JPH06192827A - Deposited film and its formation - Google Patents

Abstract

PURPOSE:To execute reactive sputtering at a high speed on a large-area substrate and to obtain the uniformly deposited film. CONSTITUTION:A target 116 contg. at least one kind of the constituting elements of the deposited film and a microwave introducing window 113 are provided within a vacuum vessel. The target and the microwave introducing window are so disposed that the shortest distance between each other is 50 to 200mm. Reactive gases are irradiated with the microwaves, the electric field direction of which is parallel with the target plane, through the microwave introducing window to generate plasma, by which the target surface is irradiated with the ions in the plasma. The material to be deposited is separated from the target and splashed so that the material to be deposited is stuck on the surface of the substrate 104 facing the target. The radicals in the material to be deposited and the plasma are brought into reaction, by which the deposited films contg. the constituting elements of the reactive gases is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film forming method and a deposited film, and more particularly to a deposited film forming method and a deposited film by reactive sputtering using microwaves. In particular, the present invention relates to a deposited film forming method having a high deposition rate and a deposited film formed thereby. The present invention also relates to a deposited film forming method capable of uniformly forming a deposited film on a large-area substrate.

[0002]

2. Description of the Related Art Generally, deposited films are used in various fields such as photovoltaic devices, semiconductor devices, magnetic recording media, magneto-optical recording media, protective films, electromagnetic wave filters, and sputtering targets. For example, a technique for forming a thin film of an oxygen compound or a nitrogen compound on a substrate is a vacuum vapor deposition method, a sputtering method, a plasma CVD method (chemical vapor deposition method).
Although a thermal CVD method, a thermal CVD method, etc. are performed, a deposited film forming method that can be formed at higher speed is required from the viewpoint of productivity.

In recent years, a deposited film formed by a sputtering method in which microwaves are introduced into a vacuum container and which has a high deposition rate has been studied. For example, the following examples can be given. "Crystal structures and optical properties of ZnO
films prepared by sputtering-type electron cyclotr
on resonance microwave plasma. "Matsuoka.M, Ono, K Journal of Vacuum Science & Tech
onology A, vol.7 No.5pp.2975 1989 "New high-rate
sputtering-type electron cyclotron resonance micro
wave plasma using an electric mirror. "Matsuoka.M, Ono, K Applied Physics Letters, vol.54
No.17 pp.1645 1989 “Characteristics of sputter type ECR microwave plasma and its application to thin film formation” Shigeto Matsuoka, Kenichi Ono Applied Physics, vol.57 N
o.9 pp.1301 1988 "Plasma properities in the open-ended region of a
coaxial-type microwave cavity. "Yoshida.Y Review o
f Scientific Instruments, vol.62 No.6 pp.1498 1991 "PIG-type compact microwave metal ion source" Yosh
ida.Y, Suzuki.N Japanese Journal of Applied Physics Part 2, vol.26
No.2 L100 1987

[0004]

However, even in the above-mentioned conventional technique, the deposition rate is not sufficient, and it is not suitable for forming a deposited film on a large-area substrate. Further, the characteristics of the deposited film are not sufficient, and a higher quality deposited film is required. Further, even in the conventional reactive sputtering, it is difficult to control the reactive radicals, and a high-quality deposited film deposited at high speed has not been obtained.

Further, in any of the above-mentioned conventional methods, the area of the substrate is small, and reactive sputtering is performed on a large-area substrate at a high speed, and a uniform deposited film has not been obtained yet, which has been a problem. In addition, there is a problem that the quality of the deposited film is deteriorated, that is, the quality of the film is degraded by irradiating the deposited film with light for a long time.

Further, there has been a problem that the vibration deterioration of the deposited film, that is, the deterioration of the film quality due to the vibration applied to the deposited film for a long time. Further, there is a demand for improvement in the quality of the deposited film formed by a continuous deposited film forming method such as a roll-to-roll method. Further, there are problems that the step coverage of the conventional deposited film is poor and the film is peeled off.

Therefore, in view of the above-mentioned drawbacks, a first technical object of the present invention is to carry out reactive sputtering on a large-area substrate at a high speed and obtain a uniform deposited film. Also,
A second technical object of the present invention is to improve productivity, and the deposited film is not limited to an oxygen compound and a nitrogen compound, but a carbon compound, a fluorine compound, a metal, which are formed at high speed,
It is to provide semiconductors, magnetic materials and the like.

A third technical object of the present invention is to provide a deposited film in which photodegradation and vibration degradation of the deposited film are suppressed, and further to provide a continuously formed high quality deposited film, and It improves the step coverage and film peeling of the deposited film.

[0009]

The present invention has been made in order to solve the conventional problems and achieve the above object, and as a result,
It has been found. The deposited film forming method of the present invention is
A target containing at least one of the constituent elements of the deposited film is arranged in the vacuum container so that the shortest distance from the microwave introduction window made of a dielectric material is 50 to 200 mm, and the reactive gas is contained in the vacuum container. Is introduced, and the reactive gas is irradiated with microwaves through the microwave introduction window so that the electric field direction is parallel to the target surface to generate plasma, and ions in the plasma are generated on the target surface. By irradiating, the deposit is made to adhere to the surface of the substrate arranged to face the target, and the deposit is reacted with the radicals in the plasma to contain the constituent elements of the reactive gas. The deposited film is formed on the surface of the substrate.

Further, the present invention is characterized in that when the deposited film is formed, DC power or high frequency power (RF power) having a frequency of 1 to 100 MHz is applied to the target. Further, the present invention is characterized in that, in the above method, a magnetic field is arranged so as to surround the target when the deposited film is formed. Further, the method of the present invention is characterized in that a positive DC voltage is applied to the substrate when the deposited film is formed.

The present invention is also characterized in that, in the above method, a negative DC voltage is applied to the substrate when the deposited film is formed. When the electrodes are arranged and a deposited film is formed, a positive DC voltage is applied to the electrodes. Further, the present invention is characterized in that, in the above method, an electrode is arranged inside the vacuum container, and RF electric power is applied to the electrode when the deposited film is formed.

According to the present invention, in the above method, the substrate is formed into a flexible strip shape, and when the deposited film is formed, the substrate is moved in the longitudinal direction thereof and the vicinity of the interface between the deposited film and the substrate. It is characterized in that the deposition film forming speed in the above step and the deposition film forming speed in the vicinity of the surface of the deposited film are lower than the deposition film forming speed in other regions. Further, the present invention is the method described above, wherein an exhaust port for evacuating the inside of the vacuum container, the microwave introduction window, the substrate, and the target are arranged so as to surround the plasma to form a deposited film. Forming is performed.

Furthermore, according to the present invention, a deposited film produced by any one of the above-described deposited film producing apparatuses can be obtained.

[0014]

According to the method for forming a deposited film of the present invention, the reactive radio frequency (RF) sputtering, the reactive direct current (DC) sputtering, and the reactive magnetron sputtering which are conventionally performed can be performed at a higher speed than the conventional method. Can be formed. That is, introducing a reactive gas containing at least one of the deposited film constituent elements into the vacuum container,
By irradiating the reactive gas with microwaves, it is possible to generate about 10 to 100 times as many ions as those obtained by an ordinary sputtering method, and about 10 to 100 times as much as usual on the target surface. Can be irradiated with ions. As a result, the sputtering rate is improved and the deposition rate is dramatically improved.

Further, since the ion density in the plasma can be increased as described above, it is possible to cover the decrease in the potential difference of the ion sheath caused by the increase in the surface area of the target, and the low energy ions can speed up the process. A deposited film can be formed. In addition, since plasma is generated by microwaves, even when the introduced reactive gas contains an element that is not a constituent element of the deposited film, it is extracted by an extraction reaction of an element that is not a constituent element of the deposited film on the surface of the deposited film. However, impurities that are not constituent elements are not mixed in the deposited film. Further, even when a small amount is mixed, the quality of the film is not deteriorated because it is mixed in an inactive state. Further, another reactive gas that activates the extraction reaction may be introduced. In addition to the reactive gas, an inert gas may be introduced at the same time in order to efficiently obtain the ions with which the target is irradiated. As the inert gas, for example, He, Ar, Ne, Kr, and Xe are used, but among them, the ionization rate is good and the economical efficiency is high.
It is preferable to use Ar, which has a large mass and high stability in a plasma state.

