffusion regions 18R and 18G are formed on the pixel electrode 13. , 18B and the functional layer 20 composed of the electron injection layer 19 is formed.
It should be noted that the first diffusion regions 16R, 16G, and 16B are formed by the diffusion step and the drying step, and the second diffusion regions 18R, 18G, and 18B are formed by the diffusion step and the drying step. The second diffusion region forming step for forming is performed at the same time.

  Next, similarly to the cross section shown in FIG. 2, aluminum is vapor-deposited on the electron injection layer 19 (see FIG. 3), the bank 12, and the circuit formation layer 4 b by vapor deposition to form the cathode 21. Further, a sealing member 23 made of a light transmissive material is formed on the cathode 21. Thereby, the display part 2 of the organic EL display 1 is manufactured.

As described above, this embodiment has the following effects.
(1) According to this embodiment, in each element formation region 10 formed in the display region 5 of the substrate 4, the hole injection layer material liquid 26 is applied, and the light emitting layer material liquids 27 </ b> R and 27 </ b> G are applied thereon. 27B was applied. Then, it was left for a predetermined time, and after the two liquids diffused at the interface between the two adjacent liquids to form the first diffusion liquids 57R, 57G, and 57B, they were dried. Accordingly, the first diffusion regions 16R, 16G, and 16B are formed between the hole injection layer 15 and the light emitting layers 17R, 17G, and 17B. In the first diffusion regions 16R, 16G, and 16B, the long chain molecules of the hole injection layer 15 and the long chain molecules of the light emitting layers 17R, 17G, and 17B are entangled and many contact portions are formed. As a result, when a voltage is applied to the electrodes of the organic EL elements 10R, 10G, and 10B, the holes generated in the hole injection layer 15 easily move to the long-chain molecules of the light emitting layers 17R, 17G, and 17B. The organic EL elements 10R, 10G, and 10B that emit light can be used.

  (2) According to the present embodiment, the material liquids 27R, 27G, and 27B of the light emitting layer are ejected and applied in each element formation region 10 formed in the display region 5 of the substrate 4, and the electron injection layer is formed thereon. The material liquid 28 was discharged and applied. Then, it was left for a predetermined time, and after the two liquids diffused at the interface between the two adjacent liquids to form the second diffusion liquids 58R, 58G, and 58B, they were dried. Therefore, the second diffusion regions 18R, 18G, and 18B are formed between the light emitting layers 17R, 17G, and 17B and the electron injection layer 19. In the second diffusion regions 18R, 18G, and 18B, the long chain molecules of the light emitting layers 17R, 17G, and 17B and the long chain molecules of the electron injection layer 19 are entangled and many contact portions are formed. As a result, when a voltage is applied to the electrodes of the organic EL elements 10R, 10G, and 10B, the electrons in the electron injection layer 19 easily move to the long chain molecules of the light emitting layers 17R, 17G, and 17B, and the organic EL emits light efficiently. It can be set as the element 10R, 10G, 10B.

  (3) According to this embodiment, in each element formation region 10 formed in the display region 5 of the substrate 4, the first diffusion region 16R is provided between the hole injection layer 15 and the light emitting layers 17R, 17G, and 17B. , 16G, 16B were formed. Further, second diffusion regions 18R, 18G, and 18B were formed between the light emitting layers 17R, 17G, and 17B and the electron injection layer 19. Therefore, when a voltage is applied to the electrodes of the organic EL elements 10R, 10G, and 10B, a path through which holes move from the hole injection layer 15 to the light emitting layers 17R, 17G, and 17B, and the electron injection layer 19 to the light emitting layer 17R, Many paths through which electrons move to 17G and 17B are formed, and light is emitted efficiently. In addition, in the light emitting layers 17R, 17G, and 17B, places where holes and electrons are combined and molecules that emit light are excited are dispersed. As a result, the long-chain molecules of the light-emitting layers 17R, 17G, and 17B are dispersed without concentrating the light-emitting places, so that the organic EL elements 10R, 10G, and 10B having a long lifetime can be obtained.

  (4) According to the present embodiment, the first diffusion regions 16R, 16G, and 16B are coated with the material liquid 26 for the hole injection layer and the material liquids 27R, 27G, and 27B for the light emitting layer and left for a predetermined time. Then, it was diffused and dried to form a gradient composition region. Similarly, in the second diffusion regions 18R, 18G, and 18B, the material liquids 27R, 27G, and 27B for the light emitting layer and the material liquid 28 for the electron injection layer are applied, and are allowed to stand for a predetermined time to diffuse, diffuse, and dry. A gradient composition region was formed. That is, the gradient composition region can be formed even when the material is a polymer by diffusing the two types of functional liquids in a liquid laminated state.

(5) According to the present embodiment, the second to fifth liquid droplet ejection heads 46 to 46 ejected to the element formation region 10 at the same position as the element formation region 10 ejected by the nozzle N1 of the first liquid droplet ejection head 45. Forty-nine nozzles N <b> 2 to N <b> 5 are arranged on the same line in the direction of scanning the substrate 4. Accordingly, since the first to fifth droplet discharge heads 45 to 49 can discharge the element forming region 10 at the same point in one scan, it is possible to obtain a device with high productivity.
(6) According to the present embodiment, element formation of the hole injection layer material liquid 26, the light emitting layer material liquids 27R, 27G, and 27B and the electron injection layer material liquid 28, which are functional liquids, is performed by the droplet discharge method. Applied to area 10. Therefore, the amount of functional liquid consumed can be reduced as compared with a method of coating the entire surface such as a spin coating method. Furthermore, since the material to be applied is not heated unlike the vapor deposition method, the material to be applied is not damaged by heat.

