WO2005059202A1 - Method for forming thin film and base having thin film formed by such method - Google Patents

Method for forming thin film and base having thin film formed by such method Download PDF

Info

Publication number
WO2005059202A1
WO2005059202A1 PCT/JP2004/018322 JP2004018322W WO2005059202A1 WO 2005059202 A1 WO2005059202 A1 WO 2005059202A1 JP 2004018322 W JP2004018322 W JP 2004018322W WO 2005059202 A1 WO2005059202 A1 WO 2005059202A1
Authority
WO
WIPO (PCT)
Prior art keywords
electric field
high
thin film
frequency electric
gas
Prior art date
Application number
PCT/JP2004/018322
Other languages
French (fr)
Japanese (ja)
Inventor
Hiromoto Ii
Original Assignee
Konica Minolta Holdings, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2003-417706 priority Critical
Priority to JP2003417706 priority
Application filed by Konica Minolta Holdings, Inc. filed Critical Konica Minolta Holdings, Inc.
Publication of WO2005059202A1 publication Critical patent/WO2005059202A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54Apparatus specially adapted for continuous coating
    • C23C16/545Apparatus specially adapted for continuous coating for coating elongated substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges

Abstract

Disclosed is a method for forming a thin film which enables to form a thin film with good quality at a high rate by generating a high-density plasma even when a low-cost discharge gas such as nitrogen is used. By this method, a base having a good and dense thin film can be produced at low cost. Specifically disclosed is a method for forming a thin film wherein a nitride film is formed on a base by supplying a gas containing nitrogen element in a discharge space and applying a high-frequency electric field, wherein a first high-frequency electric field and a second high-frequency electric field are superposed, to the discharge space at or near atmospheric pressure. In this method, the frequency (ω2) of the second high-frequency electric field is higher than the frequency (ω1) of the first high-frequency electric field, the relation among the strength (V1) of the first high-frequency electric field, the strength (V2) of the second high-frequency electric field, and the breakdown electric field strength (IV) satisfies V1 ≥ IV > V2 or V1 > IV ≥ V2, and the power density of the second high-frequency electric field is not less than 1 W/cm2.

Description

Substrate art that thin film is formed by the specification thin film forming method and the method

The present invention relates to a novel thin-film forming method and thin film type formed substrate including a thin film by a method using the atmospheric pressure plasma discharge treatment. BACKGROUND

In functional thin film formation, sputtering, various film formation methods such as CVD method forces exists S, atmospheric pressure plasma process which does not require a vacuum has attracted attention as a process technology. For example, Machimoto Document 1, by using a pulse power source, an atmospheric pressure plasma film formation technology that discharge can be achieved even in a high breakdown voltage gas such as nitrogen gas, the Patent Document 2 by the atmospheric pressure plasma method technique for forming a nitride film, also in Patent Document 3 in atmospheric pressure plasma method, decomposing the raw material in the plasma space, is disclosed respectively technology for forming a nitride film.

[Patent Document 1] JP-A-10 1 54 598 No.

[Patent Document 2] JP 2002- 324795 JP

[Patent Document 3] JP-2002- 151 513 JP

However, in the technique of Patent Document 1 plasma density is low, high-quality film is not obtained, et al. The only in the technique 峥許 Document 2 has a very surface (several nm) of the silicon substrate directly blown with nitrogen excited by plasma into the silicon substrate was replaced with nitrogen, and sufficient technical in selectivity of the substrate Ienare,. Also the present inventors have examined the technique shown open in Patent Document 3, although certainly film acids I arsenide silicon may, degradation of tetramethylsilane material is insufficient, in the silicon nitride film contaminated with many carbon component, it was found that not be expressing the functions of sufficient silicon nitride film. Further, there is no ί Maillet When a force et industrial advantages that are using the expensive argon and the helium discharge gas. The present invention has been made in view of the above problems, an object of the present invention, a high quality thin film containing nitrogen provides a thin film forming method capable of film formation at a high speed, thereby inexpensive high-performance thin film of good quality It is to provide to. Disclosure of the Invention

The present inventors have intensive studies results, by applying a specific high-frequency electric field, even at high discharge gas of discharge starting electric field strength, such as nitrogen, generation of high-density plasma can be achieved, high-quality thin film can be obtained, You can film at high speed, and further, low cost, and safely be operated, it has been found that even be achieved reduction of environmental load.

That is, the present invention comprises the following arrangement.

(Configuration 1) atmospheric or under pressure in the vicinity thereof, you containing a thin film forming gas into the discharge space a gas supply, the scan is excited by applying a high frequency electric field in the discharge space, was excited substrate in the thin film type forming method of forming a thin film on the substrate by exposure to the gas, the gas contains a gas having a nitrogen element, a thin film formed on the base material J is a nitride film, the high-frequency electric field is obtained by superposing the first high frequency electric field and the second high-frequency electric field, said first of said second high-frequency electric field than the frequency omega iota high frequency electric field frequency omega 2 is high, the first relationship between strength IV of strength the second high-frequency electric field of high-frequency electric field strength V 2 and discharge starting electric field,

V> IV> V. Or meet the V 1> IV≥V 2,

The power density of the second high-frequency electric field, a thin film forming method which is characterized in that at 1 W / cm 2 or more.

(Configuration 2) the discharge space, a thin film forming method according to Structure 1, characterized in that it is constituted by a first electrode and a second electrode opposed. '

(Configuration 3) the power density of the second high-frequency electric field, a thin film forming method according to Structure 1 or 2, characterized in that 5 OW / cm 2 or less.

(Configuration 4) the power density of the second high-frequency electric field, a thin film forming method according to configuration 3, wherein a is 2 OW / cm 2 or less.

(Configuration 5) a thin film forming method according to any one configuration of the structure 1-4 power density of the first high frequency electric field is a feature that is 1W / cm 2 or more.

(Configuration 6) the power density of the first high-frequency electric field, 5 OWZ cm 2 thin film forming method according to Structure 5, characterized in that less.

(Configuration 7) The first high-frequency electric field Contact Yopi thin film forming method according to any one configuration of the structure 1-6 wherein the second high frequency electric field is characterized in that it is a sine wave.

(Configuration 8) of the first high frequency electric field is applied to the first electrode, wherein the second high-frequency electric field to any one configuration of the configuration 2-7, characterized in that applied to the second electrode thin film forming method.

(Configuration 9) 90 to 99 of the total amount of gas supplied to the discharge space. 9 thin film forming method according to any one configuration of the structure 1-8, wherein the volume% are discharged gas.

(Configuration 10) the discharge gas, a thin film forming method according to Structure 9, characterized in that it contains 50-100% by volume of nitrogen gas. -

(Configuration 1 1) the discharge gas, a thin film forming method according to Structure 9 or 1 0 to contain a rare gas of less than 50% by volume and especially the number.

(Configuration 1 2) the thin film forming gas, an organometallic compound, metal halide, according to any one configuration of the structure 1 to 1 1, characterized in that it contains at least one selected from metal scrap hydride thin film forming method.

(Configuration 1 3) the organometallic compound, an organic silicon compound, an organic titanium compound, an organic tin compound, an organic zinc compound, characterized in that it contains at least one compound selected from organic Injiumu compound Contact Yopi organic Aruminiumuihi compound thin film forming method placing serial to configuration 1 2,.

(Configuration 1 4) Configuration 1-1 3 substrate characterized by having a thin film formed by the thin film forming method according to any one configuration of. BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic diagram showing an ^! Of atmospheric pressure plasma discharge treatment apparatus useful Jietsuto scheme present invention.

Figure 2 is a schematic diagram showing an example of an atmospheric pressure plasma discharge electrostatic processing apparatus of a system for processing a substrate between useful counter electrode to the present invention.

Figure 3 is a perspective view showing an example of a roll rotating electrode having a dielectric is coated conductive metallic base material and thereon.

Figure 4 is a perspective view showing an example of the structure of a dielectric is coated conductive metallic base material of the prismatic electrodes and thereon. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, plasma discharge treatment, on the order of 20 k P a~1 1 0 k P a is the atmospheric pressure or pressure force atmospheric or near performed at a pressure in the vicinity thereof, according to the present invention to obtain a good effect, 9 3 k P a~1 04 k P a is preferable. In the thin film forming method of the present invention, gas supplied between the opposing electrodes (discharge space) (or, even without less to form a discharge gas excited by an electric field, a thin film becomes Puwozuma state or excited state receives its energy it includes a thin film forming gas. Then, characterized by containing a gas having a nitrogen element discharging condition ί in. the present invention or, the discharge electric space, and a first high frequency electric field and the second high-frequency electric field superimposed, said first of said second high-frequency electric field than the frequency ωι of the high frequency electric field frequency omega 2 is high, and the strength of the have strength V of the first high frequency electric field and the second high-frequency electric field relationship between strength IV of V 2及Pi discharge starting electric field,

V x ≥ I V> V 2

Or meet the V 1> IV≥V 2,

The output density of the second high-frequency electric field, a is at 1 WZ cm 2 or more and especially ί insole. High frequency and refers to those having a frequency of at least 0. 5 kHz. High-frequency electric field superimposed, if are both sine wave becomes a first high-frequency electric field of a frequency ωι and the frequency ωι higher than the second high-frequency electric field of a frequency omega 2 and the superposed component, its waveform frequency on the sine wave of ωι, the維歯-shaped waveform higher than the sine wave of frequency ω 2 which it overlaps.