Further, in the present invention, the impurities contained in the deposited film can be reduced because the surface reaction is activated by high-speed deposition by microwaves. Furthermore, when the deposited film is crystalline, the crystallinity of the deposited film is improved by reducing impurities. Furthermore, photodegradation and vibration degradation are suppressed by reducing impurities.

Further, since the above reactive gas is decomposed by microwaves, neutral radicals and ions which cannot be obtained by ordinary sputtering can be obtained, and the surface reaction on the surface of the deposited film can be promoted. Therefore, it is possible to form a high-quality deposited film that cannot be obtained by the usual sputtering method. In order to form a deposited film of higher quality, it is desirable to appropriately determine the forming conditions such as the substrate temperature, the pressure and the reactive gas flow rate according to the type of the deposited film. For example, Zn
When depositing an O film, the substrate temperature is 150 to 350 ° C., the pressure is 1 to 10 mTorr, and the O ₂ gas is 20 to 100 sccc.
m, Ar gas 10 to 50 sccm are suitable.

The term "good quality deposited film" as used herein means that the conductive deposited film has a high electric conductivity, and the light reflective film has a high reflectance. In the case of a transparent deposited film, its light transmittance is high,
In the case of a transparent conductive film, both its light transmittance and electric conductivity are high, in the case of an antireflection film, its reflectance is low, and in the case of an insulating film, its resistivity is low. It is expensive.

In the present invention, plasma is generated by microwaves, but since electron cyclotron resonance (ECR) is not used, a uniform deposited film can be formed even on a large area substrate. That is, in the ECR, a strong magnetic field region is formed, and electrons are brought into a cyclotron resonance state, so that plasma can be maintained even at a relatively low pressure. However, this plasma region is currently limited to a relatively small region, and expansion in the resonance plasma state requires a huge amount of electric energy, which is not realistic. In the present invention, the microwave transmitted by the waveguide is once expanded inside the metal container serving as the applicator, radiated into the vacuum container through the microwave introduction window composed of the dielectric, and the microwave of the applicator is changed according to the size of the substrate. By appropriately determining the cross-sectional area (cross-sectional area in the microwave transmission direction), the plasma region can be expanded even at a relatively low pressure, so that a large-area target can be used and even on a large-area substrate. It is possible to form various deposited films.

Further, in the present invention, since plasma is generated by microwaves, by lowering the pressure,
Since the mean free path can be lengthened and unnecessary reactions in the vapor phase can be suppressed as much as possible, reactions on the surface of the deposited film are mainly formed, and a high-quality deposited film is formed at high speed.
Since the plasma is stable, spark discharge is unlikely to occur, and defects such as pinholes are reduced. In addition, the step coverage is greatly improved due to the long mean free path.

Further, in the present invention, since the direction of the strong electric field of the microwave is parallel to the target surface, the target is not directly heated by the microwave, alteration of the target can be prevented, and stable characteristics can be maintained for a long period of time. It is possible to form a deposited film having Further, since the substrate is arranged so as to face the target, the direction of the strong electric field of the microwave is parallel to the substrate surface, and similarly, the substrate is not directly heated by the microwave and is of high quality. In particular, when a deposited film that absorbs microwaves well is formed, it may lead to unexpected alteration of the deposited film when directly heated by microwaves, but the present invention has an effect of preventing such alteration.

The distance between the microwave introduction window for introducing the microwave into the vacuum container and the target is a parameter relating to the deposition rate and is important. The ionization rate inside the plasma decreases exponentially according to the distance from the microwave introduction window, and the deposition rate decreases as the distance from the target increases. Also, when the distance from the target is reduced, the deposit flying from the target adheres to the microwave introduction window, and the adhered matter absorbs or reflects the microwave, so that microwave power cannot be introduced into the vacuum device. Eventually, it may not be possible to generate plasma. Further, if the distance from the target is too short, uneven erosion of the target may be caused. The present inventor found the above phenomenon and searched for a quantitative range thereof, and found that such a phenomenon can be prevented if the distance between the target and the microwave introduction window is 50 to 200 mm. It should be noted that within this range, it is desirable to appropriately determine depending on the type of deposited film and the type of target. Especially 50 to 100 mm, preferably 50 to 7
0 mm is more preferable.

Next, the constitutional requirements of the present invention will be explained along with the embodiments. (Application of DC and RF Power to Target) In the present invention, DC power (DC power) or 1 is applied to the target.
It is preferable to apply high frequency power (RF power) of ˜100 MHz. That is, DC power (target is negative) is applied to the electrode on which the target is placed (target electrode),
Alternatively, the kinetic energy of the generated ions can be increased by applying RF power, and thus the sputtering rate of the target can be improved, so that the deposition rate is further increased. Further, by concentrating ions on the target, it is possible to reduce ion bombardment to the deposited film, and thus the deposited film formed is of good quality. Usually, when using a conductive target (for example, metal),
When DC power or RF power is applied and a non-conductive target (eg, oxygen compound, nitrogen compound, etc.) is used, it is desirable to apply RF power.

(Arrangement of magnetic field) Further, in the present invention,
By arranging a magnetic field surrounding the target in the vicinity of the target, it is possible to improve the stability of the discharge due to the rotational translational motion of the electrons. A deposited film with reduced electron impact can be formed. Furthermore, since the microwave energy applied to the plasma can be lowered by increasing the density of ions irradiated per unit time, a deposited film with reduced damage such as ion bombardment can be formed.

(Applying DC and RF Power to Substrate) Further, in the present invention, ion bombardment is reduced by applying a positive DC voltage to the substrate. Furthermore, since the radicals irradiated on the deposited film can be controlled, the surface reaction of the deposited film can be controlled, which is particularly effective for forming a deposited film composed of two or more elements. In addition, a deposited film with reduced defects near the interface with the substrate can be formed.

Further, in the present invention, by applying a negative DC voltage to the substrate, it is possible to accelerate the ion irradiation to the deposited film and thereby reduce the adsorbed gas, so that the film quality is improved. It is a deposited film. Further, since the substrate can be positively irradiated with ions, the surface reaction of the deposited film can be activated, and the structural relaxation is promoted. Further, a certain type of ions can be positively irradiated on the substrate to activate a certain type of surface reaction to form a deposited film with improved film quality.

(Bias Electrode) In the present invention, an electrode (bias electrode) for applying a bias is arranged inside the vacuum container, and when a deposited film is formed, a positive DC voltage (DC power) is applied to the electrode. By applying, the plasma potential can be raised, the kinetic energy of ions can be raised, and the sputtering rate can be improved, so that a deposited film with a further improved deposition rate can be formed.

The bias electrode is preferably provided near the central position of the plasma. Further, by raising the plasma potential, certain kinds of ions are positively irradiated on the surface of the deposited film to activate certain kinds of surface reaction, and a deposited film with improved film quality can be formed. Further, since the stability of plasma can be improved, the deposited film has reduced defects such as pinholes. These effects are particularly effective in a deposited film having a high deposition rate as in the present invention. In addition, a deposited film with reduced defects near the interface with the substrate can be formed.

Further, in the present invention, by applying RF power to the bias electrode, the plasma potential can be raised, the kinetic energy of ions can be raised, the sputtering rate is improved, and the deposition rate is further increased. Is. Further, by raising the plasma potential, a certain kind of ions are positively irradiated on the surface of the deposited film to activate a certain kind of surface reaction to improve the film quality. Further, since the stability of plasma can be improved, the deposited film has reduced defects such as pinholes. These effects are particularly effective in a deposited film having a high deposition rate as in the present invention. Further, it is possible to reduce defects near the interface with the substrate. Further, DC power can be applied simultaneously with RF power to further improve the film quality.

(Positional relationship of microwave introduction window, etc.)
In the present invention, by arranging the microwave introduction window, the target, the substrate, and the exhaust port so as to surround the plasma, the sputtered target can be efficiently deposited on the substrate. Further, the stability of plasma for a long period of time can be improved.

(Material of Deposited Film) Examples of the deposited film formed by the present invention include oxygen compounds, nitrogen compounds, carbon compounds, metals, semiconductors, magnetic materials, and the like. Specifically, the following compounds or These include mixtures or alloys. Structurally, it may be crystalline or polycrystalline or amorphous or a mixture thereof. Furthermore, in the case of a deposited film of two or more components, the target material and its component ratio may be slightly different.

