JP2001207260A - Film deposition method and film deposition system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the optical characteristics such as density, adhesive strength and absorption of an optical thin film deposited on a substrate under no-heating or low temperature by a vacuum deposition method. SOLUTION: MgF2 granules are charged to a crucible as an evaporation source 2 and are heated and evaporated by an electron gun 3 to deposit a metallic fluoride thin film on the object 9 to be treated as a substrate. Since a dense film with low absorption and tight adhesion cannot be obtained in the case the object 9 to be treated lies under no-heating or low temperature, the object 9 to be treated in the process of the film deposition is irradiated with neutral grains and negative ions generated by magnetron sputtering in which high frequency is applied on a target 4 as assists.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming method for forming an optical thin film such as an antireflection film for an optical component in the visible and ultraviolet regions, a fluoride thin film used for a dielectric multilayer mirror, and the like. The present invention relates to a membrane device.

[0002]

2. Description of the Related Art Conventionally, when forming an optical thin film such as a fluoride thin film used for an anti-reflection film or a mirror, a film-forming material is heated using an electron beam or the like in a vacuum and evaporated to adhere to a substrate. Vacuum evaporation has been mainly used.

In general, an antireflection film, a mirror and the like are made of a low refractive index film such as magnesium fluoride (MgF ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O).
₅ ) One of high refractive index films such as titanium oxide (TiO ₂ ) and the like, or a multilayer film combining these, and the layer configuration, film thickness, etc. are variously varied depending on the required optical performance. I am adjusting.

In general, the vacuum deposition method has a simple apparatus structure, can form a film at high speed on a large-area substrate, and can easily form a low-absorbing fluoride thin film or the like from visible to ultraviolet region. This is a film forming method with excellent properties. However, when film formation is performed in a situation where the substrate temperature is low, the density of the film decreases,
Voids and the like are easily generated in the film, and there have been problems such as changes in optical characteristics due to the influence of humidity in the atmosphere. In addition, there is a problem that the strength of the film is insufficient, the film is easily damaged, and the adhesion between the film and the substrate is low.

For this reason, a method of heating a substrate to about 300 degrees to form a film is usually used. However, optical parts such as plastics which are also used for eyeglass lenses in recent years cannot be heated up to 300 degrees. Further, even for a lens that requires a very high-precision shape, it is necessary to form a film at a temperature as low as possible in order to avoid problems such as thermal deformation. Further, since it takes time to heat and cool the substrate, improvement of the vacuum deposition method has been demanded also from the viewpoint of film formation cost and energy consumption.

Therefore, as a technique for solving such a problem, for example, Japanese Patent Application Laid-Open No. 6-102401 discloses a method of forming MgF ₂ as an antireflection film on an optical component surface. A method is disclosed in which a film is deposited while irradiating the substrate with an electron beam and the substrate is not heated.

Japanese Patent Application Laid-Open No. Hei 9-61603 discloses that
In an environment where a gas such as Ar or O ₂ is introduced, a plasma gun is arranged between the evaporation source and the substrate, a high voltage is applied to the plasma gun to form plasma, and the evaporated particles are ionized in the plasma. A filming technique is disclosed.

[0008]

However, according to the above-mentioned prior art, when a fluoride thin film or the like is basically formed, the substrate is heated for vapor deposition, or the evaporated particles are ionized and bias is applied to the substrate. Is applied to accelerate and enter the substrate, or assist such as irradiating the film substrate with an electron beam.These methods promote the migration of deposited particles on the substrate surface, Although some kind of energy is supplied for the purpose of increasing the density and adhesion, there are the following unsolved problems.

That is, the method of heating a substrate cannot be applied to a plastic substrate having a low heat-resistant temperature, and the method of forming a thin film of fluoride using ionization of evaporating particles without heating the substrate, for example, The metal and fluorine are dissociated by ionization, and the fluorine in the obtained fluoride thin film tends to be depleted.Furthermore, the fluorine in the film is desorbed due to cation damage, resulting in a film containing much metal and having a large absorption. Would.

In the method of irradiating an electron beam without heating the substrate, the absorption of the film is smaller than that of the above-mentioned ionization method, but the plastic substrate which is easily broken by the electron beam irradiation, or the method of desorbing fluorine. It cannot be applied to a CaF ₂ substrate, which is likely to occur, and has a problem that the film density and hardness are lower than those of the conventional evaporation method in which the substrate is heated.

Further, as described in JP-A-9-61603, fluoride is evaporated by an electron gun, and the evaporated particles are passed through a plasma region formed between an evaporation source and a film forming substrate. A technique for forming a film without forcibly heating the substrate has also been proposed. In this method, the ionization of the evaporated particles in the plasma and the fluorine generated by the dissociation of the evaporated particles are activated by oxygen plasma, supplied to the substrate, and recombined on the substrate to prevent fluorine deficiency. However, the fluorine generated in the plasma is very active,
It is consumed even in the inner surface of the chamber. Further, cations enter the substrate, and fluorine is desorbed from the film due to the damage, so that only a fluoride thin film lacking fluorine can be formed. Therefore, even if a thin film having a relatively low absorption was obtained in the visible region, only a fluoride thin film having a large absorption could be formed in the ultraviolet region.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned unsolved problems of the prior art, and has been developed by heating a substrate even at a low substrate temperature without heating or damaging the substrate. A film forming method and a film forming apparatus capable of forming a very low absorption fluoride thin film or the like in a wide wavelength range from the visible region to the vacuum ultraviolet region, which has the same adhesive strength and filling rate as the above and suppresses wavelength shift. The purpose is to provide.

[0013]

In order to achieve the above object, a film forming method of the present invention is a film forming method for forming an optical thin film on a substrate by a vacuum evaporation method, wherein neutral particles are assisted. Irradiation is performed on the substrate during film formation.

Further, a film forming method for forming an optical thin film on a substrate by a vacuum vapor deposition method may be performed, wherein the substrate is being irradiated with negative ions as an assist.

Further, the present invention is a film forming method for forming an optical thin film on a substrate by a vacuum deposition method, wherein the substrate being formed is irradiated with sputter particles obtained by sputtering a metal or metal compound target. A film forming method characterized by the above may be used.

According to the present invention, there is provided a film forming apparatus comprising: a vacuum chamber having vacuum evacuation means; a vapor deposition particle generating means for heating and evaporating a film forming material in the vacuum chamber to adhere to a substrate; An assist generating means for irradiating the substrate with at least one of negative ions as assist is provided.

A vacuum chamber having vacuum evacuation means, vapor deposition particle generation means for heating and evaporating a film-forming material in the vacuum chamber to adhere to a substrate, and sputter particles for assisting the substrate during film formation. A film forming apparatus having a sputtered particle generating means for irradiation may be used.

[0018]

When the present inventors assist with a high-energy particle such as a plasma gun instead of heating the substrate during the deposition of the fluoride thin film, the absorption in the ultraviolet region increases. The cause has been studied diligently. In particular, the optical characteristics of a sample formed by changing the film formation conditions such as the charge and energy of the assist particles during the film formation and the obtained film were analyzed. As a result, it has been found that as a cause of absorption of the fluoride thin film or the like, fluorine is desorbed from the fluoride thin film by a high-energy cation and a fluorine deficiency is caused, thereby causing absorption in the ultraviolet region. In particular, cations having an energy of 10 eV or more easily cause damage.

However, for example, in the process of forming a fluorinated thin film, the assist by negative ions or neutral particles is 10 e.
Even with V, little damage occurs. This is because cations incident on the substrate inject holes into the fluoride thin film, and the holes disturb the electron arrangement in the fluoride thin film, and the energy released at the time of recombination of holes and electrons causes metal-fluorine bonding. This is presumed to be due to the breakage of fluorine, which causes the desorption of fluorine and the disorder of the bonding state.

In view of this result, in a vacuum chamber, a film-forming material such as a metal or a metal fluoride is heated by an electron beam or resistance heating in a high vacuum or under an environment in which a gas containing at least fluorine is introduced. In the step of depositing the deposited particles on a substrate to form a fluoride thin film, a direct current and / or a high frequency power, or both, are applied to a metal or metal fluoride target placed in the same vacuum chamber. A structure was developed in which the sputtered particles and high-energy particles obtained by accelerating negative ions formed by the target with a target bias were used as an assist and were incident on the substrate surface on which the fluoride thin film was formed.