In the present invention, the intensity of discharge starting electric field, the actual thin film forming method (such as the electrode configuration) is that discharge electric space used and the minimum electric field strength can be between Okosuko discharge in the reaction conditions (such as gas conditions) It refers to. Discharge starting electric field strength is somewhat varies Te cowpea like dielectric species or inter-electrode distance of the gas species and electrode that will be supplied to the discharge space, in the same discharge space is governed by the discharge start electric field strength of the discharge gas . By applying a high frequency electric field that looks as though it described above the discharge space, causing a thin film capable of forming discharge, it is estimated that it is possible to generate a high density plasma necessary for high-quality thin film formation. The important here, such a high-frequency electric field is applied to the opposing electrodes, i.e., it is to be applied to the same discharge space. The application electrode 2 is juxtaposed, each spaced a different discharge spaces, in the method of applying different high frequency electric field, forming a thin film of the present invention can not be achieved. Note has been described superposition of the continuous wave of a sine wave like the above, is not limited thereto, be both pulse waves, one other is z in a continuous wave, may be a ° pulse wave Absent. Also, it may further have a third field.

As the gas containing nitrogen element in the present invention, nitrogen (N 2) in particular, nitriding oxygen (NO), nitrous oxide oxygen (N 2 0), ammonia (NH 3), hydrazine (N 2 H 4 ), Monomechiruhi hydrazine (CH 6 N 2), 1 , 1- dimethylhydrazine (C 2 H 8 N 2) , 1, 2- dimethylhydrazine (C 2 H 8 N 2), and the like, preferably nitrogen (N 2), oxygen nitride (NO), nitrous oxide oxygen (N 2 0), ammonia (NH 3). The nitride film of the present invention is that the XP S (X- ray Ph otoelectoron S pectroscopy) assay at you containing nitrogen element 1 0% or more film. Further, the ratio of the carbon element to be measured at this time is low more is not preferable. Specifically elemental nitrogen 20% or more, the carbon element is preferably 3% or less. 'Feature of the present invention, plasma density is up by devising a method of applying a high frequency, decomposition of the material is made sufficiently, by mixing into the formed film of carbon component in the original family can be extremely low is there. Further, it is possible to create more efficiently nitride film by the active nitrogen atoms excited by plasma in the case of using a nitrogen discharge gas.

The high-frequency electric field of the present invention, a specific method to be applied to the same discharge space, first applying a first high frequency electric field is a field intensity V i a frequency omega, the first electrode constituting a counter electrode 1 power connecting a Rukoto using an atmospheric pressure plasma discharge treatment apparatus connected to a second power source for applying a second high frequency electric field is a field intensity V 2 a frequency omega 2 in the second electrode. The atmospheric pressure plasma discharge treatment apparatus described above, between the opposing electrodes, it comprises a gas supply means for supplying and discharging gas and thin film forming gas. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode. The first electrode, the first power source or the one between them a first filter, and the second electrode, the second power supply or any crab between them is possible to connect the second filter preferably, the first filter comb Chasse passing a current of high frequency electric field of the 丄 to the first electrode from a first power source, a second high-frequency electric field of the current and over scan, a second from the second power source to the first power supply harder to pass a current of high-frequency electric field. The second filter in the opposite, from the second power supply easily pass through the mist flow of a second high frequency electric field to the second electrodes, and ground current of the first high-frequency electric field, first from the first power supply ability to hardly pass through the first high-frequency electric field current to the 2 haze source to use what is provided. Here, hard and passes, preferably, 2 0% current, more rather preferably refers to impervious only 1 0% or less. The easily pass Conversely, preferably 80% or more of current, and more preferably refers to the passage of more than 90%.

Furthermore, the first power of the atmospheric pressure plasma discharge treatment apparatus of the present invention preferably has the ability to apply a high frequency electric field intensity higher than the second power. Here, Le in the present invention, the Hare high frequency electric field strength (applied electric field strength) and the discharge start electric field strength is measured by the following method; refers to was.

High frequency electric field intensity V and V 2 (Unit: k V / mm) of the measuring method:

A high-frequency voltage probe (P 6 0 1 5 A) installed in the electrode portions, the high-frequency voltage probe, the output signal an oscilloscope (T ektronix Co., TDS 3 0 1 2 B) To conversion continued, the field intensity Measure. Discharge starting electric field strength IV (Unit: k V / mm) of the measuring method:

The discharge gas is supplied between the electrodes, will increase the field strength between the electrodes, a discharge is the electric field strength is defined as a discharge starting electric field strength IV that starts. Instrument is the same as the high frequency electric field strength measurement.

By taking the discharge conditions specified in the present invention, in a discharge start electric field strength is higher discharge gas as for example nitrogen gas, to start the discharge, the high density and stable plasma state, can in maintenance, high performance it is possible to perform the film formation. If the discharge gas and the nitrogen gas by the above measurement, the discharge starting electric field intensity IV (1/2 Vp-p) is about 3. 7 k V / mm, therefore, in the above relationship, the first high-frequency the electric field intensity, lambda ≥ 3. nitrogen gas was excited by applying a 7 kVZmm, it can be a plasma state. Here, as the frequency of the first power source, the following can be used 200 kHz good Mashiku. As the electric field waveform may be a pulse wave or a continuous wave. The lower limit is desirably about 1 kH z. On the other hand, the frequency of the second power supply, 8 00 or more kH z is preferably used. As the frequency of the second power supply is high, the plasma density is high, dense and high quality thin film can be obtained. Les, the upper limit is Shi desirable approximately 200MH z. To apply a high frequency electric field from such two power supplies, the first and necessary and that initiates discharge of discharge gas having a high discharge start electric field strength by the high-frequency electric field, also a high frequency of the second high-frequency electric field and a high power density by increasing the plasma density to form a dense and high quality thin film is an important point of the present invention.

Further, by increasing the power density of the first high-frequency electric field, while maintaining uniformity of discharge, thereby improving the output density of the second high-frequency electric field. Thus, that a further uniform high-density plasma can be generated, and further improvement in the deposition rate, film quality of the leaves in both. In the atmospheric pressure plasma discharge treatment apparatus used in the present invention, the first filter, the first power source to easily pass through the first high-frequency electric field current to the first electrode, the second high-frequency daughter field current ground and to the second power supply hardly passes through the second high frequency electric field of a current to the first power supply. The second filter in the opposite, to easily pass through the second high frequency electric field of the current from the second collector ¾1 to the second electrode, and the ground current of the first high-frequency electric field, first from the first power supply a first high-frequency electric field of a current to the second power less likely to pass through. Oite the present invention, it can be used without limitation as long as the filter with such properties. For example, the first filter can be used several 1 0 p F. to several tens of thousand p F of the capacitor or several H about the coil, in accordance with the frequency of the second power supply. The second filter, using a 1 0 mu H or more coils according to the frequency of the first power source, can be used as a filter by grounding through these coils or capacitors.

Atmospheric pressure plasma discharge treatment apparatus used in the present invention, as described above, is discharged between opposing electrodes, the introduced gas between the opposing electrode and a plasma state, the inter-stand or the electrode between the counter electrode Thus the exposure of the substrate to be transferred to the gas in the plasma state, is intended to form a thin film on the substrate. As another method, the atmospheric pressure plasma discharge treatment apparatus, by discharge between the same opposite electrode to excite the gas introduced between the counter electrode or a plasma state, excited also in Jietsuto shape outside the counter electrode the balloon of plasma state gas, Jietsu preparative method for forming a thin film on the resulting counter substrate in the vicinity of the electrode (standing even if the transported may also have) by the exposure of the connexion the substrate there is of the device.