Here, as the oxygen compound, Li₂O,
LiNbO₃ , LiTaO₃ , BeO, MgO, Al₂
O₃ , SiO₂ , KNbO₃ , CaO, TiO, TiO
₂ , Ti₂O₃ , BaTiO₃ , SrTiO₃ , CaT
iO₃ , Bi₂TiO_Five , PbTiO₃ , V₂O_Five , Cr
₂O₃ , MnO₂ , FeO, Fe₂O₃ , Fe₃O_Four , C
oO, NiO, CuO, ZnO, Ga₂O₃ , SrZr
O₃ , GeO₂ , Y₂O₃, YAlO₃ , ZrO, ZrO
₂ , Nb₂O_Five , MoO₃ , CdO, Cd₂SnO _Four , I
n₂O₃ , SnO₂ , Sb₂O₃ , La₂O₃ , LaAl
O₃ , LaGaO₃, HfO₂ , Ta₂O_Five , CeO
₂ , Nd₂O₃ , NdGaO₃ , Sm₂O₃ , Dy₂O
₃ , Ho₂O₃ , Eu₂O₃ , Gd₂O₃ , Er₂O₃ , W
O₃ , IrO, PbO, PbZrO₃ , Bi₂O₃ Etc.
Can be mentioned.

Y is used as an oxygen compound exhibiting superconductivity.
BaCuO, BiPbSrCaCuO, BiSrCaC
uO, LaSrCaCuO, BiSrVO, TlSrC
aCuO etc. are mentioned. As the nitrogen compound, BN,
AlN, HfN, NbN, SiN, Si ₃ N ₄ , Ta
N, TiN, VN, ZrN, etc. are mentioned.

Carbon compounds include C, B ₄ C and Hf.
C, MoC ₃ , NbC, SiC, TaC, TiC, V
C, WC, ZrC and the like can be mentioned. Also, as a metal,
Ag, Al, Au, Bi, Cd, Ce, Co, Cr, C
u, Dy, Er, Eu, Fe, Ga, Gd, Hf, H
o, Hg, In, Ir, La, Lu, Mg, Mn, M
o, Nb, Nd, Ni, Pb, Pd, Pr, Pt, S
b, Sc, Sm, Sn, Ta, Tb, Te, Ti, T
m, V, W, Y, Yb, Zn, Zr and the like.

As the semiconductor, Ge, Si, Se, Si
Ge, AlSi, SiSn, SiPb, GaAs, Ga
AlAs, ZnSe, ZnTe, ZnS, CdS, Cd
Se, CdTe, AlP, AlAs, AlSb, Ga
N, GaP, GaSb, InN, InP, InAs, I
Examples thereof include nSb, GeC, GeSn, SnC, CuInSe _{2, and the} like, which may have a conductivity type controlled by containing a doping agent.

Fluorine compounds include AlF ₃ and BaF
₂ , BiF ₃ , CaF ₂ , CeF ₃ , DyF ₃ , Er
F ₃ , EuF ₃ , GdF ₃ , HoF ₃ , LaF ₃ , LiF,
MgF ₂ , NaF, NdF ₃ , PbF ₂ , PrF ₃ , Sr
F ₂ , TbF ₃ , YF _{3 and the} like can be mentioned. As the magnetic material, FeNi, FeNiCo, PdNi, MnBi, M
nCuBi, TbFeO ₃ , GdCo, GdFe, Gd
TbFe, NdFe, TbFe, CoCr, TaPt,
CoPt, CoPd, SmFeO ₃ , GdFeO _{3 and the} like can be mentioned.

(Reactive Gas) Used in the Present Invention
As the reactive gas, the elements that make up the deposited film should be reduced.
The gas also contains one of the following, and includes the following.
By bubbling the liquid one with an inert gas, etc.
And introduce it into the deposition chamber. When depositing oxygen compounds,
Compounds containing oxygen, such as O₂ , CO₂, CO,
NO, NO₂, N₂O, H₂O, CH₃CH₂OH, CH₃O
H, SO₂Etc., and contains elements other than oxygen.
Compound, eg GeH_Four, GeF _Four, SiF_Four , S
iH_FourSi₂H₆, SiH₂Cl₂, SnH_Four, (C₂H_Five)₂
Zn, (C H₃)₂Zn, AlCl₃ , (CH₃)₃A
l, (C₂H_Five)₃Al, (iso-C _FourH₉)₃Al, (C
H₃)₃Ga, (C₂H_Five)₃Ga, (C₂H_Five)₃In, Sn
(CH₃)_Four , WF₆ Etc.

When depositing nitrogen compounds, nitrogen containing compounds such as N ₂ , NO, NO ₂ , N ₂ O, N are used.
_{H 3 O 2, NH 3,} NF 3 and the like, compounds further containing an element other than nitrogen, for example, SiF _4, SiH
₄ Si ₂ H ₆ , SiH ₂ Cl ₂ , AlCl ₃ , (CH ₃ ) ₃ A
_{l, (C 2 H 5)} 3 Al, (iso-C 4 H 9) 3 Al , and the like.

When depositing a carbon compound, a carbon-containing compound such as C _n H _{2n + 2} (n: integer), C
_n H _2n , C _n H _2n-2 , C ₂ H ₃ Cl, C ₂ ClF ₅ , CHF _{3
, C2F5, CH 2 Br 2,} C 3 F 8, CF 4, CO 2,
CO, C ₂ H ₅ OH, CH ₃ OH, etc., and compounds containing elements other than carbon, such as SiF ₄ , S
_{iH 4 Si 2 H 6, SiH} 2 Cl 2 , and the like.

When depositing a metal, a compound containing a metal such as (C ₂ H ₅ ) ₂ Zn, (CH ₃ ) ₂ Zn, A
lCl ₃ , (CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ Al, (is
_{o-C 4 H 9) 3} Al, (CH 3) 3 Ga, (C 2 H 5) 3 G
a, (C ₂ H ₅ ) ₃ In, Sn (CH ₃ ) ₄ , WF _{6 and the} like. When depositing a semiconductor, for example, GeH
₄ , GeF ₄ , SiF ₄ , SiH ₄ Si ₂ H ₆ , SiH _{2
Cl 2, SnH 4, (C} 2 H 5) 2 Zn, (CH 3) 2 Z
n, AlCl ₃ , (CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ A
_{l, (iso-C 4 H} 9) 3 Al, (CH 3) 3 Ga, (C 2
_{H 5) 3 Ga, (C} 2 H 5) 3 In, Sn (CH 3) 4 and the like.

When depositing a fluorine compound, fluorine is used.
A compound containing, for example, F₂ , PF_Five , NF₃ , B
F₃ , SF_Four , SiF_Four , SF₆ , WF₆ , C₂ClF_Five
 , CHF₃ , C₂F₆ , C₃F₈ , CF_Four Etc.
And compounds containing no fluorine, such as AlCl₃ ,
(CH₃ )₃Al, (C₂H_Five )₃Al, (iso-C_FourH
₉ )₃Examples thereof include Al.

When a magnetic substance is deposited, a compound containing oxygen such as O ₂ , CO ₂ , CO, NO and NO is used.
₂ , N ₂ O, H ₂ O, CH ₃ CH ₂ OH, CH ₃ OH, SO ₂
Etc., and the compound containing a metal element, for _{example, Fe (C 5 H 5)} , Fe (CO) 5, FeBr 2 · 6
H ₂ O, CoCl ₂ .6H ₂ O, CoBr ₂ .6H ₂ O,
CoH (CO) ₄ , Co (CO) ₃ (NO), Ni (C
O) ₄ , Pd (C ₃ H ₅ ) ₂ , Pd (C ₃ H ₅ ) (C ₅ H
₅ ), MnH (CO) ₅ , Bi (CH ₃ ) ₃ , Bi (C _{2
H 5) 3, Pt (C} 3 H 5) 2 and the like.

The above reactive gases may be mixed and introduced, or an inert gas (He, Ar, Ne, Xe, Kr).
It may be mixed with and introduced. (Substrate) The substrate used in the present invention may be composed of a single substance, or may be one in which one or more of the above-mentioned deposited films and the like are deposited on a support. Conductive simple substance substrate materials include NiCr, stainless steel, Al,
Cr, Mo, Au, Nb, Ta, V, Ti, Pt, P
Examples thereof include metals such as b, Sn and Fe, or alloys thereof. In order to use these materials as a support, it is desirable that the material has a sheet shape or a roll shape in which a belt-shaped sheet is wound around a cylindrical body. Examples of the insulating simple substance substrate material include synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, and glass, ceramics, paper, and the like. In order to use these materials as a support, it is desirable that the material has a sheet shape or a roll shape in which a belt-shaped sheet is wound around a cylindrical body.

When a deposited film is formed on a support to form a substrate, the deposited film is formed by a vacuum vapor deposition method, a sputtering method, a screen printing method, or the deposited film forming method used in this embodiment. The surface shape of the support may be smooth or, if necessary, unevenness having a peak height of 0.1 to 1 μm. When flexibility is required, the thickness of the substrate can be made as thin as possible within the range where the function as a support is sufficiently exhibited. However, it is usually 10 μm or more in terms of mechanical strength and the like in terms of manufacturing and handling of the support.

In the present invention, a plurality of deposited films can be laminated. By stacking the deposited film of the present invention, photodegradation, vibration degradation, and film peeling can be suppressed more than those of stacked films deposited by other methods.

[0046]

Embodiments Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows a deposited film 101 of the present invention formed on a substrate 102. Further, the deposited film 101 may be composed of a plurality of deposited films. The substrate 10
Reference numeral 2 may be one in which a deposited film formed by another method is formed on the support, and the deposited film may be composed of a plurality of deposited films.

FIG. 2 is a schematic explanatory view of a deposition apparatus 200 for forming the deposited film 101 of this embodiment. This deposition device 2
00 is a deposition chamber 201, a vacuum gauge 202, a substrate 204, a heater 205, a waveguide 206, a conductance valve 20.
7, auxiliary valve 208, target electrode 209 electrically insulated from the deposition chamber, gas introduction pipe 211, applicator 212, microwave introduction window 213, substrate shutter 215, target 216, target shutter 21.
7, a microwave power source 219, a vacuum exhaust pump (not shown), a gas supply device, and the like.

The vacuum exhaust pump (not shown) has an exhaust port 220.
Connected to. The gas supply device (not shown) is a gas cylinder,
It is composed of a valve and a mass flow controller, and is connected to the gas introduction pipe 211. The waveguide 206 has a rectangular cross section, and the strong electric field direction is perpendicular to the paper surface, that is, parallel to the target surface. The applicator 212 is continuously connected to the waveguide like an electromagnetic horn, and preferably has a rectangular cross section and is similar to the cross sectional shape of the waveguide. Thereby, the strong electric field direction of the microwave radiated from the microwave introduction window 213 into the inside of the vacuum container becomes parallel to the target surface.

Microwave introduction window 213 and target 21
The distance (shortest distance) from 6 is 50 to 200 mm. If necessary, a target power supply 214 may be connected to the target electrode 209 as shown in FIG. A DC power supply or an RF power supply is used as the target power supply 214. Further, the toroidal coil 221 may be arranged on the back surface side of the target electrode 209 to form a toroidal toroidal magnetic field around the target 216.

Further, the bias electrode 21 is provided in the deposition chamber 211.
You may arrange | position 0 and connect the bias power supply 203 to this. As the bias power source, DC power source and / or R
F power source is used. In addition, the heater 205 is attached to the deposition chamber 201.
The substrate bias power supply 218 may be connected to this. When a halogen lamp heater or the like is used as the heater 205, the 204 substrate is insulated from the deposition chamber 201 and a bias is directly applied to the substrate 204. A DC power supply is used as the substrate bias power supply 218.

Next, the deposited film of this embodiment is formed as follows. First, the substrate 204 is brought into close contact with the heater 205 installed in the deposition chamber 201 of FIG. 2, and the inside of the deposition chamber 201 is sufficiently exhausted to 1 × 10 ⁻⁵ Torr or less. A turbo molecular pump, an oil diffusion pump or a cryopump is suitable for this exhaust. Then, an inert gas is added to the deposition chamber 20.
1, and the heater 205 is turned on to heat the substrate 204. When the substrate temperature stabilizes at a predetermined temperature, the introduction of the inert gas is stopped if necessary, the reactive gas is introduced, and the conductance valve 207 is adjusted to set the predetermined pressure. At this time, since the pressure in the deposition chamber 201 is a parameter closely related to the formation rate of the deposited film 101, it is appropriately determined depending on the type of reactive gas, the type of target, the size of the deposition apparatus, etc. In the case of this embodiment, it is usually 0.1 to 10 mTorr. More preferably, it is 1 to 9 mTorr.

A predetermined amount of gas to be introduced is introduced into the deposition chamber 201 from each gas cylinder through the mass flow controller.
It is appropriately determined according to the volume of. Next, microwave power (MW power) is transmitted from the microwave power source 219 through the waveguide 206, introduced into the deposition chamber 201 from the applicator 212 through the microwave introduction window 213, irradiated with the reactive gas, and plasma is generated. Raise it. When generating plasma, a stub tuner, an E-H tuner, or the like may be provided in a part of the waveguide 206 to reduce the reflected power. In this embodiment, plasma is generated by microwaves, but if the microwave power is too small at that time, the discharge becomes unstable and the deposited film 10 is formed.
This leads to deterioration of the film quality of No. 1. Furthermore, if the microwave power is too high, the deposited film 101 and the target 21
Since the microwave power directly applied to 6 becomes large,
The surface temperature of the deposited film 101 and the target 216 rises more than necessary, and further, the amount of ion damage becomes larger than necessary, resulting in deterioration of the quality of the deposited film 101 or the quality of the target. The MW power is appropriately determined according to the flow rate of the reactive gas introduced into the deposition chamber 201, the desired deposition rate, and the type of target, but the preferable range is 100 to 5000 W. A preferable frequency range of the MW power is 0.5 to 10 GHz, and a frequency around 2.45 GHz is particularly suitable. Further, in order to form a reproducible deposited film and to maintain a stable glow discharge for several hours to several tens of hours, the frequency stability of the MW power is very important,
It is preferable that the fluctuation of the microwave frequency is within ± 2%. Further, the ripple of the microwave is preferably within ± 2%. The microwave introduction window 213 is composed of a dielectric material such as alumina ceramics (Al ₂ O ₃ ), quartz, and boron nitride that transmits microwaves well, and can separate vacuum and atmospheric pressure.

When the plasma is generated, the target shutter 217 is opened, then the substrate shutter 215 is opened, and the formation of the deposited film 101 is started. When the deposited film having a desired film quality is formed, the substrate shutter 215 is closed to complete the formation of the deposited film 101. Next, the target shutter 217 is closed, the MW power from the microwave power source 219 is turned off, and the plasma is extinguished. After that, the inside of the deposition chamber 201 is sufficiently evacuated to 1 × 10 ⁻⁵ Torr or less and sufficiently purged with an inert gas such as Ar, and then the deposition chamber 201 is leaked to remove the substrate 204 on which the deposited film 101 is formed. Deposition chamber 2
Take out from 01.

The shape of the target 216 depends on the shape of the substrate 204. If the base 204 plate is a square plate, a square plate target 216 is used, and if the substrate 204 is a disk, a circular plate is used. It is desirable to use the target 216 in the shape of a circle. Further, when a plurality of substrates are fixed to a substrate holder (not shown) and are rotated about a certain axis to form a plurality of deposited films at one time, it is desirable to use a target that is axisymmetrical to this axis.

Further, when a cylindrical substrate 301 surrounding plasma is used as shown in FIG. 3, it is desirable to use a coaxial cylindrical target. At this time,
The incident direction of the microwave is parallel to this axis like
Further, it is desirable that the exhaust direction be parallel to this axis. It is desirable that the substrate has its deposited film forming surface facing down or sideways (horizontal is horizontal) so that a peeled film or the like does not adhere to the deposited film surface to form a pinhole.
It is desirable that the targets also face each other accordingly.
When a peeled film or the like adheres to the target surface and spark discharge or the like occurs, it is desirable to make the target surface and the substrate surface sideways.

In order to increase the formation speed of the deposited film 101,
The surface area of the target is preferably about the same as the surface area of the substrate, and the normal direction of the target surface and the normal direction of the substrate surface are preferably parallel or have a small angle. Further, the distance between the target surface and the substrate surface is preferably as short as possible, but if they are too close to each other, uniform plasma cannot be obtained and the uniformity of the deposited film deteriorates.

Further, returning to FIG. 2, it is preferable that the strong electric field direction of the microwave and the target surface are parallel to each other so that the target 216 is not directly irradiated with the microwave power and the target 216 is not heated. Further, this can prevent the deposition film from adhering to the surface of the microwave introduction window 213 and deteriorating the incidence efficiency of microwave power. This is very important for maintaining a stable plasma discharge for several hours.

Further, as shown in FIG. 6, the microwave introduction window 2
A louver 222 made of a material that transmits microwaves is provided on the vacuum side in the vicinity of 14, and the microwaves are transmitted, but the deposit is devised so that the deposit does not fly, and the deposit is deposited on the microwave introduction window 214. May be prevented from adhering.
Substrate shutter 215, target shutter 217,
It is desirable that the material of the gas introducing pipe 211 and the wall surface of the deposition chamber 201 is Mo, Ta, W, Al, or stainless steel having a relatively small sputtering rate. When the deposited film 101 is a metal, it may be made of the metal material.

The surface of the deposited film 101 of this embodiment can be formed (textured) with irregularities of submicron order (0.1 to 1.0 μm), if necessary. In this embodiment, the surface of the deposited film can be made uneven by increasing the substrate temperature to 200 ° C. or higher or increasing the ion bombardment by increasing the microwave power. In this embodiment, it is desirable to raise the substrate temperature.

When RF power is applied to the target electrode 209 when forming the deposited film 101, the preferable range of the RF power to be introduced is 200 to 5000 W. The preferable frequency range of the RF power is 1 to 10
0 MHz is mentioned, and 13.56 MHz is particularly suitable. Further, it is preferable that the fluctuation of the RF frequency is within ± 2% and the waveform is smooth. Further, a DC voltage may be applied to the target electrode 209 at the same time. A preferable range of the DC voltage is about 100 to 1000 V, and the target electrode side has a negative polarity.

When DC power is applied to the target electrode 209 when forming the deposited film 101, a preferable range of the DC voltage to be introduced is about 100 to 1000 V, and the target electrode side has a negative polarity. When a magnetic field is arranged so as to surround the target 216 when forming the deposited film 101, for example, in the case of a disc-shaped target 216,
The magnetic field is preferably a toroidal magnetic field arranged in a torus shape, and in the case of the rectangular plate-shaped target 216, the magnetic field is preferably arranged so as to circulate the toroidal magnetic field around the end of the rectangular target. In addition, the shaft-shaped target 216
If so, the magnetic field is preferably a toroidal magnetic field arranged parallel to the coaxial. A ferromagnetic material may be used to generate the magnetic field, but an electromagnet capable of changing the strength of the magnetic field is desirable. By adjusting the strength of the magnetic field, the stability of discharge and the uniformity of the deposited film can be controlled.

When RF power is applied to the bias electrode 210 when forming the deposited film 101, the RF power to be introduced is preferably the above. Also, the bias electrode 210 has a D
The C voltage may be applied simultaneously. A preferable range of the DC voltage is about 30 to 30 OV, and the bias electrode side has a positive polarity. As the material of the bias electrode 210,
Mo, Ta, W, Al, stainless steel and the like having a small sputtering rate are preferable. When the deposited film 101 is a metal,
You may comprise with this metal material.

When DC power is applied to the bias electrode 210 when forming the deposited film 101, a preferable range of the DC voltage to be introduced is about 30 to 30 OV, and the bias electrode side has a positive polarity. At the same time, the bias electrode material is preferably made of Mo, Ta, W, Al, stainless steel, or the same metal material as the deposited film 101 when the deposited film 101 is a metal.

DC to be introduced when positive or negative DC power is applied to the substrate 204 when forming the deposited film 101.
A preferable range of the voltage is about 30 to 30 OV. Although the deposition film 101 formed by the batch method has been described above, in this embodiment, the deposition film formed continuously or intermittently by moving the flexible belt-like substrate continuously or intermittently in the longitudinal direction thereof. But it's okay.

US Pat. No. 4,400,409 describes roll to roll.
There is disclosed a plasma CVD apparatus which adopts the method 1) and continuously forms a semiconductor. The deposited film of the present invention can be dramatically improved in productivity by being continuously formed using such an apparatus. Further, it is particularly effective when a plurality of deposited films are deposited on the substrate. According to this apparatus, a plurality of deposition chambers are provided, flexible strip-shaped substrates are arranged along a path through which the substrates sequentially pass through the deposition chamber, and a desired deposited film is formed in the deposition chamber. By continuously or intermittently transporting the substrate in the longitudinal direction, the deposition chamber can be formed on the belt-shaped substrate without leaking the deposition chamber to the atmosphere. Further, when depositing a plurality of deposited films on a belt-shaped substrate, a gas gate is used so that constituent elements of another deposited film do not mix into one deposited film. The deposition chambers are separated from each other by slit-shaped separation passages, and A
A scavenging gas such as r, He, or H ₂ can be introduced to prevent mutual diffusion of the source gases.

In this embodiment, when the thickness of the deposited film is relatively thick (10 μm or more), the flexible belt-like substrate is moved intermittently, and the substrate is not moved when forming the deposited film, which is a desired value. The process of moving the substrate after the film thickness is formed and forming the deposited film on the surface of the substrate where the deposited film is not yet formed may be repeated. In this embodiment, the quality of the deposited film is not impaired by making the deposited film formation rate near the interface between the deposited film and the substrate and the deposited film formation rate near the deposited film surface smaller than the deposited film formation rate in other regions. Moreover, while maintaining a high deposition rate, stress generated near the interface between the deposited film and the substrate or on the surface of the deposited film can be relaxed, and problems such as photodegradation, vibration degradation, and film peeling can be suppressed.

[0067]

EXAMPLES The deposited film of the present invention will be described below with reference to specific examples, but the present invention is not limited thereto. << Example 1 >> Deposition apparatus (made of stainless steel) 20 shown in FIG.
0 was used to form a transparent conductive wire made of ZnO as an oxygen compound.

First, 500 × 500 mm ² , thickness 1.0
The glass substrate 204 whose surface was mirror-polished in mm, was brought into close contact with the heater, and ZnO was used as the target 216. The distance between the target 216 and the microwave introduction window 213 is 1
It was set to 00 mm. The conductance valve 207 was fully opened, and the inside of the deposition chamber 201 was evacuated to a pressure of 1 × 10 ⁻⁶ Torr by a vacuum exhaust pump (not shown).

Ar gas is supplied for 100 s through the gas introduction pipe 211.
ccm, the conductance valve 207 is adjusted so that the internal pressure is 3 mTorr, and the substrate temperature is 15
The heater 205 was set to be 0 ° C. When the substrate temperature became stable, 100 sccm of O ₂ gas was introduced,
Stop the introduction of Ar gas, and turn off the microwave power source 219-80
Transmitting 0W microwave power and irradiating O ₂ gas,
A plasma was created. Open the target shutter 217 and open the substrate shutter 215 to open the stainless steel substrate 20.
4 was started to form a deposited film 101 made of ZnO.
When the film thickness reached 2.0 μm, the target shutter 216 and the substrate shutter 215 were closed, the supply of microwave power was stopped, and the plasma was extinguished. The inflow of O ₂ gas was stopped, the conductance valve 207 was fully opened, the pressure in the deposition chamber 201 was evacuated to 1 × 10 ⁻⁶ Torr, the conductance valve 207 was closed, and the deposition chamber 201 was leaked with Ar gas. .

<Comparative Example 1> A transparent conductive wire of ZnO similar to that of Example 1 was formed by a conventional deposition apparatus using the ECR sputtering method. <Evaluation 1> When the transmittance spectrum of the deposited film 101 in the central portion of the substrate is examined, the transmittance of the deposited film of Example 1 is higher than that of the deposited film of Comparative Example 1 at the wavelength of 550 nm. It was found to be 1.04 times better. Furthermore, it was found that the reflectance of the deposited film of Example 1 was higher than that of Comparative Example 1 over the entire visible light region. Further, the deposition rate in the central portion was 2.4 times that of Comparative Example 1 in Example 1. In addition, the conductivity in the central portion of Example 1 was 2.5 times that of Comparative Example 1. The uniformity of the deposited film was also investigated. The ratio of the thickness of the peripheral portion to the thickness of the central portion of the deposited film 101 was 0.96 in Example 1 and 0.84 in Comparative Example 1. Furthermore, the transmittance of the central part (55
The ratio of the transmittance of the peripheral portion with respect to (0 nm) is 0.
In 96, the comparative example was 0.90.

As can be seen from the above evaluation, it was found that the deposited film of this example is superior to the conventional deposited film. Example 2 Using the deposition apparatus 200 shown in FIG. 2, a light reflection line made of AlSi as a metal was formed. First, 50
0 × 500 mm ² , thickness 0.5 mm, mirror-polished stainless steel substrate 204 is closely attached to the heater 205,
Al is used for the target 216, and SiH ₄ is 10 sccm and Ar is 200 sccc as the reactive gas to be introduced.
m was introduced. Substrate temperature is 250 ° C, pressure is 2mTorr
r, the film thickness was 0.3 μm, and the distance between the target 216 and the microwave introduction window 213 was 150 mm.
A light reflecting film made of AlSi was formed in the same manner as in.

Comparative Example 2 A light reflecting film made of AlSi similar to that in Example 2 was formed by the reactive magnetron sputtering method. Target electrode 2 of deposition apparatus 200 of FIG.
A DC power source was connected to 09, and a toroidal coil 221 was installed as shown in FIG. When plasma is generated, microwave power is not supplied and DC voltage of 4 is applied to the target electrode 209.
A deposited film 1 of 0.3 μm made of AlSi was formed in the same manner as in Example 2 except that 00 V was applied and the pressure was 7 mTorr.
01 was formed.

<Evaluation 2> When the reflectance spectrum in the central portion of the substrate was examined, the reflectance of the deposited film of Example 1 was 1 than that of Comparative Example 1 at the wavelength of 700 nm. It was found to be 0.07 times better.
Furthermore, it was found that the reflectance of the deposited film of Example 1 was higher than that of Comparative Example 1 over the entire visible light region. In addition, the deposition rate in the central part is more in Example 1 than in Comparative Example 1
Was 2.0 times. Furthermore, the uniformity of the deposited film was investigated.
The ratio of the thickness of the peripheral portion to the thickness of the central portion of the deposited film was 0.96 in Example 1 and 0.90 in Comparative Example 1. Further, the ratio of the reflectance of the peripheral portion to the reflectance (700 nm) of the central portion was 0.96 in Example 1 and 0.91 in Comparative Example 1.

As can be seen from the above evaluation, the deposited film of this example was found to be superior to the conventional deposited film. Example 3 Using the deposition apparatus 200 shown in FIG. 2, an insulating film made of SiN as a nitrogen compound was formed.

First, 500 × 500 mm ² , thickness 1.0
The glass substrate 204 having a mirror-finished surface of 100 mm in diameter was brought into close contact with the heater, and polycrystalline Si (non-doped) was used as the target 216. Substrate temperature 350 ° C, film thickness 10μ
m, microwave power of 500 W, reactive gas to be introduced is 200 sccm of N ₂ and 300 sccm of Ar,
A deposited film made of SiN was formed in the same manner as in Example 1 except that the pressure was 5 mTorr.

Comparative Example 3 An insulating film made of SiN similar to that of Example 3 was formed by the reactive magnetron sputtering method. An RF power source was connected to the target electrode, and RF power was set to 600W. <Evaluation 3> When the insulating property (resistivity) and uniformity of the deposited film were examined, the deposited film of Example 3 was superior to Comparative Example 3, and the deposited film of the present invention was superior to the conventional deposited film. Also proved to be excellent.

Example 4 A bias electrode 210 and a bias power source (DC power source) 203 were installed in the deposition apparatus 200 shown in FIG. 2 as shown in FIG. 6, and SiC was used as a carbon compound.
An insulating film made of was formed. First, 500 x 500 mm
² , glass substrate 2 with 1.0 mm thickness and mirror-polished surface
04 was brought into close contact with the heater 205, and polycrystalline Si (non-doped) was used for the target 216. Substrate temperature is 35
At 0 ° C., the film thickness is 5 μm, a voltage of 150 V is applied to the bias electrode 210, the microwave power is 800 W, and CH ₄
150 sccm and Ar 200 sccm were introduced, and a deposited film made of SiC was formed in the same manner as in Example 1.

<Comparative Example 4> Target 2 made of SiC
16 was used to form an insulating film made of SiC similar to that of Example 4 by ECR sputtering. <Evaluation 4> When the insulating property (resistivity) and the uniformity of the deposited film were examined, the deposited film of Example 4 was superior to Comparative Example 4, and the deposited film of this Example was deposited by conventional deposition. It turned out to be superior to the membrane.

Example 5 A bias electrode 210 and a bias power source (DC power source) 203 are installed in the deposition apparatus 200 shown in FIG. 2 as shown in FIG. 6, and a semiconductor thin film made of n-type amorphous Si is used as a semiconductor. Formed. First, 500 × 5
A glass substrate 204 having a size of 00 mm ² , a thickness of 1.0 mm and a mirror-polished surface was brought into close contact with the heater 205, and polycrystalline Si (non-doped) was used as the target 216. Substrate temperature is 600 ° C., film thickness is 1 μm, and bias electrode 210 has 1
A voltage of 00 V is applied, microwave power is set to 500 W, and PH ₃ is 10 scc as a reactive gas to be introduced.
m, Ar gas is introduced at 300 sccm, pressure is 4 mTorr
As r, a semiconductor thin film made of n-type amorphous Si was formed in the same manner as in Example 1.

Comparative Example 5 A semiconductor thin film made of n-type amorphous Si similar to that in Example 5 was formed by the reactive radio frequency (RF) sputtering method. The target and the reactive gas introduced were the same as in Example 5. <Evaluation 5> When the conductivity and uniformity of the deposited film were examined, the deposited film of Example 5 was superior to Comparative Example 5, and the deposited film of this Example was superior to the conventional deposited film. I found out that

Example 6 The heater 205 of the deposition apparatus 200 shown in FIG. 2 is insulated from the deposition chamber 201 as shown in FIG. 6, the substrate bias power source (DC power source) 218 is connected to the heater 205, and the amorphous state is obtained. A magnetic thin film made of GdTbFe was formed. First, 10 glass substrates 204 having 6 ″ φ, a thickness of 1.0 mm and a mirror-polished surface are brought into close contact with the heater 205, a mechanism for rotating the heater 205 is attached, and the heater 205 attached with the substrate is rotated. The target 216 is formed of GdT.
bFe (15:15:70) was used. Substrate temperature is 20
° C., 0.04 .mu.m thickness, substrate voltage of 100V is applied to the microwave power as 500 W, bubbled with Ar was Fe (C ₅ H ₅₎ and 100 sccm, an Ar 100
Amorphous GdTb was introduced in the same manner as in Example 1 by introducing sccm.
A magnetic thin film made of Fe was formed. Next, GdTbFe
An insulating film made of SiN of Example 3 was formed on the top.

Comparative Example 6 A magnetic thin film made of amorphous GdTbFe similar to that in Example 6 was formed by a reactive radio frequency (RF) sputtering method, and an insulating film made of SiN was formed on the magnetic thin film. <Evaluation 6> Coercive force of deposited film, Kerr rotation angle (780 n
m), the uniformity was examined, and it was found that the deposited film of Example 6 was superior to Comparative Example 6, and the deposited film of this Example was superior to the conventional deposited film.

Example 7 In the deposition apparatus 200 shown in FIG.
Install the toroidal coil 221 as shown in FIG.
gF₂ To form an antireflection film. First, Example 5
A substrate 204 on which the same n-type amorphous Si is formed as a heater
-205 and the target 216 is made of MgF.₂ To
Using. Substrate temperature 200 ℃, film thickness 0.1μm, carp
The electric current is supplied to the target 221 and the tora is rotated around the target 216.
A toroidal magnetic field on the
0W, F₂10 sccm, 30 Xe instead of Ar
Introducing 0 sccm, and in the same manner as in Example 1, MgF ₂From
An antireflection film was formed.

<Comparative Example 7> Similarly, an antireflection film made of MgF ₂ similar to that of Example 7 was formed on the same n-type amorphous Si substrate as that of Example 5 by the reactive magnetron sputtering method. did. <Evaluation 7> When the reflection spectrum and the uniformity of the deposited film were examined, the deposited film of Example 7 was superior to Comparative Example 7, and the deposited film of this Example was superior to the conventional deposited film. I found out that

Example 8 An RF power source was connected to the target electrode 209 of the deposition apparatus 200 shown in FIG.
A transparent conductive film made of ZnO was formed in the same manner as in Example 1 except that power was applied. When the same evaluation as that of Evaluation 1 was performed, ZnO having the uniformity and the transmittance which were substantially the same as those of Example 1 and the deposition rate and the conductivity which were superior to those of Example 1 were obtained.

Example 9 A DC power source was connected to the target electrode 209 of the deposition apparatus 200 shown in FIG.
A transparent conductive film made of ZnO was formed in the same manner as in Example 1 except that power was applied. When the same evaluation as that of Evaluation 1 was performed, ZnO having the uniformity and the transmittance which were substantially the same as those of Example 1 and the deposition rate and the conductivity which were superior to those of Example 1 were obtained.

Example 10 Same as Example 1 except that a bias electrode 210 as shown in FIG. 6 is arranged in the deposition apparatus 200 of FIG. 2, a bias power source (DC) is connected, and DC power of 250 V is applied. Then, a transparent conductive film made of ZnO was formed. When the same evaluation as that of Evaluation 1 was performed, ZnO was obtained, which had the same degree of uniformity as that of Example 1 and was superior to Example 1 in deposition rate, conductivity, and transmittance.

Example 11 In the deposition apparatus 200 of FIG. 2, the heater 205 is insulated from the deposition chamber 201 as shown in FIG. 6, the heater 205 is connected to the substrate bias power source (DC) 218, and the DC power of 270 V (substrate A transparent conductive film made of ZnO was formed in the same manner as in Example 1 except that the positive side was applied.

When the same evaluation as that of Evaluation 1 was performed, ZnO was obtained in which the conductivity and the transmittance were the same as those in Example 1, and the deposition rate and the uniformity were superior to those in Example 1. << Example 12 >> As in Example 1, except that the toroidal coil 221 was installed in the deposition apparatus 200 shown in FIG. 2, a current was passed, and a magnetic field was formed around the target 216, transparent made of ZnO. A conductive film was formed.

When the same evaluation as the evaluation 1 was performed, ZnO having the uniformity and the conductivity which were the same as those of the example 1 and the deposition rate and the transmittance which were superior to those of the example 1 were obtained. Example 13 Using the roll-to-roll deposition apparatus shown in FIG. 4, the tandem solar cell shown in FIG.
3) was produced.

In this apparatus, a substrate delivery chamber 410, a plurality of deposition chambers 410 to 409, and a substrate winding chamber 411 are sequentially arranged, and a separation passage 412 is connected between them to form a strip-shaped substrate 413. It is possible to continuously move from the substrate delivery chamber 410 to the substrate winding chamber 411 through the inside of the chamber and simultaneously form respective deposited films in the respective deposition chambers 401 to 409.

In the deposition chambers 401, 402, 409, the deposited film of this embodiment can be formed, and the deposition chambers 403, 40
4, 407 and 408, a microwave plasma CVD method can be performed by attaching a microwave applicator, and RF plasma CVD is performed in the deposition chambers 405 and 406 by placing an RF electrode inside.
The law can be implemented.

A halogen lamp heater for heating the substrate was installed in each deposition chamber. 450 is a deposition chamber 403-
In a top view of 08, each deposition chamber has a gas inlet 414 and an exhaust outlet 415. Deposition chamber 401, 40
In Nos. 2 and 409, microwave power can be applied from the front side of the paper surface of the figure, and the exhaust direction of the reactive gas is the back side of the paper surface. The direction of the strong electric field of the microwave is the direction of arrow A in the figure, which is parallel to the target surface.

The distance between the microwave introduction window and the target was 100 mm. Deposition chambers 401, 402, 409
Has a reactive gas inlet 426, which is connected to a gas supply device similar to that of the first embodiment, and the deposition chambers 403 to 408 each have a source gas inlet for forming a deposited film by a plasma CVD method. 414, and a raw material gas supply device for mixing and introducing a plurality of raw material gases was connected to each.

At the exhaust ports 415 of the deposition chambers 405 and 406, mechanical booster pumps are used as vacuum exhaust pumps.
An oil diffusion pump is connected to the other deposition chamber. Also,
An RF power source was connected to each RF electrode, and a MW power source was connected to the microwave applicator 417. Further, a bias electrode 431 was installed in each of the deposition chambers 404 and 407, which are i-type layer deposition chambers, and an RF power source was connected as a power source.

The target of the deposition chamber 401 is A
1Si, ZnO is used as the target of the deposition chamber 402, and In ₂ O ₃ —SnO ₂ (1: 1) is used as the target of the deposition chamber 409.
Was used. 440 is a side view of the deposition chambers 401, 402, 409. By arranging a target having a surface area slightly smaller than the substrate area in the deposition chamber substantially in the center of the deposition chamber, 440 The deposition rate is set such that the deposition rate at the central portion 442 is made higher than the deposition rate at 441 near the interface with the substrate and the deposition rate at 443 near the surface.

The separation passage 412 connected to the deposition chamber has an inlet 419 into which scavenging gas He is introduced. The substrate delivery chamber 410 has a delivery roll 420 and a guide roller 421 for applying an appropriate tension to the substrate and keeping it always horizontal. The substrate winding chamber 411 has a winding roll 422 and a guide roller 423. First, a strip-shaped stainless steel sheet having a length of 300 m, a width of 50 cm, and a thickness of 0.1 mm is wound around a delivery roll 420, set in the substrate delivery chamber 410, passed through each deposition chamber, and then the end of the substrate is taken up by a substrate winding roll 422. Wrapped around. The entire apparatus was evacuated by a vacuum exhaust pump, the lamp heater 418 in each deposition chamber was turned on, and the substrate temperature in each deposition chamber was set to a predetermined temperature.

When the pressure of the entire device is 1 mTorr or less
He gas is made to flow in through the scavenging gas inlet 419,
While moving the board in the direction of the arrow in the figure,
It is wound up by the reel 422, and SiH is deposited in the deposition chamber 401._Four 
And Ar, O in the deposition chamber 402 ₂And Ar in the deposition chamber 409
Is O₂ And Ar were flown in a predetermined amount. In other deposition chambers
Each source gas was flowed. At this time, the flow into each deposition chamber
To prevent the raw material gas to be diffused into other deposition chambers, separate each
Flow rate of He gas flowing into the path 412, or each deposition
The chamber pressure was adjusted.

Next, RF power and MW power are introduced into each deposition chamber to cause glow discharge, and the deposition chambers 401, 402, 4
In 09, the deposited film of this embodiment is formed, and the deposition chambers 405, 4
In 06, the deposited film was formed by the RF plasma CVD method, and in the other deposition chambers, the deposited film was formed by the microwave plasma CVD method, which were successively formed simultaneously. A light reflecting film of AlSi (substrate temperature 350 ° C., film thickness 0.2 μm) is formed on the substrate in the deposition chamber 401, and ZnO is further deposited in the deposition chamber 402.
Transparent conductive wire (substrate temperature 350 ° C., film thickness 4.0 μm), first n-type layer (P-doped amorphous Si: H layer thickness 0.02 μm) in the deposition chamber 403, first i-type layer in the deposition chamber 404. Mold layer (amorphous SiGe layer thickness 0.15 μm), first in deposition chamber 405
P-type layer (B-doped microcrystalline Si: H 2 layer thickness 0.01 μm
m), a second n-type layer (P-doped amorphous S) in the deposition chamber 406.
i: H layer thickness 0.02 μm), the second i in the deposition chamber 407
Mold layer (amorphous Si: H 2 layer thickness 0.23 μm), deposition chamber 4
08, the second p-type layer (B-doped microcrystalline Si layer thickness 0.0
1 μm) and a transparent conductive film made of ITO (substrate temperature 160 ° C., layer thickness 0.07 μm) was sequentially formed in the deposition chamber 409.

When the winding of the substrate is completed, the plasma is extinguished, the introduction of all gases is stopped, and when the pressure inside the deposition chamber becomes 0.1 mTorr or less, the entire deposition apparatus is leaked and the roll-shaped substrate 413 Took out. When the surface roughness of the deposited film was examined with a stylus type film thickness meter,
It was found that the height of the mountain was 0.19 μm on average. This is because the substrate temperature when forming the AlSi light-reflecting layer and the ZnO transparent conductive film was as high as 350 ° C., and the surface of these films was textured.

Next, a collector electrode having a two-layer structure as shown in FIG. 5 was formed by a screen printer using a roll-to-roll system. First, a carbon paste having a thickness of about 1 μm is printed on the surface of the transparent conductive film of ITO in a shape of FIG. 5 and dried, and then a carbon paste having the same shape and a thickness of about 3 is formed on the surface of the carbon paste.
A μm Ag paste was printed, dried, and cut into a size of 10 cm × 25 cm as shown in FIG.

Comparative Example 13 AlSi Light Reflecting Film, ZnO
A tandem solar cell (comparative ratio 13) similar to that of Example 13 in which the transparent conductive wire of Example 1 and the transparent conductive film of ITO were formed by the reactive magnetron sputtering method was produced. First, AlSi is deposited using a deposition apparatus using the reactive magnetron sputtering method.
A light reflection film and a ZnO light reflection film were formed, a semiconductor layer (pinpin layer) was formed in the deposition apparatus of FIG. 4, and an ITO transparent conductive film was formed in the deposition apparatus using the reactive magnetron sputtering method. A current collecting electrode similar to that of No. 13 was formed and cut. The conditions for forming the semiconductor layer are as in Example 1.
It carried out on the same conditions as 3.

<Evaluation 13> Tandem solar cell (actual 1
3) and (ratio 13) initial photoelectric conversion efficiency (photoelectromotive force / incident light power), vibration deterioration, light deterioration, and film peeling were measured. The initial photoelectric conversion efficiency can be measured by placing the manufactured solar cell under AM-1.5 (100 mW / cm ² ) light irradiation and measuring the VI characteristic. As a result of the measurement, the reduction rate of the initial photoelectric conversion efficiency of (Comparative 13) was 0.93 times that of (Execution 13).

To measure the vibration deterioration, a solar cell whose initial photoelectric conversion efficiency was measured in advance was placed in a dark place with a humidity of 50% and a temperature of 25 ° C., and a vibration having a vibration frequency of 60 Hz and an amplitude of 0.1 mm was conducted for 500 hours. AM1.5 (100mW after adding
/ Cm ² ) The rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after vibration deterioration test / initial photoelectric conversion efficiency). As a result of the measurement, the reduction rate of the photoelectric conversion efficiency of (Comparative 13) was 0.92 times that of (Execution 13).

Photodegradation was measured by setting a solar cell whose initial photoelectric conversion efficiency had been measured in advance in an environment of a humidity of 50% and a temperature of 25 ° C. and applying AM-1.5 (100 mW / cm ² ) light. AM1.5 (100 mW / cm after irradiation for 500 hours
² ) The rate of decrease in photoelectric conversion efficiency under irradiation (photoelectric conversion efficiency after photodegradation test / initial photoelectric conversion efficiency) was used. As a result of the measurement, the reduction rate of the photoelectric conversion efficiency of (Comparative 13) was 0.90 times that of (Execution 13).

The state of film peeling after vibration deterioration was observed using an optical microscope. In (Exemplary 13), no film peeling was observed, but in (Comparative 13), the ZnO transparent conductive film and the first n
A slight film peeling was observed between the mold layers, and the shunt resistance was about 1/5 of (Act 13). As described above, it was found that the photovoltaic element using the deposited film of this example is superior to the photovoltaic element using the conventional deposited film.

Example 14 An insulating film made of SiN was formed using a substrate 500 having a step-like unevenness as shown in FIG. The forming conditions were the same as in Example 3. <Comparative Example 14> Similarly, the same insulating film made of SiN as in Comparative Example 3 was formed on the step-like substrate.

<Evaluation 14> As a result of comparing the two, it was found that Example 14 (FIG. 5-b) was superior in step coverage to Comparative Example 14 (FIG. 5-c).
As can be seen from the above examples, the deposited film of this example was found to be superior to the conventional deposited film.

Example 15 A deposited film made of ZnO was formed in the same manner as in Example 1 except that the distance between the target and the microwave introduction window was set to 60 mm, and a deposited film better than that in Example 1 was obtained. Was obtained. <Comparative Example 15-1> A deposited film made of ZnO was formed in the same manner as in Example 1 except that the distance between the target and the microwave introduction window was set to 30 mm, and the deposited film of Example 1 was better. Met.

<Comparative Example 15-2> A deposited film made of ZnO was formed in the same manner as in Example 1 except that the distance between the target and the microwave introduction window was 220 mm, and the deposited film of Example 1 was better. It was a very deposited film.

[0111]

As described above, according to the present invention, the deposited film can be formed on a large-area substrate at a high speed, is uniform, and has good quality, so that the productivity can be improved. Further, it is possible to form a deposited film in which the photodegradation and the vibration degradation of the deposited film are suppressed.

Further, productivity can be improved by continuous formation. In addition, film peeling is improved.

[Brief description of drawings]

FIG. 1 is a sectional view of a deposited film according to an embodiment of the present invention.

FIG. 2 is a conceptual diagram of a deposition apparatus for forming a deposited film according to this embodiment.

FIG. 3 Partially enlarged view of tandem solar cell

FIG. 4 is a conceptual diagram of a deposition apparatus for forming a deposited film according to another embodiment of the present invention.

FIG. 5 is a cross-sectional view of a deposited film formed on a stepped substrate according to this example.

FIG. 6 is a conceptual diagram of another deposition apparatus for forming a deposited film according to this embodiment.

[Explanation of symbols]

 101 deposited film 102, 204, 413, 500 substrate 201 deposition chamber 202 vacuum gauge 205 heater 206 waveguide 207 conductance valve 208 auxiliary valve 209 target electrode 211 gas inlet pipe 212 applicator 213 microwave inlet window 215 substrate shutter 217 target

Claims (10)

[Claims] 1. A vacuum container is provided with a target containing at least one of constituent elements of a deposited film so that the shortest distance from a microwave introduction window made of a dielectric material is 50 to 200 mm. Introduce reactive gas inside,
By irradiating the reactive gas with microwaves through the microwave introduction window so that the electric field direction is parallel to the target surface to generate plasma, and irradiating the target surface with ions in the plasma , Depositing an object to be deposited on the surface of a substrate arranged facing the target, and reacting the object to be deposited with radicals in plasma to form the deposited film containing a constituent element of the reactive gas. A method for forming a deposited film, which comprises forming on the surface of the substrate. 2. The target, direct current power or 1 to
The deposited film forming method according to claim 1, wherein the deposited film is formed while applying a high frequency power of 100 MHz. 3. The method for forming a deposited film according to claim 1, wherein a magnetic field surrounding the target is arranged. 4. The deposited film forming method according to claim 1, wherein a positive DC voltage is applied to the substrate. 5. The deposited film forming method according to claim 1, wherein a negative DC voltage is applied to the substrate. 6. The method for forming a deposited film according to claim 1, wherein an electrode is arranged inside the vacuum container, and a positive DC voltage is applied to the electrode. 7. The deposited film forming method according to claim 1, wherein an electrode is arranged inside the vacuum container, and high frequency power of 1 to 100 MHz is applied to the electrode. 8. The base is formed into a strip having flexibility,
Further, when forming the deposited film, the substrate is moved in the longitudinal direction thereof, and the deposited film forming rate near the substrate interface and the deposited film forming rate near the deposited film surface are made smaller than the deposited film forming rate in other regions. The method for forming a deposited film according to claim 1, wherein: 9. An exhaust port for evacuating the inside of the vacuum container, the microwave introduction window, the substrate,
2. The deposited film forming method according to claim 1, wherein the target and the target are arranged so as to surround the plasma. 10. A deposited film formed by the deposited film forming method according to claim 1.