(Second Embodiment)
Next, a second embodiment of the organic EL display 1 embodying the present invention will be described with reference to the flowchart of FIG.
In the present embodiment, the same members or parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.
In the first embodiment, the material for forming the hole injection layer 15 is a material containing a material containing ADS254BE manufactured by ADS in the material liquid 26 of the hole injection layer. The first hole injection layer material liquid as the first functional liquid and the second hole injection layer material liquid as the second functional liquid were used. The first hole injection layer material liquid and the second hole injection layer material liquid are poly (3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT) which is a hole transfer material as the first main material. ) And a material containing polystyrene sulfonic acid (hereinafter referred to as PSS), which is an insulating material as the second main material, was used in a functional liquid dispersed in pure water. Here, the first hole injection layer material liquid had a ratio of PEDOT and PSS of 2: 1, and the second hole injection layer material liquid had a ratio of PEDOT and PSS of 1: 2.

  In the first embodiment, the hole injection layer material liquid 26 is applied once, but in this embodiment, the first hole injection layer material liquid and the second hole injection layer material liquid are used twice. Apply separately. Specifically, first, the first hole injection layer material liquid is applied onto the pixel electrode 13 in the element formation region 10 by discharging the fine droplets of the droplet discharge device 30 from the nozzles (step S11). Next, fine droplets of the second hole injection layer material liquid are ejected from the nozzle and applied onto the first hole injection layer material liquid applied on the pixel electrode 13 (step S12).

  Subsequently, as in the first embodiment, the fine liquid droplets 51R, 51G, and 51B of the light emitting layer material liquids 27R, 27G, and 27B are ejected from the nozzles and applied (Step S13), and the electron injection layer material liquid is applied. 28 fine droplets 52 are ejected from the nozzle and applied (step S14). It is determined whether or not the material liquid of each functional layer has been applied to all the element formation regions 10 to be applied (step S15), and in all the element formation regions 10 to be applied, there are unapplied regions, Steps S11 to S15 are repeated. When the coating is applied to all the element formation regions 10 to be coated, the coating is finished and the process proceeds to step S16. Next, it is left for a predetermined time to diffuse two adjacent functional liquids (step S16). Thereafter, the substrate 4 is dried (step S17), and the functional layer 20 is formed.

  In the functional layer 20 thus formed, first, a first hole injection layer made of the first hole injection layer material liquid is formed on the pixel electrode 13. A third diffusion region in which the first hole injection layer material liquid and the second hole injection layer material liquid are diffused is formed thereon. Furthermore, a second hole injection layer made of the second hole injection layer material liquid is formed thereon.

  In this configuration, in the hole injection layer 15 of the red organic EL element 10R, a large amount of PEDOT, which is a hole transfer material, is distributed on the pixel electrode 13 side, and a large amount of PSS, which is an insulating material, is distributed on the light emitting layer 17R side. It is a layer. On the pixel electrode 13 side, PSS limits the amount of holes generated by PEDOT flowing to the light emitting layer 17R, and PSS protects electrons flowing from the light emitting layer 17R.

As described above, according to the present embodiment, in addition to the effects of the first embodiment, the following effects are further obtained.
(1) According to the present embodiment, in the hole injection layer 15, PEDOT, which is a hole transfer material, is distributed on the pixel electrode 13 side, so holes can be efficiently generated.
(2) When applying with a droplet discharge device, a solvent to which ethylene glycol or glycerin, which is a high boiling point solvent, is added is often used in order to improve dischargeability. At that time, the dielectric constant of the hole injection layer increases, holes excessively flow into the light emitting layer 17R, and the ratio of electrons to holes becomes inappropriate. According to the present embodiment, in the hole injection layer 15, the light emitting layer 17R side is a layer in which a large amount of PSS, which is an insulating material, is distributed. Therefore, the amount of movement of holes flowing to the light emitting layer can be limited. Furthermore, the movement of electrons flowing from the light emitting layer to the hole injection layer can be restricted.

  (3) According to the present embodiment, in the hole injection layer 15, the third diffusion region is formed between the first hole injection layer and the second hole injection layer. In the third diffusion region, there are many portions where the long chain molecules of the first hole injection layer and the long chain molecules of the second hole injection layer are entangled and in contact with each other. Therefore, it can be set as the structure which the hole produced | generated by the 1st positive hole injection layer tends to flow into the 2nd positive hole injection layer.

(Third embodiment)
Next, a third embodiment which is a polymer electrolyte fuel cell (PEFC) using the membrane manufacturing method of the present invention will be described with reference to FIGS. 12 to 13 and the flowchart of FIG.

  FIG. 12 is a schematic perspective view of a fuel cell manufactured using the membrane manufacturing method of the present invention. FIG. 13 is a schematic cross-sectional view showing a fuel cell.

As illustrated in FIG. 12, the fuel cell 71 includes a first substrate 72, a power generation unit 73, and a second substrate 74.
In the present embodiment, the first substrate 72 is made of a silicon plate, and a plurality of first channels 75 each having a rectangular groove shape are formed in parallel on the upper surface thereof. A power generation unit 73 is formed on the upper surface of the first substrate 72, and hydrogen gas 76 serving as fuel is supplied from a hydrogen fuel supply device (not shown) through the first flow path 75.

  As shown in FIG. 13, a first support layer 77 formed of porous carbon particles having a coarse particle diameter is formed in the first flow path 75 so that the hydrogen gas 76 can pass therethrough. It has become. A first electrode layer 78 made of copper particles is formed on the upper surfaces of the first substrate 72 and the first support layer 77, and serves as a negative electrode (anode) of the power generation unit 73. The first electrode layer 78 is supported by the first support layer 77 so as not to fall into the first flow path 75. The first electrode layer 78 is formed in a stitch shape so that the hydrogen gas 76 passes therethrough.

  On the upper surface of the first electrode layer 78, a first diffusion region 79 and a first fluid diffusion layer 80 are laminated in this order. In the first diffusion region 79, copper particles and carbon particles that are constituent elements of the first fluid diffusion layer 80 are mixed. The first fluid diffusion layer 80 is composed of carbon particles or the like, and the hydrogen gas 76 is uniformly diffused through the gaps between the particles.

