JP4775280B2 - Plasma assist vapor deposition apparatus and plasma assist vapor deposition method - Google Patents

Description

  The present invention relates to a method for performing reactive vapor deposition by stably generating plasma used in a vacuum film formation process.

In vacuum thin film formation by vapor deposition or CVD (Chemical Vapor Deposition), a plasma assisted vapor deposition process or a plasma CVD process is effective for improving the hardness of the film and improving the adhesion. In order to generate plasma, it can be obtained by generating and maintaining ions and electrons using discharge, heat, light or the like as ionization energy. Plasma by discharge is known as a highly convenient method because it can easily perform ion / electron acceleration, collision, and ionization by an electric field in decompression. For the generation of an electric field, a direct current (DC) system, an alternating current (AC) system, a radio frequency (RF) system, a microwave (Micro)
A typical example is the Wave, MW) method. Since plasma is maintained in an electric field except for the MW system, plasma is generated between the anode and the cathode. However, in the MW system, non-polar discharge that does not require an electrode is possible. Specifically, a discharge having a high plasma density can be obtained by using a strong electric field in a waveguide or a cavity resonator.

  As disclosed in Patent Document 1, a substance to be evaporated placed in an evaporation source in a vacuum is heated and evaporated by an electron beam heating method, and the atom or molecule evaporated is ionized or excited by microwaves to generate microwave plasma. Is generated. By depositing the atoms or molecules on a substrate such as a synthetic resin film, a coating layer that improves the gas barrier property of the substrate is formed. However, in order to generate microwave plasma, a microwave horn antenna having a width substantially equal to the width of the vacuum vessel is required, and there is a problem that the apparatus becomes large-scale. In addition, it is necessary to form innumerable holes in the microwave horn antenna, adjust the number of the holes and spaces, change the impedance to the microwaves, and adjust the range of the impedances of the spaces and the microwaves. For this reason, there is a problem that microwave energy is not efficiently transmitted with respect to a large pressure fluctuation.

  As disclosed in Patent Document 2, when ECR plasma is used, a high-density plasma at a low pressure can be obtained relatively easily by the resonance effect of microwave 2.45 GHz and a magnetic field. There is a problem that is necessary, and there is a problem that the trajectory of the electron beam for heating the evaporation target substance is bent, making it difficult to evaporate the evaporation target substance by the electron beam heating method.

  In addition, reactive vapor deposition can be performed by introducing oxygen into the chamber during vapor deposition. However, for example, a gas barrier film such as aluminum oxide cannot be obtained by simply introducing oxygen gas, and its characteristics cannot be obtained. There was a problem that could not be improved.

The known literature is described below.
Japanese Patent No. 3360848 JP-A-8-60373

In particular, in the plasma assisted deposition process, there is a problem that plasma cannot be effectively generated unless the pressure condition using the plasma is higher than the pressure that is the optimum condition in the deposition process. In other words, if the pressure is set to effectively generate and maintain the plasma, the deposition rate and film quality of the vapor deposition will be reduced. Conversely, if the pressure is set to maintain the deposition rate and film quality of the vapor deposition, the plasma will be reduced. There was a problem that did not occur.

  In addition, there is a problem that the discharge plasma is not generated because the distribution of the electric field strength is not constant in a space that is sufficiently wider than the wavelength of the electromagnetic wave. In particular, since microwaves, which are electromagnetic waves with short wavelengths, are used, there is a problem that when plasma is not generated, the energy of electromagnetic waves heats the metal mesh (electromagnetic wave leakage prevention shield) etc. and consumes energy. . Further, even if plasma is generated, plasma may be generated not at a part necessary for the process but at a place other than the target place such as the back side of the pipe or in the vicinity of the observation window.