That is, neutral particles having an average energy of about several electron volts sputtered from the target and negative ion particles containing fluorine generated on the surface of the target are accelerated by the target bias voltage and collide with gas molecules on the way. Neutralized, high-energy particles that have lost most of the charge are made incident on the substrate on which the deposited film is deposited, and the assist effect compensates for the low energy of the deposited particles when the substrate is not heated. Improve density and adhesion.

Since the high-energy particles incident on the substrate are negative ions or neutral particles, a stoichiometric fluoride thin film can be formed without promoting the elimination of fluorine from the fluoride thin film as with cations. can do.

In addition, since active fluorine atoms, fluorine radicals, and the like are formed by the plasma formed on the target surface, the fluorination reaction of the metal can be efficiently promoted, and low absorption in the visible to ultraviolet region can be achieved. It is possible to form a metal fluoride thin film or the like at a high speed.

[0024]

Embodiments of the present invention will be described with reference to the drawings.

FIG. 1 shows a film forming apparatus according to an embodiment. On the right side of the bottom of a vacuum chamber 1, an evaporation source which is a film forming material contained in a crucible made of a high melting point metal is provided. 2, and an electron beam heating device 3, which is a vapor deposition particle generating means for irradiating the evaporation source 2 with an electron beam accelerated at a high voltage to heat and evaporate the electron beam. Usually, a large number of evaporation sources 2 housed in a crucible are housed in a vacuum chamber 1, and a large amount and a large variety of materials can be evaporated by exchanging evaporation materials. I have. In addition,
Instead of heating with an electron beam, heating may be performed by a resistance heating method or the like.

At the bottom left side of the vacuum chamber 1, a magnet is housed inside, and a cooling box for cooling a target 4 as sputter particle (assist) generating means by flowing cooling water supplied from the outside through the inside. 5 and a backing plate as a cathode electrode are fixed, and a high-purity MgF ₂ target 4 is fixed to this. A magnet 6 for forming a magnetron magnetic field is built in the cooling box 5. As a material of the target 4, in addition to various metals and metal fluorides, a material such as yttrium oxide which is a metal oxide which easily generates negative ions by sputtering is used.

An anode electrode 7 serving as a power supply means is disposed at a predetermined interval from the target 4, and an insulating material 8 is provided between the anode electrode 7 and the target 4.

Further, on the upper surface of the vacuum chamber 1, a workpiece 9 as a substrate is accommodated in a holder 10. A shutter 11 is provided between the object 9 and the evaporation source 2 and the target 4 so that a film does not adhere to the object 9 until the discharge is stabilized. The shutter 11 can be opened and closed at a high speed by a moving mechanism (not shown). In order to prevent leakage in the vacuum chamber 1, a seal member is provided at an appropriate place, and a vapor deposition rate monitor, a film thickness monitor, and the like are also provided to control an evaporation rate, a film thickness control, and the like. Is also possible.

An inert gas such as Ar and a fluorine-containing gas such as NF ₃ can be freely introduced from the gas introduction port 12 by a gas supply system including a mass flow controller. The flow rate, purity and pressure of the gas to be introduced are controlled with high precision,
It is kept at a constant value. As an inert gas, other than Ar,
Gases such as He, Ne, Kr, and Xe are used. Also,
As a reactive gas containing fluorine, besides NF ₃ gas, CF
It is possible to introduce a gas or the like obtained by diluting ₄ , 5% concentration F ₂ with Ar or He. In addition, a reactive gas containing oxygen such as oxygen or N ₂ О can be switched and introduced as necessary, and an oxide thin film or the like can be formed in addition to the fluoride thin film.

The vacuum chamber 1 is configured to be evacuated to a high vacuum through a main valve 14 by a vacuum exhaust system 13 as a vacuum exhaust means. This evacuation system 1
Since highly reactive gases such as NF ₃ and F ₂ flow in ₃ , pumps with high corrosion resistance should be used as exhaust pumps, and shaft purging, exhaust gas dilution, exhaust gas treatment facilities, etc. should be installed. Of course.

The target cooling water is adjusted to a desired temperature by a chiller (not shown), the flow rate is also kept constant, and the surface temperature of the target 4 is kept constant.