  On the upper surface of the first fluid diffusion layer 80, a second diffusion region 81 and a first reaction layer 82 are laminated in this order. In the second diffusion region 81, carbon particles and platinum particles that are constituent elements of the first reaction layer 82 are mixed. The first reaction layer 82 is composed of platinum particles or the like having a catalytic action, and a reaction in which the hydrogen gas 76 is separated into hydrogen ions and electrons is performed.

  A third diffusion region 83 and an electrolyte layer 84 are stacked in this order on the upper surface of the first reaction layer 82. The third diffusion region 83 is a mixture of platinum particles and perfluorosulfonic acid polymer, which is a constituent element of the electrolyte layer 84, and it has been confirmed that the power generation efficiency is improved in such a form. The reason is that in the third diffusion region 83, there are many places where the platinum particles and the perfluorosulfonic acid polymer are in contact with each other, and hydrogen ions generated in the platinum particles are It is considered that the molecules easily come into contact with each other and move to the electrolyte layer 84 through the perfluorosulfonic acid polymer. Therefore, it is considered that hydrogen ions easily move from the first reaction layer 82 to the electrolyte layer 84. The electrolyte layer 84 is formed of Nafion (registered trademark) (manufactured by DuPont), which is a perfluorosulfonic acid polymer, and the like, and hydrogen ions pass through, but electrons are blocked.

  The hydrogen gas 76 that has passed through the first electrode layer 78 and has reached the first fluid diffusion layer 80 is diffused by traveling through the gaps between the carbon particles of the first fluid diffusion layer 80, so that It is supplied to the reaction layer 82. In the first reaction layer 82, hydrogen ions and electrons are generated. Hydrogen ions move to the electrolyte layer 84. The electrons cannot pass through the electrolyte layer 84, but travel from the first reaction layer 82 to the fuel through the second diffusion region 81, the first fluid diffusion layer 80, the first diffusion region 79, and the first electrode layer 78. The current flows through a load resistor (not shown) connected to the battery 71 and becomes a current. In the second diffusion region 81, there are many places where platinum and carbon particles are in contact with each other. This facilitates the movement of electrons from the first reaction layer 82 to the first fluid diffusion layer 80, and the electrical resistance is reduced. Similarly, in the first diffusion region 79, there are many places where carbon and copper particles are in contact with each other. For this reason, electrons easily move from the first fluid diffusion layer 80 to the first electrode layer 78, and the electrical resistance is reduced.

  A fourth diffusion region 85 and a second reaction layer 86 are sequentially stacked on the upper surface of the electrolyte layer 84. In the fourth diffusion region 85, a polymer that is a component of the electrolyte layer 84 and platinum particles that are a component of the second reaction layer 86 are mixed, and the polymer and the platinum particles are in contact with each other. There are many. As in the case of the second diffusion region 81, it has been confirmed that this configuration improves the power generation efficiency of the fuel cell 71. The reason for this is that the hydrogen ions that have been transmitted through the electrolyte layer 84 are likely to come into contact with the platinum particles that are in contact with the polymer, and the hydrogen ions are transferred to the second reaction layer 86 through the platinum particles. It seems to be easier. The second reaction layer 86 is composed of platinum particles having a catalytic action, and a reaction for generating water with hydrogen ions, electrons, and oxygen gas is performed.

  On the upper surface of the second reaction layer 86, a fifth diffusion region 87 and a second fluid diffusion layer 88 are laminated in this order. In the fifth diffusion region 87, platinum particles and carbon particles that are constituent elements of the second fluid diffusion layer 88 are mixed, and there are many places where the platinum particles and the carbon particles are in contact with each other. Therefore, electrons are easily transferred from the second fluid diffusion layer 88 to the second reaction layer 86, and the electrical resistance is reduced. Similar to the first fluid diffusion layer 80, the second fluid diffusion layer 88 is composed of carbon particles or the like, and diffuses oxygen gas.

  On the upper surface of the second fluid diffusion layer 88, a sixth diffusion region 89 and a second electrode layer 90 are laminated in this order. In the sixth diffusion region 89, carbon particles and copper particles that are constituent elements of the second electrode layer 90 are mixed, and there are many places where the carbon particles and the copper particles are in contact with each other. For this reason, electrons easily move from the second electrode layer 90 to the second fluid diffusion layer 88, and the electric resistance is reduced. Similarly to the first electrode layer 78, the second electrode layer 90 is formed in a mesh shape with copper particles and serves as the positive electrode (cathode) of the power generation unit 73. Also in the sixth diffusion region 89, the copper particles are formed in a mesh shape with good air permeability.

  On the upper surface of the second electrode layer 90, a second substrate 74 made of a silicon plate is disposed. On the lower surface of the second substrate 74, a plurality of rectangular groove-like second flow paths 91 are formed in parallel to each other and in a direction substantially perpendicular to the first flow path 75. A second support layer 92 made of porous carbon particles having a coarse particle diameter is formed in the second flow path 91, and the second electrode layer 90 is deformed and enters the second flow path 91. To prevent that.

  Air 93 is supplied to the second flow path 91 from an air supply device (not shown). The air 93 passes through the second electrode layer 90, diffuses in the second fluid diffusion layer 88, and enters the second reaction layer 86. On the other hand, the second electrode layer 90 is connected to a load resistance (not shown), and electrons flowing from the first electrode layer 78 to the load resistance are the second electrode layer 90 and the second fluid diffusion layer 88. , And reaches the second reaction layer 86.

  In the second reaction layer 86, a reaction for generating water is performed by hydrogen ions that have passed through the electrolyte layer 84, oxygen in the supplied air 93, and electrons. That is, when hydrogen gas 76 is supplied to the first flow path 75 and air 93 is supplied to the second flow path 91, a load resistance is connected between the first electrode layer 78 and the second electrode layer 90. When electricity flows through the load resistance, it acts as a battery.

