JP5771372B2 - Plasma processing apparatus and pretreatment method - Google Patents

Description

  The present invention relates to a technique for pre-processing a substrate when, for example, an organic EL display or an organic EL lighting device is manufactured.

When manufacturing an organic EL device, a substrate having a transparent conductive film pattern is used on the surface, but the surface of the substrate is contaminated with organic matter and the like. There is a problem that the performance cannot be fully exhibited.
For this reason, conventionally, before forming an organic film on a substrate, a pretreatment for removing organic substances and the like is performed.

FIG. 6 is a schematic configuration diagram showing a conventional pre-processing apparatus.
As shown in FIG. 6, the pretreatment apparatus 101 includes a vacuum chamber 102 in which the substrate 100 is disposed, and a plasma generation unit 103 is provided below the vacuum chamber 102.
The plasma generation unit 103 includes, for example, a coil 105 connected to a high frequency power source 104, and high frequency power is applied to the coil 105.

A processing gas supply source 106 is connected to the plasma generation unit 103, plasma of a processing gas such as oxygen (O ₂ ) gas supplied from the processing gas supply source 106 is generated, and the surface of the substrate 100 is generated by particles such as oxygen radicals. A pretreatment is performed by cleaning the surface of the substrate 100 by reacting with the organic substance.

However, in such a conventional technique, since plasma is generated at one place, it has been difficult to perform uniform processing on the substrate 100.
On the other hand, in recent years, since the object to be processed has been increased in size, it is necessary to use a plurality of means for generating plasma to perform uniform pretreatment on the surface of the object to be processed, which increases the cost of the process. There was also a problem of end.

JP 2004-79904 A JP-A-7-90572

  The present invention has been made in order to solve the problems of the prior art, and the object of the present invention is to perform processing with a uniform distribution on the surface of a large processing object at a low cost. It is to provide a technology that can be used.

In order to achieve the above object, the present invention provides a vacuum chamber in which a processing object is disposed, a processing gas supply source provided outside the vacuum chamber, an elongated shape, and the processing target. The process gas that is movable relative to the object and that is provided in a direction that intersects the relative movement direction is discharged from the process gas supply source, and radicals of the process gas are discharged from the process gas. A radical emitter for discharging toward the object, and the radical emitter is supplied with the processing gas from the processing gas supply source, and is an elongated processing gas extending in the longitudinal direction of the radical emitter. A diffusion part; and an elongated plasma forming chamber extending in a longitudinal direction of the radical emitter for forming plasma of the processing gas diffused in the processing gas diffusion part, and the processing gas Dispersion unit includes a plurality of diffusion chamber which is stepwise divided toward the discharge side from the introduction side of the process gas, the plurality of diffusion chamber has a partition wall for isolating the mutual atmosphere The diffusion chambers adjacent to each other are connected to each other through a communication port through which the processing gas can pass, and the communication ports are arranged to face the ceiling portion of the diffusion chamber adjacent to the processing gas discharge side, respectively. Further, a final stage diffusion chamber among the plurality of diffusion chambers is connected to the plasma formation chamber via a communication port through which the processing gas can pass, and the plasma formation chamber includes the plasma formation chamber. The plasma processing apparatus is provided with a slit-like radical discharge port extending in the longitudinal direction .
In the present invention, the communication port of the processing gas diffusion portion in the radical emitter is also effective when the number is increased from the processing gas introduction side to the discharge side.
In the present invention, the plurality of communication ports of the processing gas diffusion section in the radical emitter are configured to increase by 2 ^n-1 (n is a natural number) from the processing gas introduction side to the discharge side. It is also effective when
In the present invention, the plurality of communication ports of the processing gas diffusion section in the radical emitter are configured such that the sum of the areas of the respective communication ports decreases from the processing gas introduction side to the discharge side. It is also effective.
On the other hand, the present invention is a method for performing processing on a substrate surface in a vacuum using any of the plasma processing apparatuses described above, and before the organic material is deposited on the substrate by vacuum deposition, the plasma This is a pre-processing method including a step of cleaning the substrate surface by releasing radicals of the processing gas from a radical emitter of a processing apparatus.
In the case of the present invention, the processing gas diffusion portion in the radical emitter has a plurality of diffusion chambers that are divided stepwise from the processing gas introduction side to the discharge side, and the plurality of diffusion chambers are adjacent to each other. The diffusion chamber is connected through a communication port through which the processing gas can pass, and the final stage diffusion chamber among the plurality of diffusion chambers is connected to the plasma formation chamber through a communication port through which the processing gas can pass. Therefore, after diffusing the processing gas in the plurality of diffusion chambers, the plasma of the processing gas can be formed in the plasma forming chamber to release radicals of the processing gas from the radical discharge port toward the processing target, Accordingly, for example, when film formation pretreatment is performed on a large processing target, uniform processing can be performed in each region on the processing target.
In particular, according to the present invention, the plurality of diffusion chambers of the radical emitter have partition walls for isolating each other's atmosphere, and adjacent diffusion chambers are connected via a communication port through which the processing gas can pass. In addition, since the communication port is disposed to face the ceiling portion of the diffusion chamber adjacent to the processing gas discharge side, the communication port is treated when the processing gas is diffused in the diffusion chamber of the radical emitter. Since the gas collides with the ceiling portion of each diffusion chamber and the diffusion thereof is promoted, the processing gas can be introduced into the plasma forming chamber in a sufficiently diffused state. Uniform processing can be performed.
Furthermore, according to the present invention, the radical emitter is provided in a direction that is formed in an elongated shape and is capable of relative movement with respect to the processing object and that intersects the relative movement direction of the processing object. Therefore, by moving the processing object or the radical emitter, uniform processing can be performed in each region on the processing object.
Furthermore, according to the present invention, since it is not necessary to provide a plurality of means for generating plasma, it is possible to provide an inexpensive plasma processing apparatus with a simple configuration.

