TW201408800A - Film formation method - Google Patents

Abstract

A film formation method that forms an organic layer which consists of a resin including fluorine on a substrate, the method including: an evaporated film forming process that forms the organic layer as an evaporated film; a thickness measurement process that measures a thickness of the evaporated film; a determination process that determines a parameter for a feedback by which a condition of the evaporated film forming process is adjusted, based on the measurement result of the thickness.

Description

Film formation method

The present invention relates to a film forming method.

The present application claims priority based on Japanese Patent Application No. 2012-185443, filed on Jan.

At present, in various terminals such as mobile terminals, a touch panel that operates in direct contact with the surface of the panel is used. The surface of the touch panel is easy to leave scratches or stains due to direct contact between the human body and the panel surface, and thus an antifouling layer (organic layer) is provided.

As the antifouling layer, a fluorine-based resin is often used. A vacuum vapor deposition method is known as a method of forming a film containing a fluorine-based resin (for example, Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-106344

According to Patent Document 1, a film excellent in film quality can be efficiently formed by a vacuum deposition method. However, since the film has an extremely thin film thickness of several nm, in order to maintain the film quality, it is important to maintain the uniformity of the film thickness.

Therefore, the organic layer that will become the antifouling layer is thicker than the specific film thickness of the specification. The step of forming, and then requiring removal, is required.

Further, as a result, the operation time increases, the number of steps increases, and the organic layer material is uneven, so there is a demand to reduce the manufacturing cost of the organic layer.

Further, when the plurality of sheets are treated as one batch, unevenness may occur in the film thickness of each batch, and there is a demand for preventing such a film thickness unevenness which is directly related to a decrease in film properties.

Further, in the case of performing the constant temperature and humidity treatment in which the formed antifouling layer (organic layer) is maintained in a constant temperature and humidity environment, it is relatively easy to maintain the film characteristics, but it takes a long time to process, so that it is intended to be shortened. Claim.

However, in such a case, it is also necessary that the adhesion between the antifouling layer and the lower layer is not lowered by the state of use. Alternatively, it is necessary to prevent the film properties such as sliding properties from being lowered.

The aspect of the present invention has been accomplished in view of the above circumstances, and is intended to achieve the following objects.

1. Reduce the removal step of the organic layer to reduce the manufacturing cost.

2. The film thickness of the organic layer forming the antifouling layer is set to a specific range.

3. When processing a plurality of panels (substrates) at the same time, unevenness in film thickness is also suppressed.

4. Inhibit film thickness unevenness between batches.

(1) In order to achieve the above object, a film forming method according to an aspect of the present invention is to form an organic layer containing a fluorine-containing resin on a substrate, and includes a vapor deposition film forming step of forming the organic layer as a vapor deposition film; a film thickness measuring step of measuring a film thickness of the vapor deposited film; and a determining step of determining a parameter for feedback in a manner of correcting a condition of the vapor deposition film forming step based on a measurement result of the film thickness.

(2) In the above film forming method, an inorganic layer may be formed in advance on the substrate.

(3) In the above film forming method, the inorganic layer may be exposed to the plasma before the formation of the organic layer.

(4) In the above film forming method, further comprising an insulating layer forming step of the insulating layer The forming step is to form the inorganic layer on the substrate by reactive sputtering using water vapor as a reactive gas.

(5) The film forming method may further include a final processing step for realizing stabilization and immobilization of the vapor deposited film.

(6) In the film forming method described above, the film thickness can be optically measured in the film thickness measuring step.

(1) A film forming method according to an aspect of the present invention is directed to forming an organic layer containing a fluorine-containing resin on a substrate, and comprising: a vapor deposition film forming step of forming the organic layer as a vapor deposition film; and a film thickness measuring step. The film thickness of the vapor deposition film is measured, and a determination step is to determine a parameter for giving feedback so as to correct the conditions of the vapor deposition film forming step based on the measurement result of the film thickness.

According to this method, since the film thickness of the vapor deposition film is not required to be thicker than a predetermined value and is removed in the subsequent step, the amount of raw materials used can be reduced. Moreover, the processing time can be shortened.

(2) The film forming method described above may correspond to a case where an inorganic layer is formed in advance on the substrate.

(3) In the above film forming method, the inorganic layer may be exposed to the plasma before the formation of the organic layer.

(4) The film forming method may further include an insulating layer forming step of forming the inorganic layer on the substrate by reactive sputtering using water vapor as a reactive gas.

A film forming method according to an aspect of the present invention is directed to forming an organic layer containing a fluorine-containing resin on an inorganic layer containing an inorganic film formed on a substrate, and comprising: an insulating layer forming step by using water vapor as a reaction a reactive sputtering of the gas to form the inorganic layer on the substrate; a vapor deposition film forming step of forming the organic layer on the inorganic layer as a vapor deposition film; and a film thickness measuring step of measuring the film of the vapor deposited film And a determination step of determining a parameter for feedback in such a manner as to correct the condition of the vapor deposition film forming step based on the measurement result of the film thickness.