  Next, a fuel cell manufacturing method will be described with reference to the flowchart of FIG.

  First, the first substrate 72 on which the first flow path 75 is formed is set in a droplet discharge device, and the first support layer material liquid composed of porous carbon particles and a solvent is contained in the first flow path 75. The fine liquid droplets are ejected from the nozzle of the liquid droplet ejection device and applied (step S21). Thereafter, the first substrate 72 is deaerated and vacuum-dried (step S22), and the first support layer 77 is formed in the first flow path 75. Subsequently, fine droplets of the first electrode layer material liquid composed of copper particles and the solvent thereof are ejected from the nozzle and applied to the first substrate 72 (step S23).

  Subsequently, fine droplets of the first fluid diffusion layer material liquid made of carbon particles and the solvent thereof are applied onto the first electrode layer material liquid on the first substrate 72 by discharging from the nozzle (step). S24). As a result, since the first electrode layer material liquid and the first fluid diffusion layer material liquid are laminated, the first substrate is left in this state for a while and the particles are diffused and mixed in the liquid. 72 is deaerated and vacuum-dried (step S25).

  The solvent of the first electrode layer material liquid and the solvent of the first fluid diffusion layer material liquid are composed of the same solvent, and after application of the first electrode layer material liquid and the first fluid diffusion layer material liquid Since these two liquids diffuse before drying, a diffusion region in which particles of the material of the two layers are mixed is formed. As a result, a first diffusion region 79 in which particles of the first electrode layer material liquid and the first fluid diffusion layer material liquid are mixed is formed. In addition, the first electrode layer material liquid and the first fluid diffusion layer material liquid are dried to form the first electrode layer 78 and the first fluid diffusion layer 80.

  Subsequently, fine droplets of the first fluid diffusion layer material liquid are ejected and applied a plurality of times on the first fluid diffusion layer 80 to obtain a predetermined thickness (step S26). Subsequently, fine droplets of the first reaction layer material liquid made of platinum particles and the solvent thereof are ejected and applied onto the applied first fluid diffusion layer material liquid (step S27). As a result, the first fluid diffusion layer material liquid and the first reaction layer material liquid are stacked.

  In this state, the first fluid diffusion layer material liquid and the first reaction layer material liquid are diffused and mixed, and then the first substrate 72 is degassed and vacuum dried (step S28). As a result, the first reaction layer 82 is formed on the second diffusion region 81 in which platinum particles and carbon particles are mixed.

  Subsequently, fine droplets of the first reaction layer material liquid composed of platinum particles and a solvent thereof are ejected and applied onto the first reaction layer 82 (step S29). Subsequently, fine droplets of the electrolyte layer material liquid composed of the electrolyte material and its solvent are ejected and applied (step S30). As a result, the electrolyte layer material liquid is laminated on the first reaction layer material liquid.

  In this state, the first reaction layer material liquid and the electrolyte layer material liquid are diffused and mixed, and then the first substrate 72 is degassed and vacuum-dried (step S31). As a result, a third diffusion region 83 in which platinum particles and perfluorosulfonic acid polymer are mixed is formed, and an electrolyte layer 84 is formed thereon.

  Subsequently, similarly, an electrolyte layer material liquid composed of an electrolyte material and its solvent is applied (step S32), and a second reaction layer material liquid composed of platinum particles and its solvent is applied thereon (step S33). . As a result, the electrolyte layer material liquid and the second reaction layer material liquid are laminated. After leaving for a while in this state and the electrolyte layer material liquid and the second reaction layer material liquid are diffused and mixed, the first substrate 72 is degassed and vacuum-dried (step S34). As a result, the fourth diffusion region 85 and the second reaction layer 86 in which the electrolyte material and platinum particles are mixed are formed on the electrolyte layer 84.

  Subsequently, a second reaction layer material liquid composed of platinum particles and the solvent thereof is applied (step S35), and a second fluid diffusion layer material liquid composed of carbon particles and the solvent is applied thereon (step S35). S36). As a result, the second reaction layer material liquid and the second fluid diffusion layer material liquid are stacked. In this state, the second reaction layer material liquid and the second fluid diffusion layer material liquid are diffused and mixed, and then the first substrate 72 is deaerated and vacuum dried (step S37). As a result, a fifth diffusion region 87 in which platinum particles and carbon particles are mixed and a second fluid diffusion layer 88 are formed on the second reaction layer 86.

  Subsequently, a second fluid diffusion layer material liquid composed of carbon particles and its solvent is applied (step S38), and a second electrode layer material liquid composed of copper particles and its solvent is applied thereon (step S38). S39). As a result, the second fluid diffusion layer material liquid and the second electrode layer material liquid are stacked. In this state, the second fluid diffusion layer material liquid and the second electrode layer material liquid are diffused and mixed by a predetermined thickness near the boundary surface, and then the first substrate 72 is degassed and vacuum dried. (Step S40). As a result, a sixth diffusion region 89 in which carbon particles and copper particles are mixed is formed on the second fluid diffusion layer 88, and the second electrode layer 90 is formed thereon.

  Next, the second substrate 74 on which the second flow path 91 is formed is set in a droplet discharge device, and a second support layer material made of porous carbon particles and a solvent is contained in the second flow path 91. A fine liquid droplet is applied (step S41). Thereafter, the second substrate 74 is degassed and vacuum-dried (step S42). As a result, the second support layer 92 is formed in the second channel 91.

  Subsequently, the second electrode layer 90 of the first substrate 72 on which the power generation unit 73 is formed and the second flow path 91 of the second substrate 74 are assembled (step S43) to manufacture the fuel cell. Is completed.

  As described above, the present embodiment has the following effects.