  ADVANTAGE OF THE INVENTION According to this invention, the process with uniform distribution can be performed cheaply with respect to the surface of a large sized process target object.

Schematic configuration plan view showing the overall configuration of an organic EL manufacturing apparatus using a pretreatment apparatus which is a plasma processing apparatus according to the present invention (A): Cross-sectional view showing the internal configuration of the pretreatment device (b): Schematic configuration diagram showing the internal configuration of the main body of the linear radical emitter of the pretreatment device Sectional drawing which shows the internal structure of the plasma processing apparatus of other embodiment of this invention. Sectional drawing which shows the internal structure of the plasma processing apparatus of other embodiment of this invention. The schematic block diagram which shows the other example of the linear radical emitter used for this invention Sectional drawing which shows the internal structure of the pre-processing apparatus which concerns on a prior art

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.
FIG. 1 is a schematic configuration plan view showing an overall configuration of an organic EL manufacturing apparatus using a pre-processing apparatus which is a plasma processing apparatus according to the present invention, and FIG. 2A is a cross-sectional view showing an internal configuration of the pre-processing apparatus. FIG. 2B is a schematic configuration diagram showing the internal configuration of the main body of the linear radical emitter of the pretreatment apparatus. Hereinafter, the vertical relationship will be described based on the configuration shown in FIGS. 2A and 2B, but the present invention is not limited to this.

As shown in FIG. 1, the organic EL manufacturing apparatus 1 of the present embodiment is of a multi-chamber type and has a transfer chamber 2 connected to a vacuum exhaust system (not shown).
A transfer robot 3 is provided in the transfer chamber 2, and a loading chamber 4A, a substrate pretreatment chamber 4B, organic film formation chambers 4C and 4D, an electrode film formation chamber 4E, and a substrate delivery provided around the transfer chamber 2 are provided. The substrate 5 and the mask (not shown) are transferred to and from the chamber 4F.

  The loading chamber 4A, the substrate pretreatment chamber 4B, the organic film forming chambers 4C and 4D, the electrode film forming chamber 4E, and the substrate transfer chamber 4F are each connected to a vacuum exhaust system (not shown) and independently perform vacuum exhaust. It is like that.

In the case of the present embodiment, a pretreatment device (plasma treatment device) 30 having a linear radical emitter (radical emitter) 10 described later is provided in the substrate pretreatment chamber 4B.
The substrate transfer chamber 4F is connected to a transfer chamber 6 that transfers the substrate 5 to the next process.

  As shown in FIG. 1 or FIG. 2 (a) (b), the pretreatment device 30 of the present embodiment includes a linear radical emitter 10 having a body portion 10A having an elongated box shape in a vacuum chamber 4a. I have.

The linear radical emitter 10 has a main body portion 10A in a direction intersecting the substrate transport direction X in the substrate pretreatment chamber 4B (in this embodiment, the Y direction perpendicular to the substrate transport direction X). It is arranged toward.
The main body 10A of the linear radical emitter 10 is integrally formed using a conductive metal material such as stainless steel.