Figure 1 is a schematic view showing an example of atmospheric pressure plasma discharge treatment apparatus useful jet system in the present invention. Atmospheric pressure plasma discharge treatment apparatus Jietsuto method, plasma discharge electric apparatus, in addition to the electric field applying means having two power supply, in the Figure 1 (are illustrated in Figure 2 of the discussed later) which is not shown force gas supply means, a equipment that has an electrode temperature regulating means. Plasma discharge apparatus 1 0, the first electrode 1 1 has a counter electrode and a second electrode 1 2, between the counter electrode, from the first electrode 1 1 first power supply 2 frequency omega iota from 1, the first high frequency electric field of the electric field intensity current I 1 is applied, also from the second electrode 1 2 frequency omega 2 of the second power supply 2 2, electric field strength V 2, the current I 2 second high frequency electric field is adapted to be applied. The first power supply 2 1 high-frequency electric field strength has high than the second power supply 2 2 (V i> V 2 ) can be applied, and also the first frequency ω ι of the first power? Original 2 1 of the second power supply 2 2 a lower frequency than the second frequency ω 2 can be applied. First electrode 1 1 and between the first power source 2 1, a first filter 2 3 is installed, and easily passes through the current from the first power source 2 1 to the first electrode 1 1, second ground current from the power supply 2 2, that have current from the second collector? Hara 2 2 to the first power supply 2 1 is designed to be hard to pass. -

Further, a second electrode 1 2 between the second power supply 2 2, the second filter 2 4 are installed, and from the second power supply 2 2 easily passes through the current to the second electrode, the first ground power 2 1 power et current is designed from the first power source 2 1 to hardly pass through the current to the second power supply. The first electrode 1 1 and between the second counter electrode of the electrode 1 2 (discharge space) 1 3, introducing a gas G from the gas supply means such as that shown in FIG. 2 described later, the first electrodes 1 1 and to generate applied to discharge high frequency electric field from the second electrode 1 2 and the gas G was blown into the Fine-preparative shaped lower side of the counter electrode while the plasma state (lower side), the counter electrode satisfy the processing space to create in the lower surface and the substrate F in the gas G ° in the plasma state, based on wind-(unwinder) force ^ winding loosened come to convey the force of the substrate which is not shown, there have before on a base material F coming transported from step to form a thin film in the vicinity of the processing position 1 4. During thin month trillions formed, the medium from the electrode temperature regulating means such as that shown in FIG. 2 described later to heat or cool the electrodes through a pipe. The temperature of the substrate during the plasma discharge treatment, may the physical properties and composition of the resulting thin film varies, it appropriately controlled to Rukoto respect is desired. The medium temperature control, distilled water, insulating material such as oil is used rather preferable. During the plasma discharge treatment, it is desired that the temperature unevenness of the substrate in the width direction or longitudinal direction is adjusted uniformly the internal temperature as possible occur not like electrode.

Also, showing the measurement instrument used for measurement of high-frequency electric field strength (applied electric field strength) and the discharge start electric field strength of the aforementioned first FIG. 2 5 and 2 6 are high frequency voltage probe, 2 7 及 beauty 2 8 is an oscilloscope.

Since the atmospheric pressure plasma discharge treatment apparatus Jiwetto type contact multiple groups can discharge the gas in the same plasma state simultaneously arranged in series, can also be processed at high speed is processed many times. Further, if gas Jietsuto 嘖射 a plasma state each device different, it is also possible to form a multilayer thin film of different layers.

Figure 2 is a schematic diagram showing an example of an atmospheric pressure plasma discharge electrostatic processing apparatus of a system for processing a substrate between useful counter electrode to the present invention. Atmospheric pressure plasma discharge treatment apparatus of the present invention, at least, a plasma discharge treatment apparatus 3 0, electric field applying means 4 0 having two power, gas supply means 5 0, in a device having an electrode temperature controlling means 6 0 is there. Figure 2 is a mouth Lumpur rotating electrode (first electrode) 3 5 and prismatic fixed electrodes between the opposing electrodes of the (second electrode) 3 6 (discharge space) 3 2, plasma discharge substrate F processed and is to form a thin film. The roll rotating electrode (between the counter electrodes) (first electrode) 3 5 and prismatic fixed electrodes discharge collector space between the (second electrode) 3 6 3 2, roll rotating electrode (first electrode) 3 5 the first power supply 4 1 power et frequency omega iota the first high frequency electric field, also prismatic fixed electrostatic-polar (second electrode) 3 6 frequency from the second power source 4 and second field intensity current I 1 omega 2, the electric field strength V 2, and summer to exert the second high frequency electric field of the current I 2. Between the roll rotating electrode (first electrode) 35 and the first power supply 41, first filter 43 is installed, the first filter 43 shielding pass the current to the first power supply 41 Power et first electrode comb, and ground the current from the second power source 42, is designed to the second power source 42 hardly passes through a current to the first power supply. Further, prismatic fixed electrodes (second electrode) 3 6 between the second power source 42, a second filter 44 is installed, the second Fielder 44, second electrode from the second power source 42 and easily pass through the current to, and grounded first conductive? Hara 41 force these currents are t designed to the first power source 41 hardly passes through a current to the second power supply. In the present invention, the roll rotating electrode 35 second electrode, also the prismatic fixed electrode group 36 may be used as the first electrode. The first power source to the first electrode anyway, but also to the second electrode is connected to a second power supply. The first power source is preferably applied high frequency electric field strength than the second power source, a>.

In addition, the frequency has the ability to become a ωι <ω 2. The current is preferably Rukoto Do as I 1 rather I 2. Current I 1 of the first high-frequency electric field E is preferably 0. 3~2 OmA / cm 2, more preferably 1. 0~2 OmAZcrm 2. The current I 2 of the second髙周wave electric field is preferably 10 to 100 m ZCM 2, more preferably 2 0~10 OmAZcm 2.

Gas G was generated, t in the gas generator 51 of the gas supply means 50 is introduced from the air supply port 52 into the plasma discharge processing chamber 31 to control the flow rate. Blocking the substrate F, come to convey the force or process come to convey unwound from wind-based I not been illustrated, the air, etc. come entrained is a substrate in Eppuroru 65 via guide rolls 64 and, it moved to feed between the roll rotating electrode 35 square fixed electrode group 36 while turning wind-remain in contact with the roll rotating electrode (first electrode) 35 and the square tube type fixed electrodes (second electrode) applying an electric field from both the 36, between the counter electrodes (discharge space) to generate a discharge plasma in 3 2. Substrate F is thin is formed on the surface by the wound while the plasma state gas remains in contact with the mouth Lumpur rotary electrode 35. Substrate F is - Ppuroru 6 6, via a guide roll 6 7, to transfer the force next step to take wind-in wind-up machine (not shown).

Discharge treated process waste gas G 'is discharged from the exhaust port 5 3. During film formation, to heat or cool the roll rotating electrode (first electrode) 3 5 and prismatic fixed electrode (second electrode) 3 6, the medium and the temperature was adjusted at the electrode temperature regulating means 6 0, feed sent to both electrodes through the pipe 61 in a liquid pump P, and adjust the temperature from the electrodes inside. Incidentally, 6 8 and 6 9 are partition plates for separating the flop plasma discharge treatment container 3 1 and the outside world.

Figure 3 is a perspective view showing an example of the structure of the dielectric conductive metallic base material of the roll rotating electrode that is coated thereon as shown in Figure 2. In Figure 3, roll electrode 3 5 a are those conductive metal base material 3 5 A thereon the dielectric 3 5 B coated. To control the electrode surface temperature during plasma discharge treatment, the medium for temperature control (water or silicone oil) has a structure that can be circulated.

Figure 4 is a perspective view showing an example of the structure of the dielectric conductive metallic base material of the prismatic electrode that is coated thereon. The In FIG. 4, prismatic electrode 3 6 a, compared metallic base material 3 6 A conductive, has a coating of Figure 3 similar dielectric 3 6 B, the structure of the electrode it becomes the pipe of metallic, it becomes a jacket, and summer so as to enable temperature adjustment clause in the discharge. The number of square tube type fixed electrodes are being plural placed along a larger circumference than the circle circumference of the roll electrode, the discharge area of ​​the electrode faces the mouth Lumpur rotary electrode 35 It is expressed by the sum of the areas of full-width tubular fixed electrode surface. Prismatic electrode 3 6 a shown in FIG. 2, may be a cylindrical electrode but, prismatic electrodes Te ratio base to the cylindrical electrode, since the effect of widening the discharge range (discharge area), the present invention Ru is preferably used to. In Figure 3 及 Pi Figure 4, a roll electrode 3 5 a and prismatic electrodes 3 6 a is 3 their respective conductive metallic base material 5 A and 3 6 dielectric 3 5 B over A after spraying ceramics as 及 Pi 3 6 B, it is obtained by sealing treatment using the sealing material of the inorganic compound. Ceramic Dielectric #: it may be in the coating of about 1 mm in semi meat. The ceramic box material used for spraying, alumina, silicon nitride or the like is preferably used, § Among the alumina since easily processed, particularly preferably used. The dielectric layer may be a lined dielectric body provided an inorganic material by Rainin grayed.

The metal base material 3 5 A and 3 6 A conductive, titanium metal or titanium alloy, silver, platinum, stainless steel, or aluminum, a metal such as iron or the like, a composite material of iron and ceramic task or Aruminiumu it can be mentioned a composite material of ceramics, particularly preferably titanium metal or titanium alloy for reasons described below.