(1) According to this embodiment, the first diffusion region 79 is formed between the first electrode layer 78 and the first fluid diffusion layer 80. The first diffusion region 79 is a layer in which copper particles that are the constituent material of the first electrode layer 78 and carbon particles that are the constituent material of the first fluid diffusion layer 80 are mixed. Since there are many contact points of particles, electrons are easily transferred from carbon particles to copper particles. Accordingly, a structure in which the electrical resistance between the first electrode layer 78 and the first fluid diffusion layer 80 is small can be obtained.
Similarly, a sixth diffusion region 89 in which carbon particles and copper particles are mixed is formed between the second fluid diffusion layer 88 and the second electrode layer 90. The electric resistance between the two electrode layers 90 can also be made small.

(2) According to the present embodiment, the second diffusion region 81 is formed between the first fluid diffusion layer 80 and the first reaction layer 82. The second diffusion region 81 is a layer in which carbon particles that are the constituent material of the first fluid diffusion layer 80 and platinum particles that are the constituent material of the first reaction layer 82 are mixed. Since there are many contact points of the particles, electrons easily move from the platinum particles to the carbon particles. Therefore, a layer structure having a small electric resistance can be formed between the first reaction layer 82 and the first fluid diffusion layer 80.
Similarly, since the fifth diffusion region 87 between the second reaction layer 86 and the second fluid diffusion layer 88 is a layer in which platinum particles and carbon particles are mixed, the second reaction layer 86 and the second fluid diffusion layer 88 are mixed. Between the two fluid diffusion layers 88, a layer structure having a small electric resistance can be formed.

(3) According to the present embodiment, the fifth diffusion region 87 is formed by applying the second fluid diffusion layer material liquid after application of the second reaction layer material liquid and before drying. Since the particle size of the platinum particles in the second reaction layer 86 is smaller than the particle size of the carbon particles in the second fluid diffusion layer 88 in the upper layer, the second fluid diffusion is performed after the application and drying of the second reaction layer material liquid. When the layer material liquid is applied, the carbon particles hardly diffuse into the gaps between the platinum particles. In the present embodiment, since the second fluid diffusion layer material liquid containing carbon particles is applied in a state where the fluidity of the platinum particles before drying of the second reaction layer material liquid is high, the platinum particles are formed of carbon particles. It was able to diffuse into the gap. Therefore, since the fifth diffusion region 87 is a layer in which platinum particles and carbon particles are mixed, the electrical resistance can be lowered.
Similarly, the second diffusion region 81 is also formed by the same method. Here, after the material containing carbon particles having a large particle size is applied, the material containing platinum particles having a small particle size is applied. When the first reaction layer material liquid is applied after the first fluid diffusion layer material liquid is applied and dried, a layer in which carbon particles and platinum particles are mixed is formed. Before drying, the first reaction layer material liquid is applied to facilitate diffusion. Therefore, since the second diffusion region 81 is a region in which carbon particles and platinum particles are sufficiently mixed, electric resistance can be lowered.

(4) According to the present embodiment, the third diffusion region 83 is formed between the first reaction layer 82 and the electrolyte layer 84. The third diffusion region 83 is a layer in which platinum particles as a constituent material of the first reaction layer 82 and an electrolyte polymer (polymer) as a constituent material of the electrolyte layer 84 are mixed. There are many contact points of the electrolyte polymer. Hydrogen ions in which hydrogen molecules are ionized by the catalytic action of platinum are easily transferred to the electrolyte polymer through the platinum particles, and the power generation efficiency of the fuel cell is improved. As a result, since the flow of hydrogen ions is performed efficiently, a fuel cell with high power generation efficiency can be obtained.
Similarly, a fourth diffusion region 85 is formed between the electrolyte layer 84 and the second reaction layer 86, and hydrogen ions easily move from the electrolyte layer 84 to the second reaction layer 86. The fuel cell can be made good.

(5) According to the present embodiment, the third diffusion region 83 is formed by applying the electrolyte layer material liquid after drying the first reaction layer material liquid and before drying. Since the first reaction layer 82 is in the form of platinum particles and the electrolyte layer 84 is formed of a polymer, the electrolyte layer 84 is formed when the electrolyte layer 84 is formed after the first reaction layer 82 is applied and dried. The polymer 84 is difficult to diffuse into the gaps between the platinum particles in the first reaction layer 82. In the present embodiment, before the first reaction layer 82 is dried, the electrolyte layer material liquid is applied in a state in which the fluidity of the platinum particles is high, so that the electrolyte polymer may diffuse into the gaps between the platinum particles. it can. Therefore, the fluidity of hydrogen ions is improved by the layer in which the platinum particles and the polymer of the electrolyte are mixed, so that a fuel cell with high power generation efficiency can be obtained.
Similarly, the fourth diffusion region 85 is also formed by the same method. In this example, a material containing platinum particles having a small particle diameter is applied after application of the material forming the electrolyte polymer. When the second reaction layer material liquid is applied after coating and drying the electrolyte layer material liquid, a layer in which the electrolyte polymer and platinum particles are mixed is formed, but the electrolyte layer material liquid is dried. Before, it becomes easy to spread | diffuse by apply | coating a 2nd reaction layer material liquid. Therefore, the fourth diffusion region 85 is a region in which the electrolyte polymer and the platinum particles are sufficiently mixed, so that the ion fluidity can be improved.

  (6) According to this embodiment, the material of each layer is applied by the droplet discharge device. Since the droplet discharge device discharges and applies fine droplets to a desired location on the first substrate 72, a layer having a uniform thickness without any unevenness is formed. Therefore, the power generation unit 73 can reduce the variation in the thickness of each layer, and can provide a high-quality fuel cell with no variation in the amount of power generation.