According to this aspect, since the film thickness of the vapor deposition film is not required to be thicker than a predetermined value and is removed in the subsequent step, the amount of raw materials used can be reduced. Moreover, the processing time can be shortened.

(5) The film forming method according to an aspect of the present invention further includes a final processing step for realizing stabilization and immobilization of the vapor deposited film. According to this method, unevenness in film thickness of the organic layer can be prevented.

Further, in the final processing step, a treatment for firmly bonding the organic material after vapor deposition to the inorganic layer is performed. In the final processing step, a strong oxane bond (Si-O-Si) is formed by a hydrolysis (dealcoholation) reaction and a dehydration condensation reaction. The formation of a decane bond can be confirmed by observation of, for example, FTIR (Fourier Transform Infrared Spectroscopy) spectrum.

(6) A film forming method according to an aspect of the present invention is characterized in that the film thickness is optically measured in the film thickness measuring step. According to this method, the film thickness can be measured regardless of the film formation environment or the state in which the sealing is released, and feedback can be made so as to correct the conditions of the vapor deposition film forming step.

According to the aspect of the present invention, the removal step of the organic layer can be reduced, the manufacturing cost can be reduced, and the film thickness of the organic layer forming the antifouling layer can be controlled to a specific range, and the plurality of sheets (substrates) can be simultaneously processed. In this case, unevenness in film thickness can be suppressed, and film thickness unevenness between batches can be suppressed.

1, 1A‧‧‧ laminated structure

2‧‧‧Transparent substrate

3, 3A‧‧ ‧ inorganic layer

4‧‧‧Antifouling layer

10‧‧‧ film forming device

11‧‧‧Loading room

12‧‧‧Inorganic layer forming room

13‧‧‧Decanting chamber (anti-fouling layer forming chamber)

14‧‧‧ Film thickness measurement room

15‧‧‧Final processing room

20‧‧‧ Film forming device

21‧‧‧Rotating tube

22‧‧‧1st floor forming room

23‧‧‧Second floor forming room

24‧‧‧Decanting chamber (anti-fouling layer forming chamber, final processing chamber)

25‧‧‧ Film thickness measurement room

31‧‧‧1st inorganic layer

32‧‧‧2nd inorganic layer

33‧‧‧3rd inorganic layer

121‧‧‧Substrate setting position

122‧‧‧Splating target

123‧‧‧Target support

124‧‧‧High frequency power supply

125‧‧‧1st gas filling section

126‧‧‧1st valve

127‧‧‧2nd gas filling section

128‧‧‧2nd valve

131‧‧‧Substrate setting position

132‧‧‧vapor deposition mechanism

141‧‧‧Substrate setting position

142‧‧‧Measurement light irradiation mechanism

143‧‧‧Testing agency

151‧‧‧Substrate setting position

152‧‧‧ Temperature setting mechanism

221‧‧‧1st layer sputtering target

222‧‧‧ Target support

223‧‧‧High frequency power supply

224‧‧‧3rd gas filling section

225‧‧‧3rd valve

226‧‧‧4th gas filling section

227‧‧‧4th valve

231‧‧‧Second layer sputtering target

232‧‧‧target support

233‧‧‧High frequency power supply

234‧‧‧5th gas filling section

235‧‧‧5th valve

236‧‧‧6th gas filling section

237‧‧‧6th valve

238‧‧‧7th Gas Filling Department

239‧‧‧7th valve

241‧‧‧vapor deposition mechanism

252‧‧‧Measurement light irradiation mechanism

253‧‧‧Testing agency

C‧‧‧Control agency

C1‧‧‧Control agency

S01‧‧‧Pretreatment steps

S02‧‧Inorganic layer formation step (insulation layer formation step)

S03‧‧‧Deposition of vapor deposition film

S04‧‧‧ Film thickness measurement procedure

S05‧‧‧ Determination step

S06‧‧‧Final processing steps

Fig. 1 is a schematic cross-sectional view showing a laminated structure obtained by a film forming method according to a first embodiment of the present invention.

Fig. 2 is a flow chart showing a film formation method according to the first embodiment of the present invention.

Fig. 3 is a schematic view showing a schematic configuration of a film forming apparatus according to a first embodiment of the present invention.

4(a), 4(b) and 4(c) are diagrams showing the formation of an antifouling layer according to the first embodiment of the present invention. Figure.

Fig. 5 is a schematic cross-sectional view showing a laminated structure obtained by a film forming method according to a second embodiment of the present invention.

Fig. 6 is a schematic view showing a schematic configuration of a film forming apparatus according to a third embodiment of the present invention.

Hereinafter, a film formation method according to a first embodiment of the present invention will be described based on the drawings.

Fig. 1 is a schematic cross-sectional view showing a laminated structure obtained by the film forming method of the present embodiment, and reference numeral 1 in the figure is a laminated structure.