Distance between the electrodes of the first electrode and the second electrode facing the case of providing either the dielectric of the electrode, the shortest distance between the conductive metal base material surface of the other electrode and the dielectric surface say that. If both of the electrodes is provided a dielectric refers to the shortest distance of the distance between the dielectric surface. The distance between the electrodes, conductive metallic base material provided with a dielectric thickness of the applied electric field strength magnitude, the force any cases that are determined in consideration of the purpose and the like utilizing a plasma even uniform 0 from the viewpoint of performing the discharge. 1 to 2 O tnm preferably, particularly preferably 0.. 5 to 2 mm.

It will be described in detail later for a useful conductive metallic base material and the dielectric to the present invention.

Plasma discharge vessel 3 1 it is also possible to use a metal if Torere insulation of the force electrode used rather preferably Pyrex (R) glass processing vessel and the like. For example, aluminum or the inner surface of the stainless steel frame may be affixed to polyimide resins, etc., the thermally sprayed ceramic to the metal frame row-and insulating may be convex. In FIG. 1, it is preferably covered sides parallel the both electrodes (to near the substrate surface) in those materials as described above.

The first power source installed in the atmospheric pressure plasma discharge treatment apparatus of the present invention (high-frequency power supply),

Applied power symbol Studio frequency Product Name

A1 Shinko Electric 3 kHz SPG3-4500

A2 Shinko Electric 5 kHz SPG5- 4500

A3 Kasuga Electric Works 15 kHz AG 1 -023

A4 Shinko Electric 50 kHz SPG50- 4500

A 5 Heiden Institute 100 kHz * PHF- 6 k

A6 Pearl Kogyo 200 kHz CF- 2000- 200 k A 7 Pearl Kogyo 400 kHz CF-2000-400 k commercially available ones can be cited, such as, any can be used (

Further, as the second power source (high frequency power supply),

1 power symbol menu, - car-frequency; the product name

B 1 Pas, Lumpur industrial 800 kH z CF- 2000- 800 k

B 2 Pa, - Le industrial 2MH ZCF- 2000- 2M

B 3 path, Lumpur industrial 13. 56MH Z CF- 5000- 13M

B 4 Pa, Lumpur industrial 27MH Z CF- 2000- 27M

B 5 Pa, - Le Industrial 150MH ZCF- 2000- commercially available ones can be cited, such as 150M, both also preferably used. Among the above-mentioned power supply marked * is Haiden Laboratory Inparusu high-frequency power source (100 k H z in continuous mode). Otherwise a high-frequency power source capable of applying only continuous sine waves. The Te present invention smell, by applying the electric field, it is preferable to employ electrodes capable of maintaining a uniform and stable discharge state to the atmospheric pressure plasma discharge treatment apparatus.

In the present invention, power applied between opposing electrodes, the second electrode (the second high-frequency electric field) supplies LWZcm 2 or more power (power density), to generate a plasma by exciting a discharge gas It energizes the film forming gas to form a thin film. The upper limit of the electric power to be subjected sheet to the second electrode is preferably 50 W / cm 2, more preferably 20W Z cm 2. The lower limit is preferably 1. 2 WZ cm 2. Incidentally, the discharge area (cm 2) refers to the area of the range where the discharge occurs in the electrode. Also, the first electrodes (first high-frequency electric field), by the this supplying LWZcm 2 or more power (power density), while maintaining uniformity of the second high frequency electric field, improving the output density be able to. This can generate further uniform high-density plasma, compatible improvement and enhancement of quality of the further deposition rate. Preferably is 5 W / cm 2 or more. Upper limit of the power to be supplied to the first electrode is preferably 5 OWZcm 2. Examples of the waveform of the high frequency electric field is not particularly limited. A continuous sine wave continuous oscillation mode called a continuous mode, there is an intermittent oscillation mode in which the O NZO FF called pulse mode intermittently performed, may it be performed by either the at least a second electrode side (the second high-frequency electric field) is preferred because more precise and high-quality film is more of a continuous sine wave is obtained. Electrodes to be used in thin film forming method according to the goodness UNA atmospheric pressure plasma is structurally must also be able to withstand the harsh conditions in terms of performance. As such an electrode, it is preferable that coating the dielectric on the metal base material.

In the dielectric coated electrode for use in the present invention, preferably has the characteristics fit between the various metal base material and the dielectric, as a characteristic of the one linear thermal expansion between the metal base material and the dielectric the difference of the coefficient is of the combination of the following 1 0 X 1 0 one 6 Z ° c. Preferred properly is 8 X 1 0 one 6 / ° C or less, more preferably 5 X 1 0- 6 / ° C or less, further preferable properly is less than 2 X 1 0 one 6 Z ° C. Note that the linear thermal expansion coefficient is a known material-specific physical property values. Difference in linear thermal expansion coefficient, as a combination of conductive metal base material and the dielectric in this range,

1: metal base material is pure titanium or a titanium alloy, dielectric ceramics sprayed film

2: metal base material is pure titanium or a titanium alloy, a dielectric glass lined

3: metal base material is stainless steel, the dielectric ceramics sprayed film

4: metal base material is stainless steel, dielectric glass-lined

5: metal base material is a composite material of Seramittasu and iron, dielectric ceramics sprayed

6: metal base material is a composite material of ceramics and iron, dielectric glass-lined

7: metal base material is a composite material of ceramics and aluminum, dielectric ceramic sprayed coating '

8: metal base material is a composite material of Seramittasu and aluminum, dielectric Garasurai - is ring like.

From the viewpoint of the difference in linear thermal expansion coefficient, the first term is preferred binomial and 5-8 Section 1 Section especially preferred.

In the present invention, a metal base material is from above characteristics titanium or titanium alloy is useful especially. By the metal base material and the titanium or titanium alloy, by the dielectric and the degradation of the electrode during use, in particular cracks, peeling, dropout or the like is rather Na, prolonged use in harsh conditions it can withstand.

Metallic base material of the electrodes useful in the present invention is a titanium alloy or titanium metal containing titanium 7 0 wt% or more. In the present invention, the content of titanium in the titanium alloy or titanium in the metal as long 7 0 wt% or more, can be used without problems, preferably preferably those which contain 8 0 mass% or more of titanium . Useful titanium alloy or titanium metal in the present invention can be used commercially pure titanium, which is commonly used as a corrosion-resistant titanium, high-strength titanium. The commercially pure titanium, TIA, TIB, TIC, there may be mentioned TID like, both those iron atom, a carbon atom, a nitrogen atom, an oxygen atom, are negligible containing hydrogen atoms such as, titanium the content has a higher 9 9 wt%. As the titanium alloy contains aluminum, other T 6 containing vanadium and tin 4, T 3 2 5, T 5 2 5, TA 3 or the like can be used favorable preferred, these titanium the content, those containing more than 8 5 mass%. These titanium alloy or titanium metal of stainless steel, for example in comparison with AISI 3 1 6, the thermal expansion coefficient of 1 Z 2 degrees smaller dielectric described later as the metal base material was applied over the titanium alloy or titanium metal the combination of the body is rather good, able to withstand high temperature, use of a long time.

Meanwhile, as for the characteristics required for the dielectric, specifically, it is preferable that a dielectric constant of no machine compounds of 6 to 4 5, also, as such a dielectric is alumina, nitride, of silicon ceramics etc, or Kei silicate-based glass, there is a glass lining material such as borate glass. Among these, Le Shi preferred those provided by Ya glass lining obtained by spraying a ceramic will be described later. Particularly dielectric provided by thermally spraying the alumina is preferred. Or, as one of the specifications to withstand large power as described above, the porosity of the dielectric 1 0% by volume or less, it is preferably at most 8% by volume, preferably from 0 body product. /. At most 5% by volume beyond. Incidentally, the porosity of the dielectric may be measured by BET adsorption method and mercury porosimeter. In the examples below, using the pieces of coated dielectric metal base material by steel mercury porosimeter Shimadzu fabrication plants, it measures the air porosity. Dielectric, by having a low porosity, high durability Ru is achieved. Such as a low dielectric porosity while having a gap, it may be mentioned high density by atmospheric plasma spraying method or the like described later, the ceramic thermal sprayed coating or the like of the high-adhesion. To further lower the porosity, it is preferable to perform the sealing treatment.

The atmospheric plasma spraying method. Fine powder such as ceramics, charged wire or the like in the plasma heat source, blowing the metal base material to be coated as a melt or a semi-molten state particles, techniques for forming a film it is. The plasma heat source, and the molecular gas to a high temperature, is dissociated into atomic, Ru hot plasma gases der obtained by further emit electrons energized. Injection velocity of the plasma gas is large, the conventional arc spraying or flame spraying Te ratio base, since the spray material collide with the metal base material at high speed, it is possible adhesion strength is high, to obtain a high-density target film . For details, reference can be made to the spraying method for forming a heat-shielding film to a high temperature to be 曝部 material according to 2 0 0 0 3 0 1 6 5 5 JP. By this method, it is possible to void ratio of the dielectric that covers the above-mentioned (thermally sprayed ceramic film). As another preferred specifications to withstand high power is that the thickness of the dielectric is 0. 5 to 2 mm. The variation in film thickness is desirably 5% or less, preferably 3% or less, more preferably 1% or less. In order to further reduce the void ratio of the dielectric, the sprayed coating of ceramic such as described above, Shi further row Ukoto is like the sealing treatment with inorganic compounds les. Examples of the inorganic compounds, metal Sani 匕物 are preferred, those containing particularly oxidation Kei containing in this (S i O x) as a main component is preferable.