  In order to solve this problem, the present invention includes a waveguide for propagating microwaves, a vacuum vessel for introducing microwaves from the waveguide, and closing the outlet of the waveguide to form the vacuum It has a dielectric that separates the space in the container from the space in the waveguide, has a microwave horn antenna installed at the tip of the dielectric, penetrates the side wall of the horn antenna, And a first gas pipe having a length that resonates with the microwave, and a mechanism for generating plasma by introducing gas into the microwave horn antenna from a gas inlet at the tip of the first gas pipe And a second gas pipe installed between the evaporation source and a substrate to be deposited. The plasma assisted deposition apparatus according to claim 1, further comprising: an evaporation source disposed in the vacuum vessel.

  In the present invention, when the wavelength of the microwave is λ, the installation position of the first gas pipe on the side wall of the horn antenna is set at a pipe mounting distance of λ / 2 from the dielectric, The plasma-assisted vapor deposition apparatus according to claim 1, wherein the length of the pipe from the inner wall to the tip of the microwave horn antenna of one gas pipe is λ / 4.

  The present invention is also the above plasma assisted vapor deposition apparatus, wherein the microwave horn antenna has the same shape as the waveguide.

  According to the present invention, the evaporation source evaporates the metal material, and oxygen plasma is generated by supplying oxygen from the first gas pipe to the vapor of the metal material and generating oxygen plasma from the second gas pipe. In the plasma-assisted vapor deposition apparatus, a metal oxide is obtained by adding oxygen plasma obtained by adding a gas, and the metal oxide is formed on the substrate.

  Further, the present invention is directed to propagating a microwave to a waveguide, introducing the microwave from the waveguide into a vacuum vessel, and closing the microwave outlet of the waveguide with a dielectric. The space in the waveguide is separated from the space in the waveguide, the pressure in the vacuum vessel is set to a pressure within a pressure range where plasma is easily generated, and the pressure in the waveguide is set to a pressure different from the pressure range. The first gas pipe having a length that resonates with the microwave is set inside the horn antenna through the side wall of the microwave horn antenna installed at the tip of the dielectric, and at the tip of the first gas pipe. Plasma is generated at a gas inlet, an evaporation source is installed in the vacuum vessel, and a gas is introduced by installing a second gas pipe between the deposition source and a substrate to be deposited. Plasma assisted deposition method A.

In the present invention, when the wavelength of the microwave is λ, the installation position of the first gas pipe on the side wall of the horn antenna is set at a pipe mounting distance of λ / 2 from the dielectric, In the plasma-assisted vapor deposition method, the length of the pipe from the inner wall to the tip of the microwave horn antenna of one gas pipe is λ / 4.

  The present invention is also the above plasma-assisted deposition method, wherein the microwave horn antenna has the same shape as the waveguide.

  In the present invention, the evaporation source evaporates a metal material, and oxygen plasma generated by supplying oxygen from the first gas pipe to the vapor of the metal material generates oxygen from the second gas pipe. The plasma-assisted deposition method described above, wherein a metal oxide is obtained by adding oxygen plasma obtained by adding a gas, and the metal oxide is formed on the substrate.

According to the present invention, even if the inside of the vacuum chamber becomes a wide space, the first gas pipe serves as an antenna, and the plasma generation location can be concentrated only at the gas outlet, and the plasma can be supplied to the entire vacuum vessel 8. Therefore, film formation processes such as vapor deposition and CVD can be effectively performed by plasma without selecting a place in the vacuum vessel. In addition, in the case of a resonant magnetic field of microwave and plasma, that is, a frequency of 2.45 GHz like ECR plasma, even if a strong magnetic field of 875 × 10 ⁻⁴ [T] (= 875 [Gauss]) is not generated, even under a low pressure condition Since plasma can be stably generated, plasma-assisted deposition can be easily performed without bending the electron beam trajectory of the electron beam heating type deposition source. As a result, it is possible to obtain an assist effect by plasma while maintaining the optimum pressure range in the vapor deposition, so that it is possible to obtain a high quality vapor deposition film.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. In this embodiment, as shown in FIG. 1, a microwave oscillator 6 that generates a microwave, a waveguide 1 that propagates the microwave, and a matching that is inserted in the middle of the waveguide 1 to adjust the impedance of the microwave. 7, a vacuum vessel 8 for introducing microwaves from the waveguide 1, a dielectric 2 for closing the outlet of the waveguide 1 and isolating the space in the vacuum vessel 8 from the space in the waveguide 1, and the dielectric 2 And a first gas pipe 4 penetrating the side wall is installed inside the microwave horn antenna 3. Among these, the microwave plasma generator is composed of a waveguide 1, a dielectric 2, a microwave horn antenna 3 opened on the right side of FIG. 2, and a first gas pipe 4 as shown in FIG. 2.

  The microwave oscillator 6 of FIG. 1 can use a general microwave tube represented by a magnetron, and uses an industrially assigned frequency of 2.45 GHz. The shape of the waveguide 1 is determined by the oscillation frequency, but various modes can be selected depending on the traveling direction of the electromagnetic field, but considering the use of the TE wave fundamental mode, the EIAJ model name WRJ-2 (inner diameter size 109.22 × 54). .61 mm).

  Examples of the matching unit 7 that adjusts the impedance of the microwave include an E-H tuner, a stub tuner, and a 4E tuner.

The dielectric 2 is used to make the pressure in the waveguide 1 and the vacuum vessel 8 different. Since the pressure range in which plasma is likely to be generated is about 0.1 [Pa] to 10 [Pa], the pressure in the vacuum vessel 8 is set within that range, and the pressure in the waveguide 1 is about two orders of magnitude. The plasma is not generated in the waveguide 1 by raising or lowering it. Thereby, plasma can be generated only in the vacuum vessel 8. If the inside of the waveguide 1 is in a pressure range of 0.1 to 10 [Pa], plasma is generated in the waveguide 1 and not only consumes extra energy but also plasma is supplied to a desired place. Inconvenience that does not occur occurs. The dielectric 2 is preferably a material that has a low dielectric loss of microwaves and does not deform even when there is a pressure difference, and a single crystal dielectric material is preferable because the dielectric loss is low.

  With the combination of the microwave horn antenna 3 and the first gas pipe 4, the shape of the first gas pipe 4 plays an important role as an antenna that receives electric field energy generated by the microwave. By installing the first gas pipe 4 penetrating the side wall inside the microwave horn antenna 3, and making the length of the first gas pipe 4 inside the microwave horn antenna 3 to be a length that resonates with the microwave, By concentrating the electric field on the gas inlet 5 at the tip of the first gas pipe 4, when the reactive gas is introduced from the gas inlet, the reactive gas receives a particularly strong electric field at the gas inlet, Plasma can be generated by concentrating at a location. Particularly, as shown in FIG. 2, the pipe attachment distance 10 from the dielectric 2 to the attachment position of the microwave horn antenna 3 of the first gas pipe is set to ½ of the wavelength λ of the microwave, as shown in FIG. 2 and FIG. By setting the pipe length 11 from the inner wall of the microwave horn antenna 3 to the tip of the first gas pipe to ¼ of the wavelength λ of the microwave, the electric field strength can be increased by increasing the impedance. Since it becomes the maximum, it is more preferable.

  In order to determine the maximum electric field to the first gas pipe 4, it is important that the microwave horn antenna 3 is grounded. This is because the electric field strength is maximized by setting the length from the reference potential 0 to 1/4 of the wavelength λ of the microwave.

  The microwave horn antenna 3 may have the same size and shape as the waveguide 1. Since the purpose is to generate plasma stably, there is no need for the opening to expand toward a space having a general shape. This is because energy is consumed to generate plasma before the microwave propagates into space, and the plasma is sent to the entire vacuum vessel 8. By making the microwave horn antenna 3 the same size and shape as the waveguide 1, there is an effect that the apparatus can be miniaturized.

By combining this microwave plasma generator with a known vacuum deposition method, it can be used as a plasma-assisted deposition method. The base material 9 in that case can correspond to various materials such as metal, glass, and plastic, and the thickness of the base material 9 is not particularly limited, such as a film, a sheet, or a panel. Vapor deposition is often performed in a pressure range of 10 ⁻³ [Pa] to 10 ⁻² [Pa], but the plasma generator using the first gas pipe 4 as an antenna can generate plasma even in those pressure ranges. Is possible. Therefore, the vapor deposition material is activated by the plasma, so that the adhesion to the base material 9 can be improved and the film can be densified. Further, since the microwave plasma is stably generated by the resonance of the antenna of the first gas pipe 4, the plasma generated thereby relaxes the charging of the crucible of the electron beam evaporation type evaporation source 14, and the evaporation source 14 This has the effect of alleviating charging obstacles in which reflected electrons and scattered electrons of the electron beam from the crucible enter the substrate 9 and are charged.

  The reactive gas mentioned here is a gas capable of composing various compounds, and specifically, is an active gas such as oxygen or ammonia. For example, oxygen can form a metal oxide film from metal vapor as a reactive gas, and a nitride film can be formed from ammonia or nitrogen activated by plasma. Specifically, metallic aluminum installed in the evaporation source 14 is evaporated by an electron beam heating method to generate aluminum vapor, oxygen is blown into the vapor, oxygen is converted into oxygen plasma, and oxygen plasma assists. A high quality aluminum oxide film can be produced. The high quality mentioned here means that the gas barrier property is high.

As shown in FIG. 4, the second gas pipe 13 is installed below the substrate 9 and above the evaporation source 14. The second gas pipe 13 is provided with a hole for introducing a reactive gas into the vacuum vessel 8. In order to prevent the evaporation particles from blocking the holes of the second gas pipe 13 installed on the evaporation source 14, the deposition shield 12 is provided, and the holes of the second gas pipe 13 are arranged on the deposition shield 12 side, that is, on the lower side. Turn. Thereby, the clogging of the hole of the second gas pipe 13 can be prevented and the gas flow can be ensured.

  The microwave horn antenna 3 is installed upward so that the dielectric 2 at the microwave outlet of the waveguide 1 is positioned below the evaporation source 14. When the dielectric 2 is positioned above the evaporation source 14, the evaporated particles adhere to the dielectric 2 to form a vapor deposition film, thereby blocking and losing the transmission of microwave energy supplied from the waveguide 1. In the worst case, the microwave is totally reflected and cannot be supplied into the vacuum chamber 8. Therefore, it is possible to prevent evaporation particles from adhering to the dielectric 2 by positioning the dielectric 2 below the evaporation source 14.

  Oxidation can be further promoted by installing the second gas pipe 13 in the vapor evaporated from the vapor source 14 and introducing more oxygen than the first gas pipe 4. As a result, the evaporated particles and the reactive gas are mixed, and the energy is added by the plasma, so that the activated particles are activated and the reactivity is improved.

  The plasma generation unit described so far can be used as an assist source for a take-up vacuum deposition apparatus in which a film-like substrate 9 is sent out by a roll in a vacuum vessel 8 and wound by a roll. In this case, since the flexible base material 9 is used in order to wind up and it is suitable for mass production by a roll-to-roll, it is preferable. In that case, there is no restriction | limiting in particular in the flexible base material 9 to apply. Even when the transparency of the base material 9 is regarded as important, the base material 9 of the polymer transparent plastic is not particularly limited, and a known one can be used. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol, Polycarbonate, polyethersulfone, acrylic, cellulose-based (triacetyl cellulose, diacetyl cellulose, etc.) and the like are exemplified, but not particularly limited. Moreover, although the film thickness of the base material 9 is not limited, about 6 micrometers to 200 micrometers is easy to use according to a use.

Examples are shown below.
<Example 1>
The microwave uses a frequency of 2.45 GHz, the waveguide 1 uses an EIAJ model name WRJ-2 (inner diameter size 109.22 × 54.61 mm), and the matching unit 7 uses a 4E tuner. The dielectric 2 is made of quartz glass (120 mm × 95 mm, thickness 3 mm), and the pressure in the waveguide 1 is set to 10 ⁻⁴ by a turbo pump in order to make the pressure in the waveguide 1 lower than that in the vacuum vessel 8. It was set to around [Pa]. As shown schematically in FIG. 1, the gas pipe in the microwave horn antenna 3 was a 3/8 inch pipe made of SUS316 and bent at 90 degrees so that the tip portion was L-shaped. As shown in FIG. 2, since the wavelength λ of the microwave of 2.45 GHz is 122 mm, the pipe attachment distance 10 from the quartz glass dielectric 2 to the attachment position of the first gas pipe 4 of the microwave horn antenna 3 is , 61 mm away from dielectric 2 by λ / 2.

  As shown in FIGS. 2 and 3, the pipe length 11 from the inner wall of the microwave horn antenna 3 to the tip of the first gas pipe 4 was set to λ / 4 of 31 mm. Then, oxygen gas was introduced from the first gas pipe 4. Further, as shown in FIG. 4 in detail, the second gas pipe 13 is installed between the evaporation source 14 and the base material 9, and oxygen gas is also introduced from the second gas pipe 13. . In the first embodiment, the first gas pipe 4 is installed inside the microwave horn antenna 3 so as to be perpendicular to the side wall. However, the first gas pipe 4 may be bent halfway. Also in this case, the first gas pipe can be made to resonate with the microwave by setting the pipe length 11 from the inner wall of the microwave horn antenna 3 to the tip of the first gas pipe to λ / 4.

A roll-up vacuum deposition apparatus was used, and the substrate 9 was a PET film (T60 manufactured by Toray Industries, Inc., 25 μm thick). Using an evaporation source 14 that performs electron beam heating evaporation, an ingot of metal Al (purity 99.9%) was placed in the evaporation source 14 as an evaporation target substance, and reactive assist deposition was performed. The conditions of the electron beam were a beam acceleration voltage of 40 kV and a beam current of 0.28 A, and the Al ingot was irradiated with the electron beam to generate Al vapor. As a result, Al is vapor-deposited on the base material 9 so that the light transmittance of the base material 9 is 40% at a wavelength of 380 nm, and oxygen gas 50 [sccm] is supplied from the first gas pipe 4 and from the second gas pipe 13. Oxygen gas 280 [sccm] was introduced. (Here, sccm is standard cc / min, 1 atm (atmospheric pressure 1,013 hPa), gas that expresses the density of gas standardized at 0 ℃ per 10 ^-3 liters per minute.) The pressure in the vacuum vessel 8 obtained as a result was 4.7 × 10 ⁻² [Pa]. The AlOx film was formed by setting the microwave power to 1.0 [kW]. The winding speed was changed so that the AlOx film thickness was 20 nm. The produced AlOx-attached film has an oxygen transmission rate (measurement of oxygen transmission rate by MOCON, OX-TRAN 2/20, measuring condition 30 ° C. 70% RH), light transmittance (use of spectrometer, UV-3100 manufactured by Shimadzu Corporation), AlOx The film thickness (X-ray reflectivity method, Rigaku ATX-G) was measured.

<Comparative Example 1>
As in Example 1, a film with AlOx was prepared under the same conditions except that the microwave power was set to 0 [kW], and the same evaluation as in Example 1 was performed.

<Comparative example 2>
As in Example 1, a film with AlOx was created under the same conditions except that the oxygen flow rate of the first gas pipe 4 was set to 300 [sccm] and the oxygen flow rate of the second gas pipe 13 was set to 0 [sccm]. Evaluation similar to Example 1 was performed.

<Comparative Example 3>
As in Example 1, a film with AlOx was prepared under the same conditions except that the oxygen flow rate of the first gas pipe 4 was 0 [sccm] and the oxygen flow rate of the second gas pipe 13 was 300 [sccm]. Evaluation similar to Example 1 was performed.

これらの結果を表１に示す。比較例１はプラズマが無いためガスバリア性は低くなった。比較例２は、酸素ガスがプラズマ発生部には十分存在しているが、第２のガスパイプ１３から酸素ガスを供給しなかったことによりＡｌと反応する酸素が少なかったため光線透過率は低く黒ずんだ膜となった。比較例３はプラズマが発生したり消滅したりと不安定な状態だった。これは、第１のガスパイプ４に酸素ガスが供給されていないためと考えられる。実施例１では酸素透過率が低く、光線透過率も高くなったことから、ＡｌＯｘ膜のバリアが向上したといえる。プラズマを利用しなかった比較例１からもバリア性の差は明らかである。このことはプラズマアシストによって膜質が密に変化したことと、蒸発源１４での電子ビームによるバリア性の劣化要因である帯電障害を緩和したことの２つの要因が考えられるが、いずれにしろ、マイクロ波プラズマによる蒸着により基材９のガスバリア性が向上する効果があった。すなわち、実施例１により、第１のガスパイプ４からも第２のガスパイプ１３からも酸素ガスを供給し、第１のガスパイプ４を共振アンテナとしてマイクロ波プラズマを発生することにより基材９へ蒸着することにより基材９のガスバリア性を向上させる効果があった。

These results are shown in Table 1. In Comparative Example 1, since there was no plasma, the gas barrier property was low. In Comparative Example 2, oxygen gas is sufficiently present in the plasma generation part, but since the oxygen gas was not supplied from the second gas pipe 13, the amount of oxygen that reacts with Al was small, so the light transmittance was low and blackened. It became a film. In Comparative Example 3, plasma was generated and disappeared, and was in an unstable state. This is presumably because oxygen gas is not supplied to the first gas pipe 4. In Example 1, since the oxygen transmittance was low and the light transmittance was also high, it can be said that the barrier of the AlOx film was improved. The difference in barrier properties is clear also from Comparative Example 1 in which plasma was not used. This can be attributed to two factors, that is, the film quality has been densely changed by the plasma assist, and that the charging failure, which is a cause of deterioration of the barrier property due to the electron beam in the evaporation source 14, has been alleviated. The gas barrier property of the base material 9 was improved by vapor plasma deposition. That is, according to the first embodiment, oxygen gas is supplied from both the first gas pipe 4 and the second gas pipe 13, and the first gas pipe 4 is used as a resonance antenna to generate microwave plasma to deposit on the substrate 9. This has the effect of improving the gas barrier properties of the substrate 9.

  Since a sufficiently stable microwave plasma can be generated even if there is a pressure change when there is a wide space with respect to the wavelength of the microwave, the microwave horn antenna 3 and an antenna / gas pipe having an appropriate length By using two gas pipes, the first gas pipe and the second gas pipe on the evaporation source 14, a large-scale equipment for generating a magnetic field is unnecessary, and the vacuum vessel 8 is usually used without using a large-scale apparatus. Stable plasma can be generated and maintained at a pressure lower than the optimum pressure for generating the plasma. In addition, since a strong magnetic field is not used, there is no fear that the trajectory of the electron beam for performing the electron beam heating evaporation is bent. Therefore, the current density of the electron beam of the evaporation source 14 is increased and the evaporation rate is kept high. Reactive assist vapor deposition is possible, and a high-quality deposited film with high productivity can be formed on the substrate 9.

It is the schematic of the whole plasma-assisted vapor deposition apparatus of the present invention. It is sectional drawing of the side surface of the microwave plasma generation part of this invention It is a front view of the microwave plasma generation part of this invention It is a figure which shows the detailed structure in the vacuum vessel of the plasma assist vapor deposition apparatus of this invention.

Explanation of symbols

1 ··· Waveguide 2 ·· Dielectric 3 · · Microwave horn antenna 4 · · First gas pipe 5 · · Gas inlet 6 · · Microwave oscillator 7 · · Matching device 8 · · Vacuum vessel 9 ·· Substrate 10 ·· Pipe attachment distance 11 ·· Pipe length 12 · · Protection shield 13 · · Second gas pipe 14 · · Evaporation source

Claims (8)

  A waveguide for propagating microwaves, a vacuum vessel for introducing microwaves from the waveguide, and closing the outlet of the waveguide so that the space in the vacuum vessel is separated from the space in the waveguide A dielectric horn antenna that is isolated, has a microwave horn antenna installed at the tip of the dielectric, has a length that penetrates a side wall of the horn antenna and is installed inside the horn antenna and resonates with the microwave; A first gas pipe having a mechanism for generating plasma by introducing gas into the microwave horn antenna from a gas inlet at the tip of the first gas pipe, and an evaporation installed in the vacuum vessel A plasma-assisted vapor deposition apparatus comprising a second gas pipe provided between the evaporation source and a deposition target substrate.   When the wavelength of the microwave is λ, the installation position of the first gas pipe on the side wall of the horn antenna is set at a pipe mounting distance of λ / 2 from the dielectric, and the microwave of the first gas pipe is set. 2. The plasma-assisted deposition apparatus according to claim 1, wherein the length of the pipe from the inner wall to the tip of the wave horn antenna is λ / 4.   The plasma-assisted vapor deposition apparatus according to claim 1 or 2, wherein the microwave horn antenna has the same shape as the waveguide.   The evaporation source is for evaporating a metal material, and obtained by adding oxygen gas from the second gas pipe to oxygen plasma generated by supplying oxygen from the first gas pipe to the vapor of the metal material. 4. The plasma-assisted deposition apparatus according to claim 1, wherein a metal oxide is obtained by applying an oxygen plasma, and the metal oxide is formed on the substrate. 5.   The microwave is propagated in the waveguide, the microwave is introduced from the waveguide into the vacuum vessel, and the microwave outlet of the waveguide is closed with a dielectric, and the space in the vacuum vessel and the wave guide are filled. Isolating the space in the tube, setting the pressure in the vacuum vessel to a pressure within a pressure range in which plasma is easily generated, setting the pressure in the waveguide to a pressure different from the pressure range, and A first gas pipe having a length that resonates with the microwave passes through the side wall of the microwave horn antenna installed in the horn antenna, and plasma is generated at the gas inlet at the tip of the first gas pipe. A plasma assisted vapor deposition method comprising: generating an evaporation source in the vacuum vessel; and introducing a gas by installing a second gas pipe between the vapor deposition source and a substrate to be vapor deposited.   When the wavelength of the microwave is λ, the installation position of the first gas pipe on the side wall of the horn antenna is set at a pipe mounting distance of λ / 2 from the dielectric, and the microwave of the first gas pipe is set. 6. The plasma-assisted vapor deposition method according to claim 5, wherein the length of the pipe from the inner wall to the tip of the wave horn antenna is λ / 4.   The plasma-assisted deposition method according to claim 5 or 6, wherein the microwave horn antenna has the same shape as the waveguide.   The evaporation source is for evaporating a metal material, and obtained by adding oxygen gas from the second gas pipe to oxygen plasma generated by supplying oxygen from the first gas pipe to the vapor of the metal material. A plasma-assisted vapor deposition method according to any one of claims 5 to 7, wherein a metal oxide is obtained by applying an oxygen plasma, and the metal oxide is formed on the substrate.

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