The main body portion 10A of the linear radical emitter 10 is configured, for example, such that a processing gas introduction chamber 10B is provided in the lower portion of the main body portion 10A, and high frequency power is applied from the high frequency power source 6 to the processing gas introduction chamber 10B. ing.
One end of the supply pipe 7 is connected to the processing gas introduction chamber 10B below the linear radical emitter 10, and the other end of the supply pipe 7 is provided outside the vacuum chamber 4a. A processing gas supply source 8 is connected.

In the case of the present embodiment, a connecting portion 7 a made of an insulating material is provided in the middle part of the supply pipe 7, and the processing gas introduction chamber 10 B of the linear radical emitter 10 is electrically connected to the processing gas supply source 8. It is in an insulated state.
The processing gas supply source 8 includes a reaction gas supply source 80 and a discharge auxiliary gas supply source 81.
The reactive gas supply source 80 includes a reactive gas source 8a that supplies, for example, oxygen (O ₂ ) gas, which is a reactive gas, and this reactive gas source 8a is connected to the supply pipe 7 via a flow rate adjusting unit 8b and a valve 8c. Has been.

On the other hand, the discharge auxiliary gas supply source 81 has a discharge auxiliary gas source 8d for supplying a discharge auxiliary gas such as nitrogen (N ₂ ) gas or argon (Ar) gas, for example, and this discharge auxiliary gas source 8d is a flow rate adjusting unit. It is connected to the supply pipe 7 through 8e and a valve 8f.

On the other hand, the linear radical emitter 10 according to the present embodiment has a plurality of stages (four stages in this example) as first to fourth stages as process gas diffusion sections on the substrate 5 side of the process gas introduction chamber 10B described above. Diffusion chambers 11, 21, 31, 41 are provided in this order.

Further, as will be described below, in the present embodiment, the number of first to fifth communication ports 12 increases by 2 ^n-1 (n is a natural number) from the processing gas introduction side to the discharge side. , 22, 32, 42, 52 are provided.
The first diffusion chamber 11 is configured to have a larger volume than the processing gas introduction chamber 10B, and is connected to the processing gas introduction chamber 10B through one first communication port 12 provided at the bottom thereof.

The position of the first communication port 12 is set so as to face the ceiling portion of the first diffusion chamber 11, whereby the processing gas collides with the ceiling portion of the first diffusion chamber 11 to process it. The gas diffusion is promoted (in FIG. 2B, the positions of the first communication port 12 and the second communication port 22 are drawn so as to be overlapped for easy understanding. ).
The first diffusion chamber 11 is connected to the second diffusion chamber 21 via two second communication ports 22 provided in the ceiling portion (the bottom portion of the second diffusion chamber 21).

  In the case of the present invention, although not particularly limited, from the viewpoint of preventing the backflow of the processing gas, that is, maintaining the pressure gradient, the sum of the areas of the second communication ports 22 is the first communication port. It is preferable to set so that it is not larger (smaller) than the sum of the 12 areas.

  Furthermore, from the viewpoint of evenly distributing the processing gas flow, the area and shape of the communication ports in the same stage are made the same. In the present embodiment, the areas and shapes of the first to fifth communication ports 12 to 52 are set. More preferably, they are the same.

  Further, the position of the second communication port 22 is set so as to face the ceiling portion of the second diffusion chamber 21, so that the processing gas collides with the ceiling portion of the second diffusion chamber 21. It is configured so that the diffusion of the processing gas is promoted (in FIG. 2B, the positions of the second communication port 22 and the third communication port 32 are drawn so as to overlap for easy understanding. )

  Furthermore, in the present embodiment, the second diffusion chamber 21 is partitioned into two regions by the two partition walls 21a, and the atmosphere of each region is isolated differently. These partition walls 21a are effective for promoting the diffusion thereof when the process gas collides.

In the present invention, the position where the partition wall portion 21a is provided is not particularly limited. However, from the viewpoint of more uniformly diffusing the processing gas, each of the second diffusion chambers 21 isolated by the partition wall portion 21a. It is preferable to provide at a position where the volume of the region and the passing speed of the processing gas are equal.
The second diffusion chamber 21 is connected to the third diffusion chamber 31 through four third communication ports 32 provided in the ceiling portion (the bottom of the third diffusion chamber 31).

  In the case of the present invention, although not particularly limited, from the viewpoint of preventing the backflow of the processing gas, that is, maintaining the pressure gradient, the sum of the areas of the third communication ports 32 is the above-described second. It is preferable to set so as not to be larger (smaller) than the sum of the areas of the communication ports 22.

  Further, the position of the third communication port 32 is set so as to face the ceiling portion of the third diffusion chamber 31, so that the processing gas collides with the ceiling portion of the third diffusion chamber 31. It is configured so that the diffusion of the processing gas is promoted (in FIG. 2 (b), the positions of the third communication port 32 and the fourth communication port 42 are drawn so as to overlap for easy understanding. )

  Further, in the present embodiment, the third diffusion chamber 31 is partitioned into four regions by, for example, six partition walls 31a, and the atmosphere of each region is isolated differently. These partition plates are effective for promoting the diffusion thereof when the processing gas collides.

  In the present invention, the position where the partition wall 31a is provided is not particularly limited, but from the viewpoint of more uniformly diffusing the processing gas, each region of the third diffusion chamber 31 partitioned by the partition wall 31a. It is preferable to provide at a position where the volume of the gas and the passing speed of the processing gas are equal.

Further, a fourth diffusion chamber 41 is provided in a portion of the third diffusion chamber 31 on the substrate 5 side.
Here, the third diffusion chamber 31 is connected to the fourth diffusion chamber 41 via eight fourth communication ports 42 provided in the ceiling portion (the bottom of the fourth diffusion chamber 41).

  In the case of the present invention, although not particularly limited, from the viewpoint of preventing the back flow of the processing gas, that is, maintaining the pressure gradient, the sum of the areas of the fourth communication ports 42 is the above-described third. It is preferable to set so as not to be larger (smaller) than the sum of the areas of the communication ports 32.

Further, the position of the fourth communication port 42 is set so as to face the ceiling portion of the fourth diffusion chamber 41, so that the plasma of the processing gas collides with the ceiling portion of the fourth diffusion chamber 41. Thus, the diffusion of the processing gas is promoted.
In the present embodiment, the fourth diffusion chamber 41 is partitioned into eight regions by seven partition walls 41a, and the atmosphere in each region is isolated differently. These partition walls 41a are effective for promoting diffusion when the process gas collides.

  In the present invention, the position where the partition wall 41a is provided is not particularly limited, but from the viewpoint of more uniformly diffusing the processing gas, each region of the fourth diffusion chamber 41 partitioned by the partition wall 41a. It is preferable to provide at a position where the volume of the gas and the passing speed of the processing gas are equal.

Further, a shield member 50 is provided at a portion of the fourth diffusion chamber 41 on the substrate 5 side.
The shield member 50 is configured to cover the space above the fourth diffusion chamber 41, whereby plasma of the processing gas that has passed through the fifth communication port 52 is formed in this space, that is, the plasma formation chamber 51. It is like that.
Here, the plasma formation chamber 51 is connected to the fourth diffusion chamber 41 via 16 fifth communication ports 52 provided in the ceiling portion of the fourth diffusion chamber 41 (the bottom of the plasma formation chamber 51). ing.

  In the case of the present invention, although not particularly limited, from the viewpoint of preventing gas backflow, that is, maintaining the pressure gradient, the sum of the areas of the fifth communication ports 52 is the above-described fourth communication port. It is preferable to set so as not to be larger (smaller) than the sum of the areas of 42.

The shield member 50 is made of a conductive material such as stainless steel and is grounded. The shield member 50 is attached to the main body portion 10A via the insulating portion 54, and the main body portion 10A is in an electrically floating state.
A portion of the shield member 50 that faces the substrate 5 is provided with a slit 53 that extends in a direction (Y direction) orthogonal to the X direction that is the substrate transport direction. The slit 53 is formed to have a length equivalent to the width of the substrate 5.

  In the case of performing the pretreatment of the surface of the substrate 5 in the present embodiment having such a configuration, the reaction gas is supplied from the processing gas supply source 8 through the supply pipe 7 in a state where the inside of the vacuum chamber 4a is at a predetermined pressure. And the discharge auxiliary gas are introduced into the processing gas introduction chamber 10 </ b> B of the linear radical emitter 10.

  Then, by applying a predetermined power from the high-frequency power source 6 to the linear radical emitter 10, the processing gas is discharged into the plasma in the plasma forming chamber 51 of the linear radical emitter 10.

  In this case, the processing gas in the processing gas introduction chamber 10B is diffused after passing through the first to fourth communication ports 12 to 42 of the first to fourth diffusion chambers 11 to 41 described above, and then the fifth communication. The gas is introduced into the plasma forming chamber 51 through the port 52, and the processing gas is discharged in the plasma forming chamber 51.

  Thereafter, neutral active species (oxygen radicals) in the plasma of the processing gas sufficiently mixed with the passage of time are released from the slit 53 of the plasma forming chamber 51 toward the substrate 5. Here, by moving the substrate 5 in the X direction, oxygen radical particles react with organic substances in the respective regions on the surface of the substrate 5, thereby cleaning the entire surface of the substrate 5.

  As described above, in the present embodiment, the linear radical emitter 10 includes the first to fourth diffusion chambers 11 to 41 that are divided stepwise from the process gas introduction side to the discharge side. At the same time, the first to fourth diffusion chambers 11 to 41 are connected to each other through the first to fourth communication ports 12 to 42 through which the processing gas can pass through the adjacent diffusion chambers. In the diffusion chamber 41, since the processing gas is connected to the plasma forming chamber 51 via the fifth communication port 52, the processing gas is diffused in the plasma forming chamber 51 after the processing gas is reliably diffused. Oxygen radicals can be released toward the substrate 5 from the slits 53 having the same length as the width of the substrate 5, so that when the pretreatment for film formation is performed on the large substrate 5, the substrate In each area above 5 Te uniform surface treatment can be performed.

  As a result, according to the present embodiment, the work function of the surface of the transparent conductive film on the substrate 5 can be made higher and uniform as compared with the conventional case. When a lamp is produced, it is possible to suppress short-circuiting and light emission variations due to excessive local current flow. In addition, when a display is created using an organic EL element, it is possible to suppress variations in light emission and shortening of the element life due to variations in current between elements.

FIG. 3 is a diagram showing a main part of another embodiment of the plasma processing apparatus of the present invention. In the following, parts corresponding to those in the above embodiment are denoted by the same reference numerals and detailed description thereof is omitted. To do.
As shown in FIG. 3, the plasma processing apparatus 30 </ b> A of this example moves the linear radical emitter 10.

  In the present embodiment, the linear radical emitter 10 is configured to move horizontally in the X direction with respect to the substrate 5 by a driving means (not shown), thereby performing a cleaning process using oxygen radicals on the entire surface of the substrate. It is like that.

  Further, in this embodiment, since the linear radical emitter 10 moves, the pressure in the space around the supply pipe 7 becomes a predetermined value by covering the space around the supply pipe 7 with an extendable bellows. It is configured to be retained.

According to the present embodiment having such a configuration, only the bellows is formed when the linear radical emitter 10 is moved, so that there is an effect that dust generation is reduced and uniform speed movement is possible.
Since other configurations and operational effects are the same as those of the above-described embodiment, detailed description thereof is omitted.

FIG. 4 is a cross-sectional view showing an internal configuration of a plasma processing apparatus according to another embodiment of the present invention. Hereinafter, parts corresponding to those of the above-described embodiment are denoted by the same reference numerals and detailed description thereof will be given. Omitted.
As shown in FIG. 4, the vapor deposition apparatus 30 </ b> B according to the present embodiment has a so-called deposition down type linear radical emitter 10.

  That is, the linear radical emitter 10 of the present embodiment is provided with the slit 53 described above facing downward. The substrate 5 is configured to move horizontally in the X direction below the linear radical emitter 10.

According to the present embodiment having such a configuration, since the linear radical emitter 10 is fixed and the substrate 5 can be moved, there is an effect that the present invention can also be applied to an inline apparatus. is there.
Since other configurations and operational effects are the same as those of the above-described embodiment, detailed description thereof is omitted.

FIG. 5 is a schematic configuration diagram showing another example of the linear radical emitter used in the present invention. Hereinafter, the same reference numerals are given to the portions corresponding to the above-described embodiment, and the detailed description thereof is omitted. .
As shown in FIG. 5, the linear radical emitter 15 of this example does not provide a partition wall in the first to fourth diffusion chambers 11 to 41 of the main body 10A. It has the same configuration as the radical emitter 10.