Inorganic compounds of sealing treatment is preferably one formed by curing a sol-gel reaction. Inorganic compounds of sealing treatment when as a main component metal Sani 匕物 is a metal alkoxide or the like is coated on the ceramic spray layer as a sealing solution, cured by Sorge Le reaction. In the case of those inorganic I 匕合 product is mainly composed of silica, it is preferable to use Al Kokishishiran as sealing liquid. Here, the promotion of the sol-gel reaction, it is preferable to use the energy process. As energy process, Netsukati匕 (good Mashiku is 2 0 0 ° C or less) and there is an ultraviolet radiation. Further as a method of sealing treatment, dilute a sealing solution, repeated several times and curing the coating by successively more and when improved so inorganic Shitsui匕 can not dense electrode deterioration. .

A metal alkoxide such dielectric-coated electrodes according to the present invention as a sealing solution, was coated on the ceramics sprayed film, the content of the case, the metal oxides after turned into hard to perform sealing treatment to cure by a sol-gel reaction preferably is 6 0 mol% or more. When using an alkoxysilane as a metal alkoxide Fuanaeki is, S i Ο χ after curing (x is 2 or less) it is preferable that the content is 6 0 mol% or more. S i Omicron chi content after curing, by XPS (X-ray photoelectron spectroscopy) to measure Ri by the analyzing the fault dielectric layer.

In the electrode according to the thin film forming method of the present invention, so that the maximum surface roughness defined by JISB 0 6 0 1 on the side in contact with at least the base material of the electrode height (Rm ax) is below 1 0 / m Although from the viewpoint of obtaining the effects described in force present invention to adjust the, still more preferably the maximum value of the surface roughness is less 8 mu m, particularly preferably by adjusting below 7 mu m . By a method such as this as final polishing of the dielectric surface of the dielectric-coated electrodes, dielectrics Giyappu between thickness and the electrodes can be kept constant, that the discharge state can be stabilized further thermal shrinkage difference or residual without distortion or cracking due to stress, and, with high precision, it is possible to greatly improve the durability. Polished of the dielectric surface is Shi preferred to be performed in the dielectric on the side in contact with at least a base material. Further JISB 0 6 0 1 a defined by the center line average surface roughness (R a) is 0. Less preferably 5 mu m, still more preferably 0. 1 m or less.

In the dielectric-coated electrode for use in the present invention, in the other preferred specifications to withstand high power is that the heat resistant temperature is 1 0 0 ° C or higher. More preferably more than 1 2 0, particularly preferably 1 5 0 ° C or higher. The upper limit is 5 0 0 ° C. Note that the heat resistance temperature, dielectric breakdown does not occur in the voltage used in the atmospheric pressure plasma treatment, it refers to the highest temperature that can withstand the conditions which can normally discharge. Such heat temperature is above or ceramics sprayed, the range of the difference in linear thermal expansion coefficient of the or apply settings digit dielectric glass lining different layered bubble mixing amount, the metal base material and the dielectric It can be achieved by combining the means for selecting the material of the inner appropriately needed.

Next, a description will be given gas supplied to the discharge space.

Supplying gas contains at least a discharge gas and thin film forming gas. Discharge gas and thin film forming gas may be supplied as a mixture, Kamawanare be supplied separately. The discharge gas is a gas capable of causing a thin film formation can glow one discharge. The discharge gas, nitrogen, noble gases, air, hydrogen gas, oxygen include, even with these alone as a discharge gas, may be used as a mixture. In the present invention, preferred is a nitrogen as a discharge gas. And this 5 0-1 0 0 vol% of the discharge gas is a nitrogen gas is preferred. At this time, as a discharge gas other than nitrogen as a discharge gas, it is preferable to contain a rare gas less than 5 0% by volume. Further, the amount of discharge gas, the total amount of gas supplied to the discharge space, 9 0-9 9. 9 preferably contains volume%. The thin film forming gas, itself becomes an active excites refers to a material that form a thin film by chemical deposition on a substrate.

Next, a description will be given gas supplied to the discharge space in order to form a thin film used in the present invention. It is basically the discharge gas and the thin film forming gas, further, there is also this addition of additive gas. In the total amount of gas supplied to the discharge space, a discharge gas 9 0-9 9. 9 preferably contains volume%.

The thin film forming gas used in the present invention include organic metal compounds, halogenated metal compounds, a metal hydride compound. Useful organometallic compounds in the present invention preferably exhibits the following general formula (I).

The general formula (I)

RX MR y R z

Wherein, M is a metal, R is a radical selected from an alkyl group, R is an alkoxy group, R is jS- diketone complex body group, Ketokarubon ester complex group, Ketokarubon acid complex Moto及 Pi Keto alkoxy group (Ketokishi complex group) , and the case of the valence of the metal M was set to m, it is x + y + z = m, x = 0~! II or x = 0~,! Is n- 1, y = 0~m, at z = 0 to m, all of which are 0 or a positive integer. The alkyl group of R, can be exemplified methylcarbamoyl group, Echiru group, a propyl group, a butyl group or the like. The an alkoxy group R, for example, main butoxy group, an ethoxy group, a propoxy group, a butoxy group, 3, 3, 3 - can be exemplified triflate Ruo b Provo alkoxy group. Or it may be obtained by replacing water atom alkyl groups with a fluorine atom. R of 3- diketone complexes group, the group selected from beta-Ke Tokarubon ester complex group, beta-keto carboxylic acid complex groups, and Ketokishi group (keto Okishi complex group), a beta-diketone complex group, for example, 2 , 4 (also referred to as Asechiruaseton or Asetaseton) Single-pentanedione, 1, 1, 1, 5, 5, Kisamechiru 2 to 5, 4-pentanedione, 2, 2, 6, 6 - tetramethyl one 3, 5 one heptane dione, 1, 1, -1-Bok Rifuruoro 2, 4 can be cited an base Ntanjion like, beta as Ketokarubon acid Esuteru complex groups, for example, Aseto acid methyl ester, Aseto acetate Echiruesuteru, Aseto acid propyl ester, Torimechirua Seto acetate Echiru, it can be cited triflate Ruo Roa Seto methyl acetate, etc., as Ketokarubon acids, for example, § DOO acetate, may be mentioned trimethyl Aseto acetate, also as Ketokishi, for example, can be exemplified Asetokishi group (or Asetokishi group), a propionyloxy Ruo alkoxy group, Puchirirokishi group, Atariroi Ruokishi group, methacryloyl Ruo alkoxy group. The number of carbon atoms in these groups include the examples organometallic shows compound, 1 8 or less. The intended also as straight or branched illustrative, or may be obtained by replacing hydrogen atoms with fluorine atoms.

From handling problems in the present invention, the organometallic compound is preferably an organometallic compound having a least one or more oxygen in the molecule Shi favored. Organometallic compounds containing at least one of such things as R alkoxy groups, also the R 13-diketone complex group, beta Ketokarubon ester complex group, beta-keto carboxylic acid complex groups 及 Pi Ketokishi group (Ketokishi metallic compound having at least one group selected from the complex group).

In the present invention, the gas supplied to the discharge space, a discharge gas, in addition to the film forming gas may be mixed with an additive gas for promoting the reaction of the thin film formation. The additional gas, oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, may be mentioned ammonia, oxygen, preferably one oxygenated carbon and hydrogen, a component selected from these It is preferable to mix. Its content is 0.0 is preferably contained 1-5 body volume% with respect to the gas total amount, is it by connexion reaction accelerator, and can form a dense and high quality thin film. Thickness of the thin film of oxide is the form or complex compound, 0 1~:. L 0 0 0 nm range is preferred.

In the present invention, the organic metal compound used in the film forming gas, metal halides, metal of the metal hydride, L i, B e, B, Na, Mg, A l, S i, K, C a, S c, T i, V, C r, Mn, F e, C o, n i, Cu, Zn, Ga, Ge, Rb, S r, Y, Z r, Nb, Mo, I n, I r, Sn , S b, C s, B a, L a, H f, Ta, W, T l, B i, C e, P r, Nd, Pm, Eu, Gd, Tb, Dy, Ho, E r, Tm , mention may be made of Yb, the L u like.

In the thin film forming method of the present invention, an organometallic compound as described above, halogen compounds, metal hydrogen compound having a high functionality by a metal compound for use with a discharge gas such as S i 3 N 4, NbN, T i N it is possible to obtain a thin film and the like. The present invention is not intended to be limited thereto. Incidentally, degree of nitriding of the nitride is only an example, the composition ratio of the metal may vary appropriately. Further, in the thin film, in addition to the metal compound, a carbon compound, nitrogen compound, impurities such as hydrogen compounds may be contained.