(Fourth embodiment)
Next, an electronic apparatus including the organic EL display according to the first and second embodiments described above and the fuel cell according to the third embodiment described above will be described.
FIG. 16 is a schematic perspective view showing an example in which the organic EL display 1 and the fuel cell 71 are mounted on a personal computer as a portable electronic information processing apparatus such as a word processor or a personal computer. As shown in FIG. 16, the main body of the electronic information processing apparatus 100 includes a display device 101 that displays information. One of the electro-optical devices manufactured according to the first and second embodiments is disposed on the display device 101. Since the display device 101 arranged in the electronic information processing apparatus 100 as an electronic device is equipped with the organic EL display 1 that is manufactured according to the embodiment and emits light efficiently, the display device 101 is bright and has a long display life. It becomes an electronic device having the effect.
Furthermore, the main body of the electronic information processing apparatus 100 includes a power supply unit 102 that supplies electricity, and the fuel cell manufactured according to the third embodiment is disposed in the power supply unit 102. The power supply unit 102 disposed in the electronic information processing apparatus 100, which is an electronic device, has the power generation efficiency because the fuel cell of the present invention is disposed, so that the fuel supply frequency of the battery can be reduced. . In addition, since the volume and weight necessary for supplying the necessary power can be reduced, the electronic information processing apparatus 100 can be reduced in size and weight. As a result, the electronic information processing apparatus 100 with improved portability can be obtained.

Note that the present invention is not limited to the above-described embodiment, and various changes and improvements can be added. A modification will be described below.
(Modification 1) In the first and second embodiments, the layers are formed in the order of the first layer material application step, the second layer material application step, the diffusion step, and the drying step. It is not limited to this. By including the solvent of the first layer in the material of the second layer, a drying step can be performed after the step of applying the material of the first layer. That is, as shown in the flowchart of FIG. 15, the material of the first layer is applied (step S51) and dried (step S52). Next, the material of the second layer containing the same solvent as the solvent of the first layer or a solvent capable of dissolving the first layer is applied (step S53). Next, the material of the first layer is re-dissolved in the solvent of the second layer, and the re-dissolved material of the first layer and the material of the second layer are diffused and then dried (step S54). The dispersion medium is not limited to the solvent.
According to this, in addition to the effect of the present embodiment, it becomes easy to prevent the material of the second layer from diffusing too much into the first layer, and the three layers of the first layer, the diffusion region, and the second layer. Can be separated. Furthermore, since the first layer may be naturally dried to be semi-dry, it is not necessary to control the humidity of the atmosphere so that the first layer does not dry after the first layer material application step. . After applying a certain layer, the discharge liquid of the droplet discharge device can be changed and the next layer can be applied, so that the equipment can be simplified.

(Modification 2) In the first embodiment, the material liquids of the hole injection layer 15, the light emitting layers 17R, 17G, and 17B and the electron injection layer 19 are continuously discharged by the droplet discharge device. You may apply | coat with the discharge apparatus of. The liquid of the next layer may be applied before the applied liquid dries.
(Modification 3) In the first embodiment, the electron injection layer 19 is applied by discharging a functional liquid containing a bisacetylacetonate / calcium complex (Ca (acac) 2) with a droplet discharge device. However, the film may be formed by vapor deposition. You may change suitably according to a production form.

(Modification 4) In the first embodiment, the cathode 21 is formed of an aluminum thin film by vapor deposition, but an ITO thin film may be formed by sputtering.
(Modification 5) In the first embodiment, the material of the light emitting layer is MEHPPV (poly (3-methoxy, 6- (3-ethylhexyl) paraphenylenevinylene), F8BT (dioctylfluorene and benzothiadiazole) Coalescence) and polydioctylfluorene were used, but not limited thereto.
As a material for forming the light emitting layer, (poly) fluorene derivative (PF), (polyparaphenylene vinylene derivative (PPV), polyphenylene derivative (PP), polyparaphenylene derivative (PPP), polyvinylcarbazole (PVK), polythiophene derivative, poly Polysilanes such as methylphenylsilane (PMPS) may be used, and polymer materials such as perylene dyes, coumarin dyes, rhodamine dyes, rubrene, perylene, 9 , 10-diphenylanthracene, tetraphenylbutadiene, Nile red, coumarin 6, quinacridone, and the like can also be used by doping.
In addition, polyvinyl carbazole, polyfluorene polymer derivatives, and the like may be employed.

(Modification 6) In the first embodiment, the material for the electron injection layer is bisacetylacetonato / calcium complex (Ca (acac) 2), but is not limited thereto.
An organometallic complex can be adopted as the electron injecting material constituting the electron injecting layer. As chelate ligands constituting this organometallic complex, acetylacetone (acac), dipipaloylmethane (dpm), hexafluoroacetylacetone (hfa), 2,2,6,6, -tetramethyl-3,5-octane Β-diketone ligands such as diacetone (TMOD), thenoyltrifluoroacetone (TTA), 1-phenyl-3-isohept-1,3-propanedione (trade names LIX54, LIX51; Henkel), 8 -Quinolinol ligands such as quinolinol (oxin), 2-methyl-8-quinolinol, trioctyl phosphine oxide (TOPO), tributyl phosphate (TBP), isobutyl methyl ketone (MBK), bis (2-ethylhexyl) ) Phosphoric acid ligands such as phosphoric acid (D2EHPA), acetic acid, benzoic acid, etc. Ligands carboxylic acid, may be employed diphenylthiocarbazone ligands like.

  In addition, a metal element such as an alkali metal, an alkaline earth metal, a rare earth metal, or a transition metal can be used as a central atom constituting the organometallic complex. For example, Li, Na, Cs, etc. can be adopted as the alkali metal, Ca, Ba, Sr, etc. can be adopted as the alkaline earth metal, and Sm, Tb, Er, etc. can be adopted as the rare earth metal.

  Furthermore, it is also possible to employ a metal halide or oxide as the electron injecting material. As the metal, a metal element such as an alkali metal, an alkaline earth metal, a rare earth metal, or a transition metal can be used. The metal halide is preferably a metal fluoride, but may be other metal chlorides or metal bromides. Further, lithium fluoride (LiF) may be used as a specific metal halide. In addition, it is also possible to employ organic lithium compounds such as lithium benzoate and lithium acetate.

(Modification 7) In the first embodiment, the hole injection layer 15, the first diffusion regions 16 R, 16 G, and 16 B, the light emitting layers 17 R, 17 G, and 17 B, the second diffusion region are formed on each pixel electrode 13. 18R, 18G, 18B and the electron injection layer 19 are stacked in this order to form the functional layer 20, and the cathode 21 is formed on the functional layer 20, but this stacking order may be reversed. On each pixel electrode 13, an electron injection layer 19, first diffusion regions 16R, 16G, and 16B, light emitting layers 17R, 17G, and 17B, second diffusion regions 18R, 18G, and 18B, and a hole injection layer 15 are arranged in this order. The functional layer 20 may be formed by stacking, and the anode may be formed on the functional layer 20. At this time, the first diffusion regions 16R, 16G, and 16B are regions in which the material of the electron injection layer and the material of the light emitting layer are diffused, and the second diffusion regions 18R, 18G, and 18B are the same as the material of the light emitting layer. This is a region where the material of the hole injection layer is diffused. By applying a voltage between each pixel electrode 13 and the anode so that each pixel electrode 13 becomes a cathode, an organic EL element can be obtained. Even in this case, the same effect as the first embodiment can be obtained.
(Modification 8) In the first embodiment, a polymer material is used as a material, but a low-molecular material may be used. A high molecular material and a low molecular material may be combined.

(Modification 9) In the first embodiment, xylene is used as a solvent or a dispersion medium, but a nonpolar solvent such as toluene or mesitylene may be used.
(Modification 10) In the first embodiment, drying is performed by vacuum drying, but the solvent may be removed by heat treatment or nitrogen gas flow.
(Modification 11) In the third embodiment, the polymer electrolyte fuel cell (PEFC) is used. However, the present invention is not limited to this. A direct methanol fuel cell (DMFC) may be used. Since methanol is directly supplied to the fuel cell, the apparatus can be reduced in size.

(Modification 12) In the first embodiment, the first diffusion regions 16R, 16G, and 16B are formed between the hole injection layer 15 and the light emitting layers 17R, 17G, and 17B, and the light emitting layers 17R, 17G, and 16B are formed. Although the second diffusion regions 18R, 18G, and 18B are formed between 17B and the electron injection layer 19, the present invention is not limited to this. The step of forming the second diffusion regions 18R, 18G, 18B may be omitted. After the hole injection layer 15, the first diffusion regions 16R, 16G, and 16B and the light emitting layers 17R, 17G, and 17B are stacked, the electron injection layer 19 may be formed and stacked. You may change suitably according to a production form.
(Modification 13) In the first embodiment, the first diffusion regions 16R, 16G, and 16B are formed between the hole injection layer 15 and the light emitting layers 17R, 17G, and 17B, and the light emitting layers 17R, 17G, and 16B are formed. Although the second diffusion regions 18R, 18G, and 18B are formed between 17B and the electron injection layer 19, the present invention is not limited to this. The step of forming the first diffusion regions 16R, 16G, and 16B may be omitted. First, a hole injection layer is formed. Next, a first diffusion region in which the material of the light emitting layer and the material of the electron injection layer are diffused is formed between the light emitting layer as the first layer and the electron injection layer as the second layer, and hole injection is performed. A layer, a light emitting layer, a diffusion region, and an electron injection layer may be stacked in this order. You may change suitably according to a production form.

  (Modification 14) In the first embodiment, the first diffusion regions 16R, 16G, and 16B are disposed on the pixel electrode 13 that is an anode between the hole injection layer 15 and the light emitting layers 17R, 17G, and 17B. Formed. Further, the second diffusion regions 18R, 18G, and 18B are formed between the light emitting layers 17R, 17G, and 17B and the electron injection layer 19 and the cathode 21 is formed on the electron injection layer 19, but the reverse is also possible. A cathode is formed on the circuit forming layer, and an electron injection layer as the first layer, a first diffusion region in which the material of the electron injection layer and the material of the light emitting layer are diffused, and the second layer as The light emitting layer, the second diffusion region in which the material of the light emitting layer and the hole injection layer are diffused, the hole injection layer as the third layer, and the anode may be laminated in this order. The same effect as in the first embodiment can be obtained.

  (Modification 15) In the modification 14, the cathode is formed on the circuit formation layer, and the electron injection layer, the first diffusion region in which the material of the electron injection layer and the material of the light emitting layer are diffused, light emission Although the layers, the second diffusion region in which the material of the light emitting layer and the material of the hole injection layer are diffused, the hole injection layer, and the anode are laminated in this order, the present invention is not limited to this. The step of forming the second diffusion region may be omitted. A cathode is formed on the circuit forming layer, and an electron injection layer as the first layer, a first diffusion region in which the material of the electron injection layer and the material of the light emitting layer are diffused, and the second layer as A light emitting layer is formed in this order. A hole injection layer and an anode may be laminated in this order. You may change suitably according to a production form.

  (Modification 16) In the modification 14, the cathode is formed on the circuit formation layer, and the electron injection layer, the first diffusion region in which the material of the electron injection layer and the material of the light emitting layer are diffused, light emission Although the layers, the second diffusion region in which the material of the light emitting layer and the material of the hole injection layer are diffused, the hole injection layer, and the anode are laminated in this order, the present invention is not limited to this. The step of forming the first diffusion region may be omitted. An electron injection layer is formed on the cathode on the circuit formation layer. A light emitting layer as the first layer, a first diffusion region in which the material of the electron injection layer and the material of the light emitting layer are diffused, and a light emitting layer as the second layer are formed in this order. A hole injection layer and an anode may be laminated in this order. You may change suitably according to a production form.

