JP4194466B2 - Plasma process apparatus and electronic device manufacturing method using the same - Google Patents

Description

The present invention relates to a method for manufacturing an electronic device having functionality. More particularly, the present invention relates to an electronic device manufacturing method which is constituted by a semiconductor film, an organic film, an insulating film or the like made in the electronic industry. The present invention also relates to a plasma process apparatus for forming and processing a thin film such as a semiconductor or a conductor. More specifically, plasma chemical vapor deposition apparatus using plasma-excited chemical vapor deposition, which is used for thin film manufacturing of semiconductor films and insulating films in the electronics industry, dry etching for dry etching for forming thin film patterns of semiconductor films and conductor films The present invention relates to a plasma process apparatus for forming and processing a thin film by decomposing a gas with plasma, such as an apparatus, an asher apparatus for removing a resist used for forming a thin film pattern.

  A method of manufacturing electronic devices such as integrated circuits, liquid crystal displays, organic electroluminescence elements, solar cells by depositing semiconductor films using plasma, so-called plasma-excited chemical vapor deposition (CVD) method Because of its excellent simplicity and operability, it is used to manufacture various electronic devices.

  As an apparatus using a plasma CVD method (a plasma chemical vapor deposition apparatus, hereinafter referred to as a plasma CVD apparatus), those shown in FIGS. 26 and 27 are common. The plasma CVD apparatus will be described with reference to FIGS. FIG. 26 is a schematic view of a conventional plasma CVD apparatus, and FIG. 27 is a cross-sectional view schematically showing the conventional plasma CVD apparatus. The plasma CVD apparatus includes a closed space formed by using a processing chamber (vacuum vessel) 5 and two conductor plates that are electrically insulated from each other and installed in parallel at opposite positions. It has electrodes 2a and 2b. Plasma 11 is generated between the two electrodes 2a and 2b, and a material gas is allowed to flow there to decompose and dissociate the gas. A semiconductor film or the like is formed on the substrate to be processed 4 made of silicon or glass attached to one electrode 2b.

  As means for generating the plasma 11 for decomposing the material gas for film formation, electrical energy such as a high frequency with a frequency of 13.56 MHz is generally used. One conductor plate electrode 2b is set to ground potential, a voltage is applied to the other electrode 2a facing each other, an electric field is generated between both electrodes 2a and 2b, and plasma 11 is generated as a glow discharge phenomenon by the dielectric breakdown phenomenon. . The electrode 2a to which voltage is applied, that is, the electrode 2a to which electrical energy is applied is called a cathode electrode or a discharge electrode. Since a large electric field is formed in the vicinity of the cathode electrode 2a, electrons in the plasma 11 accelerated by the electric field promote dissociation of the material gas and generate radicals. In FIG. 27, 12 indicates the flow of radicals.

  A portion of the discharge 11 in which a large electric field in the vicinity of the cathode electrode 2a is formed is referred to as a cathode sheath portion. Radicals generated at or near the cathode sheath portion diffuse to the substrate 4 to be processed on the ground potential electrode 2b and deposit on the surface of the substrate 4 to grow a film. The electrode 2b at the ground potential is referred to as an anode electrode 2b. An electric field having a certain magnitude is also formed in the vicinity of the anode electrode 2b, and this portion is referred to as an anode sheath portion. An apparatus for generating plasma between the two electrodes 2a and 2b parallel to each other and forming a film on the substrate 4 to be processed on the anode electrode 2b is hereinafter referred to as a “parallel plate type apparatus”.

  Such a plasma CVD method is widely used for electronic devices manufactured in various industries. For example, in the manufacturing process of an active drive type liquid crystal display, a switching element called TFT (Thin Film Transistor) is manufactured. In the TFT, a gate oxide film such as an amorphous silicon film or a silicon nitride film plays an important role as its constituent part. In order for each film to fulfill its role, a technique for efficiently forming a high-quality transparent insulating film is indispensable. In addition, for example, in order to fabricate an organic electroluminescence element, there is a technique for efficiently forming a high-quality transparent insulating film as a protective film for protecting a surface exposed to the atmosphere after forming an organic thin film. It is essential. Furthermore, for example, in order to manufacture a solar cell, a technique for efficiently forming a high quality film as a protective film for protecting a surface exposed to the atmosphere after forming a solar cell layer is indispensable. Electronic devices manufactured in this way are widely used.

  A dry etching apparatus for performing etching of a thin film and an asher apparatus for removing a resist are collectively known as a plasma process apparatus by changing the material gas to an etching gas and generating plasma 11 as in the plasma CVD apparatus. Yes. The generation method of the plasma 11 and the generation of radicals are the same mechanism as in the case of the plasma CVD apparatus, and the radicals that reach the substrate 4 to be processed remove the thin film and the like. A dry etching apparatus or an asher apparatus differs from a plasma CVD apparatus not only in the presence of radicals, but also in that physical sputtering by ion bombardment from plasma and energy incidence on the substrate 4 are used for the etching operation. It is.

Conventionally established plasma CVD devices have limitations, and when producing large-area electronic devices such as liquid crystal displays and amorphous solar cells, the material gas is sufficiently dissociated when the film is formed on the substrate 4 to be processed. In some cases, it was difficult to obtain a high-quality thin film. For example, in a conventionally known parallel plate type apparatus, dissociation of the material gas may be insufficient. When a silicon nitride film is formed, silane (SiH ₄ ), ammonia (NH ₃ ), nitrogen (N ₂ ), hydrogen (H ₂ ), or the like is used as a material gas, and ammonia is supplied to the film by using ammonia. It is done by disassembling. However, for example, when an attempt is made to form a silicon nitride film on a copper wiring, ammonia gas may corrode copper.

  In addition, ammonia is a gas having strong chemical activity, and there are cases where it is desired to form a silicon nitride film using only nitrogen gas without using ammonia. In such a case, in the parallel plate type apparatus, hydrogen gas and nitrogen gas which are difficult to dissociate cannot be sufficiently decomposed, and it is difficult to obtain a silicon nitride film having good insulating film properties and protective film properties. Alternatively, when an amorphous silicon film is formed, silane, hydrogen, or the like is used as a material gas, but the utilization efficiency of the gas remains at about 10%. Also in this case, it can be said that the dissociation of the material gas cannot be sufficiently promoted in the parallel plate type apparatus.

Techniques for forming a high-quality film on the substrate 4 to be processed are disclosed in Patent Documents 1 to 5 and the like.
Japanese Patent Laid-Open No. 11-144892 ([0018], [0019], FIG. 1) Japanese Patent Application Laid-Open No. 1-279761 (column “Action” on pages 3 to 4, FIG. 1) JP 2001-338885 A JP 2002-217111 A JP 2002-270522 A

  For example, in the plasma device disclosed in Patent Document 1, the discharge electrode facing the glass substrate is composed of a plurality of electrodes, and each electrode is applied with a high-frequency voltage having a different polarity to generate a horizontal discharge. Are arranged as follows. The reaction gas is released because it is between the electrodes. The gas released into the discharge plasma in the transverse electric field causes a plasma reaction, and then diffuses in the direction toward the glass substrate and is deposited on the glass substrate. Thereby, high quality film formation is possible without causing discharge damage to the glass substrate. However, even with this plasma device, dissociation of the material gas cannot be promoted as in the parallel plate type device.

  A technique for promoting the dissociation of the material gas is disclosed in Patent Document 2, for example. In the plasma device disclosed in Patent Document 2, a concave space is provided in the cathode electrode, and the plasma density is increased by the hollow cathode effect. As a result, dissociation of the material gas is promoted, and a high film formation rate can be obtained as compared with a normal parallel plate type apparatus. However, in this apparatus, since the surface of the substrate to be processed is exposed to plasma, the film formation surface suffers plasma damage.

  By setting the set temperature of the substrate to be processed 4 to 300 ° C. or higher, such plasma damage can be repaired with thermal energy. However, when it is desired to set the substrate 4 to be processed at a temperature of about 200 ° C. or lower, good film quality cannot be maintained. That is, a method for realizing a high-quality film and forming a film with high gas dissociation efficiency with a plasma CVD apparatus at a particularly low substrate temperature has not yet been established.

  A case is assumed where the configuration of the plasma apparatus described in Patent Document 1 is applied to a dry etching apparatus or an asher apparatus. Also in this case, the plasma generator and the ion bombardment controller can be controlled separately. That is, it is possible to attach the third electrode to the back of the substrate 4 and to control the ion bombardment independently of the generation of plasma, thereby improving the controllability of parameters.

  However, in this case as well, dissociation of the processing gas cannot be promoted, and the processing speed cannot be increased beyond a certain level. That is, as a whole, a plasma processing apparatus that operates with high performance and high gas dissociation efficiency has not been established yet.

  In the thin film formed by the above technique, sufficient protective film characteristics for devices have not been obtained so far. For example, in an organic electroluminescence element, it is necessary to provide a transparent insulating protective film on the outer layer of the element in order to prevent intrusion of water vapor and oxygen in the atmosphere. Since the characteristics of the organic film in the device are greatly deteriorated at a process temperature of 100 ° C. or higher, it is necessary to form a protective film at a temperature lower than that.