According to this embodiment, neutral particles, which are sputtered particles having an average energy of about several electron volts and are sputtered from the target, and negative ions containing fluorine generated on the surface of the target are accelerated by the target bias voltage. High-energy particles, which are neutralized by colliding with gas molecules on the way and almost losing charge,
In order to accelerate the migration of deposited particles by being incident on the surface of the substrate on which the deposited film is deposited, the substrate is very dense and adheres even when the substrate is not heated or at low substrate temperatures. It is possible to form an optical thin film such as a metal fluoride thin film with good quality.

Further, since active fluorine atoms, fluorine radicals, and the like are formed by the plasma formed on the target surface, the fluorination reaction of the metal is promoted very efficiently, and very high speed is obtained over the visible to ultraviolet region. A low absorption metal fluoride thin film can be obtained.

In particular, since the high-energy particles incident on the substrate are negative ions or neutral particles, it is necessary to form a stoichiometric metal fluoride thin film without promoting the desorption of fluorine from the metal fluoride thin film. Can be.

The target material is Mg,
La, Y, Li, Nd, Ba, Sr, Na, Al, C
a, Ce, Cd, Ho, Y ₂ O ₃ , MgF ₂ , LaF
_{3, LiF, NdF 3, BaF} 2, SrF 2, NaF,
AlF ₃ , BiF ₂ , CaF ₂ , PbF ₂ , CeF ₃ ,
A material containing at least one of GdF ₃ , HoF ₃ , and Na ₃ AlF ₆ is preferably used.

Example 1 Using the apparatus shown in FIG. 1, a magnesium fluoride thin film having a low absorption and a low refractive index was formed on a quartz glass substrate.

First, the vacuum chamber is evacuated to a high vacuum by a vacuum evacuation system. When the evacuation is completed to 2 × 10 ⁻⁴ Pa, the quartz substrate, which is the object to be cleaned, is moved to a substrate transfer device in a vacuum not shown. To secure it to a holder in a vacuum chamber.

MgF ₂ granules are deposited in a crucible as a film-forming material as an evaporation source, and the film-forming material is irradiated with an electron beam of 6 KV-10 mA to deposit a MgF ₂ thin film on a quartz substrate.

An MgF ₂ target was used as a target.

Ar gas is supplied at 0.1 Pa from the gas introduction port.
Introduced to the target by sputtering power supply
A high frequency of 3.56 MHz is applied to generate a magnetron discharge and sputter an MgF ₂ target. At the same time, the MgF ₂ film-forming material is irradiated with an electron beam as described above,
Deposit a gF ₂ thin film. With the magnetron discharge stabilized, the shutter was opened and an MgF ₂ thin film was formed on a quartz substrate. At this time, the heating of the substrate was not performed, and only the temperature was monitored.

The MgF ₂ thus formed on the quartz substrate
FIG. 2 shows the spectral transmittance and reflectance of the thin film. A transparent, low-refractive-index MgF ₂ thin film was formed over the visible to ultraviolet region. The film forming speed at this time was 30 nm / min. The deposition rate can be further increased, and a very thin film with very high speed and low absorption can be obtained because of the highly active neutral particles and negative ions generated by magnetron plasma. Is considered to be due to an assist effect in which F atoms, F radicals, and the like react.

At this time, if the target and the substrate are close to each other, or if the high-frequency power applied to the target is too large, the plasma induced on the target surface may be damaged by the substrate, the absorption of the thin film may increase, or the negative ion Energy and density become too high, and the fluoride thin film formed on the quartz substrate may be re-sputtered. Therefore, the target-substrate distance and the applied voltage can be improved to a level that can improve the film density and adhesion. Power needs to be controlled. According to the experiment, when the distance between the target and the substrate is 200 mm or more,
It has been found that a target applied power density of 4 W / cm ² or less is desirable.

When the spectral reflectance characteristics of this MgF ₂ thin film were measured in the air and in a vacuum, the film quality was very dense, and the reflectance did not change between the air and the vacuum. For comparison,
During deposition, the reflectivity of the MgF ₂ thin film, which was formed without using sputter particle assist, shifted to the shorter wavelength side in a vacuum, there were holes in the film, and there was a problem with the film density. I understood.

Table 1 shows the results of evaluating the adhesion and hardness of the film.

[0045]

[Table 1]

Here, the tape peeling test is a film adhesion evaluation test in which an adhesive tape is brought into close contact with a film surface and peeled off to observe the state of the film. This is a test for evaluating the abrasion resistance of the film, in which the surface of the film is rubbed with and the surface of the film is observed. Although the sample formed without assisting had problems in adhesion and hardness, it could be improved by the negative ion and neutral particles according to the present embodiment.

