WO2005116293A1 - Équipement pour former une pellicule mince et procédé pour former une pellicule mince - Google Patents

Équipement pour former une pellicule mince et procédé pour former une pellicule mince Download PDF

Info

Publication number
WO2005116293A1
WO2005116293A1 PCT/JP2005/008413 JP2005008413W WO2005116293A1 WO 2005116293 A1 WO2005116293 A1 WO 2005116293A1 JP 2005008413 W JP2005008413 W JP 2005008413W WO 2005116293 A1 WO2005116293 A1 WO 2005116293A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
electrode
film forming
impedance
gas
Prior art date
Application number
PCT/JP2005/008413
Other languages
English (en)
Japanese (ja)
Inventor
Kiyoshi Oishi
Kazuhiro Fukuda
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
Application filed by Konica Minolta Holdings, Inc. filed Critical Konica Minolta Holdings, Inc.
Priority to JP2006513834A priority Critical patent/JP4899863B2/ja
Publication of WO2005116293A1 publication Critical patent/WO2005116293A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32018—Glow discharge
    • H01J37/32045—Circuits specially adapted for controlling the glow discharge

Definitions

  • the present invention relates to an apparatus and a method for forming a thin film using an atmospheric pressure plasma discharge process.
  • Atmospheric pressure plasma CVD Chemical Vapor Deposition
  • Atmospheric pressure plasma CVD is being considered for practical use in forming deposited films in photoconductors for semiconductor devices, electrophotographic elements, various electronic elements, and optical elements.
  • an atmospheric pressure plasma processing apparatus for performing an atmospheric pressure plasma discharge process includes an atmospheric pressure plasma processing apparatus 1 using one high frequency power supply, and FIG. FIG.
  • the atmospheric pressure plasma processing apparatus 1 is connected to a power supply D which is a high-frequency power supply via a matching unit 11 for adjusting impedance, and is connected to a high-frequency electrode 12 composed of a metal base material 122 and a dielectric 121 so as to be grounded.
  • a metal base material 132 and an electrode 13 made of a dielectric material 131 on which a base material 14 is disposed are opposed to each other.
  • a gas mixture near the atmospheric pressure composed of a discharge gas and a thin film-forming gas is supplied between the high-frequency electrode 12 and the electrode 13 by a gas supply device (not shown).
  • a high-frequency voltage from D By applying a high-frequency voltage from D, a thin film is formed on the substrate 14.
  • the atmospheric pressure plasma processing apparatus includes an atmospheric pressure plasma processing apparatus la which is a high frequency power supply and has two power supplies having different frequencies.
  • the difference between the atmospheric pressure plasma processing apparatus la and the atmospheric pressure plasma processing apparatus 1 here is that the atmospheric pressure plasma processing apparatus la is connected to an electrode 13 on which a base material 14 is disposed by means of an LF matching unit 15 that boosts the voltage to an electrode 13. 1 This is the point where the power supply LF is connected.
  • the atmospheric pressure plasma processing apparatus la has a higher plasma density in the vicinity of the base material 14 and can form a better quality thin film.
  • the output of the power of the atmospheric pressure plasma processing apparatus is partially returned to the power as a reflected wave if the impedance of the power and the impedance of the plasma viewed from the electrodes are not the same, Can not be sent to In a plasma processing apparatus, it is necessary to maintain a constant power consumption in a plasma and maintain a stable plasma state in order to form a high-quality thin film having a uniform thickness at the time of film formation.
  • the atmospheric pressure plasma apparatus is provided with a matching box (matching box) for making the impedance the same, and is adjusted so that the impedance becomes the same in advance by a preliminary experiment or the like.
  • the matching device is equipped with a mechanism that automatically adjusts according to the impedance on the plasma side, which fluctuates depending on the power supply voltage, gas temperature, pressure, supply amount, and the like.
  • the matching device 11 in the atmospheric pressure plasma processing apparatus 1 and la adjusts the absolute value adjusting variable capacitor 21 for adjusting the absolute value of the impedance, and adjusts the phase of the impedance.
  • the phase adjustment variable capacitor 22, coil 23, and the absolute value adjustment variable capacitor 21 and coil 23 are automatically adjusted from the voltage value and current value between the power supply and the electrode to adjust the impedance of the power supply and the impedance of the plasma viewed from the electrode.
  • a control box 24 for making the same is attached, and an output from a power supply is sent to a maximum as a plasma output (for example, see Patent Document 1).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-268557
  • Patent Document 2 JP-A-8-96992
  • the above technique is an effective method for forming a thin film by plasma processing between a plurality of sets of electrodes.
  • the formation of high-quality thin films is still insufficient, and realizing a more stable plasma state has been a major issue. Therefore, the present invention has been made in such an industrial demand, and it is possible to generate high-density plasma while maintaining a stable discharge state, and to form a thin film capable of forming a good-quality thin film. It is to provide a device.
  • an output impedance of the AC power supply and the plurality of electrodes are provided.
  • a plurality of impedance matching devices for matching each input impedance of the pair are interposed, and based on the AC power supply or the voltage between the electrode pairs and the AC power supply or the current flowing between the electrode pairs,
  • the automatic adjustment means may use one of the plurality of impedance matching devices for any one of the impedance matching devices.
  • variable capacitor for absolute value adjustment is fixed, and the impedance is automatically adjusted using only the variable capacitor for phase adjustment.
  • said one of the impedance matching device, configured thin film forming apparatus so as to automatically adjust impedance by the absolute value adjusting variable capacitor and a phase adjusting variable capacitor scratch.
  • the impedance matching device has a variable capacitance capacitor for adjusting an absolute value of impedance, and the automatic adjusting means forms a thin film for adjusting the capacitance of the variable capacitance capacitor. apparatus.
  • the plurality of pairs of electrodes are a planar electrode in which one electrode is provided integrally in a planar shape, and the other electrode Is a thin film forming apparatus comprising a plurality of individual electrodes provided separately and separately opposed to said one electrode.
  • the plurality of pairs of electrodes are One electrode is a roll-type electrode provided so as to be rotatable in the circumferential direction, and the other electrode is a plurality of individual electrodes provided separately and opposed to the outer peripheral surface of the one electrode. Puru thin film forming equipment.
  • FIG. L (a) is a longitudinal sectional view of a thin film forming apparatus using an atmospheric pressure plasma process with one power source, and (b) is a thin film forming apparatus using an atmospheric pressure plasma process with two power sources.
  • FIG. 2 (a) is a longitudinal sectional view of a thin film forming apparatus for performing atmospheric pressure plasma processing on a substrate on a flat plate in the present invention, and (b) is an atmospheric pressure plasma on a substrate on a film in the present invention. It is a longitudinal section of a thin film formation device by processing.
  • FIG. 3 is a diagram showing an internal configuration of a matching device 11.
  • the plasma discharge treatment is performed at or near atmospheric pressure, and the pressure at or near atmospheric pressure is about 20 kPa to: about L10 kPa, which is a good value according to the present invention.
  • the pressure at or near atmospheric pressure is about 20 kPa to: about L10 kPa, which is a good value according to the present invention.
  • 93 kPa to 104 kPa is preferable.
  • the gas supplied between the opposed electrodes is at least a discharge gas excited by an electric field, and a plasma state or an excited state by receiving the energy to form a thin film. Contains a thin film forming gas to be formed.
  • the discharge condition in the present invention is that the first high-frequency electric field and the second high-frequency electric field are superimposed on the discharge space, and the frequency f of the second high-frequency electric field is higher than the frequency f of the first high-frequency electric field.
  • the frequency f of the second high-frequency electric field is 0.8 MHz or more and 200 MHz or less and the second high frequency
  • the electric field strength V of the wave electric field is 0.5 kVZmm or more, and
  • the frequency ⁇ of the first high-frequency electric field is 1 kHz or more and 500 kHz or less, and the electric field strength V force of the first high-frequency electric field is 4 kVZmm or more.
  • the frequency f of the first high-frequency electric field is 50 kHz or more and 100 kHz or less, the electric field strength of the first high-frequency electric field V force lOkVZmm or more, and the frequency f of the second high-frequency electric field f force ⁇ MHz or more 50 MHz
  • the electric field strength V of the second high-frequency electric field is 1.
  • High frequency refers to a high frequency of 0.5 kHz or more.
  • the intensity of the electric field at the start of discharge refers to the intensity of discharge occurring in a discharge space (such as the configuration of electrodes) and reaction conditions (such as gas conditions) used in an actual thin film forming apparatus. Refers to the lowest possible electric field strength.
  • the discharge starting electric field intensity varies depending on the kind of gas supplied to the discharge space, the dielectric material of the electrode, the distance between the electrodes, and the like. In the same discharge space, the discharge starting electric field intensity is dominated by the discharge starting electric field intensity of the discharge gas.
  • the force described for the superposition of the continuous wave such as the sine wave is not limited to this. If both the first high-frequency electric field V and the second high-frequency electric field V are pulse waves,
  • the high frequency electric field may be a pulse wave. Further, it may have a third electric field.
  • a first high-frequency electric field having a frequency f and an electric field strength V is applied to a first electrode constituting a counter electrode. Connect the first power supply to be applied, and connect the second electrode to the second electrode with frequency f and electric field strength V
  • the above-mentioned atmospheric pressure plasma discharge treatment apparatus includes a gas supply means for supplying a discharge gas and a thin film forming gas between opposed electrodes. Further, it is preferable to have an electrode temperature control means.
  • the first power supply of the atmospheric pressure plasma discharge treatment apparatus according to the present invention is higher than the second power supply.
  • V preferably having the ability to apply high frequency electric field strength.
  • the output density of the first high-frequency electric field V can be improved while maintaining the uniformity of the discharge.
  • Uniform high-density plasma can be generated, and further improvement in film forming speed and film quality can be achieved.
  • FIGS. 2 (a) and 2 (b) are longitudinal sectional views showing an example of an atmospheric pressure plasma discharge treatment apparatus of a type for treating a substrate between a plurality of counter electrodes useful in the present invention.
  • the number is preferably 10 or less, more preferably 2 to 5.
  • the atmospheric pressure plasma processing apparatus 2a includes a plurality of second power supplies HF1 to HF3 as second power supplies, dielectrics 121a to 121c, and a metal base material 122a.
  • a matching device 11a- Lie connected between the second power supply and the electrode for matching impedance with the electrodes arranged in close proximity to each other, and a first power supply as the first power supply.
  • LF matching device 15 connected between first power supply and electrode 13 to boost the voltage, film-like base material 14 placed on top of roll-type electrode and subjected to plasma treatment, and discharge space
  • a gas supply device 16 for supplying a mixed gas of a rare gas and a thin film to the gas.
  • the matching devices l la to l lc were connected to the variable capacitor 21 for absolute value adjustment and the variable capacitor 22 for phase adjustment to maximize the power output from the power supply through preliminary experiments. Is set in advance so as to be sent. Then, during operation of the apparatus, the absolute value adjusting variable capacitor 21 and the phase adjusting variable capacitor 22 are automatically adjusted by the control box 24 in any one of the matching devices l la to l lc. In other matching devices, only the absolute value adjusting variable capacitor 21 is fixed, and the phase adjusting variable capacitor 22 is automatically adjusted by the control box 24.
  • a single matching device automatically adjusts the absolute value of the impedance, which makes it possible to cope with fluctuations in the plasma state due to fluctuations in the gas inflow, etc., and stabilizes the formation of multiple thin films simultaneously. You can do it.
  • a plasma treatment can be continuously performed on a film-shaped substrate.
  • the atmospheric pressure plasma processing apparatus 2 shown in FIG. 2 (a) is configured by connecting a plate electrode 13 to a first power supply LF which is a first power supply of the atmospheric pressure plasma processing apparatus 2a, This is a device that performs plasma processing on 14.
  • the first power supply (high-frequency power supply) installed in the atmospheric pressure / atmospheric pressure plasma discharge treatment apparatus of the present invention includes:
  • A7 Pearl Industry 400kHz CF-2000-400k and other commercially available products can be used, and any of them can be used. [0038]
  • the second power supply high-frequency power supply
  • the asterisk (*) is the high-frequency power supply from Hyden Laboratory, Inc. (100 kHz in continuous mode). Others are high-frequency power supplies that can apply only continuous sine waves.
  • an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field to an atmospheric pressure plasma discharge treatment apparatus.
  • the first electrode (first high-frequency electric field) supplies an electric power (output density) of 1 WZcm 2 or more to excite the discharge gas. Energy to the thin film forming gas to form a thin film.
  • the upper limit value of the power supplied to the first electrode is preferably 50 WZcm 2 , more preferably 20 WZcm 2 .
  • the lower limit is preferably 1.2 W / cm 2 .
  • the discharge area (cm 2 ) refers to an area in a range where discharge occurs in the electrode.
  • the output density can be further improved.
  • the power of the second high-frequency electric field is preferably 5 WZcm 2 or more.
  • the upper limit is 50 WZcm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called continuous mode
  • an intermittent oscillation mode called pulse mode in which ONZOFF is performed intermittently.Either of these may be adopted, but at least the second electrode side (the second high frequency For the electric field, a continuous sine wave is preferable because a denser and higher quality film can be obtained.
  • the electrodes used in such a thin film formation method using atmospheric pressure plasma have a high performance even in terms of structure. It must be able to withstand severe conditions.
  • Such an electrode is preferably a metal base material coated with a dielectric.
  • the dielectric coated electrode used in the present invention One of the characteristics that preferably has characteristics between various metallic base materials and dielectrics is one of the characteristics.
  • the difference in the linear thermal expansion coefficient between the metallic base material and the dielectric is 10 ⁇ 10 — Combination of less than 6 Z ° C.
  • the linear thermal expansion coefficient is a physical property value of a known material.
  • the combination of a conductive metallic base material and a dielectric material having a difference in linear thermal expansion coefficient within this range is as follows: 1: The metallic base material is pure titanium or a titanium alloy, and the dielectric material is a ceramic. Sprayed coating 2: Metallic base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metallic base material is stainless steel, dielectric is ceramic sprayed coating 4: Metallic base material is stainless steel, Dielectric material is glass lining 5: Metallic base material is ceramic and iron composite material, dielectric material is ceramic sprayed coating 6: Metallic base material is ceramic and iron composite material, dielectric material is glass lining 7: Metallic The base material is a composite material of ceramics and aluminum, and the dielectric is a ceramic sprayed coating. 8: The metal base material is a composite material of ceramics and aluminum, and the dielectric is glass lining. . From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are particularly preferable, and 1 is particularly preferable.
  • titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics.
  • titanium or titanium alloy as the metallic base material and using the dielectric material as described above, it is possible to use the electrode for a long time under severe conditions where deterioration of the electrode during use, especially cracks, peeling, and falling off, etc. will not occur. Can withstand.
  • the metallic base material of the electrode useful in the present invention is titanium alloy or titanium metal containing 70% by mass or more of titanium.
  • the content of titanium in the titanium alloy or the titanium metal is 70% by mass or more, it can be used without any problem. /, Prefer things.
  • titanium alloys or titanium metals useful in the present invention those generally used as industrial pure titanium, corrosion-resistant titanium, high-strength titanium and the like can be used.
  • industrial pure titanium include TIA, TIB, TIC, and TID, all of which have very few iron, carbon, nitrogen, oxygen, and hydrogen atoms.
  • the titanium content is 99% by mass or more.
  • T15PB can be preferably used as the corrosion resistance titanium alloy, which contains lead in addition to the above-mentioned contained atoms, and has a titanium content of 98% by mass or more.
  • the titanium alloy in addition to the above-mentioned atoms except for lead, T64, ⁇ 325, ⁇ 525, ⁇ 3 and the like containing aluminum and also containing vanadium and tin can be preferably used. The content is 85% by mass or more.
  • These titanium alloys or titanium metals are made of a stainless steel, for example, having a coefficient of thermal expansion smaller than that of AISI316 by about 1/2, as a metallic base material, and a later-described dielectric applied on the titanium alloy or titanium metal. The combination can withstand high temperature and long time use.
  • an inorganic compound having a relative dielectric constant of 6 to 45 is preferably used.
  • glass lining materials such as silicate glass and borate glass. Among them, those formed by spraying ceramics described later and those provided by glass lining are preferred. In particular, a dielectric provided by spraying alumina is preferable.
  • the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, and more preferably more than 0% by volume. Less than 5% by volume.
  • the porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment coated on a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved by the dielectric having a low porosity.
  • a dielectric material having such voids but having a low porosity there can be mentioned a ceramic sprayed film having a high density and a high adhesion by an atmospheric plasma spraying method described later.
  • a sealing treatment it is preferable to perform a sealing treatment.
  • the above-mentioned atmospheric plasma spraying method is a technique in which fine powders such as ceramics, wires and the like are charged into a plasma heat source and sprayed as molten or semi-molten fine particles onto a metal base material to be coated to form a film.
  • the plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further applied with energy to emit electrons.
  • the spray speed of this plasma gas is higher than that of conventional arc spraying or flame spraying. Since the material collides with the metal base material at a high speed, a high-density coating film having high adhesion strength can be obtained.
  • the thickness of the dielectric is 0.5 to 2 mm. This variation in film thickness is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.
  • a sprayed film of ceramics or the like is used as described above.
  • an inorganic compound it is preferable to perform a sealing treatment with an inorganic compound.
  • inorganic compounds metal oxides are preferred, and those containing silicon oxide (SiO 2) as a main component are particularly preferable.
  • the inorganic compound for the pore-sealing treatment is preferably formed by curing by a sol-gel reaction.
  • a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction.
  • the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.
  • the energy treatment include thermal curing (preferably at 200 ° C. or lower) and ultraviolet irradiation.
  • thermal curing preferably at 200 ° C. or lower
  • ultraviolet irradiation ultraviolet irradiation
  • the cured metal oxide is used.
  • the content of the substance is preferably 60 mol% or more.
  • the content of SiO (X is 2 or less) after curing is preferably 60 mol% or more.
  • the SiO content after curing is measured by analyzing the tomography of the dielectric layer by XPS (X-ray photoelectron spectroscopy).
  • the maximum height (R) of the surface roughness defined by JIS B 0601 on at least the side of the electrode which is in contact with the substrate is set to be 10 m or less. Adjustment is preferable from the viewpoint of obtaining the effects described in the present invention, but more preferably, the maximum value of the surface roughness is 8 m or less, particularly preferably 7 m or less. In this way, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and the heat shrinkage can be achieved by polishing the dielectric surface of the dielectric coated electrode. Distortion and cracks due to differences and residual stress can be eliminated, and high accuracy and durability can be greatly improved.
  • Polishing of the dielectric surface is preferably performed on at least the dielectric in contact with the substrate.
  • the center line average surface roughness (Ra) specified in JIS B 0601 is preferably 0.5 ⁇ m or less, more preferably 0.1 m or less.
  • the heat-resistant temperature is 100 ° C or higher. It is more preferably at least 120 ° C, particularly preferably at least 150 ° C. The upper limit is 500 ° C.
  • the heat-resistant temperature refers to the highest temperature that can withstand a state in which dielectric breakdown does not occur and a normal discharge can be performed with respect to a voltage used in atmospheric pressure plasma processing.
  • Such a heat-resistant temperature is determined by applying the above-described ceramic spraying or a dielectric provided with a layered glass lining having a different amount of bubbles mixed therein, or a range of a difference in linear thermal expansion coefficient between the metallic base material and the dielectric. It can be achieved by appropriately combining the means for appropriately selecting the materials within.
  • the supplied gas contains at least a discharge gas and a thin film forming gas.
  • the discharge gas and the thin film forming gas may be supplied as a mixture, or may be supplied separately.
  • the discharge gas is a gas that can generate plasma capable of forming a thin film.
  • the discharge gas include nitrogen, a rare gas, air, hydrogen gas, and oxygen, and these may be used alone as a discharge gas or may be used as a mixture.
  • nitrogen is preferable as the discharge gas.
  • 50 to 50% of discharge gas It is preferable that LOO volume% is nitrogen gas.
  • the discharge gas other than nitrogen preferably contains a rare gas in an amount of less than 50% by volume.
  • the amount of the discharge gas is preferably 90 to 99.9% by volume based on the total amount of gas supplied to the discharge space.
  • the thin film forming gas itself is activated by dissociation or excitation and becomes chemically active on the substrate. It is a raw material that is deposited on to form a thin film.
  • a gas supplied to a discharge space for forming a thin film used in the present invention will be described.
  • a discharge gas and a thin film forming gas Further, an additive gas may be added.
  • the discharge gas preferably contains 90 to 99.9% by volume of the total gas supplied to the discharge space.
  • the thin film forming gas used in the present invention includes an organometallic compound and a halogen metal compound.
  • Organometallic compounds useful in the present invention are preferably those represented by the following general formula (I).
  • M is a metal
  • R is an alkyl group
  • R is an alkoxy group
  • R is a j8-diketone complex group
  • the alkyl group for R include a methyl group, an ethyl group, a propyl group, and a
  • alkoxy group for R for example, methoxy group, ethoxy
  • a group selected from a diketone complex group, a ⁇ -ketocarboxylic ester complex group, a ⁇ -ketocarboxylic acid complex group and a ketoxoxy group ketoxoxy complex group
  • a ⁇ -diketone complex group such as 2,4 pentanedione Cetylacetone or acetacetone), 1,1,1,5,5,5hexamethyl- 2,4 pentanedione, 2,2,6,6-tetramethylenole 3,5 heptanedione, 1,1,1-
  • j8-ketocarboxylic acid ester complex groups include, for example, methyl acetate acetate, ethyl acetate acetate, propyl acetate acetate, propyl acetate acetate, ethyl trifluoroacetate, and trifluoroacetate.
  • methyl 13-ketocarboxylic acids include acetoacetic acid and trimethylacetovinegar.
  • Ketokishi for example, Asetokishi group (or Asetokishi group), propionic - Ruokishi group, Buchiriro alkoxy group, Atari Roy Ruo alkoxy group and a methacryloyloxy Ruo alkoxy group.
  • the number of carbon atoms of the above group is preferably 18 or less, including the organometallic compounds described in the above examples.
  • it may be a straight-chain or branched one or a hydrogen atom substituted with a fluorine atom.
  • organometallic compounds having at least one or more oxygen atoms in the molecule which are preferred for safe organometallic compounds, are preferred.
  • Such compounds include organometallic compounds containing at least one alkoxy group of R,
  • a metal compound having at least one group selected from a ketone complex group, a ⁇ -ketocarboxylic ester complex group, a ⁇ -ketocarboxylic acid complex group, and a ketoxoxy group (ketoxoxy complex group) is preferable.
  • the gas supplied to the discharge space may be mixed with an additive gas that promotes a reaction of forming a thin film, in addition to a discharge gas and a thin film-forming gas.
  • the additive gas include oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and ammonia. Among them, components selected from oxygen, carbon monoxide and hydrogen are preferred. Mixing is preferred. The content is preferably 0.01 to 5% by volume with respect to the total amount of the gas, whereby the reaction is promoted, and a dense and high-quality thin film can be formed.
  • the thickness of the formed oxide or composite compound thin film is preferably in the range of 0.1 to: LOOO nm.
  • the metal of the organometallic compound, the metal halide, and the metal hydride used in the thin film forming gas Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti , V, Cr, Mn, Fe ⁇ Co, Ni ⁇ Cu, Zn, Ga ⁇ Ge ⁇ Rb ⁇ Sr ⁇ Y, Zr ⁇ Nb ⁇ Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Examples include Hf, Ta, W, Tl, Pb, Bi ⁇ Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.
  • the thin film forming apparatus of the present invention can obtain various highly functional thin films by using a metal compound such as an organometallic compound, a halogen metal compound, or a metal hydride compound together with a discharge gas. .
  • a metal compound such as an organometallic compound, a halogen metal compound, or a metal hydride compound together with a discharge gas.
  • Examples of the thin film of the present invention are shown below, but the present invention is not limited thereto.
  • Magnetic recording film Fe—Ni, Fe—Si—Al, y—FeO, Co, FeO, Cr, SiO, AIO
  • the nitriding degree of the nitride, the oxidation degree of the oxide, the sulfide degree of the sulfide, and the carbonization degree of the carbide are merely examples, and the composition ratio with the metal may be changed as appropriate.
  • the thin film may contain impurities such as a carbon compound, a nitrogen compound, and a hydrogen compound in addition to the metal compound.
  • metals of the metal compound are Si (silicon), Ti (titanium), Sn (tin), Zn (zinc), In (indium) and A1 (aluminum).
  • Si silicon
  • Ti titanium
  • Sn titanium
  • Zn zinc
  • In indium
  • A1 aluminum
  • the antireflection layer of the antireflection film among the high-performance films according to the present invention is formed by laminating a thin film of a medium refractive index layer, a high refractive index layer, and a low refractive index layer.
  • an antireflection film having an antireflection layer is obtained by laminating each refractive index layer directly or via another layer on a substrate.
  • three units can be arranged in series and processed continuously. It is suitable for forming the thin film of the present invention.
  • winding may be performed after each layer processing, and the layers may be sequentially processed and laminated.
  • an antifouling layer is provided on the antireflection layer
  • another one of the above-mentioned atmospheric pressure plasma discharge treatment apparatuses may be continuously installed, and four antifouling layers may be arranged and the antifouling layer is finally laminated.
  • a hard coat layer or an anti-glare layer may be provided in advance by coating on the base material, or a knock coat layer may be provided in advance by coating on the back side.
  • the gas for forming an antireflection layer thin film of the antireflection film according to the present invention can be used without limitation as long as it is a compound capable of obtaining an appropriate refractive index. Titanium conjugate as a reactive gas, and a mixture of a tin compound or a titanium compound and a silicon compound (or a layer formed of a titanium compound for forming a high refractive index and a low refractive index layer as a medium refractive index layer thin film forming gas).
  • the low refractive index layer thin film forming gas may preferably be a silicon compound, a fluorine compound, or a mixture of a silicon compound and a fluorine compound. . In order to adjust the refractive index, two or more of these compounds may be used as a thin film forming gas for forming any of the layers.
  • the tin compound used in the gas for forming a medium refractive index layer thin film useful in the present invention is an organic tin compound, a tin hydride compound, a halogenated tin, and the like.
  • two or more of these thin film forming gases may be mixed and used at the same time.
  • Sani ⁇ layer formed in order to be able to lower the surface specific resistance value 10 u Q Zcm 2 or less, are also useful as anti-static layer.
  • Examples of the titanium conjugate used in the high refractive index layer thin film forming gas useful in the present invention include an organic titanium conjugate, a titanium hydrogen compound, a halogen titanium, and the like.
  • organic titanium conjugate e.g., triethoxytitanium, trimethoxytitanium, triisopropoxytitanium, tributoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, methyldimethoxytitanium, ethyltriethoxytitanium, methyltriisopropoxytitanium, triethyltitanium, triisopropyltitanium , Tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, tetradimethylamino titanium, dimethyl titanium di (2,4-pentanedionate), ethyl titanium tri (2,
  • Examples of the silicon compound used in the low-refractive index layer thin film forming gas useful in the present invention include an organic silicon compound, a silicon hydride compound, a halogenated silicon compound, and the like.
  • silicon hydrogen compounds such as tetrabutoxy silane, dimethinoresimethoxy silane, ethynole ethoxy silane, ethynole silane di (2,4-pentanedionate), methyl trimethoxy silane, methyl triethoxy silane, and ethyl triethoxy silane
  • the halogenated silicon compound such as tetrahydrosilane, hexahydrogendisilane and the like include tetrachlor
  • the above-mentioned fluorine compounds can be used. Two or more of these thin film forming gases can be mixed and used at the same time. For fine adjustment of the refractive index, two or more of these tin compounds, titanium compounds and silicon compounds may be appropriately mixed and used at the same time.
  • the above-mentioned organotin compound, organotitanium compound or organosilicon compound is preferably a metal hydrogen compound or an alkoxy metal from the viewpoint of handling. Alkoxy metals are preferably used because they are small.
  • both may be in a gas, liquid or solid state at normal temperature and normal pressure. I do not care. In the case of gas, it can be directly introduced into the discharge space, but in the case of liquid or solid, it is used after being vaporized by heating, decompression, ultrasonic irradiation or the like.
  • a metal alkoxide such as tetraethoxy metal or tetraisopropoxy metal which is liquid at ordinary temperature and has a boiling point of 200 ° C or less is used. It is suitably used for forming an anti-reflection film.
  • the alkoxy metal may be used after being diluted with a solvent. In this case, the alkoxy metal may be vaporized into a rare gas by a vaporizer or the like and used as a mixed gas.
  • organic solvents such as methanol, ethanol, isopropanol, butanol, n-xane and the like and a mixed solvent thereof can be used.
  • the content in the total gas is preferably 0.0110% by volume. , the more preferred are 0.01 1 volume 0/0.
  • the medium refractive index layer can be obtained by appropriately mixing the silicon compound, the titanium compound or the tin compound according to the target refractive index. Can be.
  • the preferable refractive index and film thickness of each refractive index layer are, for example, 1.6 to 1.8 as a refractive index and about 50 to 70 nm as a film thickness for a tin oxide layer as a medium refractive index layer.
  • the high refractive index titanium oxide layer has a refractive index of 1.9 to 2.4
  • the film thickness is about 80 to 150 nm
  • the low refractive index silicon oxide layer has a refractive index of 1.3 to 1.5.
  • the thickness is about 80 to 120 nm.
  • the metal component of the organometallic compound used for forming the anti-reflection layer described above slightly differs in that it forms a thin film having transparency and conductivity such as indium. Almost the same components are used.
  • the metal of the organometallic compound for forming the transparent conductive film is at least one metal selected from indium (In), zinc (Zn) and tin (Sn) forces.
  • preferred examples of the preferred organometallic compound include indium tris (2,4 pentanedionate), indium tris (hexafluoropentanedionate), indium triacetate acetate, and triacetate.
  • the transparent conductive film is formed in order to further enhance the conductivity of the transparent conductive film formed from the organometallic compound.
  • the organic metal compound as a thin film-forming gas, which is preferable to dope a film, and an organic metal compound gas for doping be mixed and used at the same time.
  • the gas for forming a thin film of an organometallic compound or a fluorine compound used for doping include triisopropoxyaluminum and tris (2,4 pentanedionate).
  • the ratio of the organometallic compound necessary for forming the transparent conductive film to the gas for forming a thin film for doping varies depending on the type of the transparent conductive film to be formed.
  • tin is used for indium oxide.
  • the amount of the thin film-forming gas so that the atomic ratio of the ratio of In to Sn is in the range of 100: 0.1 to: LOO: 15. You. It is preferable to adjust the ratio to 100: 0.5 to: L00: 10.
  • a transparent conductive film obtained by doping fluorine to tin oxide
  • the atomic ratio of the ratio of Sn to F in the obtained FTO film is 100: 0.01 to: L00: 50. It is preferable to adjust the quantity ratio of the thin film-forming gas so as to fall within the range.
  • O ZnO-based amorphous transparent conductive film In O ZnO-based amorphous transparent conductive film
  • the amount ratio of the thin film forming gas so that the atomic ratio of the ratio of In to Zn is in the range of 100: 50 to L00: 5.
  • Sn ratio, 311: ratio and 111: 211 ratio In: Sn ratio, 311: ratio and 111: 211 ratio
  • the transparent conductive thin film forming gas is used in an amount of 0.01 to 10 volumes with respect to the mixed gas.
  • the obtained transparent conductive film is, for example, an oxide of SnO, InO, ZnO.
  • O) Complex oxides doped with dopants such as O) can be mentioned, and an amorphous film mainly containing at least one of these forces is preferable.
  • non-oxide films such as chalcogenide, LaB, TiN, and TiC
  • metal films such as Pt, Au, Ag, Cu, and CdO
  • a transparent conductive film can be given.
  • the thickness of the formed oxide or composite oxide transparent conductive film is preferably in the range of 0.1 to: LOOO nm.
  • the substrate used in the present invention may have a plate-like, sheet-like, or film-like planar shape.
  • a thin film such as a three-dimensional one such as a lens or a molded article such as a lens can be formed on its surface.
  • the form or material of the substrate there is no limitation on the form or material of the substrate as long as the substrate is exposed to the mixed gas in a plasma state in a stationary state or a transported state and a uniform thin film is formed.
  • a planar shape or a three-dimensional shape may be a glass plate, a resin film, or the like.
  • Various materials such as glass, resin, pottery, metal, and nonmetal can be used.
  • glass includes a glass plate and a lens
  • resin includes a resin lens, a resin film, a resin sheet, and a resin plate.
  • the resin film can be continuously transferred between the electrodes or in the vicinity of the electrodes of the atmospheric pressure plasma discharge treatment apparatus according to the present invention to form a transparent conductive film
  • the resin film can be used in a vacuum system such as sputtering. It is suitable for mass production, which is not a batch type, and is suitable as a production system with continuous high productivity.
  • the material of the molded product such as a resin film, a resin sheet, a resin lens, and a resin molded product is, for example, cellulose paste acetonate, cellulose paste diacetate, cellulose acetate butyl acetate, or cellulose acetate butyrate.
  • cellulose esters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl alcohol copolymer, and syndiotactic polystyrene.
  • Polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfone, polyetherimide, polyamide, fluorine resin, polymethyl Ruatalylate, atarilate copolymer and the like can be mentioned.
  • a cellulose ester film that is nearly optically isotropic is preferably used for the optical element of the present invention.
  • cellulose ester film as described above, cellulose triacetate film and cellulose acetate propionate are one of those preferably used.
  • commercially available Co-Katak KC4 UX and the like are useful.
  • the surface of these resins coated with gelatin, polybutyl alcohol, acrylic resin, polyester resin, cellulose ester resin or the like can also be used.
  • An antiglare layer, a clear hard coat layer, a barrier layer, an antifouling layer and the like may be provided on the thin film side of these resin films.
  • an adhesive layer, an alkali barrier coat layer, a gas barrier layer, a solvent-resistant layer, and the like may be provided as necessary.
  • the substrate used in the present invention is not limited to the above description.
  • the film thickness of the film is preferably 10 to: LOOO ⁇ m, more preferably 40 to 200 ⁇ m.
  • the present example is an experiment of plasma treatment of a film by a roll rotating electrode and a plurality of electrodes placed opposite to the roll rotating electrode (see FIG. 2 (b)).
  • stainless steel SUS316 was used as the electrode base material, and the dielectric material was sprayed with a single layer of alumina ceramic on the discharge surface of the electrode facing the electrode, and then the alkoxysilane monomer was applied. A coating solution dissolved in an organic solvent was applied to the ceramic coating, dried, and then heated at 150 ° C.
  • a film substrate was placed on the electrode system thus prepared, and a SiO film was formed.
  • the mixed gas for forming the SiO film is as follows: Discharge gas: Nitrogen gas
  • Reaction gas oxygen gas (0.1 to 21% based on the volume of nitrogen gas)
  • the impedance absolute value and the phase adjustment of only one matching device are automatically variable, and the other matching devices have the fixed impedance absolute value and only the phase is adjusted (this application).
  • An experiment in which the absolute value of the impedance and the phase adjustment were automatically varied for all matching devices (Comparative 1), and an experiment in which the absolute value of the impedance was fixed for all the matching devices and only the phase adjustment was automatically varied. (Comparison 2) was performed, and the results shown in Table 1 were obtained.
  • the setting outputs of HF1 to HF3 were set at 300, 1000, and 2000W.
  • the reflection power was measured from the current and voltage between the power supply and the electrodes. The measured value and the maximum measured value are described.
  • the reflected power was The value of was small and the fluctuation was small.
  • a uniform, high-quality thin film could be formed on the base material.
  • Comparative 2 has the same fluctuation range as Comparative 1, and the discharge state does not fluctuate frequently, but once matching cannot be achieved, it cannot be dealt with, and the state of mismatch continues. For this reason, although the thin film on the substrate is somewhat uniform, it has been difficult to form a film having a desired thickness.
  • At least one matching device 11 is provided between the plurality of second power sources HF and the high-frequency electrodes 12 and matches the impedance during operation of the device. Automatically adjusts the absolute value of the impedance and the phase value, and the other matching device 11 fixes the absolute value of the impedance and automatically adjusts only the phase value.
  • a plasma treatment can be performed on a film-shaped substrate, and by rotating the roll-type electrode, Can be subjected to continuous plasma processing.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Un équipement pour former une pellicule est procuré pour générer un plasma à haute densité conservant des conditions stables d’évacuation et pour fabriquer une pellicule mince de grande qualité. Une boîte de correspondance est fournie entre une pluralité d'alimentations électriques (HF) et des électrodes haute fréquence pour faire correspondre l’impédance. Une valeur absolue d'impédance et une valeur de phase sont automatiquement ajustées par au moins une boîte de correspondance pendant le fonctionnement de l’équipement, la valeur absolue d’impédance est fixée par une autre boîte de correspondance et seule la valeur de phase est automatiquement ajustée.
PCT/JP2005/008413 2004-05-28 2005-05-09 Équipement pour former une pellicule mince et procédé pour former une pellicule mince WO2005116293A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006513834A JP4899863B2 (ja) 2004-05-28 2005-05-09 薄膜形成装置及び薄膜形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004159491 2004-05-28
JP2004-159491 2004-05-28

Publications (1)

Publication Number Publication Date
WO2005116293A1 true WO2005116293A1 (fr) 2005-12-08

Family

ID=35450914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/008413 WO2005116293A1 (fr) 2004-05-28 2005-05-09 Équipement pour former une pellicule mince et procédé pour former une pellicule mince

Country Status (2)

Country Link
JP (1) JP4899863B2 (fr)
WO (1) WO2005116293A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007077871A1 (fr) * 2006-01-06 2007-07-12 Konica Minolta Holdings, Inc. Film d’ester de cellulose etanche a l’humidite, film protecteur pour polarisateur et polarisateur
CN103370805A (zh) * 2011-03-30 2013-10-23 海洋王照明科技股份有限公司 一种柔性有机电致发光器件及其制备方法
JP2018504864A (ja) * 2015-01-06 2018-02-15 北京北方華創微電子装備有限公司Ｂｅｉｊｉｎｇ Ｎａｕｒａ Ｍｉｃｒｏｅｌｅｃｔｒｏｎｉｃｓ Ｅｑｕｉｐｍｅｎｔ Ｃｏ．， Ｌｔｄ． パルス高周波電源のインピーダンス整合方法および装置
CN109881198A (zh) * 2019-04-10 2019-06-14 浙江大学 二氧化锡/五氧化二钒核壳结构的多色电致变色薄膜的制备方法
WO2021157051A1 (fr) * 2020-02-07 2021-08-12 株式会社日立ハイテク Dispositif de traitement au plasma et procédé de traitement au plasma

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0896992A (ja) * 1994-09-22 1996-04-12 Nissin Electric Co Ltd プラズマ処理装置の運転方法
WO1998032154A1 (fr) * 1997-01-17 1998-07-23 Balzers Aktiengesellschaft Reacteur a plasma rf a couplage capacitif

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2775656B2 (ja) * 1991-09-30 1998-07-16 株式会社島津製作所 成膜装置
JP2003268557A (ja) * 2001-12-20 2003-09-25 Canon Inc プラズマ処理方法およびプラズマ処理装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0896992A (ja) * 1994-09-22 1996-04-12 Nissin Electric Co Ltd プラズマ処理装置の運転方法
WO1998032154A1 (fr) * 1997-01-17 1998-07-23 Balzers Aktiengesellschaft Reacteur a plasma rf a couplage capacitif

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007077871A1 (fr) * 2006-01-06 2007-07-12 Konica Minolta Holdings, Inc. Film d’ester de cellulose etanche a l’humidite, film protecteur pour polarisateur et polarisateur
US8236427B2 (en) 2006-01-06 2012-08-07 Konica Minolta Holdings, Inc. Moistureproof cellulose ester film, polarizer-protective film, and polarizer
JP5029366B2 (ja) * 2006-01-06 2012-09-19 コニカミノルタホールディングス株式会社 防湿性セルロースエステルフィルム、偏光板保護フィルム及び偏光板
CN103370805A (zh) * 2011-03-30 2013-10-23 海洋王照明科技股份有限公司 一种柔性有机电致发光器件及其制备方法
JP2018504864A (ja) * 2015-01-06 2018-02-15 北京北方華創微電子装備有限公司Ｂｅｉｊｉｎｇ Ｎａｕｒａ Ｍｉｃｒｏｅｌｅｃｔｒｏｎｉｃｓ Ｅｑｕｉｐｍｅｎｔ Ｃｏ．， Ｌｔｄ． パルス高周波電源のインピーダンス整合方法および装置
US10643822B2 (en) 2015-01-06 2020-05-05 Beijing Naura Microelectronics Equipment Co., Ltd. Impedance matching method and device for pulsed radio frequency power supply
CN109881198A (zh) * 2019-04-10 2019-06-14 浙江大学 二氧化锡/五氧化二钒核壳结构的多色电致变色薄膜的制备方法
CN109881198B (zh) * 2019-04-10 2020-04-17 浙江大学 二氧化锡/五氧化二钒核壳结构的多色电致变色薄膜的制备方法
WO2021157051A1 (fr) * 2020-02-07 2021-08-12 株式会社日立ハイテク Dispositif de traitement au plasma et procédé de traitement au plasma
JPWO2021157051A1 (fr) * 2020-02-07 2021-08-12
JP7085031B2 (ja) 2020-02-07 2022-06-15 株式会社日立ハイテク プラズマ処理装置及びプラズマ処理方法

Also Published As

Publication number Publication date
JP4899863B2 (ja) 2012-03-21
JPWO2005116293A1 (ja) 2008-04-03

Similar Documents

Publication Publication Date Title
JP5115522B2 (ja) 薄膜形成方法
JP4433680B2 (ja) 薄膜形成方法
JP5082242B2 (ja) 薄膜形成方法
JP4876918B2 (ja) 透明導電膜
WO2006067952A1 (fr) Stratifie de couches minces impermeable aux gaz, base en resine impermeable aux gaz et dispositif electroluminescent organique
JP4899863B2 (ja) 薄膜形成装置及び薄膜形成方法
JPWO2005059202A1 (ja) 薄膜形成方法並びに該方法により薄膜が形成された基材
JP2007038445A (ja) ガスバリア性薄膜積層体、ガスバリア性樹脂基材及び有機エレクトロルミネッセンスデバイス
JP2005272957A (ja) 表面処理方法及び該表面処理方法により表面処理された基材
JP2004198590A (ja) 薄膜有するを物品、その製造方法及び低反射体並びに透明導電性体
JP4140289B2 (ja) 大気圧プラズマ放電処理装置、大気圧プラズマ放電処理方法及び光学素子
JP4534081B2 (ja) 薄膜形成装置
JP2004022441A (ja) 透明導電性基板及びその製造方法
JP4254190B2 (ja) 薄膜形成方法
JP4349052B2 (ja) ディスプレイ用フレネルレンズの製造方法
JP4797318B2 (ja) 透明導電膜積層体及びその形成方法
JP2005071837A (ja) 透明導電膜積層体の製造方法及び透明導電膜積層体並びにそれを用いた物品
JP2006321127A (ja) バリアフィルム、及び有機エレクトロルミネッセンスデバイス
JP2005060770A (ja) 薄膜形成装置
JP2006175633A (ja) ガスバリア性薄膜積層体、及びガスバリア性樹脂基材、及び有機ｅｌデバイス
JP2005200737A (ja) 透明導電膜形成方法
JP2006267347A (ja) 薄膜、反射防止基材、半導体デバイスと微粒子製造方法及び薄膜製造方法
JP4821324B2 (ja) 透明でガスバリア性の高い基材及びその製造方法
JP4432429B2 (ja) ディスプレイ用レンチキュラーレンズの製造方法
JP2004246241A (ja) 光学素子及びその製造方法

Legal Events

Date Code Title Description
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 KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

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

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: 2006513834

Country of ref document: JP

NENP Non-entry into the national phase

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