In the present invention, particularly metals of the preferred metal compounds, among the S i (silicon), T i (titanium), S n (tin), Zn (zinc), I n (indium) 及 Pi A 1 (Al Miniumu ), and, among the metal compounds that bind to these metals, the organometallic compound represented by the above general formula (I) are preferred. Useful tin compounds in the present invention, the organic stannided compounds, tin hydride, a tin halide, etc. Examples of the organic tin compounds, for example, di-butyl Honoré jet carboxymethyl tin, Puchinore tin tris (2, 4 one pentanedionate), Tetorae butoxy tin, methyltriethoxysilane tin, Jefferies chill jet alkoxy tin, triisopropyl E preparative carboxymethyl tin, Echiruetokishi tin, Mechirume butoxy tin, isopropyl propoxy tin, tetrabutoxytitanate tin, Jetokishi tin, dimethyl butoxy tin, Jiisopuropokishi tin, Jibutoki sheet tin, Jibuchirirokishi tin, Jechiru tin, tetrabutyl tin, tin bis (2, 4-penta Njionato), Echiru tin § Seto § Seto diisocyanate, ethoxy tin (2, 4-Pentanji. Onato), dimethyl tin di (2, 4 one pentanedionate), di § Seto methyl § cell start tin, Jiase Carboxymethyl tin, dibutoxy § Seto carboxymethyl tin, Jiasetokishi tin Jiase Tasetonato. Examples of the tin halide, tin chloride, can be exemplified Yonshioi 匕錫 like, both in the present invention can be preferably used . It is also possible to use a mixture of these thin film forming gas of two or more simultaneously.

Useful titanium compounds in the present invention, an organic titanium compound, titanium hydrogen compound, there are titanium halides such as organic titanium compounds, e.g., Torietokishichi Tan, trimethylene Tokishichitan, triisopropoxy titanium, tributoxy titanium, Te tiger ethoxy titanium, titanium tetraisopropoxide, Mechinorejime Tokishichitan, E Chino Les triethoxy titanium, methyl triisopropoxy titanium, triethyl Chino Les titanium, triisopropyl titanium, tributyl titanium, tetra E chill titanium, Tetoraisopu port Piruchitan, tetrabutyl titanium, tetra dimethyl Aminochitan, Jimechiruchita Nji (2, 4 one pentanedionate), Echiruchitantori (2, 4-Pentanjio diisocyanate), titanium tris (2, 4 _ pentanedionate), titanium Ntorisu (Aseto Mechiruasetato), tri § Seth alkoxy titanium, dipropoxy propionyloxy Ruo alkoxy titanium such as, dibutyltin Lilo alkoxy titanium, mono-titanium hydride as titanium hydride, Jichitan hydrogen compound such as titanium halide, trichloro port titanium, tetrachloroethene Rorochitan like can be cited, both as possible out preferably used in the present invention. Further away in it is used as a mixture of these thin film forming gas of two or more thereof.

Useful silicon compound in the present invention, organosilicon compounds, silicon hydride, etc. can be mentioned halogen of silicon compounds, the organic silicon compound, for example, tetra Echirushiran, tetramethylsilane, tetra isopropyl building silane, Tetorabuchirushi orchid, tetraethoxysilane, tetra-isopropoxide volume silane, tetra butoxy Sila down, Jimechirujime Tokishishiran, Jefferies chill jet silane, Jechirushiranji (2, 4 one pentanedionate), Mechirutorime Tokishishiran, methyl triethoxysilane down, Echirutori silane. Examples of the silicon hydrogen compounds, tetra-hydrogenated silane, to hexa hydrogenated disilane, etc., as the halogenated silicon I 匕合 thereof, include tetrachlorosilane, methyltrichlorosilane, the Jechirujiku port π silane Rukoto can both can be preferably used in the present invention. Further, it is possible to use the fluorine compound. These thin film forming gas can be used as a mixture of two or more thereof. These tin compounds for fine-tuning of the refractive index, titanium compound, may be used by mixing silicon compound suitably two or more simultaneously. The thin film forming gas, discharged from the viewpoint of forming a bra Zuma uniform thin film on the substrate by the process, content in the total gas is 0 0 1 -. 1 0 Although it is preferred to have a volume%, more preferably is 0.0 1-1% by volume.

It will be described base material used in the present invention. The substrate used in the present invention, plate-like, particularly limited as long as it a sheet-like or film-like planar shape, or a lens thin films such as those of the three-dimensional shape such as other molded product can be formed on the surface thereof Hana had. Les, restriction exposed to a mixed gas in a plasma state, the form or material of as long as the uniformity of the thin film is formed substrate be either transported state substrate is stationary state. Morphologically planar shape may be a three-dimensional shape, those planar shape, it may be mentioned a glass plate, a resin film or the like. As the material, a glass, a resin, ceramics, metals, and the that the various non-metallic or the like can be used. Specifically, the glass, a glass plate or lens or the like, as the resin, mention may be made of resin lens, a resin film, a resin sheet, a resin plate or the like. Since 榭 fat film can form an atmospheric pressure plasma discharge treatment apparatus of the inter-electrode or a transparent conductive film continuously transported near near the electrode according to the present invention, a patch, such as a vacuum system, such as sputtering not an expression, suitable for mass production, is suitable as a highly continuous productivity production system. A resin film, a resin sheet, a resin lens, a material of the resin molded product such as moldings, cellulose tri § cetearyl Ichito, cellulose diacetate, Senorerosu such as cellulose § cetearyl one Topurobione Ichito or cellulose § cetearyl one Tobuchire Ichito Esutenore, polyesters such as polyethylene terephthalate Ya polyethylene naphthalate over preparative, polyolefin down, polyvinylidene chloride, such as polyethylene Ya polypropylene, polyvinylidene chloride Bulle, poly Bulle alcohol, Echirenbini alcohol copolymer, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone, Indianapolis Honoré von, Porieteruimi de, made of polyamide, fluorine Fat, polymethyl § chestnut rate, can be cited Atari rate copolymers and the like. These materials alone is Rere can also be used by being appropriately mixed. Of these peptidase O Nex Ya Zeonoa (manufactured by Nippon Zeon Co.), (manufactured by diethyl yes Earl Co.) ARTON amorphous cyclo polio reflex in the resin off Ilm, Pure Ace (manufactured by Teijin Limited) of polycarbonate film, a cellulose triacetate film of Konikatatsu click KC 4 UX, it is possible to use preferably used commercially available products such as KC 8 UX (manufactured by Konica force Minolta Co.). Further, polycarbonate, polyarylate, size V of intrinsic birefringence, such as polysulfone and polyethersulfone, be filed by the material, solution casting film, conditions such as melt extrusion casting, even vertically, laterally it can be obtained which can be used by you to configure the stretching conditions and the like as appropriate. Of these cellulose ester film close to the optical isotropy is preferably used in an optical element of the present invention. The cellulose ester film, a cellulose tri § Se Tate film as described above, cellulose acetate propionate is one of those is preferably used. The cellulose triacetate film Konica tack KC4UX etc. 巿販 products are useful. Gelatin on the surface of these resins, poly Bulle alcohol, acrylic resins, polyester resins, may also be used those coated with a cellulose ester resin. The anti-glare layer on the thin film side of 榭脂 films, chestnut § hard coat layer, Paglia layer may be provided an antifouling layer or the like. The adhesive layer optionally alkali barrier coat layer may be provided a gas barrier layer Ya solvent resistance layer. Further, Rumotozai used in the present invention is not limited to the above described. Preferably 1 0~ 1 000 μπι the film thickness of those film-shaped, and more preferably from 40 to 200 im.

【Example】

Detail by the present invention through examples, but is not limited thereto.

Example 1

Using a long film Konica tack KC 4UX (1 500 m wind-film) as a substrate, coated with a hard coat layer backcoat layer and the front side on the back side as described below, it was wound as a film roll. Using this substrate, to produce a silicon nitride film on Fi Lum using the apparatus of Figure 2. That is, it loosened plated substrate from en winder one of the film roll to prepare barrier film (Sample No. 1 to 9) at atmospheric pressure plasma discharge treatment apparatus on the hard coat layer.

[Preparation of the substrate]

<Production of chestnut § hard coat layer-coated substrate>

On one side of Konica tack KC 4 UX provided a backcoat layer coating composition described below, on the other side, the dry film thickness 4 mu center line surface roughness of the m (R a) 1 5 nm chestnut § hard coat layer provided, to prepare a chestnut § hard coat layer-coated substrate.