In this embodiment, the assist effect by the negative ions generated on the target surface is clearly effective. Therefore, in order to form a metal fluoride thin film having uniform properties over a large area, it is necessary to uniformly irradiate the substrate with negative ions. In such a case, the target surface may be swung, and the substrate surface may be uniformly irradiated with the negative ions, by utilizing the characteristic that negative ions are emitted in a direction perpendicular to the target surface. Alternatively, the substrate may be configured to be capable of uniformly irradiating negative ions from the target by eccentric rotation of the substrate.

Further, in this embodiment, M having a low refractive index is used.
Although the formation of the gF ₂ single-layer film has been described, various materials can be vapor-deposited by changing a vapor deposition material and a gas type to be introduced. Needless to say, these various materials can be applied in the form of various optical elements such as an antireflection film, a filter, and a mirror by laminating them in a multilayer. In particular, since a metal fluoride thin film having low absorption, high density, high adhesion, and high durability can be formed at a low substrate temperature, it is suitable for manufacturing an optical element required from ultraviolet to vacuum ultraviolet.

In this embodiment, the magnetron sputtering cathode is used as the assist generation source. However, a negative ion source for generating negative ions such as hydrogen and tritium may be used. In particular, hydrogen and tritium are suitable because they do not affect optical performance even when mixed into a fluoride thin film.

Example 2 In Example 1, MgF ₂ was used as a target material, and a high frequency of 13.56 MHz was used as a sputtering power applied to the target. You need to be careful not to get bigger. 13.56
In a high-frequency discharge of MHz, the electron temperature tends to be high.
When the thickness is less than 00 mm, a bias voltage of 10 V or more is induced on the substrate, so that cations of 10 eV or more may be incident on the substrate from plasma induced on the target surface to cause damage.

In order to prevent this problem, a system in which the sputtering power applied to the target is DC is suitable. However, in this case, a fluoride target such as MgF ₂ cannot be used as the target.

Therefore, in FIG. 1, the target is metallic Mg, and F ₂ (5%) / Ar (9
5%) was introduced at 0.2 Pa, a DC voltage was applied to the target, and the Mg target was sputtered, and at the same time, an MgF ₂ evaporation material as an evaporation source was heated and evaporated with an electron beam.

At this time, if the DC power applied to the target is too large or the F ₂ partial pressure is too low, Mg metal is sputtered from the target, and the obtained fluoride thin film becomes a metal-rich thin film having large absorption. turn into. This state can be monitored from a change in the voltage of the target.

FIG. 3 shows the relationship between the F ₂ flow rate and the target voltage. Target negative voltage indicates the (absolute value decreases the voltage) changes rapidly decreases with increasing F ₂ partial pressure.
In the region where the partial pressure of F ₂ is low and the negative voltage is large, metallic Mg
Was sputtered, and in a region where the partial pressure of F ₂ was high and the negative voltage was small, it was found that sputtering was performed in a state of a metal fluoride such as MgF or MgF ₂ . When the DC power applied to the target increases, as shown in FIG.
The target negative voltage tends to increase.

From the above results, the target voltage is monitored, the target applied power and the F ₂ flow rate are adjusted in consideration of the relationship between the target applied power and the target voltage, and the target is sputtered always in a fluoride state. It has been found that by controlling the voltage, a MgF ₂ thin film with low absorption can be stably formed.

At this time, even when the distance between the target and the substrate was 200 mm or less, a thin film having low absorption, high density, and high adhesion as in Example 1 could be obtained.

However, even if the power applied to the target is DC, if the applied power is 4 W / cm ² or more, re-sputtering due to negative ions will occur, leading to a reduction in the rate and non-uniformity of the thin film. It costs. The maximum allowable power at this time varies depending on the pressure at the time of film formation, and thus cannot be specified unconditionally.

In this embodiment, F ₂ (5%) / Ar (95
%) Gas was introduced, but dissociated in the plasma and F, F ₂
NF ₃ , CF _3, etc. can be used. In addition to He, K, as a diluent gas, other than Ar,
r, Xe etc. may be used, it may be used other metal fluoride thin film less likely to be taken N _2, H ₂ or the like.