  However, a conventional plasma CVD apparatus cannot form a high-quality protective film under such temperature conditions. For example, in Applied Physics Letters, volume 65, pages 2229-2231, when a silicon nitride film is formed as a protective film at 100 ° C., the film quality is poor, so that water vapor in the atmosphere enters the film, and silicon and oxygen It has been reported that this occurs. From this report, it is expected that water vapor and oxygen will finally permeate the membrane. At present, only a protective film having a poor quality can be realized, so that the glass substrate for the cap is sealed in a nitrogen atmosphere for isolation from the atmosphere. Devices using a silicon nitride film as a protective film include polycrystalline silicon solar cells and gallium / arsenic electronic devices, and these devices also have the above-mentioned quality problems.

  The present invention has been made in view of these points, and the main object of the present invention is to improve the accuracy of plasma processing by promoting the decomposition and dissociation of gas by plasma, thereby improving the accuracy of plasma processing. To improve quality.

The plasma processing apparatus of the present invention is provided in a processing chamber in which a substrate to be processed is disposed, a gas introduction port for introducing a gas into the processing chamber, and the processing chamber. A plasma process apparatus comprising a plasma discharge generator for performing plasma processing, wherein the plasma discharge generator includes a plurality of insulating portions extending in a stripe shape in a direction parallel to the substrate to be processed, and at least the insulating portions adjacent to each other A first electrode provided between the first electrodes; and a second electrode provided in a state separated from the first electrode at an end portion of the insulating portion on the substrate side to be processed.

Before SL gas inlet is preferably provided on the first electrode side. The first electrode preferably has a concave plasma discharge surface. Furthermore, the area of the plasma discharge surface of the first electrode is preferably larger than the area of the plasma discharge surface of the second electrode.

  The plasma discharge generator preferably includes a plurality of plasma discharge surface regions of the first electrode and a plurality of plasma discharge surface regions of the second electrode. Further, a plurality of regions of the plasma discharge surface of the first electrode and a region of the plasma discharge surface of the second electrode are alternately formed along one surface direction of the substrate to be processed, and the second electrode and the substrate to be processed are formed. It is preferable that the distance between the processing substrates is not less than the distance between the electrodes of the second electrodes adjacent to each other.

It is effective that the apparatus further includes a power source that applies electrical energy to the first electrode and the second electrode, and the frequency of the power source is 300 kHz or more and 300 MHz or less .

Also, the plasma processing apparatus of the present invention, plasma discharge surface of the first electrode has a concave curved surface portion.

  The plasma discharge surface of the first electrode and the plasma discharge surface of the second electrode preferably constitute a part of a continuous curved surface.

  A plurality of depressions may be formed on the plasma discharge surface of the first electrode. Furthermore, it is preferable that a gas inlet is formed at the bottom of at least a part of the recess.

  The plasma discharge surface of the first electrode may be sandblasted.

The first electrode is preferably provided with a plurality of recesses that open toward the substrate to be processed. Furthermore, it is preferable that the opening shape of the said recessed part is a square. Further, the opening shape of the recess may be circular .

Before Symbol Each first electrode provided between the respective insulating portions may be separated from each other.

The plasma processing apparatus of the present invention is a plasma processing apparatus for performing plasma processing on a substrate to be processed, wherein a processing chamber in which the substrate to be processed is placed and a gas introduction for introducing gas into the processing chamber. A plasma discharge generator provided in the processing chamber, wherein the plasma discharge generator is provided with a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode. The first electrode and the second electrode are premised on a plasma process apparatus in which only a surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface. The first electrode has a concave plasma discharge surface. The plasma discharge surface of the first electrode may have a concave curved surface portion. A plurality of depressions may be formed on the plasma discharge surface of the first electrode. The plasma discharge surface of the first electrode may be sandblasted. The first electrode may be provided with a plurality of recesses that open toward the substrate to be processed.

The plasma processing apparatus of the present invention is a plasma processing apparatus for performing plasma processing on a substrate to be processed, wherein a processing chamber in which the substrate to be processed is placed and a gas introduction for introducing gas into the processing chamber. And a plasma discharge generator provided in the processing chamber. The plasma discharge generator includes a first electrode, an insulating layer formed on a part of an electrode surface of the first electrode, and the insulation. A plasma process apparatus having a second electrode formed on a layer is assumed. The first electrode has a concave plasma discharge surface. The plasma discharge surface of the first electrode may have a concave curved surface portion. A plurality of depressions may be formed on the plasma discharge surface of the first electrode. The plasma discharge surface of the first electrode may be sandblasted. The first electrode may be provided with a plurality of recesses that open toward the substrate to be processed.

Further, the electronic device manufacturing method of the present invention is a method of manufacturing an electronic device using the plasma process apparatus, the step of placing the substrate to be processed inside the processing chamber, and the processing target Introducing the gas from the gas inlet into the processing chamber on which the substrate is placed, generating plasma discharge by the plasma discharge generating unit, and performing plasma processing on the surface of the substrate to be processed; Is included.

  According to the plasma process apparatus of the present invention, it is possible to promote the decomposition and dissociation of gas by the plasma while suppressing the plasma damage on the film formation surface even at a low substrate temperature to be processed, thereby improving the accuracy of the plasma processing. Thus, the quality of the electronic device to be manufactured can be improved.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, this invention is not limited to the following embodiment.

Embodiment 1 of the Invention
The structure of the plasma CVD apparatus according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective view schematically illustrating the plasma CVD apparatus according to the first embodiment, and FIG. 2 is a cross-sectional view schematically illustrating the plasma CVD apparatus according to the first embodiment.

  The plasma CVD apparatus is provided in a processing chamber (vacuum container) 5 in which the substrate 4 to be processed is placed, a gas inlet 6 for introducing a material gas into the processing chamber 5, and the processing chamber 5. And a plasma discharge generator 15. Typically, a substrate holder 9 that holds the substrate to be processed 4 is provided in the processing chamber 5, and the substrate to be processed 4 is placed on the substrate holder 9.

  Outside the processing chamber 5, a high-frequency power source 1 for supplying electric power to the plasma discharge generating unit 15, in other words, applying electric energy, and a material gas (hereinafter also simply referred to as “gas”) inside the processing chamber 5. A gas supply unit 13 for supplying gas to the gas chamber and a gas discharge unit 10 for discharging the gas in the processing chamber 5 are provided. For example, a mechanical booster pump or a rotary pump is used as the gas discharge unit 10. The high frequency power source 1 is connected to the plasma discharge generator 15 via the wiring 8.

  The plasma discharge generator 15 is provided in the processing chamber 5 so as to be separated from the substrate 4 to be processed and opposed to the substrate 4. The cathode electrode (cathode) 2 a serving as the first electrode and the electrode surface of the cathode electrode 2 a Inter-electrode insulating part (hereinafter also referred to as “insulating layer” or “insulating part”) 3 formed in the part, and an anode electrode (anode) 2b that is a second electrode formed on the insulating layer 3 . The anode electrode 2b is provided closer to the substrate 4 to be processed than the cathode electrode 2a.

  In the present embodiment, a plurality of anode electrodes 2b are provided in a stripe shape along one direction (one surface direction) of the surface directions of the substrate 4 to be processed. Thereby, the region of the plasma discharge surface of the cathode electrode 2a and the region of the plasma discharge surface of the anode electrode 2b are alternately and repeatedly formed on the same plane. The plasma discharge surface will be described later.

  The cathode electrode 2a is provided with a gas inlet 6 that penetrates the cathode electrode 2a in the thickness direction. After the gas supplied from the gas supply unit 13 once stays in the gas retention unit 7, the gas is introduced into the processing chamber 5 through the gas introduction port 6.

  The detailed structure of the plasma discharge generator 15 is as follows.

  That is, the plasma discharge generator 15 includes a plurality of insulating portions 3 extending in a stripe shape in a direction parallel to the substrate 4 to be processed, a cathode electrode 2a provided between at least adjacent insulating portions 3, and each insulating portion. 3 is provided with an anode electrode 2b provided in a state separated from the cathode electrode 2a at the end of the substrate 3 to be processed.

  The plate-like cathode electrode 2 a is disposed in parallel with the substrate 4 to be processed. The intervals between the adjacent insulating portions 3 are equal to each other. The upper end surface of each insulating portion 3 is covered with an anode electrode 2b. That is, the anode electrode 2b is also formed in a stripe shape. Thus, a plurality of grooves 18 having a concave cross section are formed in the plasma discharge generating portion 15 by the two side surfaces of the insulating portion 3 and the anode electrode 2b facing each other and the upper surface of the cathode electrode 2a exposed therebetween. It will be. The cathode electrode 2a in the groove 18 constitutes a plasma discharge surface. A plurality of gas inlets 6 are formed in the groove 18 so as to be arranged at predetermined intervals in the groove length direction. Each gas inlet 6 is provided at the center position of the groove 18 in the groove width direction.

  When manufacturing the plasma discharge generator 15, for example, as shown in FIG. 1, a large number of aluminum bars having a cross-sectional shape of 5 mm × 3 mm and a length of 300 cm are prepared. In addition, an aluminum plate having a size of 110 cm × 110 cm and a thickness of 3 mm is prepared. A large number of aluminum rods serving as the anode electrode 2b are arranged on an aluminum plate serving as the cathode electrode 2a so as to be substantially parallel to each other. The aluminum rod is installed with electrical insulation from the aluminum plate. Specifically, the cathode electrode 2a and the anode electrode 2b are separated from each other, and alumina as an insulator is interposed in the space to form the interelectrode insulating portion (insulating layer) 3. The height of the interelectrode insulating part 3, in other words, the distance between the cathode electrode 2a and the anode electrode 2b is 10 mm. Hereinafter, the substrate having the cathode electrode 2a, the anode electrode 2b, and the interelectrode insulating portion 3 is referred to as an “electrode substrate”. The electrode substrate has a size of 110 cm × 110 cm as a whole, and the plasma discharge generation portion 15 has a size of 100 cm × 100 cm. The cathode electrode 2a may be formed by an integral member.

  In a cross section in a direction substantially orthogonal to the direction in which the anode electrode 2b extends, the width d1 of the anode electrode 2b and the interelectrode insulating portion 3 is 5 mm, the width d2 of the cathode electrode 2a is 10 mm, and the interelectrode insulating portion 3 The height d3 is 10 mm, and the distance between the anode electrode 2b and the interelectrode insulating part 3 is 15 mm. The high frequency voltage is applied to the aluminum plate of the electrode substrate. The aluminum plate served as the cathode electrode 2a, and the aluminum rod insulated from the aluminum plate by the interelectrode insulating portion 3 was set to the ground potential to be the anode electrode 2b.

  As the substrate 4 to be processed, a glass substrate having a thickness of 1.1 mm was placed at a position 20 mm above the anode electrode 2b. A heater (not shown) for heating the substrate to be processed 4 is provided behind the substrate holder 9 (on the side opposite to the surface to be processed of the substrate 4 to be processed). The substrate 4 to be processed is heated so that the temperature becomes 200 ° C., for example.

  The plasma discharge generator 15 generates a discharge (plasma) 11 according to a voltage (potential difference) applied between the anode electrode 2b and the cathode electrode 2a. By flowing a gas through the plasma discharge generator 15, the gas is decomposed and dissociated to generate radicals. 2 in FIG. 2 indicates the flow of radicals. The generated radicals diffuse to the substrate 4 to be processed and adhere and deposit on the surface of the substrate 4 held by the substrate holder 9. That is, a film grows on the surface of the substrate 4 to form a thin film.

  The generated radicals successively reach the surface of the thin film and the thickness of the thin film increases. After the voltage is continuously applied until the set film thickness is reached, the voltage application between the cathode electrode 2a and the anode electrode 2b (power supply to the plasma discharge generator 15) is stopped. In this way, plasma processing is performed on the surface of the substrate 4 to be processed. Thereafter, when the substrate to be processed 4 is removed from the substrate holder 9 and taken out of the processing chamber 5, a thin film-formed substrate on which a thin film is formed is obtained.

  Next, the operation of the plasma CVD apparatus of this embodiment and the method for manufacturing an electronic device using the plasma CVD apparatus will be described. Moreover, the plasma CVD apparatus of this embodiment was actually produced and the operation result of the apparatus is shown below. In addition, the specific numerical value shown below is only showing the case of one Example of this invention, Comprising: This invention is not limited at all.

The material gas used is SiH ₄ (200 sccm), H ₂ (10 slm) and N ₂ (20 slm). Here, “sccm” is a gas flow rate in cubic centimeters flowing every minute at 0 ° C. “Slm” is a gas flow rate in liters flowing every minute. The material gas was introduced from the gas inlet 6 aligned with the cathode electrode 2a as shown in FIG. In order to apply electric energy, a high frequency power source 1 having a frequency of 13.56 MHz was used.

  With respect to the apparatus shown in FIGS. 1 and 2, a silicon nitride film was formed by changing the substrate temperature while setting the gas pressure to 200 Pa and the high frequency power to 7 kW. The film quality of the formed silicon nitride film was evaluated. The results are shown in Table 1. The deposition rate of the silicon nitride film was 0.4 nm (4 Å) / second, and the film thickness uniformity within the film was ± 3%.

  On the other hand, for comparison, the same operation test was performed on the devices shown in FIGS. The apparatus shown in FIGS. 26 and 27 is the same as the apparatus of this embodiment except for the following points. The apparatus shown in FIGS. 26 and 27 is a parallel plate type apparatus, and applies high frequency power to the cathode electrode 2a to form a film on a glass substrate provided on the opposing anode electrode 2b. The distance between the electrodes is 20 mm.

  The film quality parameters in Table 1 were measured as follows. The resistivity was calculated by measuring a leakage current flowing when an electric field of 1 MA / cm was applied in the thickness direction of the film. The unit of resistivity is Ωcm. A more detailed measurement method is described below. A conductive substrate for film quality measurement, for example, a conductive substrate such as a P-type silicon wafer is placed on the edge of the glass substrate for film formation. A glass substrate for film formation is formed together with the conductive substrate. A metal thin film such as aluminum, chromium or titanium is deposited on the film after the film formation. A voltage is applied up to about 500 V between the conductive substrate and the metal thin film, the minute current flowing is measured, and the resistivity is calculated. Alternatively, it is also possible to adopt a method in which mercury is brought into contact with the film surface without applying a metal thin film and a voltage is applied via the mercury.

The amount of hydrogen bonding is identified from the bonding amount of silicon and hydrogen and the bonding amount of nitrogen and hydrogen by Fourier transform infrared spectroscopy. The unit of hydrogen bond amount is cm ⁻³ . The oxygen bond amount is a relative intensity according to the Fourier transform infrared spectrum method, and is a relative value of the bond spectrum intensity of silicon and oxygen with respect to the bond spectrum intensity of silicon and nitrogen. A more detailed measurement method for the hydrogen bond amount and the oxygen bond amount will be described below. Similar to the measurement of resistivity, a conductive substrate for film quality measurement, for example, a conductive substrate such as a P-type silicon wafer, is placed on the end of the glass substrate for film formation. A glass substrate for film formation is formed together with the conductive substrate. Irradiation with infrared laser light and Fourier transform processing of the interference waveform make it possible to measure the absorption of infrared light by the film as a wave number spectrum. Then, from the intensity of the peak (1070 cm around ^-1) attributable to the oxygen bond peak (2150 cm around ^-1 and near 3350 cm ^-1) due to the hydrogen bond, it can be determined each binding. The bond amount of nitrogen and hydrogen, the bond spectrum intensity of silicon and nitrogen, and the bond spectrum intensity of silicon and oxygen are described in, for example, Takeshi Imura, “Evaluation of Amorphous Thin Films”, pages 53 to 55 (1989, Kyoritsu Shuppan Co., Ltd.). Can be measured with reference to FIG.

  Other methods for measuring the amount of hydrogen bonding include a method of applying a gas chromatography method during sample heating (up to several hundred degrees) and a secondary ion mass spectrometry method. According to the secondary ion mass spectrometry, the measurement resolution is several hundred μm, and the analysis in the depth direction of the film is possible. Therefore, the analysis can be performed even when the film to be measured is a device constituent film. Become.

  As shown in Table 1, regarding the resistivity, according to the present embodiment, a film having a higher insulating property than that of the parallel plate type device was obtained in each temperature zone. This is because film formation with almost no plasma damage is possible with the apparatus of the present invention, so high quality film formation is possible, whereas plasma damage to the film formation surface is unavoidable with a parallel plate type apparatus. This is probably because a film with good film quality cannot be obtained.

  In the case of the present embodiment, the amount of hydrogen bonds is a substantially constant value in each temperature zone, whereas in the case of a parallel plate type apparatus, the amount of hydrogen bonds greatly decreases when the temperature of the substrate 4 to be processed is 100 ° C. is doing. This may be because the amount of dissociation of hydrogen molecules is small in the case of a parallel plate type apparatus. Specifically, when the temperature of the substrate to be processed 4 is high, hydrogen atoms can diffuse on the film surface, so that hydrogen termination of dangling bonds is sufficiently possible. However, when the temperature of the substrate 4 to be processed is low, the distance over which hydrogen atoms can diffuse on the film surface is reduced, and the hydrogen atoms that originally have a small amount cannot sufficiently terminate the unbonded hands. This is probably because it remains in the film. When dangling bonds are present in the film, not only the film quality is lowered, but it is difficult to maintain long-term stability as a film.

According to the plasma CVD apparatus of this embodiment, since the dissociation amount of hydrogen molecules is large, even if the temperature of the substrate to be processed 4 is low and the distance over which hydrogen atoms can diffuse on the film surface is small, It is considered that the unbonded hand is sufficiently terminated. Therefore, the electronic device obtained by the plasma CVD apparatus of the present embodiment has a larger amount of hydrogen bonds in the insulating film than the conventional one. For example, as shown in Table 1, an electronic device having a hydrogen bond amount in the insulating film of 7 × 10 ²¹ cm ⁻³ or more, preferably 1 × 10 ²² cm ⁻³ or more is obtained.

  Regarding oxygen bonding, neither the present embodiment nor the parallel plate apparatus is observed at the initial stage of production, and the amount of oxygen bonding is zero. However, in the measurement for one month after being left in the atmosphere, oxygen bonds are observed in the case of the parallel plate type apparatus. The amount of the binding increases as the film quality deteriorates. On the other hand, in this embodiment, no oxygen bond is observed even in the measurement after one month. Therefore, according to the plasma CVD apparatus of this embodiment, a transparent insulating film having excellent protective film properties can be obtained. An electronic device in which such an insulating film is formed as an outer layer (referred to as the outermost layer; hereinafter the same) can maintain long-term stability.

  When the state in the reaction chamber after film formation was observed, many products of powder were observed when the temperature of the substrate 4 to be processed in the parallel plate type apparatus was 100 ° C. This powder is considered to be a polymer of silane. It is known that when powder is generated, the powder is taken in during film formation to deteriorate the film quality. In this embodiment, almost no powder was seen in each temperature zone. Also from this viewpoint, the apparatus of the present embodiment shows excellent apparatus performance.

  In the plasma CVD apparatus of this embodiment, only the surface (part) visible from the normal direction of the substrate 4 to be processed among the electrode surfaces of the cathode electrode 2a and the anode electrode 2b functions as a plasma discharge surface. In other words, both the cathode electrode 2a and the anode electrode 2b have a structure in which the entire plasma discharge surface can be viewed from the substrate 4 side. Here, the plasma discharge surface does not mean the surface of the member used for the electrodes 2a and 2b, but is a surface that substantially exchanges charged particles (charges) with the plasma part and functions as a discharge electrode. That is.

  Specifically, the surface of the anode electrode 2b on the cathode electrode 2a side and the surface of the cathode electrode 2a in the region overlapping the region where the anode electrode 2b is formed are surfaces that are not visible from the normal direction of the substrate 4 to be processed. Since the interelectrode insulating portion 3 exists between the surface of the anode electrode 2b on the cathode electrode 2a side and the surface of the cathode electrode 2a in the region overlapping the formation region of the anode electrode 2b, the cathode electrode 2a of the anode electrode 2b Neither the side surface nor the surface of the cathode electrode 2a in the region overlapping with the formation region of the anode electrode 2b functions as a plasma discharge surface.

  When the interelectrode insulating portion 3 does not exist between the electrodes 2a and 2b, the surface of the anode electrode 2b on the cathode electrode 2a side and the surface of the cathode electrode 2a in the region overlapping the region where the anode electrode 2b is formed also function as a plasma discharge surface. To do. When high frequency power is applied to the cathode electrode 2a in this state, main discharge is generated between the surface of the cathode electrode 2a and the side surface of the cathode electrode 2a of the anode electrode 2b. However, even if the material gas is dissociated by the plasma generated in the space, most of the dissociated radicals adhere as a film to the side surface of the cathode electrode 2a of the anode electrode 2b. Therefore, the film forming speed cannot be increased as intended, so that the throughput of the apparatus is limited. According to the plasma CVD apparatus of the present embodiment shown in FIGS. 1 and 2, since the entire electrode surface functioning as a plasma discharge surface is visible from the substrate 4 side, in other words, the plasma discharge surface of the cathode electrode 2a. Since the plasma discharge surfaces of the anode electrode 2b are not opposed to each other, most of the dissociated radicals can be effectively guided to the substrate 4 to be processed.

  As shown in FIGS. 1 and 2, another advantage of adopting a structure in which the surface of all electrodes functioning as a plasma discharge surface can be viewed from the substrate 4 side is that the settable pressure is wide. . In the case of the parallel plate type apparatus shown in FIGS. 26 and 27, since the distance between the electrodes is determined structurally, the distance between the electrodes becomes the length of the discharge path itself, and the material gas pressure at which plasma is easily generated is increased. It will be fixed to a certain range. This is because it is governed by Paschen's law, which is well known in electrical discharge engineering. Paschen's law is that the spatial electric field intensity at which discharge can be started is determined by the product of the material gas pressure and the length of the discharge path, and the minimum value of the spatial electric field intensity at which discharge can be started at a certain value. In other words, the spatial electric field intensity at which discharge can be started increases before and after that.

  On the other hand, if the structure shown in FIGS. 1 and 2 is taken, the electrode surfaces of both electrodes 2a and 2b are not opposed to each other, and therefore the path of the discharge generated between them is the material gas pressure as shown in FIGS. It becomes shorter or longer depending on the height. 3b in FIG. 3 and FIG. 4 shows a typical path of discharge. In the case of FIG. 3, the material gas pressure is relatively high, and the discharge path is shortened. In the case of FIG. 4, the material gas pressure is relatively low, and the discharge path becomes long.

  There is also an advantage that both electrodes 2a and 2b are not on the same plane. Specifically, since the electrodes 2a and 2b are substantially on the same plane (see, for example, Patent Documents 3 to 5), the discharge path becomes longer by approximately the height of the interelectrode insulating portion 3. , Gas dissociation efficiency increases. Furthermore, since the distance of the discharge path can be adjusted by adjusting the height of the interelectrode insulating part 3, there is also an advantage that the degree of freedom in adjusting the material gas pressure is increased. By changing the length of the discharge path in this way, the pressure range of the material gas in which plasma is likely to be generated becomes wide.

  As a position where the gas inlet 6 is provided, as shown in FIGS. 1 and 2, the cathode electrode 2a side is preferable. In the apparatus of the present embodiment, the cathode electrode 2a is further away from the substrate 4 to be processed than the anode electrode 2b. Therefore, by introducing the gas from the cathode electrode 2a side, a smooth gas flow 14 toward the substrate 4 is realized. Further, there is a plasma region between the cathode electrode 2a and the anode electrode 2b, and the material gas flows along the discharge path of plasma discharge. Thereby, dissociation of gas can be accelerated | stimulated because the distance which material gas flows in plasma becomes long.

  The area of the plasma discharge surface of the cathode electrode 2a is preferably larger than the area of the plasma discharge surface of the anode electrode 2b. The reason is as follows. The anode sheath portion has a smaller electric field in the parallel plate type device than the cathode sheath portion. This is because even if the areas of both electrodes 2a and 2b are substantially equal, the peripheral wall and the like are at the same ground potential as the anode electrode 2b, so that the total area of the ground potential portion is substantially larger than the area of the cathode electrode 2a Because it ’s big. Therefore, the electric field of the anode sheath portion can be further increased by making the area of the plasma discharge surface of the cathode electrode 2a larger than the area of the plasma discharge surface of the anode electrode 2b. In such a state, gas dissociation is promoted not only in the cathode sheath portion but also in the anode sheath portion, so that the amount of gas dissociation as a whole further increases.

  In the present embodiment, the repetitive distance between adjacent anode electrodes 2b, in other words, the pitch of the anode electrodes 2b is 15 mm, while the distance between the anode electrode 2b and the surface of the substrate 4 to be processed is 20 mm. In this case, the film thickness distribution is within ± 3%. However, if the distance between the anode electrode 2b and the surface of the substrate 4 to be processed is changed to 14 mm, in other words, shorter than the pitch of the anode electrode 2b, the film thickness distribution becomes ± 8% and depends on the pattern of the electrodes 2a and 2b. As a result, a wavy film thickness distribution is obtained. As shown in FIGS. 1 and 2, since the anode electrode 2b has a stripe pattern, it is important that the pattern is not transferred as a film formation pattern. For this purpose, it is desirable that the distance between the anode electrode 2b and the surface of the substrate 4 to be processed is not less than the repetition distance of the anode electrode 2b.

  In the apparatus of the present embodiment, as shown in FIG. 5A, each of the plurality of rod-like anode electrodes 2b is connected to the high-frequency power source 1 via the wiring 8 at the end, but the apparatus of the present invention is However, the present invention is not limited to this. For example, as shown in FIG. 5B, one end of a plurality of rod-shaped anode electrodes 2b may be connected with a bar made of the same material, and the wiring 8 from the power source 1 may be connected to the connected bar. Alternatively, as shown in FIG. 5C, both ends of the plurality of rod-shaped anode electrodes 2b may be connected with the same material rod, and the wiring 8 from the power source 1 may be connected to the connected rod.

  The processing substrate holder 9 that holds the substrate to be processed 4 only holds the end of the substrate to be processed 4 in FIG. 2, and therefore the substrate to be processed 4 is at a floating potential. On the other hand, for example, in order to make the substrate temperature uniform within the surface, a conductor plate may be placed behind the substrate 4 to be processed. In this case, the conductor plate may be a floating potential or a ground potential. The reason why the potential of the substrate to be processed 4 does not need to be considered in particular is that the plasma 11 exists away from the substrate 4 to be processed, so that only radicals that are electrically neutral are scattered on the substrate 4 to be processed. In the case of a film forming process that requires a certain degree of ion bombardment with respect to the substrate surface, it is possible to install a conductor plate behind the substrate to be processed 4 and actively control its potential. In that case, the ion flux is extracted from the plasma 11 at a distant position by the potential of the conductor plate behind the substrate 4 to be processed, and the surface of the substrate 4 is irradiated with ions.

  In the present embodiment, a glass substrate is used as the substrate 4 to be processed, but the type of the substrate 4 to be processed is not limited to the glass substrate. As described above, since a high-quality film is formed even at a substrate temperature of 100 ° C., a substrate formed from an organic material can be used. For example, a resin substrate such as a plastic substrate having a glass transition point of around 200 ° C. can be used. According to the apparatus of the present invention, it is possible to produce a TFT device by forming a silicon nitride film or an amorphous silicon film on a resin-based substrate or the like.