"Grasshopper coat layer coating composition" acetone 3 0 parts by weight acetic Echiru 4 5 parts by weight isopropyl Honoré alcohol "Lumpur

Di § cetyl cellulose 0.2 wt% of 5 parts by Aerojiru 2 0 0 V (manufactured by Nippon § E port Gilles Co.) Aseton dispersion

0.1 part by weight

"Chestnut § hard coat layer coating composition"

Jipentaerisuri to Tall hexa Atari rates monomer 6 0 parts by Jipentaerisuri to Tall hexa Atari rate dimer 2 0 parts by Jipentaerisuri, Kisaakuri rate trimer or more components to Ichiru

2 0 parts by weight

. Dimethoxy benzophenone 4 parts acetic Echiru 5 0 parts by mass of methyl E chill ketone 5 0 parts by mass of isopropyl alcohol 5 0 'parts by

Preparation of Electrode]

In the atmospheric pressure plasma discharge treatment apparatus of FIG. 2 described above, and the set of prismatic electrode coated roll electrode and also the dielectric coated with a dielectric fabricated as follows. Roll electrode serving as the first electrode, to the titanium alloy T 6 4 jacket roll metal base material having a cooling means by cooling water, high density by an atmospheric pressure plasma method, coating the high adhesion of the alumina sprayed film It was made to be a mouth Lumpur diameter 1 0 0 0 mm φ. Perform dielectric surface polishing was sealing treatment 及 Pi coating was Rm a X and 5 m. The final dielectric porosity (porosity with a penetrating) is approximately 0% by volume, in this case S i O x content of the dielectric layer 7 5 mo 1%, also the final dielectric the film thickness was 1 0 the dielectric constant of 1 mm, the dielectric. Furthermore the difference in linear thermal expansion coefficient of the conductive metal base material and the dielectric 1. 7 X 1 0- 6, the heat resistance temperature was 2 6 0 ° C.

Meanwhile, prismatic electrode of the second electrode, to a hollow square tube type titanium alloy T 6 4 of the same dielectric coated under the same conditions, was opposed prismatic fixed electrodes. The dielectric of the square tube type electrode and that of the roll electrode, S i Omicron chi content of R max, the dielectric layer of the dielectric surface and the thickness of the dielectric and the dielectric constant, metallic base material and the difference in linear thermal Rise expansion coefficient of the dielectric, heat-resistant temperature of the addition electrode is finished almost the same physical properties as the first electrode. The prismatic electrode of this around the roll rotating electrode, the counter electrode gap was 2 five placed as l mm. Discharging the total area of ​​the square tube type fixed electrode group, 1 5 0 cm (length in the width direction) X 4 cm (length in the conveying direction) X 2 5 present (number of electrodes) = 1 5 0 0 0 cm It was 2. Note that both filters were placed the appropriate ones. During the plasma discharge, the first electrode (roll rotating electrode) and the second electrode (prismatic fixed electrodes) is heated and maintained to be 8 0 ° C, the roll rotating electrode is rotated with the drive following the good urchin a thin film formation was performed. The first field and the second field as the following conditions were grounded Zorezore to ground.

(First field)

Power supply type; A 5

Frequency ω ι; 1 0 0 k H ζ

The electric field strength; 8 k V / mm

(Second field)

; B 3 frequency ω 2; 13. 56Μ

Field intensity V 2; 0. 8 k V / mm

Pressure was 103 kP a, introduced mixed gas below the to the respective discharge spaces 及 Pi plasma discharge electrostatic processing apparatus inside, on the back coat layer 及 Pi chestnut § hardcoat layer-coated substrate chestnut § hard coat layer by plasma discharge thin film formation to obtain a sample 1-9 to prepare a barrier film. The discharge starting voltage of the nitrogen gas in the system was 3. 7 k V / miji. Both were conducted by installing a filter.

"Mixed gas composition"

Discharge gas: nitrogen 98.9 volume 0/0 film forming gas: tetra titanium isopropoxycarbonyl 0.1 volume 0/0

(Vaporized mixed argon gas by Lintec Corporation vaporizer)

Additive gas: N 2_Rei gas 1 vol 0 / o Note nitrogen-containing gas as shown in Table 1, a discharge gas species, and a barrier film 1-9 adopted. Measurement of the film thickness was formed, was 100 nm.

[Evaluation of membrane]

"Measurement of carbon content, nitrogen content"

The content of the carbon element-nitrogen element was measured using an XPS surface analyzer. Using VG Sa Yan Ti fixes Co. ES CALAB- 200 R in this embodiment. Mg is used for X-ray anode, output 600W (acceleration voltage 15 k V, E Mission current 4 OMA) was measured in. Energy resolution, when defined by the half-value width of the Ag 3 d 5Z2 peak was set to be 1. 5~1. 7 e V.

"Gas barrier properties of the ratings"

Oxygen permeability tester (Mo dern Co ntorol Co.; OX- TRAN2 / 2 0) was thus measured oxygen permeability excessively in 23 ° C, relative humidity of 80% of the target film. The results are shown in Table 1..

【table 1】

※ unit of oxygen transmission density [ml · 1 μ τα / m 2 · Idyn · atm]

Thin film forming method titanium nitride film produced by the present invention has a low carbon atom ratio, permeability of oxygen gas is lower than the comparative example, Paglia property was good. Industrial Applicability

The present invention, by using an inexpensive and safe discharge gas, such as nitrogen, can generate high-density plasma, also it is possible to obtain a dense thin film, the thin film makes possible the film more quality thin films at high speed forming method can provide. Thereby providing a substrate that have a high-performance thin film of good quality inexpensively.

Claims

The scope of the claims
1. under a pressure of atmospheric pressure or near, the discharge space by supplying a gas containing a thin film forming gas, the gas is excited by applying a high frequency electric field in the discharge space, the base material to the gas that caused excitation in the thin film formation how to form a thin film on the substrate by exposing the gas contains a gas having a nitrogen element, a thin film formed on the substrate is a nitride film, the high-frequency electric field is obtained by superimposing the first high frequency electric field and the second high-frequency electric field, the first frequency omega 2 is higher in the second high-frequency electric field than the frequency ωι high frequency electric field, said first high-frequency relationship between the intensity IV intensity V 2, and a discharge start electric field strength V 1 and the second high-frequency electric field of the electric field,
V x ≥ I V> V 2
Or V 1> IV≥V 2 to meet the power density of the second high frequency electric field is, thin film forming method which is characterized in that at 1 W / cm 2 or more.
2. the discharge space, a thin film forming method ranges first claim of claim, characterized in that it is composed of a first electrode and a second electrode opposed.
3. The power density of the second high-frequency electric field, a thin film forming method ranges first claim of claim, characterized in that at 5 OW / cm 2 or less.
4. The power density of the second high-frequency electric field, 2 OWZ thin film forming method ranges third claim of claim, wherein the cm 2 or less.
5. The first high-frequency electric field thin film forming method according to the range set forth in claim 1, wherein you wherein the output density of 1 W / cm 2 or more.
6. The power density of the first high-frequency electric field, 5 O WZ thin film forming method ranges fifth claim of claim, wherein the cm 2 or less.
7. The first high frequency electric field and a thin film forming method ranges first claim of claim to feature said second high frequency electric field is a sine wave.
8. The first high-frequency electric field is applied to the first electrode, the second thin film forming method ranges second claim of claim, characterized in that the applied before Symbol second electrode a high frequency electric field.
9. Thin film forming method ranges first claim of claims 9 0-9 9. 9% by volume of the total gas amount and said discharge gas der Rukoto supplied to the discharge space.
1 0. The discharge gas is 5 0-1 0 0 range paragraph 9 thin film forming method according to claim, characterized in that it contains% by volume of nitrogen gas.
1 1. The discharge gas, 5 0 thin film forming method billed ranging Section 9 wherein the containing rare gas than volume percent.
1 2. The film forming gas is an organometallic compound, metal halide, thin film forming method ranges first claim of claim, characterized in that it contains at least one selected metal hydride mosquito et al.
1 3. The organic metal compound is an organic silicon compound, an organic titanium compound, an organic tin compound, an organic zinc compound, claims, characterized in that it contains at least one compound Bareru selected from organic indium compound and an organoaluminum compound range thin film forming method of the first 2 Claims.
1 4. Claims first term - the first three terms any one substrate characterized by having a thin film formed by the thin film forming method according to.
PCT/JP2004/018322 2003-12-16 2004-12-02 Method for forming thin film and base having thin film formed by such method WO2005059202A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2003-417706 2003-12-16
JP2003417706 2003-12-16

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005516295A JPWO2005059202A1 (en) 2003-12-16 2004-12-02 Substrate including a thin film by a thin film forming method and the method

Publications (1)

Publication Number Publication Date
WO2005059202A1 true WO2005059202A1 (en) 2005-06-30

Family

ID=34697077

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/018322 WO2005059202A1 (en) 2003-12-16 2004-12-02 Method for forming thin film and base having thin film formed by such method

Country Status (2)