In this embodiment, a DC voltage was applied to the target in order to suppress the substrate bias voltage.
Even a low-frequency power of about 0 KHz or a VHF frequency of 50 MHz or more can be used because the substrate bias voltage can be suppressed.

In particular, low-frequency power having a frequency of about 1 to 50 KHz can be sputtered even when a metal fluoride target is used, so that it is not necessary to supply a gas containing fluorine. It is simpler and more secure.

When a frequency in the VHF region of 50 MHz or more is applied, since the target negative voltage is as low as about 50 V, the target voltage control range can be widened by superimposing a DC voltage to irradiate the substrate. The energy control range of negative ions or particles that change from negative ions to neutral can be widened, and the optimum assist energy can be controlled according to the type of film.

[0062]

Since the present invention is configured as described above, the following effects can be obtained.

Even without heating or with a low substrate temperature,
A high-quality metal fluoride thin film or the like that is dense, has high adhesion, and has low absorption in a wide wavelength range from the visible region to the vacuum ultraviolet region can be formed.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a film forming apparatus according to one embodiment.

FIG. 2 is a graph showing spectral characteristics of an MgF ₂ thin film according to Example 1.

FIG. 3 is a graph showing a relationship between an F ₂ flow rate and a target voltage.

FIG. 4 is a graph showing the relationship between target applied power and target voltage.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum chamber 2 Evaporation source 3 Electron beam heating device 4 Target 5 Cooling box 6 Magnet 7 Anode electrode 8 Insulation material 9 Workpiece 10 Holder 11 Shutter 12 Gas introduction port 13 Vacuum exhaust system 14 Gate valve 15 Sputter power supply device

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Otani 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Ryuji Bilo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Hidehiro Kanazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (13)

[Claims] 1. A film forming method for forming an optical thin film on a substrate by a vacuum deposition method, wherein the substrate is being irradiated with neutral particles as an assist. 2. A film forming method for forming an optical thin film on a substrate by a vacuum deposition method, wherein the substrate is being irradiated with negative ions with the aid of negative ions. 3. A film forming method for forming an optical thin film on a substrate by a vacuum vapor deposition method, wherein the substrate being formed is irradiated with sputtered particles obtained by sputtering a metal or metal compound target as an assist. A film forming method characterized by the above-mentioned. 4. The method according to claim 1, wherein the optical thin film is a fluoride thin film. 5. The film forming method according to claim 3, wherein the target is a metal compound containing at least one of a metal fluoride and a metal oxide. 6. He, Ar, Ne, Sputter gas
6. The film forming method according to claim 3, wherein an inert gas containing at least one of Xe and Kr is used. 7. The film forming method according to claim 3, wherein a gas containing fluorine gas is used as the sputtering gas. 8. F ₂ as a sputtering gas, CF _4, NF
At least claims 3 to 7 film forming method according to any one is characterized by using a gas containing one of the of the _three. 9. The target material is Mg, La, Y,
Li, Nd, Ba, Sr, Na, Al, Ca, Ce, C
d, Ho, Y_Two O_Three , MgF_Two , LaF_Three , LiF, N
dF_Three , BaF_Two , SrF_Two , NaF, AlF_Three , Bi
F_Two , CaF _Two , PbF_Two , CeF_Three , GdF_Three , Ho
F_Three , Na_Three AlF₆ Must include at least one of the following:
The component according to any one of claims 3 to 8, characterized in that:
Membrane method. 10. The film forming method according to claim 1, wherein the substrate is not heated. 11. A vacuum chamber having vacuum evacuation means, vapor deposition particle generation means for heating and evaporating a film-forming material in the vacuum chamber to adhere to a substrate, and at least one of neutral particles and negative ions. A film forming apparatus having an assist generating means for irradiating the substrate as assist. 12. A vacuum chamber having a vacuum exhaust means, a vapor deposition particle generating means for heating and evaporating a film-forming material in the vacuum chamber to attach the film-forming material to a substrate, and assisting sputtering on the substrate during film formation. A film forming apparatus having a sputtered particle generating means for irradiating particles. 13. The film forming apparatus according to claim 12, wherein the sputtered particle generating means has a target containing at least one of a metal and fluorine, and a power supply means for applying a voltage to the target.