JPH01198480A - Formation of deposited film by microwave plasma cvd - Google Patents

Abstract

PURPOSE:To uniformly and stably form a high-quality and large-area functional deposited film with good reproducibility by allowing a hydrogen atom excited in a plasma producing chamber in a cavity resonator to chemically react with a gaseous raw compd. in a film forming space. CONSTITUTION:A bell jar 102 is provided in the cavity resonator 101 integrated with two impedance matching circuits in a microwave circuit, and gaseous hydrogen is excited by the plasma produced in the bell jar 102. The excitation state is measured through a condensing probe 122, and controlled. The excited hydrogen atom is passed through a metallic mesh 103, and introduced into the film forming space 116. The gasified raw material consisting of a silicon compd., a compd. expressed by the general formula AaBb [A is a group IV element other than silicon, B is H, X, and hydrocarbonic groups, (a) is an integer times the valence of B, and (b) is a positive integer], and, if necessary, a compd. contg. an element capable of electronically controlling the deposited film is activated in an activation space 114, and introduced into the space 116. The raw material is allowed to chemically react with the excited hydrogen atom, and a deposited film is formed on a substrate 118.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention relates to a functional film, particularly a semiconductor device, a photovoltaic element, a thin film semiconductor element, a line sensor for image input,
The present invention relates to a method for forming a semiconductor deposited film useful for applications such as imaging devices and electrophotographic photosensitive devices.

[Description of prior art]

Conventionally, functional films, especially semiconductor a-films, have been formed using appropriate film-forming methods in consideration of desired electrical and physical properties and various points of use.For example, plasma CVD method, reactive sputtering method, Ion blating method, photo CVD method,
Thermal CVD method, MOCVD method, MBE method, etc. have been tried, and some of these methods have been adopted as standard methods for forming semiconductor devices and have been commercialized. However, even with the most commonly used plasma CVD method, the electrical and physical properties of the deposited film obtained are not fully satisfactory for forming semiconductor devices, and the deposited film In some cases, the stability and reproducibility of the plasma during formation are also lacking, which is sometimes one of the factors that greatly reduces the production yield.

On the other hand, as a means to solve the above-mentioned problems, for example, Japanese Patent Laid-Open No. 61-97813 discloses the HR-CVD method (llydrogen radical as5ist).
In depositing and forming a high-quality group-III alloy semiconductor film using the edCVD method, a method has been disclosed to dramatically improve the productivity of film formation by increasing the film deposition rate. As a means of efficiently generating high-density plasma by using microwaves of about 100 mL, a method of arranging electromagnets around a cavity resonator and establishing ECR (electron cyclotron resonance) conditions was disclosed in Japanese Patent Laid-Open No. 55-1.
It was proposed in Japanese Patent Application No. 41729 and Japanese Patent Application Laid-Open No. 133636/1983, and it has been reported in academic societies that various semiconductor thin films can be formed using this high-density plasma, and this type of microwave has already been proposed. The reality is that plasma CVD apparatuses are now commercially available.

By the way, in the above-mentioned HR-CVD method, hydrogen atoms in an excited state (hydrogen radicals) play an important role in controlling the film properties and uniformity in the formation of a deposited film. Regarding the method of controlling the chemical reaction during the formation of the deposited film by controlling the excited state of hydrogen atoms in large quantities and uniformly during the formation of the deposited film, and controlling the properties of the deposited film arbitrarily and stably. Sufficient consideration has not been made and there is still room for improvement.

On the other hand, in microwave plasma CVD equipment using ECR, the pressure inside the plasma generation chamber must be maintained at approximately 10-3 Torr or less in order to satisfy the ECR conditions, and is therefore limited by the pressure during deposited film formation. In other words, under this level of pressure, the mean free path of gas molecules is long (
~1 m), the raw material gas for forming the deposited film diffuses to the vicinity of the microwave introduction window, decomposes and reacts, and the deposited film adheres to the microwave introduction window and the inner wall of the cavity resonator, making the discharge unstable and causing adhesion. The deposited film on the substrate is contaminated by scattering of the deposited film over 1) 4 m. Further, the plasma generated in the plasma generation chamber diverges into the film formation chamber along the divergent magnetic field of the disposed electromagnet, and the substrate is exposed to the plasma at a relatively high density. Therefore, the formed deposit is susceptible to damage by charged particles, etc. (there may be a limit to the improvement of film properties, and in the process of stacking deposited films as part of the process of forming semiconductor devices, Problems have been pointed out, such as deterioration of interface properties due to damage, making it impossible to improve the properties of semiconductor devices.

[Purpose of the invention]

The present invention overcomes the problems of conventional deposited film formation methods as described above, and reproduces functional deposited films over a large area with good uniformity and stability, which are effective for forming high-quality semiconductor devices. It is an object of the present invention to provide a method for forming a deposited film with good performance.

[Structure and effects of the invention]

The present inventors have conducted intensive research to solve the above-mentioned problems in conventional deposited film formation and to achieve the object of the present invention, and have found that two impedance matching circuits can be integrated into a microwave three-dimensional circuit. A plasma generation chamber was set up inside the hollow resonator, and microwave plasma discharge was performed using hydrogen gas or a gas mixture with hydrogen gas. As a result, hydrogen atoms in any excited state could be generated stably and efficiently with good reproducibility. We have learned that we can supply it.

The deposited film forming method of the present invention was completed as a result of further studies based on the above-mentioned knowledge, and its gist is that a deposited film is formed in a film forming space for forming a deposited film on a substrate. Compound (1) containing silicon as a raw material for film formation, a compound represented by the following general 2), and, if necessary, a compound containing as an element constituting an element capable of controlling valence electrons of the deposited film. (Introducing each of 31 in a gaseous state or in a state in which at least one compound among these compounds is activated in advance in an activation space provided separately from the film forming space, These gaseous or activated compounds (1), (2), and (3)
A deposited film in which hydrogen atoms in an excited state that chemically react with at least one of the above are generated in an activation space different from the film forming space and introduced into the film forming space to form a deposited film on the substrate. In the formation method, the excited hydrogen atoms are formed in a cavity resonator integrated with two impedance matching circuits in a three-dimensional microwave circuit using hydrogen gas or a mixed gas of hydrogen gas and a rare gas. The present invention relates to a method for forming a deposited film, which is generated using microwave plasma generated in a plasma generation chamber, and which is characterized by controlling the excited state of hydrogen atoms.