Country Link
JP (1) JPWO2005059202A1 (en)
WO (1) WO2005059202A1 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7934232B1 (en) 2000-05-04 2011-04-26 Jerding Dean F Navigation paradigm for access to television services
US7961643B2 (en) 2005-09-07 2011-06-14 Mcdonald James F Optimizing data rates for video services to a subscriber
US7962370B2 (en) 2000-06-29 2011-06-14 Rodriguez Arturo A Methods in a media service system for transaction processing
US7975277B1 (en) 2000-04-03 2011-07-05 Jerding Dean F System for providing alternative services
US7992163B1 (en) 1999-06-11 2011-08-02 Jerding Dean F Video-on-demand navigational system
US8006262B2 (en) 2001-06-29 2011-08-23 Rodriguez Arturo A Graphic user interfaces for purchasable and recordable media (PRM) downloads
US8006273B2 (en) 2001-06-29 2011-08-23 Rodriguez Arturo A Updating download options for unavailable media content
US8020184B2 (en) 1999-06-11 2011-09-13 Jerding Dean F Channel control system for exiting from an interactive program guide
US8032914B2 (en) 2000-11-10 2011-10-04 Rodriguez Arturo A Systems and methods for dynamically allocating bandwidth in a digital broadband delivery system
US8037504B2 (en) 1999-06-11 2011-10-11 Jerding Dean F Video on demand system with selectable options of configurable random-access control
US8069259B2 (en) 2000-06-09 2011-11-29 Rodriguez Arturo A Managing removal of media titles from a list
US8161388B2 (en) 2004-01-21 2012-04-17 Rodriguez Arturo A Interactive discovery of display device characteristics
US8191093B2 (en) 2001-06-29 2012-05-29 Rodriguez Arturo A Providing information pertaining to audio-visual and personal bi-directional services
US8516525B1 (en) 2000-06-09 2013-08-20 Dean F. Jerding Integrated searching system for interactive media guide
US8640172B2 (en) 2001-06-29 2014-01-28 Cisco Technology, Inc. System and method for characterization of purchasable and recordable media (PRM)
US8707153B2 (en) 2000-06-09 2014-04-22 Cisco Technology, Inc. Displaying comment data corresponding to a video presentation
US8745656B2 (en) 2002-02-11 2014-06-03 Cisco Technology, Inc. Tracking of presented television advertisements
JP2016062803A (en) * 2014-09-19 2016-04-25 パナソニックIpマネジメント株式会社 Device and method for plasma processing, and manufacturing method of electronic device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09326387A (en) * 1996-06-06 1997-12-16 Matsushita Electric Ind Co Ltd Film formation method and its device
JP2002043286A (en) * 2000-07-19 2002-02-08 Tokyo Electron Ltd Plasma processing device
JP2003092200A (en) * 2000-12-12 2003-03-28 Canon Inc Method and apparatus for vacuum treatment, semiconductor apparatus and production method for semiconductor apparatus
JP2003105541A (en) * 2001-09-28 2003-04-09 Konica Corp Method of forming film, base material and display device
JP2004068143A (en) * 2002-06-10 2004-03-04 Konica Minolta Holdings Inc Thin film depositing method, and base material with thin film deposited thereon by the thin film depositing method
JP2004084027A (en) * 2002-08-28 2004-03-18 Konica Minolta Holdings Inc Functional body and method for forming the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09326387A (en) * 1996-06-06 1997-12-16 Matsushita Electric Ind Co Ltd Film formation method and its device
JP2002043286A (en) * 2000-07-19 2002-02-08 Tokyo Electron Ltd Plasma processing device
JP2003092200A (en) * 2000-12-12 2003-03-28 Canon Inc Method and apparatus for vacuum treatment, semiconductor apparatus and production method for semiconductor apparatus
JP2003105541A (en) * 2001-09-28 2003-04-09 Konica Corp Method of forming film, base material and display device
JP2004068143A (en) * 2002-06-10 2004-03-04 Konica Minolta Holdings Inc Thin film depositing method, and base material with thin film deposited thereon by the thin film depositing method
JP2004084027A (en) * 2002-08-28 2004-03-18 Konica Minolta Holdings Inc Functional body and method for forming the same

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8020184B2 (en) 1999-06-11 2011-09-13 Jerding Dean F Channel control system for exiting from an interactive program guide
US8056106B2 (en) 1999-06-11 2011-11-08 Rodriguez Arturo A Video on demand system with dynamic enablement of random-access functionality
US7992163B1 (en) 1999-06-11 2011-08-02 Jerding Dean F Video-on-demand navigational system
US8037504B2 (en) 1999-06-11 2011-10-11 Jerding Dean F Video on demand system with selectable options of configurable random-access control
US7975277B1 (en) 2000-04-03 2011-07-05 Jerding Dean F System for providing alternative services
US7992166B2 (en) 2000-04-03 2011-08-02 Jerding Dean F Providing alternative services based on receiver configuration and type of display device
US8739212B2 (en) 2000-05-04 2014-05-27 Cisco Technology, Inc. Configuration of presentations of selectable TV services according to usage
US7934232B1 (en) 2000-05-04 2011-04-26 Jerding Dean F Navigation paradigm for access to television services
US8707153B2 (en) 2000-06-09 2014-04-22 Cisco Technology, Inc. Displaying comment data corresponding to a video presentation
US8516525B1 (en) 2000-06-09 2013-08-20 Dean F. Jerding Integrated searching system for interactive media guide
US8069259B2 (en) 2000-06-09 2011-11-29 Rodriguez Arturo A Managing removal of media titles from a list
US7962370B2 (en) 2000-06-29 2011-06-14 Rodriguez Arturo A Methods in a media service system for transaction processing
US8032914B2 (en) 2000-11-10 2011-10-04 Rodriguez Arturo A Systems and methods for dynamically allocating bandwidth in a digital broadband delivery system
US8191093B2 (en) 2001-06-29 2012-05-29 Rodriguez Arturo A Providing information pertaining to audio-visual and personal bi-directional services
US8006273B2 (en) 2001-06-29 2011-08-23 Rodriguez Arturo A Updating download options for unavailable media content
US8006262B2 (en) 2001-06-29 2011-08-23 Rodriguez Arturo A Graphic user interfaces for purchasable and recordable media (PRM) downloads
US8640172B2 (en) 2001-06-29 2014-01-28 Cisco Technology, Inc. System and method for characterization of purchasable and recordable media (PRM)
US8745656B2 (en) 2002-02-11 2014-06-03 Cisco Technology, Inc. Tracking of presented television advertisements
US9615139B2 (en) 2004-01-21 2017-04-04 Tech 5 Determining device that performs processing of output pictures
US8161388B2 (en) 2004-01-21 2012-04-17 Rodriguez Arturo A Interactive discovery of display device characteristics
US7961643B2 (en) 2005-09-07 2011-06-14 Mcdonald James F Optimizing data rates for video services to a subscriber
US8189472B2 (en) 2005-09-07 2012-05-29 Mcdonald James F Optimizing bandwidth utilization to a subscriber premises
JP2016062803A (en) * 2014-09-19 2016-04-25 パナソニックIpマネジメント株式会社 Device and method for plasma processing, and manufacturing method of electronic device

Also Published As

Publication number Publication date
JPWO2005059202A1 (en) 2007-07-12

Similar Documents

Publication Publication Date Title
RU2462534C2 (en) Plasma treatment of surface using dielectric barrier discharges
JP4388804B2 (en) Composite of substrate material and barrier layer material
EP0605534B1 (en) Apparatus for rapid plasma treatments and method
US20120107607A1 (en) Multilayered material and method of producing the same
US7112370B2 (en) Vapor-deposited film
US20040091637A1 (en) Corona-generated chemical vapor deposition on a substrate
US5304407A (en) Method for depositing a film
EP1729892B1 (en) Method for coating a substrate using dielectric barrier discharge
JP4821610B2 (en) Transparent gas barrier film
Alexandrov et al. Chemical Vapor Deposition Enhanced by Atmospheric Pressure Non‐thermal Non‐equilibrium Plasmas
KR100949218B1 (en) Dielectric-Coated Electrode, Plasma Discharge Treatment Apparatus and Method for Forming Thin Film
JP5362941B2 (en) Composite materials having improved chemical resistance
EP0601166A4 (en) Methods and apparatus for depositing barrier coatings.
US20110086178A1 (en) Ceramic coatings and methods of making the same
JP4254236B2 (en) Thin film forming method
JP4168676B2 (en) Film forming method
JPH08505186A (en) Protective films and methods for the article
EP1286382A2 (en) Atmospheric pressure plasma treatment apparatus and method
CN101031669A (en) Multilayer coatings by plasma enhanced chemical vapor deposition
JP2000017457A (en) Thin film forming apparatus and thin film forming method
JP2003049272A (en) Atmospheric pressure plasma treating device, atmospheric pressure plasma treating method and electrode system for atmospheric pressure plasma treating device
EP2123445A1 (en) Transparent gas barrier film and method for producing the same
Baba et al. Synthesis and properties of TiO2 thin films by plasma source ion implantation
CN1312319C (en) Transparent conductive film forming method
US20040213920A1 (en) Layer formation method, and substrate with a layer formed by the method

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005516295

Country of ref document: JP

NENP Non-entry into the national phase in:

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase