JP2003272837A - Surface treatment apparatus, manufacturing method and manufacturing device of organic el device, organic el device, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment apparatus capable of uniformizing plasma distribution when applying a plasma treatment to a sample. <P>SOLUTION: The surface treatment apparatus S comprises a sample stage 12 supporting a sample 43, a plasma discharging electrode 20 having a porous body 21 located to the position facing the surface to be treated of the sample 43 put on the sample stage 12, and a gas passage 15 supplying a prescribed gas between the plasma discharging electrode 20 and the sample 43 put on the sample stage 12 through the porous body 21. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention utilizes a plasma generated by a gas discharge and a surface treatment apparatus for treating a surface of a sample to be treated with excited active species generated in the plasma. The present invention relates to an apparatus for manufacturing an organic EL device including the organic EL device, an organic EL device manufactured by the manufacturing apparatus, and an electronic apparatus including the organic EL device.

[0002]

2. Description of the Related Art In recent years, a light emitting material such as an organic fluorescent material is formed into droplets like ink, and the ink (composition) is ejected onto a substrate by an inkjet method (droplet ejection method) to pattern the light emitting material. By adopting the method described above, a color display device having a structure in which a light emitting layer made of the light emitting material is sandwiched between an anode and a cathode, particularly an organic EL (electroluminescence) using an organic light emitting material as the light emitting material.
Inescence) display devices are being developed. Organic EL
A display device (hereinafter, referred to as “organic EL device”) has a structure in which a plurality of circuit elements, a light emitting element in which an organic light emitting layer is sandwiched between electrode layers of an anode and a cathode, and the like are stacked on a substrate. Then, in the organic EL device, a hole that is injected from the anode side and an electron that is injected from the cathode side are recombined in the light emitting layer having a light emitting ability, and light is emitted when the excited state is collapsed. Are using.

An organic EL device is a laminate of a plurality of material layers, and is manufactured by arranging a material on a substrate, performing a predetermined treatment such as a drying treatment or a surface treatment, and repeating the treatment in sequence. The surface treatment includes a treatment for treating the surface of the material layer to be lyophobic or lyophilic, a treatment for adjusting the work function of the electrode, a cleaning, etc., and a plasma treatment may be applied to this. Many. In recent years, by utilizing chemically activated excited species generated by plasma discharge under a pressure near atmospheric pressure, the surface to be treated can be treated with a relatively low cost and simple structure that does not require vacuum equipment. Various plasma surface treatment techniques have been proposed. For surface treatment with plasma under atmospheric pressure, a processing gas is sent between the electrode and the surface to be treated, and the excited active species created by the discharge between the electrode and the object to be treated are directly exposed to the surface to be treated. There are a direct method and an indirect method in which excited active species generated by plasma generated by gas discharge between a pair of electrodes are transported to expose the surface to be treated.

The direct method may not be able to sufficiently cope with damage to the surface to be processed due to charge-up, a surface having a complicated shape or unevenness, or a restriction on the processing range, but has an advantage that a high processing rate can be obtained. is there. Further, the indirect method has an advantage that the surface to be processed is not damaged by charge-up and the shape of the surface to be processed and the processing range can be limited by adjusting the shape of the gas injection nozzle and the gas flow rate. Since the active species generated by the method are transferred, the number of active species that can contribute to the reaction is smaller than that in the direct method, and the processing rate is low. Therefore, high-speed treatment of a large area is disadvantageous as compared with the direct method.

FIG. 14 is a schematic diagram showing an example of a conventional plasma processing apparatus using a direct atmospheric pressure plasma.
The plasma processing apparatus shown in FIG. 14 has an electrode 2 connected to an AC power supply 1 and a sample stage 10 which is a ground electrode. The sample stage 10 is movable in the Y-axis direction while supporting the sample 3. On the lower surface of the electrode 2, two parallel discharge generating portions 4, 4 extending in the X-axis direction orthogonal to the moving direction are provided in a protruding manner, and the dielectric member 5 surrounds the discharge generating portion 4. Is provided. The dielectric member 5 is for preventing abnormal discharge of the discharge generating section 4. The lower surface of the electrode 2 including the dielectric member 5 is substantially flat, and a slight space (discharge gap) is formed between the discharge generating portion 4 and the dielectric member 5 and the sample 3. It has become. In addition, a gas ejection port 6 elongated in the X-axis direction is provided at the center of the electrode 2. The gas ejection port 6 is connected to the gas introduction port 9 via the gas passage 7 inside the electrode and the intermediate chamber 8.

The predetermined gas injected from the gas ejection port 6 through the gas passage 7 separately flows in the space in the front direction and the rear direction in the moving direction (Y-axis direction), and the front end of the dielectric member 5 and Exhausted from the rear end to the outside. At the same time, a predetermined voltage is applied from the power source 1 to the electrode 2, and the discharge generating unit 4,
A gas discharge is generated between the sample 4 and the sample stage 10. Then, excited active species of the predetermined gas are generated by the plasma generated by this gas discharge, and the entire surface of the sample 3 passing through the discharge region is continuously processed.

Usually, the predetermined gas is a treatment gas such as oxygen (O ₂ ) or carbon tetrafluoride (CF ₄ ) which is suitable for the intended surface treatment, and discharges easily under a pressure near atmospheric pressure. It is a mixture of a rare gas such as helium (He) and argon (Ar) for starting and keeping it stable, and an inert gas such as nitrogen (N ₂ ). By appropriately selecting the processing gas, various surface treatments such as etching, ashing, modification and film formation on the sample surface are performed.
In particular, by using oxygen as a processing gas, organic E
The work function of the electrode in the L device is adjusted.

[0008]

However, the above-mentioned conventional plasma processing apparatus has the following problems. In the conventional plasma processing apparatus, the gas ejection port 6
Is formed in the central portion of the lower surface of the electrode 2, and the discharge generating portion 4 and the gas ejection port 6 are provided at a distance from each other. In this case, in the discharge region 4a in a region close to the gas ejection port 6 (see reference numeral Y1 in FIG. 14), plasma processing is performed using the fresh gas (fresh gas) supplied from the gas ejection port 6. But the gas outlet 6
In the region farther from the target (see Y2 in FIG. 14), the gas that has passed through the discharge region 4a (non-fresh gas)
Is used for plasma treatment. That is, in the conventional plasma processing apparatus, since the processing is performed with the gas having different freshness at each position of the discharge region 4a, the plasma processing distribution becomes non-uniform. If the plasma processing distribution is not made uniform, an electrode having a non-uniform work function will be formed when the surface to be processed is an electrode of an organic EL device, for example. In this case, the light emitting characteristics of the organic EL device are also non-uniform or unstable, and the light emitting performance is deteriorated.

The present invention has been made in view of the above circumstances, and is directed to a surface treatment apparatus capable of making the plasma treatment distribution uniform when performing plasma treatment on a sample, and an organic EL device provided with this surface treatment apparatus. It is an object to provide a manufacturing apparatus, an organic EL device manufactured by this manufacturing apparatus, and an electronic device.

[0010]

In order to solve the above problems, a surface treatment apparatus of the present invention is a surface treatment apparatus for performing a predetermined treatment on a surface to be treated of a sample, and a sample stage for supporting the sample. And a plasma discharge electrode provided at a position facing the surface to be processed of the sample supported by the sample stage and having a porous body portion, and the sample and the plasma discharge electrode supported by the sample stage. Between,
And a gas supply unit that supplies a predetermined gas through the porous body unit.

According to the present invention, a part of the plasma discharge electrode is a porous body portion, and the gas is supplied to the discharge gap through the porous body portion. Therefore, the gas of uniform freshness is supplied. Therefore, the plasma processing distribution is made uniform. Further, since the gas is supplied through the porous body portion, the gas flow rate distribution per unit area supplied to the discharge region is also made uniform.

Further, in the surface treatment apparatus of the present invention,
The structure in which the porous body portion is a discharge generating portion is adopted.
As a result, the gas is directly supplied to the discharge region, so that the freshness of the supplied gas can be made more uniform and the plasma processing distribution can be made more uniform.

Further, in the surface treatment apparatus of the present invention,
The porous body portion is formed of a porous metal portion and a porous dielectric portion. As a result, deterioration of the porous body portion due to discharge is suppressed, the life of the porous body portion is extended, and stable discharge can be maintained for a long period of time.

Further, in the surface treatment apparatus of the present invention,
A configuration including a moving device that relatively moves the sample stage and the plasma discharge electrode is adopted. This allows plasma processing while scanning the sample,
A wide surface can be uniformly processed.

An apparatus for manufacturing an organic EL device of the present invention is an apparatus for manufacturing an organic EL device having an electrode provided on a substrate and an organic light emitting layer provided adjacent to the electrode. A processor is provided.

According to the present invention, since the plasma treatment can be performed in a state where the discharge intensity is uniform, it is possible to realize the uniform plasma treatment distribution. Therefore,
For example, liquid repellency and lyophilicity can be adjusted, and etching and ashing can be performed in a desired state.

Further, in the apparatus for manufacturing an organic EL device of the present invention, the predetermined gas contains a compound containing oxygen or fluorine, and the surface treatment device reforms the surface of the electrode of the organic EL device. Alternatively, a configuration for adjusting the work function of the electrode is adopted. As a result, the work function of the electrode is adjusted to be uniform, so that it is possible to manufacture an organic EL device having good light emission performance. Here, the surface modification includes treatments such as lyophilicity, lyophobicity, and cleaning.

The organic EL device of the present invention is characterized by being manufactured by the above-described organic EL device manufacturing apparatus. According to the present invention, since the plasma processing distribution is made uniform, good light emission performance can be obtained.

The electronic device of the present invention is an organic EL device as described above.
It is characterized by having a device. According to the present invention, since the organic EL device of the present invention is mounted, highly reliable operation can be realized.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION <Surface Treatment Apparatus> An embodiment of the apparatus for manufacturing an organic EL device of the present invention will be described below with reference to FIGS. FIG. 1 shows an example of a surface treatment apparatus (plasma treatment apparatus) as a manufacturing apparatus of an organic EL device of the present invention, seen from the −Y direction side, and FIG. 2 shows the plasma treatment apparatus shown in FIG. 1 on the + Y direction side. View from Figure 3, Figure 3
5 is a cross-sectional view taken along the line AA of FIG. 1, FIG. 4 is an external perspective view showing a sample stage of the plasma processing apparatus shown in FIG. 1, and FIG.
Is a partially enlarged view of FIG. 3, and FIG. 6 is a sectional view taken along the line BB of FIG.

The processing step using the plasma processing apparatus in the following description will be described as one of the manufacturing steps of the organic EL device, but the object to be processed is not limited to the organic EL device, and, for example, color filter manufacturing. It can be applied to an apparatus, and various samples requiring surface treatment can be treated.

In FIGS. 1, 2 and 3, the plasma processing apparatus S includes a sample stage 1 that supports a sample (substrate) 43.
2 and an electrode portion 11 having a plasma discharge electrode 20 provided at a position facing the sample stage 12. An actuator (moving device) 12A for moving the sample stage 12 is connected to the sample stage 12, and the sample stage 12 can move in the Y-axis direction while supporting the sample 43 under the drive of the actuator 12A. Has become. In addition, the sample stage 12 supports the sample 4
A temperature adjusting device for adjusting the temperature of 3 is provided.

In the following description, the moving direction (scanning direction) of the sample stage 12 in the horizontal plane is the Y-axis direction, the direction orthogonal to the Y-axis direction in the horizontal plane (non-scanning direction) is the X-axis direction, and the X-axis direction is the X-direction. The direction orthogonal to the axial direction and the Y-axis direction is the Z-axis direction. Further, in the following description, the X-axis direction may be referred to as “width direction”, and both ends thereof may be referred to as “left end, right end”. The front side in the moving direction (+ Y direction side) may be referred to as the “front end”, and the rear side in the moving direction (−Y direction side) may be referred to as the “rear end”.

As shown in FIG. 3, the electrode portion 11 includes an electrode holding block 13 made of an insulating material such as alumina,
And a substantially rectangular parallelepiped front block 14 made of an insulating resin material of polytetrafluoroethylene. An upper block 16 is provided above the electrode holding block 13 and the front block 14. Further, as shown in FIGS. 1 and 2, side plates 17a and 17b are connected to both sides of the blocks 13, 14 and 16 in the X-axis direction by fixing members (not shown) such as bolts.

As shown in FIG. 3, the electrode holding block 13
Has a stepped recess 19 on its lower surface. Recess 19
Are formed with the X-axis direction as the longitudinal direction. Recess 19
A plasma discharge electrode 20 is provided inside. The plasma discharge electrode 20 is formed in an L shape in a side view,
It has a discharge generation part (plasma discharge electrode) 21 at the tip of the character. The plasma discharge electrode 20 is arranged inside the recess 19 with the discharge generating portion 21 facing downward. The discharge generation part 21, which is the tip of the plasma discharge electrode 20, is composed of a porous body (porous metal part) made of alumina (aluminum oxide), and allows gas to flow therethrough. The plasma discharge electrode 20 is fixed to the electrode holding block 23 by a bolt 23 via a mounting block 22 made of a dielectric material such as alumina or quartz (see FIG. 1). The plasma discharge electrode 20 is an AC power supply 24
It is connected to the.

Below the electrode holding block 13, a gas flow control plate 25 made of a dielectric thin plate such as alumina or quartz having the same length and width as the block is provided at a height corresponding to the lower surface of the front block 14. Mounted horizontally. The position corresponding to the discharge generation part 21 in the gas flow control plate 25 is also a porous body (porous dielectric part), and gas can flow therethrough. Here, at least the dielectric portion is preferably formed of a material having excellent plasma resistance. In addition to alumina, examples of dielectric materials having excellent plasma resistance include alumina nitride. However,
Depending on the purpose of the treatment, the dielectric may be quartz or the like, or the quartz or the like may be subjected to a surface treatment so as to have plasma resistance.

A main gas passage (gas supply section) 15 is provided between the electrode holding block 13 and the front block 14. One end (upper end) of the main gas passage 15 is connected to the intermediate chamber 30 formed in the upper block 16, and the other end (lower end) of the main gas passage 15 is a discharge generating portion (porous body portion). 21 is connected. Here, a part of the main gas flow path 15 is formed so as to pass a part of the plasma discharge electrode 20. The intermediate chamber 30 communicates with a gas introduction port 31 that opens at the upper surface of the upper block 16 at approximately the center thereof. The gas inlet 31 is provided with a joint 32, and the joint 32 is connected to a supply source 32A of a discharge gas such as helium. The discharge gas introduced from the supply source 32A to the gas introduction port 31 through the joint 32 has a substantially uniform gas pressure in the width direction (X-axis direction) in the intermediate chamber 30, and the discharge gas flows through the main gas passage 15 in the width direction. Flows almost uniformly. The gas from the main gas flow path 15 is supported on the lower surface of the discharge generation part 21 and the sample stage 12 via the discharge generation part 21 made of a porous body and the porous body part of the gas flow control plate 25. The sample is supplied to a space (discharge gap) 47 between the sample 43 and the sample 43. Although the number of the gas inlet 31 is one in the present embodiment, a plurality of the gas inlets 31 may be provided as necessary to make the flow of the discharge gas more uniform over the entire width of the main gas passage 15.

As shown in FIG. 1, leg members (wall portions) 26a, 26b made of an insulating material such as mica are provided on both left and right sides (both sides in the X-axis direction) of the lower side of the gas flow control plate 25.
Is provided. Each of the leg members 26a and 26b is provided with a side plate 17a along the left and right sides of the gas flow control plate 25.
It is attached inside 17b and arranged so as to abut the inner end surface of the electrode holding block 13. Leg member 26
Each of a and 26b and the electrode holding block 13 are integrally connected by a fixing member such as a bolt. The gas flow control plate 25 and the legs 26a and 26b form a downward U-shaped space.

As shown in FIG. 2, protrusions (wall portions) 27a and 27b are formed on both left and right sides (both sides in the X-axis direction) of the lower surface of the front block 14. Each of the protrusions 27a and 27b and each of the leg members 26a and 26b of the electrode holding block 13 are formed so as to be continuous with each other and have the same shape and dimension in cross section. Each of the protrusions 27a and 27b is provided along the entire length of the left and right sides of the front block 14, and as shown in FIG. 2, the lower surface of the front block 14 and the protrusions 27a and 27b face downward. A "U" shaped space is formed.

As shown in FIGS. 2 and 3, polyvinyl chloride (PVC) is provided on the back surface of the front block 14 so that the lower surface of the front block 14 and the inner surfaces of the protrusions 27a and 27b are extended rearward. 28) made of a resin material such as
Is attached.

Inside the front block 14, a specific processing gas suitable for the surface treatment to be carried out is supplied to the main gas passage 1.
In order to introduce the auxiliary gas passageway 5 in the width direction, a sub gas passage 33 formed of a large number of horizontal small circular holes arranged at equal intervals in the width direction is formed. One end of the sub gas passage 33 is provided at the electrode holding block 13
Is connected to the main gas flow path 15 via the above, and the other end of the sub gas flow path 33 has an intermediate chamber 34 provided inside the front block 14.
Through, and is connected to a gas introduction port 35 that opens to the rear surface of the front block 14. The gas inlet 35 is provided with a joint 36 for connecting to a processing gas supply source 36A, which is O ₂ or CF ₄ in many cases. The processing gas introduced from the joint 36 has a substantially uniform gas pressure in the width direction in the intermediate chamber 34.
Each of the three flows at a substantially uniform flow rate.

In this embodiment, the plasma processing apparatus S
Is used for adjusting the work function of the electrode of the organic EL device, so O ₂ is used as a processing gas. When oxygen (O ₂ ) is used as the processing gas, the O ₂ plasma treatment is often applied to the ashing treatment and the lyophilic treatment.
When carbon tetrafluoride (CF ₄ ) is used as the processing gas, CF ₄ plasma treatment is often applied to etching and liquid repellent treatment.

The processing gas from the supply source 36A is supplied from the supply source 3
With the discharge gas from 2A, the electrode section 1 is passed through the main gas flow path 15 and the discharge generating section 21 made of a porous body.
1 and the bottom surface of the sample 4 and the sample 4 supported by the sample stage 21.
3 is supplied to the space (discharge gap) 47.

Here, on the lower surface of the electrode portion 11, the leg members 26a, 2 are provided along the entire length of the left and right sides (both sides in the X-axis direction).
6b and the projections 27a, 27b are provided with a wall portion (gas flow restricting portion), so that both sides of the discharge gap 47 in the X-axis direction are closed by these wall portions, and the inside and outside of the discharge gap 47 are closed. The distribution of gas is regulated.

As shown in FIG. 4, the sample stage 12 is made of a rectangular metal plate such as aluminum which is long in the moving direction (Y-axis direction), and functions as a ground electrode for the plasma discharge electrode 20. The sample stage 12 is formed on the upper surface 37 that is slightly narrower than the width between the left and right leg portions 26a, 26b, 27a, 27b of the electrode portion 11 and the left and right sides thereof over the entire length, and has the same height as the left and right leg portions. Height difference 38a, 38b
Have and.

On the upper surface 37 of the sample stage 12, a slight step 39 is formed in the vicinity of the center in the X-axis direction.
A sample support surface 40 extending rearward is provided on the lower side of the sample support member 9. At the rear end of the sample support surface 40, the protrusion 41 is provided on the upper surface 37.
It is formed to a height not exceeding.

In this embodiment, a mount plate 42 made of a thin plate of an insulating material such as alumina is provided on the sample support surface 40.
Is placed, and the sample 43 is placed on it. The mount plate 42 has the same dimensions as the sample support surface 40, and the step 39
And the protruding edge 41 are positioned and held so as not to move in the front-rear direction. A corresponding rectangular recess 44 is formed on the upper surface of the mount plate 42 at a slight distance from the front end in the moving direction to accommodate a rectangular sample such as a substrate. The recess 44 has a depth and a length corresponding to the thickness and the length of the sample 43 so that the surface of the sample 43 accommodated therein does not become uneven in the moving direction by matching the upper surface of the mount plate. It is preferably formed.

In FIG. 4, the recess 44 of the mount plate is rectangular, but the shape of the sample to be processed
It is possible to use mount plates having recesses of various shapes and sizes corresponding to the sizes. For example, to process a circular sample, a corresponding diameter circular recess is formed in the mount plate.

Of course, the sample 43 can be placed directly on the sample support surface 40 of the sample stage 12 without using the mount plate. Also in this case, if a recess corresponding to the sample to be processed is formed on the sample support surface,
Similarly, since unevenness does not occur in the moving direction, it is preferable.

As shown in FIGS. 1 and 2, the electrode portion 11 is located above the sample stage 12 and has left and right leg portions 26a, 26 thereof.
The upper surface 37 is arranged to pass between b, 27a, and 27b. As shown in FIG. 5, a slight gap is maintained between the lower surface of the electrode portion 11 and the upper surface 37 of the sample stage 12 so that they do not come into contact with each other, and the step 39 arranges the mounting plate 42 at a lower position. A space (discharge gap) 47, which is sufficiently larger than the gap, is formed between the sample 43 and the lower surface of the electrode portion 11. Similarly, as shown in FIG. 6, the wall portions 26a and 27a (26
(b, 27b) between the lower surface 48 and the inner side surface 49 and the bottom surface 50 and the side wall surface 51 of the step portion 38a (38b) of the sample stage 12, respectively, the space (discharge gap) 4
A slight gap that is sufficiently narrower than that of No. 7 is formed.

Next, a procedure for performing plasma processing on the sample 43 using the plasma processing apparatus S having the above configuration will be described. When the sample 43 to be processed is supported by the sample stage 12, the sample stage 12 is
It is set on the Y side (left side in FIG. 3). While the sample stage 12 moves in the + Y direction, the discharge gas is supplied into the main gas passage 15 through the joint 32, and the processing gas is supplied from the joint 36 to the sub gas passage 33.
Is supplied to the main gas flow path 15 via the, and the discharge gas and the processing gas are mixed in the main gas flow path 15. This mixed gas (predetermined gas) is used for the porous body portion (discharge generation portion) 21.
And is injected into the discharge gap 47 through the porous body portion of the gas flow control plate 25. At the same time, a predetermined voltage is applied to the plasma discharge electrode 20 from the AC power supply 24. Then, as shown in FIG. 3 and FIG.
A discharge is generated between the discharge generator 21 of No. 7 and the sample stage 12.

The gas from the discharge generating portion 21 is discharged into the discharge region 5
Directly supplied to 2. In addition, a uniform flow rate (discharge region 5
The gas is supplied at a flow rate per unit area for 2).

As described above, the plasma discharge electrode 2
A part of 0 is a porous body, a part of the dielectric portion having excellent plasma resistance is a porous body, and these porous portions are a porous body portion 21. Since the gas is supplied to the discharge gap 47 via the gas, the gas having a uniform freshness is supplied from a position close to the discharge region 52. Therefore, the plasma processing distribution is made uniform. Further, since the gas is supplied through the porous body portion 21, the flow rate distribution of the gas supplied to the discharge region 52 is also made uniform.

The discharge gap 47 has a step 39 in front thereof.
And the left and right sides are partitioned by
Since the gas is divided by a, 26b, 27a, and 27b and is substantially closed, the mixed gas injected from the gas ejection port 29 moves in the discharge gap 47 in the direction opposite to the moving direction (that is, -Y direction). It flows in one direction. Further, as described above, the surface of the sample 43 and the upper surface of the mount plate 42 are on the same plane, and the discharge gap 47 is uniform over the entire length.
Flows evenly through.

In the present embodiment, a step 39 is provided near the center of the sample stage 12 to make the distance from the front end thereof relatively long, and the front block 14 is provided with the cover 28 extending the lower surface of the electrode section 11. As a result, a gap between the lower surface of the electrode unit 11 and the upper surface 37 of the sample stage 12 is provided long in front of the discharge gap 47. For this reason, it is possible to effectively prevent the mixed gas from leaking forward from the discharge gap 47 through this gap and from invading the atmosphere into the discharge gap 47 from the outside. Also, the discharge gap 4
On both left and right sides of 7, right and left wall portions 26a, 26b, 27a and 27b as a gas flow restricting portion and left and right step portions 38a,
Since a narrow gap continues in the vertical direction and the horizontal direction due to 38b, it is difficult for the gas to flow between the inside and the outside of the discharge gap 47. Similarly, the mixed gas leaks to the left and right sides and the atmosphere. It is possible to effectively prevent intrusion from the left and right sides. Therefore, it is possible to suppress the generation of turbulence near the left and right ends of the sample 43, and when the surface to be processed of the sample 43 is an electrode of the organic EL device, plasma discharge is stabilized at any position on the electrode surface. It Therefore, the work function of the electrode is adjusted uniformly.

In addition, the wall portion 26a, which is a gas flow control portion,
26b, 27a, and 27b can limit the diffusion of the mixed gas supplied to the discharge gap 47 to the outside (that is, the atmosphere) of the discharge gap 47 and the invasion of the atmosphere into the discharge gap 47, so that the flow rate of the discharge gas can be reduced. However, the discharge can be easily started and the discharge can be stabilized. On the other hand, since it is possible to increase the amount of the processing gas added for the target surface treatment, it is possible to improve the processing efficiency and reduce the processing cost.

Further, since a certain distance is provided between the step 39 and the sample 43 placed on the upper surface of the mount plate 42 as described above, the discharge gap 47 is formed as shown in FIG. Defines a space that is closed between before the sample 43 enters the discharge region 52 and the step 39 that extends ahead of the gas ejection port 29. Since a part of the mixed gas injected from the gas ejection port 29 once spreads into the closed space to form a gas pool, a space between the lower surface of the electrode unit 11 and the upper surface 37 of the sample stage 12 is formed. The invasion of the atmosphere through the gap is more reliably prevented.

In the discharge area 52, excited active species of the mixed gas are generated by the plasma generated by the discharge, and thereby the surface of the sample 43 passing through the discharge area 52 is treated. As described above, since the discharge gap 47 is provided to extend rearward of the discharge region 52 and the gas flow in the discharge gap 47 is limited to one direction, the reactive gas containing the excited active species is , Discharge area 52
Immediately after being diffused into the atmosphere, the gas flows backward along the surface of the sample 43 to the end of the gas flow control plate 25, and then is discharged to the outside.

In the above-described embodiment, the wall portions 26a, 26b, 27a, 2 protruding downward on the left and right sides of the lower surface of the electrode portion 11 are used.
7b and the step portions 38a and 38b are provided on both the left and right sides of the sample stage 12, but of course, the upwardly projecting wall portions are provided on both the left and right sides of the sample stage 12, and the lower surface of the electrode portion 11 is left and right. A stepped portion may be provided on both sides.

Further, an exhaust device is attached to the plasma processing apparatus, and its exhaust inlet is arranged near the end of the gas flow control plate 25 so that the exhaust gas from the discharge gap 47 can be collected without being discharged into the atmosphere. -It may be processed. By doing so, the pollution of the atmosphere due to ozone or the like generated by the gas discharge is prevented.

Although the present invention has been described in detail with reference to the preferred embodiments, the present invention can be implemented by making various modifications and changes to the above embodiments within the technical scope thereof. For example, the electrode portion 11 can have various structures other than those in the above embodiments, and a gas in which the discharge gas and the processing gas are mixed in advance at an appropriate ratio can be supplied to one gas passage. Further, the sample stage 12 can be moved in the reverse direction under the electrode portion 11 with the sample support surface 40 side first. Further, the electrode part 11 can be moved while fixing the sample 43 side.

<Organic EL Device> Next, an example of the organic EL device and its manufacturing process will be described. Figure 7 shows an organic EL
It is the figure which expanded the cross-sectional structure of the display area in a display device. Here, the organic EL device shown in FIG. 7 has a form in which light is extracted from the substrate 202 side on which a thin film transistor (TFT: Thin Film Transistor) is arranged. As shown in FIG. 7, the organic EL device E includes a substrate 202, a light emitting element (organic EL element) 203 provided on the substrate 202, and a TF.
T204 and. The light emitting element 203 includes a pixel electrode (anode) 223 made of a transparent electrode material such as indium tin oxide (ITO) and a pixel electrode 22.
3, a hole transport layer 270 capable of transporting holes from the light emitting layer 3, an organic light emitting layer 260 containing an organic light emitting material, an electron transport layer 250 provided on the upper surface of the light emitting layer 260, and an electron transport layer 250.
And an opposing electrode (cathode) 222 made of aluminum (Al), magnesium (Mg), gold (Au), silver (Ag), calcium (Ca), or the like provided on the upper surface of the.

The TFT 204 is provided on the surface of the substrate 202 through a base protective layer 281 composed mainly of SiO ₂ . The TFT 204 includes a silicon layer 241 formed on an upper layer of the base protective layer 281, a gate insulating layer 282 provided on the upper layer of the base protective layer 281 so as to cover the silicon layer 241, and an upper surface of the gate insulating layer 282. Gate electrode 24 provided in a portion facing the silicon layer 241
2 and the gate insulating layer 28 so as to cover the gate electrode 242.
The first interlayer insulating layer 283 provided on the second upper layer, the source electrode 243 connected to the silicon layer 241 through the contact hole opened over the gate insulating layer 282 and the first interlayer insulating layer 283, and the gate electrode 242. The drain electrode 244, which is provided at a position opposed to the source electrode 243, and is connected to the silicon layer 241 through a contact hole opened over the gate insulating layer 282 and the first interlayer insulating layer 283, the source electrode 243, and the drain electrode And a second interlayer insulating layer 284 provided on the first interlayer insulating layer 283 so as to cover 244.

Then, the pixel electrode 223 is disposed on the upper surface of the second interlayer insulating layer 284, and the pixel electrode 223 and the drain electrode 244 are connected through the contact hole 223a provided in the second interlayer insulating layer 284. There is. Also,
Of the surface of the second interlayer insulating layer 284, the light emitting element (organic EL
A bank layer 221 made of synthetic resin or the like is provided between the counter electrode 222 and a portion other than the area where the element is provided.

Note that a region of the silicon layer 241 which overlaps with the gate electrode 242 with the gate insulating layer 282 interposed therebetween serves as a channel region. Further, in the silicon layer 241, a source region is provided on the source side of the channel region, while a drain region is provided on the drain side of the channel region. Of these, the source region is connected to the source electrode 243 through a contact hole that is opened across the gate insulating layer 282 and the first interlayer insulating layer 283. On the other hand, the drain region is the gate insulating layer 2
The drain electrode 244, which is formed of the same layer as the source electrode 243, is connected to the drain electrode 244 through a contact hole which is opened between the first electrode 82 and the first interlayer insulating layer 283. Pixel electrode 2
3 is a silicon layer 241 via the drain electrode 244.
Connected to the drain region of.

In this example, since the emitted light is extracted from the substrate 202 side on which the TFT 204 is provided, the substrate 202 is preferably transparent or semitransparent.
In this case, as the substrate material, glass, quartz, resin or the like having high transparency (high transmittance) is used. Further, a color filter film, a color conversion film containing a light emitting substance, or a dielectric reflection film may be arranged on the substrate to control the emission color.

On the other hand, the light emitted from the light emitting layer can be taken out from the side opposite to the substrate on which the TFT is provided. When the emitted light is taken out from the side opposite to the substrate, the substrate 202 may be opaque. In that case, a ceramic sheet such as alumina or a metal sheet such as stainless steel that has been subjected to an insulation treatment such as surface oxidation, A thermosetting resin, a thermoplastic resin or the like can be used.

Next, the manufacturing process of the organic EL device E shown in FIG. 7 will be described with reference to FIGS. First, the silicon layer 241 is formed on the substrate 202. When forming the silicon layer 241, first, as shown in FIG.
As shown in (a), a base protective layer 281 made of a silicon oxide film having a thickness of about 200 to 500 nm is formed on the surface of the substrate 202 by plasma CVD using TEOS (tetraethoxysilane) or oxygen gas as a raw material.

Next, as shown in FIG. 8B, the substrate 20
The temperature of No. 2 is set to about 350 ° C., and the semiconductor layer 241A made of an amorphous silicon film with a thickness of about 30 to 70 nm is formed on the surface of the base protection film 281 by the plasma CVD method or the ICVD method. Then, this semiconductor layer 2
41A is subjected to a crystallization process by a laser annealing method, a rapid heating method, a solid phase growth method, or the like, and the semiconductor layer 2
41A is crystallized into a polysilicon layer. In the laser annealing method, for example, an excimer laser beam with a beam length of 400
A line beam of mm is used and its output intensity is, for example, 20
It is set to 0 mJ / cm ² . As for the line beam, the line beam is scanned so that the portion corresponding to 90% of the peak value of the laser intensity in the short direction overlaps each region.

Next, as shown in FIG. 8C, the semiconductor layer (polysilicon layer) 241A is patterned into an island-shaped silicon layer 241, and TEOS is applied to the surface of the island-shaped silicon layer 241.
A gate insulating layer 282 made of a silicon oxide film or a nitride film having a thickness of about 60 to 150 nm is formed by plasma CVD using a raw material such as silicon dioxide or an oxidizing gas.

The surface of the gate insulating layer 282 may be subjected to hydrogen (H ₂ ) plasma treatment. As a result, the dangling bond in the Si-O bond on the surface of the void becomes
It is replaced by H bond and the moisture absorption resistance of the film is improved. Then, another SiO ₂ layer may be provided on the surface of the plasma treated gate insulating layer 282. By doing so, an insulating layer having a dielectric constant can be formed.

Next, as shown in FIG. 8D, a conductive film containing a metal such as aluminum, tantalum, molybdenum, titanium, or tungsten is formed on the gate insulating layer 282 by a sputtering method and then patterned. Thus, the gate electrode 242 is formed. Then, in this state, a high concentration of phosphorus ions is implanted, and the silicon layer 2
41, a source region 241s and a drain region 241d are formed in self-alignment with the gate electrode 242.
In this case, the gate electrode 242 is used as a patterning mask. The portion into which the impurities are not introduced becomes the channel region 241c.

Next, as shown in FIG. 8E, the first interlayer insulating layer 283 is formed. First interlayer insulating layer 283
Like the gate insulating layer 282, is formed of a silicon oxide film or a nitride film, a porous silicon oxide film, or the like, and is formed on the gate insulating layer 282 in the same procedure as the method of forming the gate insulating layer 282. Then, by patterning the first interlayer insulating layer 283 and the gate insulating layer 282 by using a photolithography method, contact holes corresponding to the source electrode and the drain electrode are formed. Then, a conductive layer made of a metal such as aluminum, chromium, or tantalum is formed so as to cover the first interlayer insulating layer 283, and then a region of the conductive layer where the source electrode and the drain electrode are to be formed is covered. A source electrode 243 and a drain electrode 244 are formed by providing a patterning mask and patterning the conductive layer. Next, although not shown, the first
A signal line, a common power supply line, and a scan line are formed over the interlayer insulating layer 283. At this time, since a portion surrounded by these becomes a pixel for forming a light emitting layer and the like as described later, for example, when the emitted light is taken out from the substrate side, TF
Each wiring is formed so that T204 is not located immediately below the portion surrounded by each wiring.

Next, as shown in FIG. 9A, the second interlayer insulating layer 284 is the first interlayer insulating layer 283 and each electrode 24.
3, 244 and the wirings (not shown) are formed to cover the wirings. Like the first interlayer insulating layer 283, the second interlayer insulating layer 284 is formed of a silicon oxide film, a nitride film, or the like, and is formed on the first interlayer insulating layer 283 by the same procedure as the method of forming the first interlayer insulating layer 283. It is formed. And the second
After forming the interlayer insulating layer 284, the second interlayer insulating layer 284 is formed.
A contact hole 223a is formed in a portion corresponding to the drain electrode 244. Then, a conductive material such as ITO is patterned so as to be continuous with the drain electrode 244 through the contact hole 223a to form the pixel electrode 223.

The pixel electrode 223 is made of a transparent electrode material such as ITO or SnO ₂ doped with fluorine, ZnO or polyamine, and is connected to the drain electrode 244 of the TFT 204 through the contact hole 223a.
To form the pixel electrode 223, a film made of the transparent electrode material is formed on the upper surface of the second interlayer insulating layer 284, and the film is patterned.

After forming the pixel electrode 223, FIG.
As shown in, the bank layer 221 is formed so as to cover a predetermined position of the second interlayer insulating layer 284 and a part of the pixel electrode 223. The bank layer 221 is made of synthetic resin such as acrylic resin or polyimide resin. As a specific method of forming the bank layer 221, for example, an acrylic resin, a polyimide resin or the like, or a resist of a precursor thereof melted in a solvent is applied by spin coating, dip coating or the like to form an insulating layer. It is formed. The constituent material of the insulating layer may be any material as long as it does not dissolve in the solvent of the ink described later and is easily patterned by etching or the like. Further, the insulating layer is simultaneously etched by a photolithography technique or the like to form the opening 221a, so that the opening 22
A bank layer 221 with 1a is formed.

After the pixel electrode 223 and the bank portion 221 are formed, the plasma processing step, which is a feature of the present invention, is performed. That is, the sample 43 is in the state shown in FIG. The plasma treatment process is performed in the pixel electrode 223.
Is performed for the purpose of activating the surface of, and further surface-treating the surface of the bank portion 221. Particularly, the activation step is performed mainly for cleaning the pixel electrode 223 (ITO) and adjusting the work function. Furthermore, the pixel electrode 2
The lyophilic treatment of the surface of 23 and the lyophobic treatment of the surface of the bank portion 221 are performed.

The plasma treatment process is roughly classified into, for example, a preheating process, an activation treatment process (a lyophilic process for making it lyophilic), a lyophobic treatment process, and a cooling process. Note that the number of steps is not limited to such steps, and steps may be reduced and additional steps may be added as necessary.

FIG. 10 shows a plasma processing system SYS including the plasma processing apparatus S described with reference to FIGS.
FIG. Plasma processing system S shown in FIG.
YS is the preheat treatment chamber 551, the first plasma treatment chamber 5
52, a second plasma processing chamber 553, a cooling processing chamber 554,
It is composed of a transfer device 555 that transfers the sample 43 to each of these processing chambers 551 to 554. Each processing chamber 551
˜554 are arranged radially around the transport device 555. The plasma processing apparatus S according to the present invention described above is arranged in each of the first plasma processing chamber 552 and the second plasma processing chamber 553. The first and second
The plasma processing apparatuses S installed in the plasma processing chambers 552 and 553 have the same configuration, but in the following description, the first and second plasma processing chambers 552 and 552 will be described.
The plasma processing apparatus installed in each of the 553 is referred to as “first plasma processing apparatus S1” and “second plasma processing apparatus S2” as appropriate.

First, the general steps using these devices will be described. The preheating process is performed in the preheating treatment chamber 551 shown in FIG. Then, in the processing chamber 551, the sample 43 conveyed from the bank portion forming step is heated to a predetermined temperature. After the preheating step, the lyophilic step and the lyophobic treatment step are performed. That is, the sample 43 is sequentially transferred to the first and second plasma processing chambers 552 and 553, and the plasma treatment is performed on the bank portion 221 in each of the processing chambers 552 and 553 to make it lyophilic. After the lyophilic treatment, the lyophobic treatment is performed. After the lyophobic treatment, the sample 43 is transported to the cooling processing chamber, and the sample 43 is cooled to the room temperature in the cooling processing chamber 554. After this cooling step, the transport device 555 transports the sample 43 to the next step of forming a hole injection / transport layer.

Each step will be described in detail below. (Preliminary heating step) The preliminary heating step is performed in the preliminary heating processing chamber 551.
By. In this processing chamber 551, the bank unit 22
The sample 43 containing 1 is heated to a predetermined temperature. Sample 4
In the heating method of No. 3, for example, a heater is attached to a stage on which the sample 43 is placed in the processing chamber 551, and the heater is used to heat the sample 43 together with the stage.
It is also possible to adopt a method other than this. In the preheat treatment chamber 551, the sample 43 is heated to, for example, 70 ° C. to 80 ° C. This temperature is a processing temperature in the plasma processing which is the next step, and the purpose is to preheat the sample 43 in accordance with the next step and eliminate the temperature variation of the sample 43. If the preliminary heating step is not added, the sample 43 is heated from room temperature to the above temperature, and the temperature is constantly changed during the plasma processing step from the start to the end of the step. Become. Therefore, performing plasma processing while changing the substrate temperature may lead to non-uniformity of characteristics. Therefore, preheating is performed to keep the processing conditions constant and obtain uniform characteristics.

Therefore, in the plasma processing step, the sample 43 is placed on the sample stage 12 of the plasma processing apparatus S installed in the first and second plasma processing chambers 552 and 553.
Since the lyophilic process or the lyophobic process is performed with the substrate placed, it is preferable that the preheating temperature be substantially equal to the temperature of the sample stage 12 in which the lyophilic process or the lyophobic process is continuously performed. Therefore, the temperature at which the sample stage of the first and second plasma processing apparatuses S1 and S2 rises, for example, 7
By preheating the sample 43 to 0 to 80 ° C. in advance, even when the plasma treatment is continuously performed on a large number of samples 43, the plasma treatment conditions immediately after the start of treatment and immediately before the end of treatment can be made substantially constant. it can. As a result, the surface treatment conditions of the samples 43 are the same, the wettability of the bank portion 221 with the composition can be made uniform, and a display device having a certain quality can be manufactured. Further, by preheating the sample 43 in advance, it is possible to shorten the processing time in the subsequent plasma processing.

(Activation Processing) Next, in the first plasma processing chamber 552, activation processing is performed. For activation processing,
This includes adjustment and control of the work function of the pixel electrode 223, cleaning of the surface of the pixel electrode, and lyophilic treatment of the surface of the pixel electrode 223. As the lyophilic treatment, a plasma treatment (O ₂ plasma treatment) using oxygen as a treatment gas in the atmosphere is performed by the first plasma treatment apparatus S1. The conditions of the O ₂ plasma treatment are, for example, plasma power of 100 to 800 W,
The oxygen gas flow rate is 50 to 100 ml / min, the substrate transfer speed is 0.5 to 20 mm / sec, and the substrate temperature is 70 to 90 ° C. The heating by the sample stage 12 is
It is performed mainly for keeping the temperature of the preheated sample 43.

By this O ₂ plasma treatment, the pixel electrode 2
23, the upper surface of the bank layer 221, and the opening 221.
a The wall surface is lyophilic processed. By this lyophilic treatment, hydroxyl groups are introduced into each of these surfaces to impart lyophilicity. The O ₂ plasma treatment not only imparts lyophilicity, but also serves to clean the ITO that is the pixel electrode 223 and adjust the work function as described above.

(Liquid-repellent treatment) Next, the second plasma treatment chamber 5
In 53, as the lyophobic process, plasma processing (CF ₄ plasma processing) using tetrafluoromethane as a processing gas is performed by the second plasma processing apparatus S2 in the atmosphere. That is, the sample 43 is transported by the sample stage 12 at a predetermined transport rate while being heated by the sample stage 12, and the sample 43 is irradiated with tetrafluoromethane (carbon tetrafluoride) in a plasma state during that period. CF
₄ Plasma processing conditions include, for example, plasma power 10
0-800 W, 4-fluoromethane gas flow rate 50-100 m
l / min, substrate transfer speed 0.5 to 20 mm / sec,
The substrate temperature is 70 to 90 ° C. Note that the heating by the heating stage is performed mainly for keeping the temperature of the preheated sample 43 as in the case of the first plasma processing chamber 552. The processing gas is not limited to tetrafluoromethane (carbon tetrafluoride), and other fluorocarbon-based gas can be used.

The bank layer 22 is formed by CF ₄ plasma treatment.
The upper surface of 1 and the wall surface of the opening 221a are subjected to liquid repellent treatment. By this liquid repellent treatment, a fluorine group is introduced into each of these surfaces to impart liquid repellency. Organic substances such as acrylic resin and polyimide resin that constitute the bank layer 221 can be easily made liquid-repellent by irradiation with fluorocarbon in a plasma state. In addition, the pretreatment with O ₂ plasma is more likely to be fluorinated, which is particularly effective in this embodiment. Although the electrode surface of the pixel electrode 223 is somewhat affected by this CF ₄ plasma treatment,
Less likely to affect wettability.

(Cooling Step) Next, as the cooling step, the cooling treatment chamber 554 is used to cool the sample 43 heated for the plasma treatment to the control temperature. This is a process performed for cooling to the control temperature of the inkjet process (droplet discharging process) which is the subsequent process. The cooling processing chamber 554 has a plate for placing the sample 43,
The plate has a structure in which a water cooling device is incorporated so as to cool the sample 43. Further, by cooling the sample 43 after the plasma treatment to room temperature or a predetermined temperature (for example, a control temperature at which the inkjet process is performed), the temperature of the sample 43 becomes constant in the next hole injection / transport layer forming process, The next step can be performed at a uniform temperature at which the temperature of the sample 43 does not change. Therefore, by adding such a cooling step, it is possible to uniformly form the material discharged by the discharging means such as an inkjet method. For example,
When the first composition containing the material for forming the hole injecting / transporting layer is ejected, the first composition can be ejected continuously in a constant volume, and the hole injecting / transporting layer can be made uniform. Can be formed.

Next, as shown in FIG. 9C, the hole transport layer 270 is formed on the upper surface of the pixel electrode 223. Here, as the material for forming the hole transport layer 270, known materials can be used without particular limitation, and examples thereof include a pyrazoline derivative, an arylamine derivative, a stilbene derivative, and a triphenyldiamine derivative. Specifically, JP-A-63-70257 and 63-1758.
No. 60, JP-A-2-135359 and JP-A-2-135.
No. 361, No. 2-209988, No. 3-37992
Nos. 3,152,184 and the like are exemplified, but a triphenyldiamine derivative is preferable, and among them, 4,4′-bis (N (3-methylphenyl)).
-N-phenylamino) biphenyl is preferred.

The hole injection layer may be formed instead of the hole transport layer, or both the hole injection layer and the hole transport layer may be formed. In that case, as the material for forming the hole injection layer, for example, copper phthalocyanine (C
uPc), polytetrahydrothiophenylphenylene, polyphenylene vinylene, 1,1-bis- (4-
Examples thereof include N, N-ditolylaminophenyl) cyclohexane and tris (8-hydroxyquinolinol) aluminum, but it is particularly preferable to use copper phthalocyanine (CuPc).

When forming the hole injecting / transporting layer 270, an inkjet method (droplet discharging method) is used. That is, the composition droplets (composition ink) containing the hole injection / transport layer material described above are ejected onto the electrode surface of the pixel electrode 223, and then a drying process and a heat treatment are performed, so that holes are formed on the pixel electrode 223. An injection / transport layer 270 is formed. After this hole injection / transport layer forming step, hole injection /
In order to prevent oxidation of the transport layer 270 and the light emitting layer 260, it is preferable to carry out in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere. For example, an unillustrated inkjet head (droplet ejection head) is filled with a composition ink containing a hole injecting / transporting layer material, and the ejection nozzle of the inkjet head is opposed to the electrode surface of the pixel electrode 223, and the inkjet head and the sample While relatively moving (substrate 202), ink droplets having a controlled liquid amount per droplet are ejected from the ejection nozzle onto the electrode surface. Next, the ejected ink droplets are dried to evaporate the polar solvent contained in the composition ink, whereby the hole injecting / transporting layer 270 is formed.

As the composition ink, it is possible to use, for example, a mixture of a polythiophene derivative such as polyethylenedioxythiophene and polystyrene sulfonic acid dissolved in a polar solvent such as isopropyl alcohol. Here, the ejected ink droplets spread on the electrode surface of the pixel electrode 223 that has been subjected to the ink-philic treatment, and fill the vicinity of the bottom of the opening 221a. On the other hand, ink drops are repelled and do not adhere to the upper surface of the bank layer 221 that has been subjected to the ink repellent treatment. Therefore, even if the ink droplet is ejected from the predetermined ejection position onto the upper surface of the bank layer 221, the upper surface is not wetted by the ink droplet, and the repelled ink droplet enters the opening 221a of the bank layer 221. It is supposed to roll in.

Next, a drying process is performed. By performing the drying step, the composition ink after ejection is dried,
The hole injection / transport layer 270 is formed by evaporating the polar solvent contained in the composition ink.

The above-mentioned drying treatment is performed, for example, in a nitrogen atmosphere.
The pressure is, for example, 13.3 Pa (0.1 T at room temperature to about 50 ° C).
orr). If the pressure is too low, the composition ink will blister, which is not preferable. Also,
If the temperature is set to room temperature or higher, for example, 80 ° C. or higher, the evaporation rate of the polar solvent increases, and a flat film cannot be formed. After the drying treatment, it is carried out in nitrogen, preferably in vacuum.
It is preferable to remove the polar solvent and water remaining in the hole injecting / transporting layer 270 by performing a heat treatment of heating at 0 ° C. for about 10 minutes.

Next, as shown in FIG. 9D, the light emitting layer 260 is formed on the upper surface of the hole injection / transport layer 270. The material for forming the light-emitting layer 260 is not particularly limited, and examples thereof include polyphenylene derivatives, polyfluorene derivatives, polyvinylcarbazole, polythiophene derivatives shown in [Chemical Formula 1] to [Chemical Formula 5], or perylene of these polymer materials. A dye, a coumarin-based dye, a rhodamine-based dye such as rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, Nile red, coumarin 6, and quinacridone can be doped and used.

[0085]

[Chemical 1]

[0086]

[Chemical 2]

[0087]

[Chemical 3]

[0088]

[Chemical 4]

[0089]

[Chemical 5]

The light emitting layer 260 is a hole injecting / transporting layer 270.
It is formed by the same procedure as the forming method. That is, a composition ink containing a light emitting layer material is ejected onto the upper surface of the hole injecting / transporting layer 270 by an inkjet method, and then a drying treatment and a heat treatment are performed, so that the positive portion inside the opening 221a formed in the bank layer 221 is positive. A light emitting layer 260 is formed on the hole injection / transport layer 270. This light emitting layer forming step is also performed in an inert gas atmosphere as described above. Since the ejected composition droplets (composition ink, liquid material) are repelled in the liquid-repellent-treated area, even if the droplet droplets deviate from a predetermined ejection position, the repelled droplet droplets are bank layer 221.
Rolling into the opening 221a. After the composition ink containing the material for forming the light emitting layer 260 is provided, a drying process is performed under predetermined conditions.

The electron transport layer 2 is formed on the upper surface of the light emitting layer 260.
50 may be formed. The material for forming the electron transport layer 250 is not particularly limited, and includes oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, and tetracyanoanthraquinodines. Methane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives,
Examples thereof include diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of their derivatives. Specifically, as in the case of the material for forming the hole transport layer, the method disclosed in JP-A-63-702 is used.
57, 63-175860, and JP-A 2-13.
No. 5359, No. 2-135361, No. 2-20998
No. 8, No. 3-37992, No. 3-152184 and the like are exemplified, and particularly 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,
Preference is given to 3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum.

The material for forming the hole injecting / transporting layer 270 and the material for forming the electron transporting layer 250 described above are used as the light emitting layer 260.
It may be mixed with the above-mentioned forming material and used as a light emitting layer forming material. In that case, the amount of the hole injecting / transporting layer forming material or the electron transporting layer forming material used may depend on the kind of the compound used and the like. Although different, it is appropriately determined in consideration of them within a range that does not impair sufficient film-forming properties and light emission characteristics. Usually, it is 1 to 40% by weight, more preferably 2 to 30% by weight, based on the light emitting layer forming material.

Next, as shown in FIG. 9E, the counter electrode 222 is formed on the upper surfaces of the electron transport layer 250 and the bank layer 221.
Is formed. The counter electrode 222 is formed on the entire surfaces of the electron transport layer 250 and the bank layer 221, or in a stripe shape. As for the counter electrode 222, of course, simple materials such as Al, Mg, Li, and Ca or Mg: Ag
It may be formed as one layer made of an alloy material of (10: 1 alloy), but may be formed as a metal (including alloy) layer made up of two layers or three layers. Specifically, Li ₂ O
(About 0.5 nm) / Al or LiF (about 0.5 nm)
A laminated structure such as / Al or MgF ₂ / Al can also be used. The counter electrode 222 is a thin film made of the above-mentioned metal, and may be made of a material or structure capable of transmitting light.

<Electronic Equipment> Examples of electronic equipment provided with the organic EL device of the above-described embodiment will be described. FIG. 11 shows
It is a perspective view showing an example of a mobile phone. In FIG. 11, reference numeral 1000 indicates a mobile phone body, and reference numeral 1001.
Indicates a display unit using the above organic EL display device.

FIG. 12 is a perspective view showing an example of a wrist watch type electronic device. In FIG. 12, reference numeral 1100 indicates a watch body, and reference numeral 1101 indicates a display unit using the above organic EL display device.

FIG. 13 is a perspective view showing an example of a portable information processing device such as a word processor and a personal computer. In FIG. 13, reference numeral 1200 is an information processing apparatus, reference numeral 1202 is an input unit such as a keyboard, reference numeral 1204 is the information processing apparatus main body, and reference numeral 1206 is a display unit using the above organic EL display device.

Since the electronic equipment shown in FIGS. 11 to 13 is equipped with the organic EL display device of the above-described embodiment, it is possible to realize an electronic equipment which is excellent in display quality and has an organic EL display portion with a bright screen. You can

[0098]

As described above, according to the surface treatment apparatus of the present invention, a part of the plasma discharge electrode is a porous body portion, and gas is supplied to the discharge gap through the porous body portion. Therefore, the gas of uniform freshness is supplied from a position close to the discharge region. Therefore, the plasma processing distribution is made uniform. Further, since the gas is supplied through the porous body portion, the flow rate distribution of the gas supplied to the discharge region is made uniform, and the plasma processing can be satisfactorily performed.

According to the apparatus for manufacturing an organic EL device of the present invention, the plasma processing can be performed in a state where the discharge intensity is uniform, so that the plasma processing distribution can be uniform. Therefore, for example, liquid repellency and lyophilicity adjustment, etching and ashing can be performed in a desired state.

According to the organic EL device of the present invention, since the plasma processing distribution is made uniform, good light emitting performance can be obtained.

According to the electronic equipment of the present invention, since the organic EL device of the present invention is mounted, highly reliable operation can be realized.

[Brief description of drawings]

FIG. 1 is a diagram showing an embodiment of a plasma processing apparatus which is a surface processing apparatus of the present invention, as viewed from the −Y direction side.

FIG. 2 is a diagram of FIG. 1 viewed from the + Y direction side.

3 is a sectional view taken along the line AA of FIG.

FIG. 4 is an external perspective view showing a sample stage.

5 is an enlarged view of a main part of FIG.

6 is a cross-sectional view taken along the line BB of FIG.

FIG. 7 is a partial cross-sectional view of an organic EL device.

FIG. 8 is a diagram for explaining a manufacturing process of the organic EL device.

FIG. 9 is a diagram for explaining a manufacturing process of the organic EL device.

FIG. 10 is a schematic configuration diagram of a plasma processing system.

FIG. 11 is a diagram showing an electronic device in which the organic EL device of the present invention is mounted.

FIG. 12 is a diagram showing an electronic device equipped with the organic EL device of the invention.

FIG. 13 is a diagram showing an electronic device equipped with the organic EL device of the invention.

FIG. 14 is a diagram showing a plasma processing apparatus which is a conventional surface processing apparatus.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 Electrode part 12 Sample stage 12A Moving device 15 Main gas flow path (gas supply part) 20 Plasma discharge electrode 21 Discharge generating part (porous body part) 26a, 26b Leg member (wall part) 27a, 27b Projection part (wall part) ) 43 sample 47 discharge gap (space) 202 substrate 203 light emitting element 222 electrode (cathode, counter electrode) 223 electrode (anode, pixel electrode) 260 light emitting layer E organic EL device S plasma treatment device (surface treatment device) SYS plasma treatment system (Manufacturing device of organic EL device)

Claims (9)

[Claims] 1. A surface treatment apparatus for performing a predetermined treatment on a surface to be processed of a sample, comprising: a sample stage supporting the sample; and a position facing the surface to be processed of the sample supported by the sample stage. A plasma discharge electrode that is provided and has a porous body portion, and a gas supply unit that supplies a predetermined gas through the porous body portion between the sample supported on the sample stage and the plasma discharge electrode. A surface treatment apparatus comprising: 2. The surface treatment apparatus according to claim 1, wherein the porous body portion is a discharge generating portion. 3. The surface treatment apparatus according to claim 1, wherein the porous body portion is formed of a porous metal portion and a porous dielectric portion. 4. The surface treatment apparatus according to claim 1, further comprising a moving device that relatively moves the sample stage and the plasma discharge electrode. 5. An apparatus for manufacturing an organic EL device, which comprises an electrode provided on a substrate and an organic light emitting layer provided adjacent to the electrode, and the organic EL device manufacturing method according to claim 1. An apparatus for manufacturing an organic EL device, comprising: 6. The predetermined gas contains at least oxygen or fluorine, and the surface treatment device performs surface modification of the electrode of the organic EL device or adjustment of a work function of the electrode. An apparatus for manufacturing an organic EL device according to claim 5. 7. The method for manufacturing an organic EL device, comprising: an electrode provided on a substrate; an organic light emitting layer provided adjacent to the electrode; and a bank for forming the light emitting layer. 5. A method of manufacturing an organic EL device, comprising the step of subjecting at least the electrodes and the banks to a predetermined surface treatment using the surface treatment device according to claim 4. 8. An organic EL device manufactured by the apparatus for manufacturing an organic EL device according to claim 5. 9. An electronic device comprising the organic EL device according to claim 8.