  In the present embodiment, 13.56 MHz is used as the frequency of the high-frequency power source 1 to be used, but the frequency of the high-frequency power source 1 is not limited to this. In the apparatus of this embodiment, since the plasma 11 hardly exists on the surface of the substrate 4, there is no adverse effect of increased plasma damage, which is usually a problem at a low frequency of 13.56 MHz or less. Therefore, a low frequency of 13.56 MHz or less can be used. However, 300 KHz is appropriate as the lower limit frequency. This is because the limit of the effect that ions are trapped between the electrodes 2a and 2b and the ion density is increased is 300 kHz.

  Further, the present invention can be applied to a high frequency normally called a VHF (Very High Frequency) band of 13.56 MHz or higher. In the case of a parallel plate type device, as a frequency becomes higher and a free space wavelength becomes shorter, it becomes a problem that a standing wave is generated in a large-sized device. This will be described in detail. The high frequency exists with a distribution in the plasma (specifically, the outermost surface portion of the plasma). Therefore, when the magnitude of the plasma is about the magnitude that a standing wave can exist, for example, about 1.5 m in the case of a ½ wavelength and a frequency of 100 MHz, the standing wave is generated and the high frequency intensity becomes non-uniform. . As a result, there arises a problem that the film thickness at the high frequency intensity is thick and the film thickness at the low high frequency intensity is thin.

  According to the present invention, the plasma parts are small and independent, and no standing wave is generated in principle. This will be described in detail. In the case of the present invention, a large number of small plasmas corresponding to the electrode pattern, for example, plasma having a few cm or less in the normal direction of the cathode electrode 2a are generated. In FIG. 2, FIG. 3 and FIG. 4, the adjacent plasma parts appear to be in contact with each other, but are actually divided on the anode electrode 2b. As a result, high-frequency propagation is divided at the gap between adjacent plasmas, and as a result, no standing wave is generated. Therefore, it is possible to introduce the VHF band high frequency into a large plasma CVD apparatus. However, 300 MHz is appropriate as the upper limit frequency. 300 MHz is a frequency at which the effect of trapping electrons between the electrodes 2a and 2b and increasing the electron density is saturated. Therefore, even if the frequency is increased further, the effect of capturing electrons does not change, and conversely it is difficult to input high-frequency power. Because it becomes.

<< Embodiment 2 of the Invention >>
FIG. 6 is a perspective view schematically showing the plasma CVD apparatus according to the second embodiment of the present invention, and FIG. 7 is a cross-sectional view schematically showing the plasma CVD apparatus according to the second embodiment. FIG. 8 is a partially enlarged view of FIG. The plasma CVD apparatus according to the second embodiment will be described with reference to FIGS. In the following description, components having substantially the same functions as those of the plasma CVD apparatus of Embodiment 1 are denoted by the same reference numerals, and the description thereof is omitted.

  The plasma CVD apparatus according to the present embodiment is different from the plasma CVD apparatus according to the first embodiment in which the plasma discharge surface of the cathode electrode 2a is a flat plate, in that the plasma discharge surface of the cathode electrode 2a is concave.

  That is, as shown in FIG. 8, the cathode electrode 2 a in the groove 18 has a pair of inclined surfaces extending obliquely upward outward from a position near the gas inlet 6. In other words, the lower portion of the groove 18 is configured to have a tapered cross section that increases from the gas inlet 6 toward the substrate 4 to be processed. The pair of inclined surfaces constitutes the plasma discharge surface of the cathode electrode 2a.

  For example, in this embodiment, as the anode electrode 2b, a large number of aluminum bars having a rectangular cross-sectional shape and a length of 300 cm are prepared. An aluminum plate having a size of 110 cm × 110 cm and a thickness of 3 mm is prepared as the cathode electrode 2a. In addition, a large number of aluminum bars having a cross-sectional shape of a right triangle and a length of 100 cm are prepared. Place the triangular aluminum rod on the surface of the aluminum plate so that the vertical plane of the triangular aluminum rod faces the vertical plane of the adjacent triangular aluminum rod and each aluminum rod extends substantially parallel to each other. Fix it.

  The space sandwiched between the vertical surfaces of the adjacent triangular aluminum bars is filled with alumina as an insulator. Thereby, the interelectrode insulating part 3 is formed between the aluminum bars having a triangular cross section. An aluminum bar having a rectangular cross section is disposed on the interelectrode insulating portion 3. Thereby, the aluminum bar having a rectangular cross section for the anode electrode 2b is electrically insulated from the aluminum plate serving as the cathode electrode 2a and the aluminum bar having a triangular cross section.

  In a cross section in a direction substantially orthogonal to the direction in which the anode electrode 2b extends, the width d1 of the anode electrode 2b and the interelectrode insulating portion 3 is 5 mm, the width d2 of the cathode electrode 2a is 10 mm, and the interelectrode insulating portion 3 The height d3 is 10 mm, and the distance between the anode electrode 2b and the interelectrode insulating part 3 is 15 mm. The height d4 from the end of the cathode electrode 2a to the anode electrode 2b is 5 mm, and the width d5 is 3 mm at the bottom of the triangular section of the cathode electrode 2a.

  The high frequency voltage is applied to the aluminum plate portion of the electrode substrate. As a result, the aluminum plate and the aluminum bar having a triangular section acted as the cathode electrode 2a, and the aluminum bar insulated from these by the interelectrode insulating portion 3 was set to the ground potential, thereby forming the anode electrode 2b.

  When a silicon nitride film was produced using the apparatus of this embodiment, the deposition rate was 0.6 nm (6 Å) / second, and the in-film uniformity of the film thickness was ± 3%. The reason why the film formation rate is increased as compared with the case of Embodiment 1 can be explained as follows.

  In the case of the first embodiment, since the surface of the interelectrode insulating portion 3 for insulating between the electrodes 2a and 2b is perpendicular to the surface of the cathode electrode 2a, plasma particles generated on the surface of the cathode electrode 2a Radical particles easily collide with the interelectrode insulating portion 3 and disappear. On the other hand, in the case of the present embodiment, the angle formed by the surface of the interelectrode insulating portion 3 and the inclined surface of the cathode electrode 2a is set to an obtuse angle, preferably approximately 180 ° by the presence of an aluminum bar having a triangular cross section. Can do. Therefore, it is possible to reduce the probability that plasma particles or radical particles generated on the surface of the cathode electrode 2a collide with the interelectrode insulating portion 3 and disappear. Further, since the cross-sectional shape of the plasma discharge surface of the cathode electrode 2a is concave, a hollow cathode effect is also produced. Therefore, by making the plasma discharge surface of the cathode electrode 2a concave, the throughput of the apparatus can be improved while maintaining other performance such as film quality.

  In the first and second embodiments, the case where the plasma process apparatus of the present invention is applied to a plasma CVD apparatus has been described. However, the plasma process apparatus of the present invention is not limited to the plasma CVD apparatus. The present invention can be used for plasma processing apparatuses in general that perform plasma processing such as thin film formation and processing using plasma, and can be suitably used for, for example, dry etching apparatuses and asher apparatuses.

For example, when applied to a dry etching apparatus, an etching gas such as CF ₄ , SF ₆ , Cl ₂ , HCl, BCl ₃ , or O ₂ is used as a gas introduced into the processing chamber 5. In general, in a dry etching apparatus, not only radicals generated by plasma discharge but also ion bombardment to a surface to be processed of a substrate to be processed may be used for an etching operation. For example, an ion bombardment control electrode is separately attached to the back surface of the substrate 4 to be processed, and this electrode is connected to a power source to give a predetermined potential, thereby making it possible to control the ion bombardment.

  By using the apparatus of the present invention, the gas is efficiently dissociated, the etching rate is increased, and the ion bombardment can be adjusted separately from the plasma part for dissociation, so the controllability is improved.

  In the first and second embodiments, the anode electrode 2b is closer to the substrate 4 to be processed than the cathode electrode 2a. However, the cathode electrode 2a is closer to the substrate 4 to be processed than the anode electrode 2b. Also good. Further, the potential relationship between the anode electrode 2b and the cathode electrode 2a may be reversed over time.

  In the first and second embodiments, the case where the gas inlet 6 is provided on the cathode electrode 2a side has been described, but the formation position of the gas inlet 6 is not limited to this. For example, the gas introduction port 6 may be provided so as to be positioned between the plasma discharge generation unit 15 and the substrate 4 to be processed. In this case, the gas is introduced into the processing chamber 5 from the gas inlet 6 along the surface direction of the substrate 4 to be processed.

<< Embodiment 3 of the Invention >>
As an electronic device manufactured using the plasma CVD apparatus of Embodiment 1 or 2, an actually manufactured organic electroluminescence element is shown below. FIG. 9 is a cross-sectional view schematically showing an organic electroluminescence element.

  9 includes an anode 26 made of aluminum, an organic hole transport layer 25, an organic light emitting layer 24, a cathode 23 made of calcium, and a transparent electrode 22 made of indium tin oxide. It has a structure in which the substrate 4 is sequentially laminated. A diamine derivative ((1,1′-bis (4-di-p-tolylamino-phenyl) cyclohexane; TPD) is used as the organic hole transport layer 25, and an 8-quinolinol aluminum complex ( Using tris (8-hydroxyquinolinato) aluminum (III); Alq3), each film was formed by vacuum deposition.

  The organic EL element of this embodiment has a transparent insulating film 21 as a protective film on the outer layer. A silicon nitride film (film thickness 500 nm (5000 mm)) was formed as the transparent insulating film 21 to complete the electronic device. Hereinafter, this electronic device is referred to as device a. The silicon nitride film is formed under the condition that the temperature of the substrate 4 to be processed is 80 ° C., and the other conditions are as described in the first and second embodiments.

  As Comparative Example 1, a silicon nitride film was formed under the same conditions using the parallel plate type apparatus shown in FIGS. An electronic device having this silicon nitride film as a protective film is called a device b. Further, as Comparative Example 2, an electronic device was fabricated in which a protective film was not formed, and instead a glass substrate with a cover was placed on top and sealed in a nitrogen atmosphere. This electronic device is referred to as device c. The structure of the device c has been generally used conventionally.

  As a result, there was no difference in the initial and long-term light emission characteristics between the device a and the device c in either structure. Therefore, according to the present invention, an electronic device having a protective film as good as the cover glass can be realized without using the cover glass. This means that the electronic device of the present invention has a higher throughput than a conventional electronic device using a glass substrate for a cover.

  On the other hand, in the device b, a number of non-light emitting black spots were generated in the light emitting part during the operation test, indicating a defective operation. This is presumably because the silicon nitride film produced by the parallel plate type apparatus is inappropriate as a protective film and has allowed oxygen in the atmosphere to permeate.

  In the present embodiment, a device including an organic film is shown. Since the film characteristics of an organic film are deteriorated by a thermal process of 100 ° C. or higher, it is desired to form a protective film having good film quality even when formed at a temperature in the vicinity thereof. According to the plasma process apparatus of the present invention, as shown in Embodiment 1, a high-quality protective film can be formed even when the temperature of the substrate 4 to be processed is around 100 ° C. By using this device, the advantage is exhibited.

  As the protective film, a film containing nitrogen such as a silicon nitride film or a silicon nitride oxide film that can easily maintain a good film quality even when the temperature of the substrate 4 to be processed is low is effective. In a film containing nitrogen, if the protective film properties are inferior due to the sparse film structure, the bond between silicon, nitrogen and hydrogen in the film is replaced by the bond between silicon and oxygen by moisture in the atmosphere. Therefore, the protective film containing nitrogen has an advantage that the film quality can be checked by Fourier transform infrared spectroscopy or the like. In particular, since it can be easily monitored even during the production process, there is an advantage of high throughput.

  In this embodiment, a device including an organic film is shown. However, a similar film can be used as a protective film for other devices, for example, an electronic device that does not include an organic film, such as a solar cell or a GaAs electronic device. It is.

In the electronic device of this embodiment, the transparent insulating film 21 as a protective film is formed using the apparatus of Embodiment 1 or 2. However, the electronic device of the present invention is not limited to a device manufactured using the plasma process apparatus of the present invention or the manufacturing method of the present invention. An electronic device in which an insulating film containing silicon and nitrogen is formed on an insulating substrate, and the amount of hydrogen bonds in the insulating film is 7 × 10 ²¹ cm ⁻³ or more. A device obtained by using the method is also included in the electronic device of the present invention.

  In addition, any electronic device that does not substantially generate oxygen bonds in the insulating film formed as an outer layer during use of the device can be used regardless of the insulating film forming apparatus and method. Of electronic devices.

  According to the plasma process apparatus of the present invention, film formation / processing on a substrate to be processed can be performed with high quality and high gas dissociation efficiency. For example, in order to manufacture an active drive type liquid crystal display, it is necessary to form a TFT portion using an amorphous silicon film, a silicon nitride film, or the like. When manufacturing using a plasma CVD apparatus, there is no plasma damage in the manufacturing process, and it is realized with high gas dissociation efficiency, so that a parameter region that could not be realized until now (for example, a condition where the substrate temperature is around 100 ° C.) ) Can be formed. This makes it possible to fabricate a TFT on a resin-based substrate that has been difficult to use.

  Alternatively, in fields other than liquid crystal displays, amorphous silicon is similarly formed by plasma CVD as a light conversion layer of an amorphous silicon solar cell. The plasma processing apparatus of the present invention has the same effect in the field of amorphous silicon solar cells.

  Furthermore, in an organic electroluminescence element, a polycrystalline silicon solar cell, a gallium arsenide-based electronic device, etc., it can be used as an apparatus for forming a transparent insulating film serving as an outer layer protective film. In particular, a process temperature of 100 ° C. or lower is essential as a protective film for an organic electroluminescence element. According to the apparatus of the present invention, high-quality film formation can be performed even in such a temperature range. For polycrystalline silicon solar cells, the same protective film as before can be realized at a lower process temperature. Thereby, stable operation of the apparatus and ease of apparatus maintenance can be ensured.

  In the process of manufacturing an active drive type liquid crystal display, when the pattern formation of a thin film is performed by dry etching, not only high controllability of parameters but also high gas dissociation efficiency is realized by using the plasma process apparatus of the present invention. can do. Moreover, not only high controllability of parameters but also high gas dissociation efficiency can be realized by applying to an asher device. In both cases, by realizing high gas dissociation efficiency, an increase in the processing capacity of the apparatus can be expected.

  According to the present invention, an electronic device having a high-quality protective film as an outer layer can be realized. In particular, when the present invention is applied to an organic electroluminescence element having an organic film, a high-quality protective film can be formed at a process temperature of 100 ° C. or less. Therefore, the original characteristics of the organic film can be maintained. Moreover, since it is not necessary to cover the upper part of the element with a glass substrate for cover, the device can be produced with high production efficiency. As a result, a lighter and thinner organic electroluminescence display can be realized.

<< Embodiment 4 of the Invention >>
FIG. 10 shows Embodiment 4 of the present invention. FIG. 10 is a cross-sectional view showing the plasma discharge generator 15 partially enlarged.

  In this Embodiment 4, the inclined surface in the groove | channel 18 in the said Embodiment 2 is formed in the curved surface part 31 which curves below. That is, the plasma discharge surface of the cathode electrode 2 a has a concave curved surface portion 31. And the curved surface part 31 is comprised by the circular arc surface which connects the side surfaces of the adjacent insulation part 3, and the groove | channel 18 is comprised by the U-shaped groove | channel.

  Therefore, according to the fourth embodiment, the cross-sectional area of the groove 18 can be made larger than that of the second embodiment having the inclined surface with the tapered section. That is, the plasma region in the vicinity of the cathode electrode 2a can be increased. As a result, the amount of gas decomposition per unit gas flow rate and the gas decomposition efficiency can be increased, so that the film formation rate and film quality can be improved.

  By the way, when the flow of the gas introduced from the gas introduction port 6 stagnates, powder is easily generated in the stagnation region. In contrast, in the present embodiment, the surface of the cathode electrode 2a around the gas inlet 6 is formed into a concave curved surface, so that the gas flow can be made smooth and the generation of powder can be suppressed. As a result, since the mixing of powder into the film can be suppressed, the film quality can be improved.

  Here, in order to evaluate the film quality and the film formation rate of the formed film, values obtained by actually measuring the film stress and the etching rate, which are residual stresses of the SiN film, are shown in Table 2.

  The one having the tapered inclined surface of the second embodiment shown in FIG. 8 is referred to as Example 1, and the one having the curved surface portion 31 of the fourth embodiment shown in FIG. Then, film stress and etching rate were measured for Examples 1 and 2. Regarding the film stress, a SiN (silicon nitride) film was formed on a Si wafer, and the warpage of the substrate before and after the film formation was measured with a known stress measuring device. As for the etching rate, BHF (buffered hydrofluoric acid) diluted to 1/100 was used to measure the etching rate of SiN on the Si wafer (at room temperature) with a known step measuring device.

  At this time, the cross-sectional area of the groove 18 in the second embodiment is twice that in the first embodiment. The film stress was found to be about 16% smaller in Example 2 than in Example 1 and the etching rate was about 5.5% smaller. That is, by forming the plasma discharge surface into a concave curved surface, the film stress can be reduced, and the etching rate can be reduced and the film can be densified.

<< Embodiment 5 of the Invention >>
FIG. 11 shows Embodiment 5 of the present invention. FIG. 11 is a view corresponding to FIG. 10 showing the plasma discharge generator 15 partially enlarged.

  In this embodiment, the ratio of the groove depth to the groove width is increased to make the groove 18 relatively deep compared to the second embodiment. That is, the depth of the groove 18 is larger than the groove width. Further, the side surface and the bottom surface of the groove 18 are continuously connected by the curved surface portion 31. Even if it does in this way, the effect similar to the said Embodiment 4 can be acquired. In this embodiment, since the cross-sectional area of the groove 18 is larger than that in the fourth embodiment, the amount of gas decomposition and the decomposition efficiency can be improved, and the film quality can be further improved.

Embodiment 6 of the Invention
FIG. 12 shows Embodiment 6 of the present invention. FIG. 12 is a view corresponding to FIG. 10 showing the plasma discharge generator 15 partially enlarged.

  In this embodiment, the surface of the anode electrode 2b is formed in a curved surface as well as in the groove 18 as compared with the fourth embodiment. That is, the plasma discharge surface of the cathode electrode 2a and the plasma discharge surface of the anode electrode 2b form part of a continuous curved surface. The previous curved surface is composed of a concave curved surface portion 31 of the cathode electrode 2a, a curved surface portion 32 formed on the side surface of the insulating portion 3, and a convex curved surface portion 33 of the anode electrode 2b. In other words, the surface of the plasma discharge generator 15 on the substrate 4 side is formed into a continuous wavy curved surface.

  In the fourth embodiment, although the anode electrode 2b and the insulating portion 3 are simple in shape, they can be easily formed. However, the electric field concentrates on the edge (corner portion) of the anode electrode 2b and abnormal discharge may occur. is there. On the other hand, in the present embodiment, since the anode electrode 2b has a curved shape, electric field concentration can be prevented and generation of powder due to abnormal discharge can be suppressed. As a result, the film quality can be further improved.

<< Embodiment 7 of the Invention >>
FIG. 13 shows Embodiment 7 of the present invention. FIG. 13 is a view corresponding to FIG. 10 showing the plasma discharge generator 15 partially enlarged.

  In this embodiment, a recess 35 is provided at the position where the gas inlet 6 is formed, as compared with the second embodiment. In other words, a plurality of depressions 35 are formed in a line in the groove direction in the groove 18 on the plasma discharge surface of the cathode electrode 2a, and the gas inlet 6 is formed at the bottom of the depression 35. .

  Therefore, according to this embodiment, since the hollow cathode effect can be produced in each recess 35, the amount of electrons jumping out from the cathode electrode 2a can be increased to further promote the decomposition of the gas. That is, it is possible to improve the film formation rate and film quality by increasing the decomposition amount per unit gas flow rate and the decomposition efficiency. Further, since the gas inlet 6 through which gas is ejected is provided at the bottom of the recess 35, an unnecessary film does not adhere to the recess 35.

<< Embodiment 8 of the Invention >>
FIG. 14 shows an eighth embodiment of the present invention. FIG. 14 is a view corresponding to FIG. 10 showing the plasma discharge generator 15 partially enlarged. In this embodiment, in contrast to the second embodiment, a recess 35 is provided at the position where the gas inlet 6 is formed, as in the seventh embodiment.

  As a result, the same effect as in the seventh embodiment can be obtained. In addition, since the plasma area can be increased by increasing the cross-sectional area of the groove 18, the film formation rate and film quality can be further improved.

<< Ninth Embodiment of the Invention >>
FIG. 15 shows Embodiment 9 of the present invention. FIG. 15 is an enlarged perspective view showing the plasma discharge generator 15.

  In this embodiment, a plurality of depressions 35 are formed on the inclined surface in the groove 18 of the cathode electrode 2a as compared with the second embodiment. The recess 35 is provided side by side in the width direction of the groove 18 and the groove length direction.

  Therefore, according to this embodiment, since the holocathode effect is generated as a whole of the cathode electrode 2a formed in a substantially V shape, the holocathode effect is also generated in each depression 35 on the plasma discharge surface of the cathode electrode 2a. Many electrons can be emitted. As a result, since the gas can be decomposed efficiently, the film quality can be improved.

  Incidentally, a cathode sheath portion that is not a plasma region is formed in a region at a predetermined height from the plasma discharge surface. In the cathode sheath portion, the gas supplied from the gas introduction port 6 passes at a high speed. Therefore, even if a large number of depressions 35 are formed on the plasma discharge surface, the gas flow is not constrained in the plasma region.

<< Embodiment 10 of the Invention >>
FIG. 16 shows a tenth embodiment of the present invention. FIG. 16 is a partially enlarged perspective view showing the plasma discharge generator 15.

  In this embodiment, sandblasting is applied to the plasma discharge surface of the cathode electrode 2a in the ninth embodiment instead of providing the recess 35. In other words, the plasma discharge surface of the cathode electrode 2a has a relatively large surface roughness, and microscopically, a large number of irregularities are formed on the plasma discharge surface. Therefore, by performing sandblasting on the plasma discharge surface of the cathode electrode 2a, the holocathode effect can be produced and the film quality can be improved.

<< Embodiment 11 of the Invention >>
17 and 18 show Embodiment 11 of the present invention. FIG. 17 is an enlarged perspective view showing the plasma discharge generator 15, and FIG. 18 is a plan view showing the plasma discharge generator 15.

  In this embodiment, a plurality of recesses 37 that are open toward the substrate to be processed 4 between adjacent insulating portions 3 are provided to the cathode electrode 2 a so as to be aligned in the groove direction at the bottom of the groove 18. It is. In other words, in the present embodiment, partitioning portions 38 for partitioning the grooves 18 are provided at predetermined intervals in the groove direction with respect to the second embodiment.

  That is, the concave portion 37 has a quadrangular opening shape, and is constituted by the bottom surface of the groove 18, a pair of inclined surfaces of the cathode electrode 2 a, and a pair of partition surfaces of the partition portion 38. The partition surface of the partition part 38 is inclined so that the lower part of the partition part 38 spreads on both sides in the groove direction. Therefore, the opening cross section of the concave portion 37 becomes smaller downward.

  Further, as shown in FIG. 18, the plurality of concave portions 37 provided between the insulating portions 3 are arranged in a staggered manner as viewed from the normal direction of the substrate 4 to be processed. In the recess 37, a plurality of gas inlets 6 arranged in the groove direction are provided across the bottom of the groove 18 in each recess 37 and the partition surface of the partition portion 38.

  Therefore, according to this embodiment, since the surface area of the cathode electrode 2a can be increased, the gas decomposition efficiency and the film formation rate can be improved. Further, since the concave portions 37 are arranged in a staggered manner, the quality of the film formed on the substrate to be processed 4 can be made uniform. The shape of the recess is not limited to a quadrangle, and may be a polygon such as an octagon.

<< Embodiment 12 of the Invention >>
19 and 20 show a twelfth embodiment of the present invention. FIG. 19 is an enlarged perspective view showing the plasma discharge generator 15, and FIG. 20 is a plan view showing the plasma discharge generator 15.

  In this embodiment, the opening shape of the concave portion 37 is changed to a circle with respect to the eleventh embodiment. That is, a plurality of mortar-shaped concave portions 37 are provided in the bottom of the groove 18 in the groove direction. A slight space is provided between the adjacent concave portions 37. Then, for example, two gas inlets 6 are formed in the bottom of each recess 37 side by side in the groove direction.

  Thus, even if the opening shape of the concave portion 37 is circular, the same effect as in the eleventh embodiment can be obtained. In addition, since the inside of the recess 37 is configured by a curved surface, the flow of gas introduced from the gas inlet 6 can be made smooth. The opening shape of the recess 37 is not limited to a perfect circle, and may be a circle such as an ellipse.

<< Embodiment 13 of the Invention >>
21 and 22 show Embodiment 13 of the present invention. FIG. 21 is a perspective view showing the plasma discharge generator 15 and the substrate 4 to be processed, and FIG. 22 is a cross-sectional view showing the plasma discharge generator 15 partially enlarged.

  This embodiment is different from the second embodiment in that the cathode electrodes 2 a provided between the insulating portions 3 are electrically separated from each other on the left and right sides of the insulating portion 3. That is, as shown in FIG. 21 and FIG. 22, the plasma discharge generator 15 includes an insulating plate 40 facing the substrate 4 to be processed, a plurality of insulating portions 3 provided in stripes on the insulating plate 40, A cathode electrode 2 a provided between adjacent insulating portions 3 and an anode electrode 2 b provided at the upper end of each insulating portion 3 are configured.

  Therefore, as shown in FIG. 22, also in this embodiment, the groove 18 is constituted by two side surfaces of the insulating portion 3 and the anode electrode 2b facing each other and the upper surface of the cathode electrode 2a, as in the second embodiment. Yes. The gas inlet 6 is formed through the cathode electrode 2 a and the insulating plate 40. The cathode electrode 2a has an inclined plasma discharge surface similar to that of the second embodiment. Even if it does in this way, the effect similar to the said Embodiment 2 can be acquired.

<< Embodiment 14 of the Invention >>
FIG. 23 shows Embodiment 14 of the present invention. FIG. 23 is a partially enlarged cross-sectional view of the plasma discharge generator 15.

  This embodiment differs from the thirteenth embodiment in that the plasma discharge surface of the cathode electrode 2a is configured by a plane parallel to the substrate 4 to be processed as in the first embodiment. That is, each cathode electrode 2 a is electrically separated on the left and right sides of the insulating portion 3. Even if it does in this way, the effect similar to the said Embodiment 1 can be acquired.

<< Embodiment 15 of the Invention >>
24 and 25 show Embodiment 15 of the present invention. 24 and 25 are cross-sectional views showing the plasma discharge generator 15 partially enlarged.

  In this embodiment, the insulating plate 40 is not provided in the thirteenth and fourteenth embodiments. That is, FIG. 24 corresponds to the upper part of the plasma discharge generator 15 of the thirteenth embodiment shown in FIG. On the other hand, FIG. 25 corresponds to the upper part of the plasma discharge generator 15 of the fourteenth embodiment shown in FIG. Even if it does in this way, the effect similar to the said Embodiment 1 or 2 can be acquired.

  As described above, the present invention is useful for a plasma process apparatus, an electronic device, and a manufacturing method thereof that include a plasma discharge generator that generates a plasma discharge between a first electrode and a second electrode. It is suitable for improving film quality even at temperature.

1 is a perspective view schematically showing a plasma CVD apparatus according to Embodiment 1. FIG. It is sectional drawing which shows the plasma CVD apparatus of Embodiment 1 typically. It is a figure which shows the discharge path | route in case material gas pressure is comparatively high. It is a figure which shows the discharge path | route in case material gas pressure is comparatively low. It is a top view which shows typically the connection of a high frequency power supply and the anode electrode 2b. It is a perspective view which shows typically the plasma CVD apparatus of Embodiment 2. FIG. It is sectional drawing which shows the plasma CVD apparatus of Embodiment 2 typically. It is sectional drawing which expands and shows a part of plasma discharge generation | occurrence | production part of Embodiment 2. FIG. It is sectional drawing which shows an organic electroluminescent element typically. FIG. 9 is an enlarged view corresponding to FIG. 8 illustrating an enlarged plasma discharge generation portion of the fourth embodiment. FIG. 10 is an enlarged view corresponding to FIG. 10 illustrating an enlarged plasma discharge generation portion of the fifth embodiment. FIG. 10 is an enlarged view corresponding to FIG. 10 illustrating an enlarged plasma discharge generation portion of the sixth embodiment. FIG. 10 is an enlarged view corresponding to FIG. 10 showing an enlarged plasma discharge generation part of the seventh embodiment. FIG. 10 is an enlarged view corresponding to FIG. 10 illustrating an enlarged plasma discharge generation portion of the eighth embodiment. It is a perspective view which shows the plasma discharge generation part of Embodiment 9. It is a perspective view which expands and shows the plasma discharge generation part of Embodiment 10. FIG. It is a perspective view which shows the plasma discharge generation part of Embodiment 11. It is a top view which shows the plasma discharge generation part of Embodiment 11. It is a perspective view which shows the plasma discharge generation part of Embodiment 12. FIG. 22 is a plan view showing a plasma discharge generating part of embodiment 12. It is a perspective view which shows the plasma discharge generation | occurrence | production part and to-be-processed substrate 4 of Embodiment 13. It is sectional drawing which expands and shows the plasma discharge generation | occurrence | production part of Embodiment 13. FIG. 23 is an enlarged view corresponding to FIG. 22 illustrating an enlarged plasma discharge generation unit according to a fourteenth embodiment. FIG. 22 is an enlarged view corresponding to FIG. 22 illustrating an enlarged plasma discharge generation unit according to a fifteenth embodiment. FIG. 22 is an enlarged view corresponding to FIG. 22 illustrating an enlarged plasma discharge generation unit according to a fifteenth embodiment. It is the schematic of the conventional plasma CVD apparatus. It is sectional drawing which shows the conventional plasma CVD apparatus typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 High frequency power supply 2a Cathode electrode 2b Anode electrode 3 Interelectrode insulation part (insulation layer)
4 Substrate 5 Processing chamber (vacuum container)
6 Gas introduction port 7 Gas retention part 8 Wiring 9 Process substrate holder 11 Discharge (plasma)
11b Typical path of discharge 12 Radical flow 13 Gas supply unit 14 Gas flow 15 Plasma discharge generation unit 21 Transparent insulating film 22 Transparent electrode 23 Cathode 24 Organic light emitting layer 25 Organic hole transport layer 26 Anode 31 Curved portion 35 Recess 37 Recess

Claims (31)

A processing chamber in which a substrate to be processed is disposed;
A gas inlet for introducing gas into the processing chamber;
A plasma process apparatus comprising a plasma discharge generator provided in the processing chamber and performing plasma processing on the substrate to be processed;
The plasma discharge generator includes a plurality of insulating portions extending in a stripe shape in a direction parallel to the substrate to be processed, a first electrode provided at least between the insulating portions adjacent to each other, A plasma processing apparatus, comprising: a second electrode provided in a state separated from the first electrode at an end portion on a substrate to be processed side. The gas inlet is provided in the first electrode side, a plasma processing apparatus according to claim 1. The first electrode is a plasma discharge surface is concave, the plasma processing apparatus according to claim 1 or 2. The area of the plasma discharge surface of the first electrode is larger than the area of the plasma discharge surface of the second electrode, the plasma processing apparatus according to any one of claims 1 to 3. The plasma discharge generation unit is a plurality chromatic and a region of the plasma discharge surface of the first electrode of the plasma discharge surface region and the second electrode, the plasma processing apparatus according to any one of claims 1 4 . A plurality of regions of the plasma discharge surface of the first electrode and a region of the plasma discharge surface of the second electrode are alternately formed along one surface direction of the substrate to be processed, and the second electrode and the substrate to be processed the distance between the is more than the distance between the electrodes of the second electrodes adjacent to each other, the plasma processing apparatus according to any one of claims 1 to 5. The plasma process according to any one of claims 1 to 6 , further comprising a power source for applying electrical energy to the first electrode and the second electrode, wherein the frequency of the power source is 100 kHz or more and 300 MHz or less. apparatus. The plasma processing apparatus according to claim 1 , wherein a plasma discharge surface of the first electrode has a concave curved surface portion. The plasma processing apparatus according to claim 8 , wherein the plasma discharge surface of the first electrode and the plasma discharge surface of the second electrode constitute a part of a continuous curved surface. The plasma processing apparatus according to claim 1 , wherein a plurality of depressions are formed on a plasma discharge surface of the first electrode. The plasma processing apparatus according to claim 10 , wherein a gas introduction port is formed in at least a part of the bottom of the recess. The plasma processing apparatus according to claim 1 , wherein the plasma discharge surface of the first electrode is sandblasted. The plasma processing apparatus according to claim 1 , wherein the first electrode is provided with a plurality of recesses that open toward the substrate to be processed. The plasma processing apparatus according to claim 13 , wherein an opening shape of the concave portion is a quadrangle. The plasma processing apparatus according to claim 13 , wherein an opening shape of the recess is circular. The plasma processing apparatus according to claim 1 , wherein the first electrodes provided between the insulating portions are separated from each other. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator has a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode,
In the first electrode and the second electrode, only the surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface,
The first electrode is a plasma processing apparatus, wherein a plasma discharge surface is concave. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator includes a first electrode, an insulating layer formed on a part of the electrode surface of the first electrode, and a second electrode formed on the insulating layer,
The first electrode is a plasma processing apparatus, wherein a plasma discharge surface is concave. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator has a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode,
In the first electrode and the second electrode, only the surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface,
The plasma process apparatus, wherein the plasma discharge surface of the first electrode has a concave curved surface portion. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator includes a first electrode, an insulating layer formed on a part of the electrode surface of the first electrode, and a second electrode formed on the insulating layer,
The plasma process apparatus, wherein the plasma discharge surface of the first electrode has a concave curved surface portion. 21. The plasma processing apparatus according to claim 19 or 20, wherein the plasma discharge surface of the first electrode and the plasma discharge surface of the second electrode constitute a part of a continuous curved surface. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator has a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode,
In the first electrode and the second electrode, only the surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface,
A plasma processing apparatus, wherein a plurality of depressions are formed on a plasma discharge surface of the first electrode. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator includes a first electrode, an insulating layer formed on a part of the electrode surface of the first electrode, and a second electrode formed on the insulating layer,
A plasma processing apparatus, wherein a plurality of depressions are formed on a plasma discharge surface of the first electrode. The plasma processing apparatus according to claim 22 or 23, wherein a gas introduction port is formed in at least a part of the bottom of the recess. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator has a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode,
In the first electrode and the second electrode, only the surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface,
The plasma process apparatus, wherein the plasma discharge surface of the first electrode is sandblasted. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator includes a first electrode, an insulating layer formed on a part of the electrode surface of the first electrode, and a second electrode formed on the insulating layer,
The plasma process apparatus, wherein the plasma discharge surface of the first electrode is sandblasted. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator has a first electrode and a second electrode provided closer to the substrate to be processed than the first electrode,
In the first electrode and the second electrode, only the surface visible from the normal direction of the substrate to be processed functions as a plasma discharge surface,
The plasma processing apparatus, wherein the first electrode is provided with a plurality of recesses that open toward the substrate to be processed. A plasma processing apparatus for performing plasma processing on a substrate to be processed,
A processing chamber in which the substrate to be processed is placed;
A gas inlet for introducing gas into the processing chamber;
A plasma discharge generator provided in the processing chamber,
The plasma discharge generator includes a first electrode, an insulating layer formed on a part of the electrode surface of the first electrode, and a second electrode formed on the insulating layer,
The plasma processing apparatus, wherein the first electrode is provided with a plurality of recesses that open toward the substrate to be processed. 29. The plasma processing apparatus according to claim 27 or 28, wherein an opening shape of the recess is a quadrangle. 29. The plasma processing apparatus according to claim 27 or 28, wherein an opening shape of the recess is circular. A method for manufacturing an electronic device using the plasma processing apparatus according to any one of claims 1 to 30,
Placing the substrate to be processed inside the processing chamber;
Introducing the gas from the gas inlet into the processing chamber on which the substrate to be processed is placed;
And a step of generating a plasma discharge by the plasma discharge generator and performing a plasma treatment on the surface of the substrate to be processed.

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