1 is a front view of an organic EL display according to a first embodiment. Sectional drawing of an organic electroluminescent display. Sectional drawing of an organic electroluminescent display. The perspective view which shows a droplet discharge apparatus. The perspective view which shows a droplet discharge head. Sectional drawing which shows a droplet discharge head. The flowchart which shows the manufacturing process of an organic electroluminescent display. (A) And (b) is a figure for demonstrating the manufacturing method of an organic electroluminescent display. (A)-(c) is a figure for demonstrating the manufacturing method of an organic electroluminescent display. (A)-(c) is a figure for demonstrating the manufacturing method of an organic electroluminescent display. The flowchart which shows the manufacturing process of the organic electroluminescent display which concerns on 2nd Embodiment. The perspective view which shows the fuel cell which concerns on 3rd Embodiment. Sectional drawing which shows a fuel cell. The flowchart which shows the manufacturing process of a fuel cell. The flowchart which shows the manufacturing process different from the manufacturing process of the film | membrane of 1st Embodiment. The perspective view which shows the electronic device of 4th Embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Organic EL display as an electro-optical device, 4 ... Board | substrate, 10R, 10G, 10B ... Organic EL element as a device, 15 ... Hole injection layer as 1st layer, 16R, 16G, 16B ... 1st Diffusion region, 17R, 17G, 17B ... light emitting layer as second layer, 18R, 18G, 18B ... second diffusion region, 19 ... electron injection layer as third layer, 26 ... as first functional liquid Hole injection layer material liquid, 27R, 27G, 27B ... light emitting layer material liquid as second functional liquid, 28 ... electron injection layer material liquid as third functional liquid, 71 ... fuel cell, 72 ... as substrate First substrate, 78 ... first electrode layer, 80 ... first fluid diffusion layer, 82 ... first reaction layer, 84 ... electrolyte layer, 86 ... second reaction layer, 88 ... second fluid. Diffusion layer, 90 ... second electrode layer, 100 ... as electronic equipment Child information processing apparatus.

Claims (18)

A method of manufacturing a film in which a plurality of films are stacked on a substrate,
A first layer disposing step of applying a first functional liquid on the substrate and disposing a first layer;
Applying a second functional liquid having compatibility with the first functional liquid on the first layer, and arranging a second layer;
At the interface between the first layer and the second layer, the first functional liquid and the second functional liquid are diffused to form a first diffusion region between the two layers. A film manufacturing method comprising: a first diffusion region forming step. A method for producing a film according to claim 1,
The first diffusion region forming step includes a diffusion step of diffusing the materials of the first functional liquid and the second functional liquid for a predetermined time after the application of the second layer, and the first diffusion region after the diffusion step. The manufacturing method of the film | membrane characterized by including the drying process of drying 1 layer and said 2nd layer. A method for producing a film according to claim 1,
Applying a third functional liquid having compatibility with the second functional liquid on the second layer, and arranging a third layer;
At the boundary surface between the second layer and the third layer, the second functional liquid and the third functional liquid are diffused to form a second diffusion region between the two layers. A film manufacturing method comprising a second diffusion region forming step. A method for producing a membrane according to claim 3,
The method for producing a film, wherein the first diffusion region forming step and the second diffusion region forming step are performed simultaneously. A method for producing a film according to claim 1,
The first functional liquid and the second functional liquid both include a first main material and a second main material,
The first main material is contained in the first functional liquid more than the second functional liquid,
The second main material is more contained in the second functional liquid than the first functional liquid,
In the first diffusion region, the first functional liquid and the second functional liquid diffuse,
The content of the first main material decreases in the order of the first layer, the first diffusion region, and the second layer,
A method of manufacturing a film, wherein the second layer, the first diffusion region, and the first layer are formed in this order so that the content of the second main material decreases. In the manufacturing method of the film | membrane as described in any one of Claims 1-5,
The method for producing a film is characterized in that the functional liquid is applied by using a droplet discharge method. A device manufacturing method using the film manufacturing method according to claim 1 or 2,
The device has a hole injection layer, a light emitting layer, and an electron injection layer,
The device according to claim 1, wherein the first layer is the hole injection layer, and the second layer is the light emitting layer. A device manufacturing method using the film manufacturing method according to claim 1 or 2,
The device has a hole injection layer, a light emitting layer, and an electron injection layer,
The device according to claim 1, wherein the first layer is the light emitting layer, and the second layer is the electron injection layer. A device manufacturing method using the film manufacturing method according to claim 1 or 2,
The device has an electron injection layer, a light emitting layer, and a hole injection layer,
The device manufacturing method, wherein the first layer is the electron injection layer, and the second layer is the light emitting layer. A device manufacturing method using the film manufacturing method according to claim 1 or 2,
The device has an electron injection layer, a light emitting layer, and a hole injection layer,
The device according to claim 1, wherein the first layer is the light emitting layer, and the second layer is the hole injection layer. A device manufacturing method using the film manufacturing method according to any one of claims 3 to 5,
The device has a hole injection layer, a light emitting layer, and an electron injection layer,
The device manufacturing method, wherein the first layer is the hole injection layer, the second layer is the light emitting layer, and the third layer is the electron injection layer. A device manufacturing method using the film manufacturing method according to any one of claims 3 to 5,
The device has an electron injection layer, a light emitting layer, and a hole injection layer,
The device manufacturing method, wherein the first layer is the electron injection layer, the second layer is the light emitting layer, and the third layer is the hole injection layer.   A device manufactured using the device manufacturing method according to claim 7. A fuel cell manufacturing method using the membrane manufacturing method according to claim 1 or 2,
The first layer and the second layer include a first electrode layer, a first fluid diffusion layer, a first reaction layer, an electrolyte layer, a second reaction layer, a second fluid diffusion layer, and a second layer. A method for manufacturing a fuel cell, which corresponds to two layers adjacent to each other in the stacking order.   An electro-optical device comprising the device according to claim 13.   An electronic apparatus comprising the electro-optical device according to claim 15 as a display unit. A fuel cell manufactured by the method for manufacturing a fuel cell according to claim 14. An electronic apparatus comprising the fuel cell according to claim 17 as a power supply source.

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