According to the linear radical emitter 15 of this example, the configuration is simpler and the cost can be reduced.
However, from the viewpoint of more uniformly diffusing and mixing the plasma of the processing gas, partition walls are provided in the first to fourth diffusion chambers 11 to 41 of the main body 10A as in the linear radical emitter 10 described above. It is preferable. Since other configurations and operational effects are the same as those of the above-described embodiment, detailed description thereof is omitted.

The present invention is not limited to the above-described embodiment, and various changes can be made.
For example, in the above embodiment, the case where four stages of diffusion chambers of radical emitters are provided has been described as an example. However, the present invention is not limited to this, and if there are a plurality of stages, the number of stages of diffusion chambers may be set arbitrarily. Can do.

Further, the number of communication ports provided in the diffusion chamber and the plasma forming chamber is not limited to those in the above embodiment, and can be changed as appropriate.
However, from the viewpoint of reliably diffusing the plasma of the processing gas, it is preferable to provide eight or more communication ports at the bottom of the plasma forming chamber.

Furthermore, in the above embodiment, a plurality of regions are provided by providing a partition wall in the main body of the linear radical emitter. However, the present invention is not limited to this, and each region is individually separated using a box-shaped member. It is also possible to provide it.
Furthermore, in the above embodiment, a so-called multi-chamber apparatus has been described as an example, but the present invention is not limited to this, and can be applied to a so-called in-line apparatus.

DESCRIPTION OF SYMBOLS 1 ... Organic EL manufacturing apparatus 4a ... Vacuum chamber 4B ... Substrate pretreatment chamber 10 ... Linear radical emitter (radical emitter)
DESCRIPTION OF SYMBOLS 10A ... Main-body part 10B ... Process gas introduction chamber 11 ... 1st diffusion chamber 12 ... 1st communication port 21 ... 2nd diffusion chamber 21a ... Partition part 22 ... 2nd communication port 30 ... Pre-processing apparatus (plasma processing apparatus)
31 ... third diffusion chamber 31a ... partition wall 32 ... third communication port 41 ... fourth diffusion chamber 41a ... partition wall portion 42 ... fourth communication port 50 ... shield member 51 ... plasma formation chamber 52 ... fifth communication port 53 …slit

Claims (5)

A vacuum chamber in which the object to be treated is placed;
A processing gas supply source provided outside the vacuum chamber;
A processing gas supplied from the processing gas supply source is formed in an elongated shape, is relatively movable with respect to the processing object, and is provided in a direction crossing the relative movement direction. A radical emitter for discharging and releasing radicals of the processing gas toward the object to be processed;
The radical emitter includes an elongated processing gas diffusion portion extending in a longitudinal direction of the radical emitter, to which the processing gas is supplied from the processing gas supply source, and a processing gas diffused in the processing gas diffusion portion. An elongated plasma forming chamber extending in the longitudinal direction of the radical emitter for forming plasma;
The processing gas diffusion section has a plurality of diffusion chambers divided in stages from the processing gas introduction side to the discharge side, and the plurality of diffusion chambers are partition walls for isolating each other's atmosphere And the diffusion chambers adjacent to each other are connected via a communication port through which the processing gas can pass, and the communication ports respectively face the ceiling portion of the diffusion chamber adjacent to the processing gas discharge side. Further, among the plurality of diffusion chambers, the final diffusion chamber is connected to the plasma formation chamber through a communication port through which the processing gas can pass.
A plasma processing apparatus, wherein the plasma forming chamber is provided with a slit-like radical discharge port extending in a longitudinal direction of the plasma forming chamber. The communication port of the processing gas diffusion portion in the radical emitters, Configured claim 1 Symbol placement of the plasma processing apparatus so that the number is increased toward the discharge side from the introduction side of the process gas. 2. The plurality of communication ports of the processing gas diffusion portion in the radical releasing device are configured to increase by 2 ⁿ⁻¹ (n is a natural number) from the processing gas introduction side to the discharge side. Or the plasma processing apparatus according to any one of 2 ; Wherein the plurality of communication ports of the processing gas diffusion portion in the radical emitters, said processing each claim sum of the areas of the communication port is configured to be smaller 1 to 3 toward the discharge side from the introduction side of the gas The plasma processing apparatus according to any one of the above. A method for processing a substrate surface in a vacuum using the plasma processing apparatus according to any one of claims 1 to 4 ,
A pretreatment method including a step of cleaning the surface of the substrate by releasing radicals of the processing gas from a radical emitter of the plasma processing apparatus before depositing an organic material on the substrate by vacuum deposition.

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