A a B b ・・・---TII (However, A
represents an element other than silicon among the elements belonging to Group Ⅰ of the periodic table; B represents an element selected from hydrogen (H), halogen (X), and a hydrocarbon group; a represents B; b is a positive integer that is equal to or an integral multiple of the valence of , and b is a positive integer.) The method for controlling the excited state of the hydrogen atom is to Some Hlx
, Hβ emission intensity, and in order to set the intensity ratio to a desired value, the microwave input power into the cavity resonator, impedance matching conditions, hydrogen gas flow rate or mixed flow rate ratio of hydrogen gas and rare gas, This is achieved by controlling one or more of the total pressures.

In addition, the impedance matching circuit in the cavity resonator integrated with two impedance matching circuits in the microwave three-dimensional circuit is the cavity length variable plunger and the aperture provided at the connection part between the microwave waveguide and the cavity resonator. By adjusting these, the impedance matching conditions are controlled.

The impedance matching circuit may be a variable cavity length plunger and an E-H tuner or a three-stub tuner.

Further, the plasma generation chamber is composed of a metal mesh and a microwave-transparent bell jar, and is connected to the film forming space via the metal mesh, and the excited hydrogen atoms are allowed to form the film through the metal mesh. introduced into the space.

On the other hand, the base body is 3
Compound fil, compound (2), and compound (3) are provided at an angle of 0@ or less and within 100 degrees from the surface of the metal mesh, and are in the gaseous or activated state.
) is introduced into the film forming space from a gas blowing means disposed between the metal mesh surface and the base.

The gas blowing means is disposed so as to surround the base in an annular manner, and the intervals between the gas blowing holes are gradually shortened from the gas introduction side to the final blowing inlet side of the gas blowing means, so that each gas blowing hole You can make the amount of gas blowing out from the hole uniform (or you can change the diameter of the gas blowing hole).
The amount of gas blown from each gas blowing hole is made uniform by increasing the gas gradually from the gas introduction side to the final blowing inlet side of the gas blowing means, or the gas blowing means The gas blowing holes are uniformly distributed, and the hole diameter of each gas blowing hole is gradually increased from the gas introduction side to the gas blowing means toward the center, so that the amount of gas blowing out from each gas blowing hole is made uniform. do.

According to the deposited film forming method of the present invention, when forming a deposited film with desired functionality, the above-mentioned = general bins (1) and (2) are introduced into the film forming space in a gaseous state or an activated state. Hosei
By introducing a compound (3) containing an element capable of controlling the valence electrons of the deposited film as a constituent as well as a hydrogen atom whose excited state is controlled separately from these, and causing a chemical reaction. A group Ⅰ alloy semiconductor thin film is formed on the substrate, and by appropriately controlling the excited state of hydrogen atoms, the crystallinity, hydrogen content, etc. of the group Ⅰ alloy semiconductor thin film can be controlled stably and with good reproducibility. can.

The excited state of atomic hydrogen in the present invention is determined from light emission observed in microwave plasma of hydrogen gas or a mixed gas of hydrogen gas and rare gas,
Specifically, the emission from microwave plasma was measured using optical emission spectrometry, and among the emission lines of atomic hydrogen (Ho), 656 Tsuru m attributed to Hct and 486 Tsuru m attributed to Hβ were detected. Focusing on the emission line, the excited state is determined based on the intensity ratio, and the microwave input power into the cavity resonator, impedance matching conditions, hydrogen gas flow rate, or hydrogen gas and rare gas ratio are adjusted to obtain the desired intensity ratio. One or more parameters of the mixing flow rate ratio and the total pressure are controlled.

In the present invention, to control the excited state of hydrogen atoms,
The intensity ratio of Hct/Hβ is preferably 1/1 to 1000/
It is preferable to control the ratio to IO/1 to 500/1.

In the above range of intensity ratios, especially the i! The combination of ilQ and substrate temperature is a factor that determines modification, etc., and by appropriately combining these, the desired Il! A deposited film of high quality and film properties is formed. Therefore, in the present invention, it is necessary to use an emission spectrophotometer having sensitivity capable of measuring the intensity ratio.

In the present invention, the monitoring position of the microwave plasma is for compounds (1), +21 and (
Since it is provided upstream of the gas blowing means in 3),
Substantially no deposition mucosa is formed, and stable monitoring can be performed from the start to the end of film formation.

Mistake in the above-mentioned -1 ro 1) used in the present invention +8) 7
The compound (2) and the compound (3) containing an element capable of controlling the valence electrons of the deposited film are those that have the above-mentioned excited state hydrogen atoms in the space where the substrate on which the film is formed exists. It is more desirable to select a species that spontaneously generates chemical species that cause molecular collisions to cause chemical reactions and contribute to the formation of the deposited film formed on the substrate. , if the hydrogen atom in the excited state is inert or does not have much activity, in compounds (1), +21 and (3),
Among these compounds (21), excitation energy strong enough to not completely dissociate Si and A in the above general formula is applied before or during film formation to form compounds (1) and (2) with hydrogen in an excited state. It is necessary to bring the compound into an excited state where it can chemically react with atoms, and it is necessary to bring the compound into such an excited state.
1 of compounds (1) and (2) used in the method of the present invention
It is adopted as a species.

In the present invention, the compounds that can be effectively used as the compound (1) and the compound (2) to be distributed on every day of the month include the following.

That is, when obtaining a deposited film based on an alloy of group Ⅰ of the periodic table having semiconducting properties according to the present invention, specifically, as the silicon-containing compound (1), for example, some of the hydrogen atoms of a chain or cyclic silane compound or A compound in which all halogen atoms are substituted is used, specifically, for example, SiuYg, (u is 1
or greater, Y is F.

Cf, Br or ■. ) Chain silicon halide represented by 5ivYiv (V is an integer of 3 or more, Y has the above meaning), cyclic silicon halide represented by S
Examples include chain or cyclic compounds represented by i w HX Y y (u and Y have the above-mentioned meanings; x+y=2u or 2u+2).

Specifically, for example, 5iHa, 5iFa + (SiF
t)S.

(SiFz)h, (SiFt)a, SigFi
, 5i3Fs.

5iHFz, 5iHzFz +5itH*Fn +5
itH*Fn 1SiCj! 4(SiCj!z)s,
SiB ra , (SiB rt)s 1SizCIl
b +5iHC/3 lS+HBrz+5iHzC1x
.

Examples include those in a gaseous state or those that can be easily gasified, such as S:zCllsFs.

Further, rAJ of compound (2) is an element belonging to Group Ⅰ of the periodic table, specifically, Ge, C, and Su.

Examples include pb. As a compound (2) containing these elements, as a compound containing germanium, GeuYz
u*t (u is an integer greater than or equal to 1, Y is H, F, (1°Br
as well as! At least one element selected from )
Chain germane or germanium halide represented by GewYzv (v is an integer of 3 or more, Y has the meaning described above), cyclic germane or germanium halide, Ce, HxYy (U is an integer of 1 or more, Y
are F, C1, Br and! At least one element selected from the above, a chain or cyclic germanium compound represented by x+y=2u or 2u+2), and an organic germanium compound having an alkyl group, specifically GeHa.

Ge@Hh + Ges Ha + n Gea H
1) 1+ t Gea H1) 1) GeHh , Ge
5H+o, Gf3HzF, GeH:+C1゜GeH*F
1, Ge(CH3)4. Ge(CxHs)n.

Ge(CiHs)4. Ge(CHs)gFz', GeF
x.

Examples include GeFa, GeS, and the like.

Further, as a compound containing carbon, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used, such as CuYz-
Chain halide carbon represented by t (u is an integer of 1 or more, Y is at least one element selected from H, F, CA!, Br, and ■), CH4 + CzHh +C
3HI, I'1-CaH+o.

C%Hat, CtHa, C5Hs, CaHs, C
sH+. .

CaHs, CaHs, C4H6 and CvYzv(
V is an integer of 3 or more, and Y has the meaning described above. ), a chain or cyclic carbon represented by CuHxYy (u is an integer of 1 or more, Y is at least one element selected from F, CI, Br and I, x+y=2u or 2u+2) Compound CFa, (C
Fx)s, (CFz)h, (CFI)4.

CIF&, CaHs, CHF5, CHgF*,
CC1a.

(CC12)s, CBr, (cBrt)s,c,
cj,.

Examples include Cz, C1s, Fx, etc.

Furthermore, compounds containing tin include 5nHa,
5nC1a, SnBr4.5n(CHa).

5n(CtHs)4+ 5n(CsHt)a, 5n
(C4HJs +5n(OCHs>a, 5n(OC
xHs)4゜Sn(i 0 C3H?)4 +
Examples include Sn(tOC4H9)4.

And, as a compound containing lead, Pb(CHs).

Examples include Pb(C2H5)4, Pb(C,H9), and the like.

For compounds +1) and (2), one kind or two or more kinds of the above raw materials may be used as necessary.

In the method of the present invention, the compound (3) containing a component serving as a valence electron control agent is in a male state at normal temperature and normal pressure, or is in a gaseous state at least under deposited film forming conditions, and may be suitably Preferably, a compound is selected that can be easily vaporized in a vaporizer.

As the compound (3) used in the method of the present invention, when obtaining a deposited film based on an alloy of group Ⅰ of the periodic table, compounds containing elements of groups ① and ② of the periodic table are effective. can be mentioned. Specifically, compounds containing group ■ include:
BXs, BzHh, B-H+. .

BsH9・Bs H+ +・B island H+o・B(
CH3)3・B(CzHs)s, BiH+x, AlX
5.

A It (CHs)zcl, A I (CH3
)! .

AI (OCHs) a, An (CHs) Cj! T.

A It (CsHsh, A I (OCtHs)a
.

A I (CH3)3Cis, A 1 (i C
4H*)s.

8l (i −CxHJ:+, A It (Ctl
lt)i.

All(OC4H9)2, GaX1, G
a(OC1ft)z.

Ga(OCzHs)x, Ga(OCi+1v)i
.

Ga(OC4H9)! , Ga(CHz)z
, Gag Summer 1. .

GaH(CzHs)z, Ga(OCzHs)(CzH
s)z.

In(CHs>3. In(CsHt)s, In(
CaHJi, NH as a compound containing group V elements,
)iN! .

N*HsNs, N! H4, NHaNs, PXs.

P(OCHs)s, P(OCzHs)i, P(C3
HJ3.

P(OC4HJ*, P(CHs)3.P(CgHs)
s.

P(C-Hy)s, P(CaHJs, P(OCHs)
)s.

P (OCxHs)s, P (OC1HJx, P
(OGaH9)s.

P(SCN)3, PzH4, PHs, ASH3.

AsXt, As(OCH3)! , ASCOCt
HJs.

As(OCzHt)s, As(OC4H9)31 A
s(CH3)! .

As(CH3):+, As(CzHs)*, As(
CaHs)x.

5bXs, 5b(OCHz)x, 5b(OCzHs
)x.

5b(OC1Ht)x, 5b(OC-1)Jz,
5b(C1)ri x.

Examples include 5b(CiHt)z, 5h(C,1), )j, and the like.

In the above, X is halogen (F, Cj!, Br.

1) is shown.

Of course, one type of these raw materials may be used, but two or more types may be used in combination.

When the above-mentioned raw material is in a gas state at room temperature and pressure, the amount of people entering the film forming space or activation space is controlled by a mass flow controller, etc., and when it is in a liquid state, rare gases such as Ar and He are used. Gas or hydrogen gas is used as a carrier gas, and if necessary, it is gasified using a bubbler that can control the temperature.If it is in a solid state, it is heated in a sublimation furnace using a rare gas such as Ar or He or hydrogen gas as a carrier gas. The amount of gas introduced is controlled mainly by controlling the carrier gas flow rate and temperature.

The excited hydrogen atoms used in the present invention are simultaneously introduced into the film forming space when forming a deposited film in the film forming space, and are added to the compound containing the constituent elements that will be the main constituents of the deposited film to be formed. 1) 1 and (2) or/and the compound (1
) or/and chemically interacts with the excited state of compound (2). As a result, a deposited film based on a Group I alloy of the periodic table having desired functionality can be easily formed on a desired substrate at a lower substrate temperature than in the past.

In order to activate the compounds (l), (2), and (3) in advance in an activation space provided separately from the film-forming space, the energy applied to the activation space includes heat, light, Examples include activation energy such as electrical discharge.

Specifically, thermal energy such as resistance heating and infrared heating, optical energy such as laser light, mercury lamp light, and halogen lamp light, microwave, and RF.

These activation energies may be applied singly or in combination of two or more types in the activation space. In order to effectively utilize the action of activation energy, the action of a catalyst may be used simultaneously.

In the present invention, hydrogen gas or a mixed gas of hydrogen gas and a rare gas is used to generate excited hydrogen atoms. When microwave plasma is not stabilized or plasma is not generated with hydrogen gas alone, it is effective to mix a rare gas as appropriate.

The rare gases used in the present invention include +1a, N
o, 8r, I(rhXc, Rn are mentioned as preferred.

Next, a microwave plasma generation method having a cavity resonator structure integrated with two impedance matching circuits in the microwave three-dimensional circuit used in the present invention will be described.

First, for comparison, a conventional microwave plasma generation method will be described. FIG. 7 shows a schematic cross-sectional view of the device configuration.

In FIG. 7, 701 is a rectangular thin wave tube, 702 is a microwave four-person window, 703 is a plasma generation chamber, 704 is a film forming chamber, 705 and 710 are gas supply pipes, 70G is an exhaust port, and 70
Reference numeral 7 indicates an object to be processed, 708 a holder for the object to be processed, and 709 a metal mesh.

As shown in FIG. 7, the apparatus consists of a plasma generation chamber 703 using microphone n-waves and a film forming chamber 704 using plasma.
The chamber 704 is separated from the chamber 704 by a metal mensure 09, and their i3 passage is restricted so that microwaves and charged particles do not directly enter the film forming chamber 704. The plasma generation chamber 3 has a cavity resonator structure, and the microwave propagated through the rectangular waveguide 1 is made of quartz (SiOm), alumina, etc.
The microwave is introduced into a plasma generation chamber 703 through a microwave introduction window 702 made of a dielectric material such as ceramics (Al, Os) or Teflon. A processing object 707 is arranged in the film forming chamber 704, and a gas supply pipe 705 and
An exhaust lower OG for exhausting the plasma generation chamber 703 and the film formation chamber 704 is provided.

When the microwave plasma generation device having the above configuration is operated, microwaves are introduced into the plasma generation chamber 703 from the rectangular waveguide 701, and the hydrogen gas etc. introduced from the gas Hirojin 0710 are absorbed by the electric field energy of the microwaves. It turns into plasma and generates many excited hydrogen atoms. Excited hydrogen atoms are introduced into the film forming chamber 704 through the metal meshure 09, collide with the gas supplied from the gas introduction pipe 705 to cause a chemical reaction, and form a deposited film on the object to be processed 707. It can be performed.

However, when using the conventional microwave plasma generation device with the above configuration, when the rectangular waveguide 701 and the plasma generation chamber 703, which is a cavity resonator, are connected, the input impedances do not match. The problem is that most of the energy is reflected and the energy is not used effectively.

As one solution to this problem, a method has been adopted in which electromagnets are placed around the cavity resonator to create ECR (Electron Cyclotron Resonance) (Japanese Unexamined Patent Publication No. 55-141729). The method requires a magnetic flux density of 875 Gauss, which makes the device quite large and heavy.Also, since it is usually designed as a cavity resonator in a vacuum, the plasma is generated by the discharge. When a plasma is generated, the refractive index of the plasma becomes smaller than 1, so there is a problem that it is no longer a cavity resonator.
Chapter P, 298), furthermore, when creating a static magnetic field with an electromagnet,
As the current changes due to the heating of the coil wire, it not only takes a considerable amount of time to suppress the change and create a stable ECR condition (that is, a magnetic flux density of 875 Gauss), but also during that time, the ECR condition changes. If it deviates, the microwave absorption rate decreases, and there is also the problem that it is difficult to increase the efficiency of electric field energy use until it stabilizes.

Therefore, in the present invention, as a means to solve the above-mentioned problems, the structure is such that it can operate as a cavity resonator regardless of the presence or absence of plasma or the plasma density, and a bell jar serving as a plasma generation chamber is provided in the cavity resonator. It has been found that it is effective to excite the 7M mode by arranging a 7M mode.

Specifically, in the cavity resonator structure, a cavity length variable plunger is provided, and the rectangular waveguide and the cylindrical cavity resonator are fastened so that their axes are perpendicular to each other, as shown in Figure 1. Furthermore, when performing impedance matching, in combination with the variable cavity length plunger, a diaphragm provided at the connection between the rectangular waveguide and the cavity resonator, or an E
It is preferable to employ either one of a -H tuner or a three-stub tuner.

The bell jar for plasma generation disposed inside the cavity resonator is made of a material that is microwave transparent but capable of maintaining airtightness, such as quartz (Sins), alumina ceramics (A 1 *Ox ), and nitride. Boron (BN), silicon nitride (SisN4), silicon carbide (SiC), beryllia (Boo), magnesia (MgO), zirconia (
It is formed of so-called new ceramics such as ZrO, ).

The variable cavity length plunger is provided on the microwave introduction side, that is, on the atmosphere side with respect to the bell jar. Therefore,
Since impedance matching can be performed by changing the cavity length in the atmosphere, the cavity length can be easily adjusted in response to changes in cavity resonance conditions due to changes in the presence or absence of plasma or changes in plasma density, etc., and stable microwave operation with good reproducibility. Plasma can be generated.

In the present invention, the metal mesh provided between the bell jar and the film-forming space has the role of an end plate for establishing cavity resonance conditions, so the mesh diameter is determined by the internal wavelength of the microwave used ( λ) preferably λ/2
Hereinafter, the optimum value is preferably λ/4 or less.

Examples of the shape of the metal mesh include a wire mesh shape, a thin metal plate shape with round or polygonal holes, etc., and its constituent materials include A1. Fe, Ni.

It may be composed of a so-called single metal such as Ti, Me, W, Pt, Au, Ag, or stainless steel, or it may be a composite of glass, ceramics, or metal that has been surface-treated with the metals mentioned above by plating, sputtering, vapor deposition, etc. It may be.

Furthermore, it is preferable that the hole diameter and distribution of the metal mesh be changed in order to efficiently and uniformly introduce the excited hydrogen atoms generated in the bell jar into the film forming space. In this case, the total aperture ratio is preferably It is desirable that it be 10% or more, more preferably 20% or more, and optimally 30% or more.

In order to ensure uniformity of the film thickness and film properties of the deposited film formed on the substrate in the present invention, the distance from the metal mesh on which the substrate is disposed and the angle of the metal mesh with respect to the horizontal axis were studied. However, we obtained the results described below.

Figure 3 shows two typical examples of the relationship between the distance between the substrate and the metal mesh and the deposition rate of the formed deposited film. The curves obtained by connecting the film forming conditions (A) and (B) shown in Table 1
) was obtained.

Further, FIG. 4 shows that under the film forming condition (B), the distance between the substrate and the metal mesh is 30 m (curve wAC).

The film thickness distribution of the deposited film deposited on the substrate is expressed as the difference in deposition rate when the angle between the substrate and the metal mesh is changed in the case of 70 mm (curve d, △ mark) It is.

As can be seen from Fig. 3, as the distance between the substrate and the metal mesh increases, the degree of deposited film tends to decrease rapidly, but especially under film forming condition (A), when the degree of deposited film exceeds 100, the degree of deposited film decreases rapidly. The formation of
Also in B), the film properties of the deposited film formed over 100 fi were poor and unworthy of practical use. Also, the fourth
The figure shows that at any substrate position, the film thickness distribution increases rapidly when the angle between the substrate and the metal mesh exceeds 30°, and in correlation with this, the distribution of film properties also increases, resulting in uniformity. was found to be significantly reduced.

Table 1 *) Compound (2B was used after being diluted to 10% with He gas.

The same study as described above was carried out under several conditions when forming other Group Ⅰ alloy semi-exclusive thin films, and almost the same results were obtained in all cases.

Therefore, in the present invention, the distance between the base and the metal mesh is preferably 100 cm or less, more preferably 70 cm -
The angle between the substrate and the horizontal axis of the metal mesh is preferably set within 30 degrees, more preferably within 20 degrees, to increase the uniformity of the film thickness distribution and film properties by ±5%.
This has been set as a necessary condition for payment within the specified period.

Furthermore, in order to improve the uniformity of film thickness distribution and film properties, in the present invention, gas blowing means for compounds (1) and (2), and if necessary, compound (3), was investigated.

The pressure region preferably used in the present invention is an intermediate flow region located between viscous flow and molecular flow in fluid engineering, and conductance calculation formulas in the molecular flow region cannot be used. We focused on the hole diameter, spacing, and distribution of the gas blowing holes provided in the gas blowing means, and conducted the experiments described below.
The results shown in the figure were obtained.

In FIG. 5, under the film forming conditions (A) shown in Table 1, the substrate position is set at 30, and the deposited film is formed using the gas blowing ring 201 shown in FIG. 2 (al). The results obtained are shown in Figure 2(a).

The gas blowing ring 201 has 201a to 20
1d, 201a' to 201d' are opened at equal intervals, starting from the closest outlet holes 201a, 201a' in the direction of the arrow (→) in the figure to 201d, 201d' toward the downstream side. The diameter was gradually increased. FIG. 5 shows changes in the film thickness distribution of the deposited film formed using each of the gas blowing rings manufactured by changing the increase rate of the hole diameter from 0 to 80%.

As can be seen from this result, the film thickness distribution is improved when the hole diameter increase rate is 0 to 40%, but when it exceeds 40%, the film thickness distribution becomes larger, and when the hole diameter increase rate is 60% or more, the film thickness distribution is improved. It was observed that the film thickness distribution was further increased than in the case of the same hole diameter (hole diameter increase rate of 0%).

Membrane properties showed a correlation with the distribution of membrane thickness.

This tendency was almost the same under other film forming conditions.

Therefore, in the present invention, the hole diameter increase rate is preferably 0.
It is desirable to set it to 50%, more preferably 20 to 40%.

Next, Fig. 6 shows the film formation conditions similar to those described above.
The results are shown when using the gas blowing ring 202 shown in FIG.

20 in the gas blowing ring 202 (Fig. 2)
Eight air outlet holes 2a to 202d and 202a to 202d' having the same diameter are air outlet holes 202a and 202a'.
Figure 6 shows the changes in the film thickness distribution of the deposited film formed using each of the gas blowing rings manufactured by changing the reduction rate from 0 to 70%. It was shown to.

From this result, the film thickness distribution is improved when the hole spacing reduction rate is about 0 to 40%, but when it exceeds 40%, the film thickness distribution becomes larger, and when the hole spacing decrease rate is 50% or more, the film thickness distribution is improved. It was observed that the film thickness distribution was further increased than in the case of the spacing (hole spacing reduction rate of 0%).

Membrane properties showed a correlation with the distribution of membrane thickness.

This tendency was almost the same under other film forming conditions. Therefore, in the present invention, the hole spacing reduction rate is preferably 0 to 50%, more preferably 20 to 40%. is desirable.

Furthermore, using the gas blowing ring 203 shown in FIG. 2 (C1), an experiment similar to the experiment to obtain the relationship shown in FIG. 6 was conducted.The gas blowing ring 203 shown in FIG.
The blow holes 203a to 203d are uniformly distributed, and the hole diameter increases in the direction of 203a to 203d. The tendency of change in film properties is almost the same as the 6th one.
The results were the same as shown in the figure.

Therefore, in the present invention, when the gas blowing holes have a distribution as shown in FIG. desirable.

In the present invention, the conditions under which microwave plasma of hydrogen gas or a mixed gas of hydrogen gas and rare gas is stably generated, and the selected types and conditions of compounds (1), (2) and (3) , and the internal pressure of the film forming space during film formation is appropriately determined based on the desired characteristics of the deposited film, etc., but is preferably 100 to I x 10-'Torr, more preferably 10 to 5 x 10-'Torr, Optimally 1-I
It is desirable to set the value to X 10-”Torr.

According to the method of the present invention, a deposited film having desired crystallinity can be formed on any crystalline substrate, regardless of whether it is amorphous or crystalline.

In the present invention, in order to stably establish cavity resonance conditions, the oscillation mode in the microwave oscillator is continuous oscillation,
Preferably, the ripple width is 30 in the used output range.
It is desirable that it be within %.

According to the method of the present invention, hydrogen atoms in an excited state.

Microwave plasma using a cavity resonator integrated with two impedance matching circuits in a three-dimensional microwave circuit can generate stable and reproducible plasma with good tHII performance.
The controllability of the reaction between the excited hydrogen atoms and the raw material compound for forming the deposited film is significantly improved.

Also, it has properties such as desired crystallinity and hydrogen content.
Group alloy semiconductors can be formed with good uniformity, high efficiency, and good reproducibility.

A typical example of a deposited film forming apparatus suitable for carrying out the present invention will be described below, but the present invention is not limited to this deposited film forming apparatus.

FIG. 1 is a schematic perspective view of a deposited film forming apparatus suitable for carrying out the present invention.

In FIG. 1, 101 is a cylindrical cavity resonator, which mainly includes a bell jar 102 serving as a microwave plasma generation chamber, a metal mesh 103, a variable cavity length plunger 104, a rectangular waveguide 108, and an aperture 1)0. It is constructed as a component. 105 is a plunger 10 with a phosphor bronze spring.
2 and the cylindrical cavity resonator 101, to prevent abnormal discharge. The variable cavity length plunger 104 can be moved toward the bell jar 102 by a motor 106 and transmission gear LOT. 109 is an E-H tuner or a three-stub tuner, which constitutes one of the impedance matching circuits constituting the microwave three-dimensional circuit in the present invention, and a variable cavity length plunger which is one of the other impedance matching circuits. A pair with 102 is used for impedance matching.

The aperture 1)0 is also one of the impedance matching circuits and is used in pair with the variable cavity length plunger 102.

Aperture 1) 0 is a rectangular waveguide 108 and a cylindrical cavity resonator 10
A pair of left and right are provided at the connection part with 1, and each can be slid independently along the cylindrical surface in the longitudinal direction of the rectangular waveguide 108, and a cylindrical cavity resonance is generated by a phosphor bronze spring (not shown). Contact with the container 101 is maintained.

The blowout hole for hydrogen gas or a mixed gas of hydrogen gas and rare gas from the gas introduction pipe 1) 1 is directed into the bell jar 102 through a metal mesh, and the hydrogen gas etc. introduced into the bell jar 102 is directed into the bell jar 102 through the metal mesh. The microwaves input into the resonator 101 turn the plasma into plasma, producing excited hydrogen atoms and the like, which are introduced into the film forming space 1) 6 through the metal mesh 103. The pressure inside the film forming space is measured by a pressure gauge 12.
5.

In the film forming space 1) 6, the raw material gas blowing ring 1) 2 for forming the deposited film is connected to the substrate 1) 8 and the substrate holder 1) 9.
is placed between.

1) 4 is an activation space used to pre-activate the raw material gas for deposited film formation supplied by the gas supply vibrator 120 as needed, and the surrounding area is surrounded by activation space such as heat, light, electric discharge, etc. energy generating means 1) 5 is provided.

If the transport pipe 1) 7 is to introduce the deposited film raw material gas after being activated in advance, it is desirable that the transport pipe 1) is configured with a diameter and a material that can maintain the activated state.

The gas blowing ring 1)2 is provided with gas blowing holes 1)3 having the configuration described in FIG. 2.

The raw material gas for forming a deposited film, etc. placed in the success/failure space 1) 6 by four people is exhausted by an exhaust pump (not shown) in the direction of the arrow in the figure.

! 21 is a port provided for a microwave plasma monitor, to which a light collecting probe 122 is connected.

A quartz fiber 123 is connected to the light collecting probe 122, which is further connected to a spectrometer (not shown) to perform emission spectroscopic analysis. 124 is a spare port for plasma monitoring on the film forming space side.

【Example〕

The deposited film forming method of the present invention will be described below with reference to specific examples.

Note that the present invention is not limited to this example.

First, place the Corning #70S9 glass substrate 1)B with a diameter of 15G into the substrate holder 1).B in the film forming space 1)6. 9, and was evacuated by an exhaust pump (not shown), and the pressure inside the film forming cavity 1) 6 was set to IXN) Torr. Further, the substrate holder was heated by a substrate temperature controller (not shown), and the surface temperature of substrate 1)B was set to 230°C.

When the substrate surface temperature stabilizes, 20 sccm+ of H gas and 200 sccm of Ar gas are supplied from a gas cylinder (not shown).
A mixed state of tm is introduced into the quartz bell jar 102 through the gas introduction pipe 1), and the pressure in the film forming space 1) 6 is reduced to 0.
．． The pressure was controlled to 2 Torr by an automatic pressure controller (not shown).

Next, microwaves are transmitted to the cavity resonator 101 via the rectangular waveguide 108 from a continuous wave microwave oscillator (not shown).
I put it inside. Immediately, the variable cavity length plunger 10
4 is operated by a motor 106 and a transmission gear 107, and is adjusted to a position where the ratio of reflected power/incident power measured by a power monitor installed in a microwave three-dimensional circuit (not shown) is the smallest. 1) The opening degree of 0 was adjusted to the position where the ratio of reflected power/incident power is the smallest. The operation of finely adjusting the position of the variable cavity length plunger 104 and the opening degree of the aperture 1)0 is repeated again, and the value of the effective incident power expressed by the ratio of reflected power/incident power is the smallest and is expressed by incident power - reflected power is obtained. was adjusted so that it was 350W.

At this point, the intensity ratio of the emission line Ha/Hβ from the hydrogen atoms in the device state consisting of port 121 is 20
It was 0.

Substrate 1) The distance between B and the combined pressure mesh 103 is set to 40 types,
They were set parallel to each other. For the fully bent mesh 103, a punching board made of Al and having aperture ratio of 50% was used, in which holes of all diameters φ150 and φ8 were uniformly distributed. The gas blowing ring 1) 2 has the configuration shown in FIG. 2 (al), and includes 201a,
The hole diameter corresponding to 201a' was 1.5fi, and the hole diameter increase rate was 30%.

Next, add 10 5i2F4 gas from a gas cylinder (not shown).
scc+a, , G diluted to 10% with He gas
e F a gas is flowed for 10 sec++ to mix each gas, and the gas is passed through the gas supply pipe 120 to the gas blowing ring 1).
Four people went to the film forming space 1)6 from 2. At this time, the pressure inside the film forming space 1) 6 was controlled to be maintained at 0.2 Torr by an automatic pressure controller.

Immediately, a chemical reaction occurs between the hydrogen atoms in the excited state and S; zF, and GcFa, and 7.5
A film with a thickness of μm was formed. The substrate was cooled and taken out 1) (designated INul-1).

Next, insert another well 7059 board and increase the gas flow rate to 2.
Qsccm, and the pressure in the film forming space was 0.05 Torr.

The deposited film was formed using the same monolithic method except that the substrate temperature was set at 270°C. The intensity ratio of II tt /Hβ at this time was 120. After 60 minutes of deposition, the substrate was taken out and designated as sample 1kl-2.

Furthermore, using a 6-inch n+5i(1)0) wafer as the substrate, the Hmin gas flow rate was 100 sec, and the Ar gas flow rate was 5 sec.
The deposited film was formed using the same T5 cycle except that the pressure in the film forming space was 0.01 Torr, and the aperture ratio of the punching board was 30%.

The intensity ratio of H,/liβ at this time was 40.

The obtained sample was designated as 1lhl-3. The film thickness distribution of each of the obtained deposited film samples was measured, and the crystals of the deposited film were evaluated by X-ray diffraction and electron beam diffraction (RHEED). Each sample has good uniformity; sample 1-1 is amorphous IIQ, Nnl-2 is polycrystalline, and I! 1) For -3, the plane parallel to the substrate is (+1
It was confirmed that the epitaxial film had an orientation close to 0).

In addition, a portion of each sample was cut out and assembled using SIMS.

A compositional analysis was performed. H content is sample Na1-1, sample 1)
It decreases in the order of m1-2 and sample Na1-3.

Each sample was placed in a vacuum evaporator, and an aluminum φ2 crane dot electrode was deposited using a resistance heating method, and the hole mobility (μm) was measured using the van der Pauw method. The characteristic distribution is shown in Table 2, with results of 0 or more drawn at approximately ±3% over the entire surface of the sample.

From the results shown in Table 2 and above, it was found that the crystallinity of the deposited film could be easily controlled by the present invention.

Jashengou I - Using the same operation as in Example 1, Si was prepared under the following conditions:
A Ge:H:F film was formed. Sample N1) in Example 1 except that the flow rate of GeFa gas was reduced to 55 cca+.
Success and failure were conducted under the same conditions as those for creating -1. The obtained sample was designated as N12-1. Next, film formation was performed three times in the same manner as described above, except that the GeF gas flow rate was 7sccs+s, 12sccemm, 15scc-, and the resulting sample was -2, ll&L2-3,
It was set as magnetic 2-4.

The film thickness distribution of each of the obtained deposited film samples was measured, and the crystallinity of the deposited film was evaluated by X-ray diffraction and electron beam diffraction (RHB ED). Each sample has good uniformity and is an amorphous film! It has been certified.
'Additionally, a portion of each sample was cut out and subjected to compositional analysis using sIMs to determine the composition ratio of Si and Ge.Furthermore, the optical absorption spectrum of each sample was measured using a visible spectrometer to determine the optical band gap. Furthermore, each sample was placed in a vacuum evaporator, a comb-shaped aluminum gap electrode (gear tooth width 250 μm, 1 mm width 5' am) was deposited, the dark conductivity was measured with an applied voltage of 10 V, and then an AM-1 light (100
mW/d), the photoconductivity was measured, and the ratio of dark conductivity to photoconductivity was determined. Each characteristic is about 1 in the plane
Table 3 shows the results of 0 or more that were within the range of 35. From this result, by changing the gas flow rate, Si and G
It has been found that it is possible to arbitrarily change the composition ratio of e, and also to control the optical band gap, forming a deposited film having desired characteristics.

From the above results, it was found that the optical film quality of the deposited film can be easily controlled by the present invention.

Table 3 Example 3 In the same operation as in Example 1, tl, gas 50 sec
.

The microwave input power was 300 W, and the Si:C:H:F film was formed under the conditions described below.

The substrate is a #7059 glass substrate with a diameter of 150 mm.
F, gas 20SCCI1% CHa gas 4 people were placed in the deposition space at a flow rate of 1Qsccm, and the pressure inside the deposition space was 0.2T.
orr and the substrate temperature was set at 260°C. Film formation was performed for 60 minutes using the same gas blow ring, metal mesh, and substrate positions as in Example 1.

Next, B F s gas diluted to 10% with He gas was added to I
The film was formed in the same manner as described above except that Qsccm was added. The ratios of H and /Hβ during film formation were both 180. The obtained samples were designated as 1lh3-1 and -3-2.

Next, set the H2 gas to 100sccta and the internal pressure to 0.03T.
The film was formed in the same manner as Sample No. 3-2 except that the sample No. 3-3 was obtained.

The obtained sample was evaluated for crystallinity and II content (2) in the same manner as in Example 1, and further thermoelectromotive force was measured to determine the conductivity type. Separately, a portion of each sample was cut out, placed in a vacuum evaporator, and a comb-shaped aluminum gap electrode (250 mm in the gap) was cut out.
pm, width 5 cm), measure the dark conductivity with an applied voltage of 10 V, then irradiate AM-1 light (100 mW/cd) to measure the photoconductivity, and calculate the ratio of the dark conductivity to the photoconductivity. I asked for it.

Each characteristic was within a range of about 135 in the plane. The results obtained are shown in Table 4.

From the above results, it was found that according to the present invention, the conductivity type of the deposited film can be easily controlled, and the electrical characteristics can also be controlled.

Table 4 In Example 1, the microwave input power was changed from 350W to 200W, and the activation space 1)4 composed of the quartz tube provided on the gas supply pipe 120 was 700℃ by infrared heating furnace 1)5 as a generating means
A deposited film was formed using the same procedure except that the heating was performed at .

In the first film formation, the substrate was 97059 glass, H,
A sample of the deposited film obtained by forming a film at a gas flow rate of 100 sec and an internal pressure of 0.05 Torr was used as a 6-inch n+s i (1) 0) wafer as a 0-order substrate with a H8 gas flow rate of 20 sccrmm. A second film was formed with the pressure in the film forming space set to 0.01 Torr, and the resulting deposited film sample was designated as 1lh4-2.

When these samples were evaluated in the same manner as in Example 1, there was no decrease in the deposition rate despite the reduction in the microwave input power, and the properties were as shown in Table 5 (Example 1). Almost the same thing as that obtained was obtained.

Table 5 A deposited film was formed using the same operations and film forming conditions as in Example 1, except that some of the raw material compounds for forming the deposited film and the film forming conditions were replaced with those shown in Table 6.

When the obtained sample was evaluated in the same manner as in Example 3, the results shown in Table 7 were obtained.

Table 6 Table 7 Table blade 1) (+I + moxibustion example! 1) Z gas 5Qsccm
A Si:C:H:F film was formed under the following conditions using a microwave input power of 200 W.

SiF as the first raw material gas, gas 20 sec, Si
Using a mixed gas of 55 ccpa of H4 gas and CF as the second raw material gas, the gas is 103 CC! The film was introduced into the film forming space at a flow rate of 1, the pressure inside the film forming space was set at 0.03 Torr, and the substrate temperature was set at 200°C. The aperture ratio of the metal mesh is 3
The gas blowing ring and the substrate position were the same as in Example 1. Both ratios of H#x/Hβ during film formation were 100. The obtained samples were designated as Na6-1 and Na6-2.

When the obtained sample was evaluated in the same manner as in Example 3, the results shown in Table 8 were obtained.

Each characteristic had variations within a range of approximately ±3% within the plane.

Table 8 (Summary of Effects of the Invention) As understood from the above detailed description and examples,
According to the deposited film forming method of the present invention, the film characteristics and film formation rate of the Group 1 alloy semiconductor thin film formed are significantly improved, and the thin film with the desired film quality is stable, reproducible, and efficient. It can be formed with good uniformity, and it is easy to improve productivity and mass production of thin films.

Furthermore, the substrate temperature required to form the deposited film can be lowered than in conventional deposited film formation methods, and this does not adversely affect the film properties. Further, by controlling the excited state of hydrogen atoms, the amount of introduced raw material compounds, etc., film quality can be easily controlled stably and with good reproducibility.

[Brief explanation of the drawing]

FIG. 1 is a schematic perspective view of a deposited film forming apparatus suitable for carrying out the present invention, and FIG.
) is a schematic diagram of a gas blowing ring used in the present invention. Furthermore, FIG. 3 is a diagram showing the relationship between the deposition rate and the distance between the substrate and metal mesh obtained in the present invention, and FIG. 4 is a graph showing the relationship between the substrate and metal mesh obtained in the present invention. FIG. 3 is a diagram showing the relationship between the in-plane deposition rate difference and the angle with respect to the angle. FIG. 5 is a diagram showing the relationship between the in-plane film thickness distribution and the hole diameter increase rate of the gas blowing ring used in the present invention, and FIG.
FIG. 3 is a diagram showing the relationship between the in-plane film thickness distribution and the hole interval reduction rate of the gas blowing ring used in the present invention. FIG. 7 is a schematic sectional view of a conventional microwave plasma CVD apparatus. Regarding FIG. 1, 101...Cylindrical cavity resonator, 10
2...Bell jar, 103...Metal mensch, 10
4... variable cavity length plunger, 105... spring,
106...Motor, 107...Speed gear, 10B
...Rectangular waveguide, 109...E-H tuner, 1
) 0... Throttle, 1) 1... Gas introduction pipe, 1) 2...
・Gas blow ring, 1) 3... gas blow hole,
1) 4... Activation space, 1) 5... Activation energy generation means, 1) 6... Film forming space, 1) 7... Transport pipe, 1) 8... Substrate, 1 )9... Board holder, 1
20... Gas supply pipe, 121... Port, 12
2... Light collecting probe, 123... Quartz fiber, 124... Spare boat. Regarding FIG. 2, 201, 202. 203... gas blowing ring, 201 a to 201 d, 201 a
'~201d', 202a~202d, 202a'~
202d', 203a to 203d... Gas blowout holes. Regarding FIG. 7, 701... rectangular waveguide, 702...
・Microwave introduction window, 703...Plasma generation chamber, 7
04... Film forming chamber, 705.710... Gas supply pipe,
706...Exhaust port, 707...Object to be processed, 708...
... Processed object holder, 709... Metal mesh.

Claims (10)

[Claims] (1) A compound (1) containing silicon, which is a raw material for forming a deposited film, and a compound (2) represented by the following general formula (I) are placed in a film forming space for forming a deposited film on a substrate. , if necessary, each of the compounds (3) containing as an element constituting an element capable of electronically controlling the deposited film in a gaseous state, or at least one or more of these compounds in the film forming space. At least one of the compounds (1), (2) and (3) in a gaseous or activated state is introduced into a separately provided activation space in a pre-activated state. In a deposited film forming method in which hydrogen atoms in an excited state that chemically react are generated in an activation space different from the film forming space and introduced into the film forming space to form a deposited film on the substrate, the excited Hydrogen atoms in the state are generated using hydrogen gas or a mixed gas of hydrogen gas and a rare gas in a plasma generation chamber installed in a cavity resonator integrated with two impedance matching circuits in a three-dimensional microwave circuit. A deposited film formation method characterized by generating using microwave plasma and controlling the excited state of hydrogen atoms. AaBb・・・・・・(I) (However, A represents an element other than silicon among the elements belonging to Group IV of the periodic table, and B represents hydrogen (H), halogen (X)
, represents a hydrocarbon group selected from hydrocarbon groups, a represents a positive integer equal to or an integral multiple of the valence of B, and b is
Indicates a positive integer. ) (2) The excited states of the hydrogen atoms are determined by measuring the emission intensities of Hα and Hβ, which are the excited states of hydrogen, using optical emission spectroscopy, and in order to adjust the intensity ratio to a desired value, According to claim (1), the method is controlled by controlling any one or more of wave input power, impedance matching conditions, hydrogen gas flow rate or mixed flow rate ratio of hydrogen gas and rare gas, and total pressure. Deposited film formation method. (3) The impedance matching circuit in the cavity resonator integrated with two impedance matching circuits in the microwave three-dimensional circuit is an aperture provided at the cavity length variable plunger and the connection part between the microwave waveguide and the cavity resonator. The deposited film forming method according to claim 1 or 2, wherein the impedance matching conditions are controlled by adjusting these. (4) The deposited film forming method according to claim (3), wherein the impedance matching circuit is a variable cavity length plunger and an E-H tuner or a three-stub tuner. (5) Claims (1) to (4), wherein the plasma generation chamber is configured with a metal mesh and a microwave-transparent bell jar, and is connected to the film forming space via the metal mesh. The method for forming a deposited film according to any one of paragraphs. (6) Claim No. 1, wherein the excited hydrogen atoms are introduced into the film forming space through the metal mesh.
The method for forming a deposited film according to any one of items (5) to (5). (7) The base body is located at an angle within 30 degrees to the horizontal axis of the metal mesh surface, and at an angle of 100 degrees from the metal mesh surface.
mm, and the compound (1), compound (2), and compound (3) in a gaseous state or in an activated state are arranged between the metal mesh surface and the base. The deposited film forming method according to any one of claims (1) to (6), wherein the deposited film is introduced into the film forming space by a blowing means. (8) The gas blowing means is disposed so as to annularly surround the base, and the intervals between the gas blowing holes are gradually shortened from the gas introduction side to the gas blowing means toward the final blowing hole, The deposited film forming method according to claim (7), wherein the amount of gas blown out from each gas blowing hole is made uniform. (9) The gas blowing means is disposed so as to annularly surround the base, and the diameter of the gas blowing hole is gradually increased from the gas introduction side to the gas blowing means toward the final blowing hole. The deposited film forming method according to claim 7, wherein the amount of gas blown out from each gas blowing hole is made uniform. (10) The gas blowing holes of the gas blowing means are uniformly distributed at least within the plane of the base, and the hole diameter of each gas blowing hole gradually increases from the gas introduction side to the gas blowing means toward the center. By being enlarged,
The deposited film forming method according to claim (7), wherein the amount of gas blown out from each gas blowing hole is made uniform.