The laminated structure 1 of the present embodiment includes a transparent substrate 2 (substrate), an inorganic layer 3 formed on the transparent substrate 2, and an antifouling layer 4 (organic layer) laminated on the inorganic layer 3.

The transparent substrate 2 protects an element housed on one side (opposite to the inorganic layer 3) to constitute a touch panel. As a material of the transparent substrate 2, a transparent resin film, glass, etc. are mentioned, for example. The transparent substrate 2 contains glass in this embodiment. Further, the transparent substrate 2 in the present embodiment is not limited to a transmittance of 100%, and includes a so-called translucent one.

The inorganic layer 3 is used to improve the adhesion between the antifouling layer 4 and the transparent substrate 2. The inorganic layer 3 is formed by reactive sputtering using water vapor during film formation, and the details are as follows. Thereby, the adhesion to the antifouling layer 4 is improved.

This can be etched by cleaning with a plasma treatment step in which the surface of the inorganic layer 3 is exposed to the plasma. Thereby, the adhesion to the antifouling layer 4 can be improved more than before.

The inorganic layer 3 contains an inorganic material. Examples of the inorganic material include oxides, oxynitrides, and nitrides of at least one selected from the group consisting of Si, Al, Ta, Nb, Ti, zr, Sn, Zn, Mg, and In.

Specifically, the inorganic material includes cerium oxide, cerium nitride, cerium oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, magnesium oxide, indium oxide, tin oxide, and oxidation. Zinc, cerium oxide, cerium oxide, zirconium oxide, and the like. One of them may be used alone or in an arbitrarily mixed manner.

Further, in the present embodiment, the inorganic layer 3 contains a SiO ₂ (yttria) film having a preferable transmittance.

The film thickness of the inorganic layer 3 can be appropriately set within the range of 1 to 1000 nm, preferably 5 to 150 nm. When the film thickness of the inorganic layer 3 is less than 1 nm, it may be difficult to express the adhesion.

Moreover, when the film thickness of the inorganic layer 3 exceeds 1000 nm, cracks due to stress or the like are likely to occur, and the time required for film formation becomes long.

The antifouling layer 4 is a fluorine-containing organic layer, and one of the fluorine-containing organic layers is a fluorine-containing resin. The antifouling layer 4 protects the surface of the touch panel from scratches or fingerprints caused by, for example, human contact.

Examples of the fluorine-based resin (fluororesin) constituting the antifouling layer 4 include those in which the polymer main chain has a repeating unit such as CF ₂ =, -CF ₂ - or -CFH-. In the present embodiment, a perfluoropolyether group having a linear structure is used.

Further, in the present embodiment, the fluorine-based resin (fluororesin) constituting the antifouling layer 4 has a ruthenium atom at the end of the polymer main chain. The alkoxy group is added to the ruthenium atom at the end of the polymer main chain by an oxygen-oxime bond.

The film thickness of the antifouling layer 4 is not particularly limited, and can be appropriately set in the range of 0.5 nm to 5 μm. When the film thickness is less than 0.5 μm, it may be difficult to express a sufficient anti-fouling adhesion function. Moreover, when the film thickness exceeds 5 μm, a decrease in light transmittance or the like may occur.

The above laminated structure 1 is formed as follows.

First, the inorganic layer 3 is formed on the transparent substrate 2 as a glass substrate. Examples of the film formation method of the inorganic layer 3 include a CVD (Chemical Vapor Deposition) method, a plasma CVD method, a sputtering method, and an ion plating method. Examples of the sputtering method include an ECR (Electron Cyclotron Resonance) sputtering method, a reactive sputtering method, a bias sputtering method, and an AC/DC electromagnetic field sputtering method.

In the present embodiment, a reactive sputtering method is used.

One example of the film formation conditions based on reactive sputtering is a sputtering target: Si target, inert gas: Ar, reactive gas: water vapor (H ₂ O), Ar gas flow rate: 10 to 200 sccm (30 sccm), water vapor flow rate : 100~400sccm (300sccm), input power: 1~12kW (8kW).

Further, as the inert gas, an inert gas which is generally used in sputtering, for example, He, Ne, or the like can be used. Further, pretreatment such as O ₂ ashing may be performed before sputtering.

As described above, in the present embodiment, the inorganic layer 3 is formed by a reactive sputtering method using water vapor as a reactive gas. Thereby, OH contained in the water vapor is bonded to the surface of the inorganic layer 3.

By bonding OH to the surface of the inorganic layer 3 as described above, the adhesion to the antifouling layer 4 is improved. That is, in the case where the antifouling layer 4 is formed on the inorganic layer 3, an alkoxy group is added by an oxygen-hydrazine bond in a germanium atom at the end of the polymer main chain of the fluororesin constituting the antifouling layer 4. This alkoxy group becomes a hydroxyl group by hydrolysis. Then, the hydroxyl group undergoes a dehydration condensation reaction with OH on the surface of the inorganic layer 3 to form a decane bond.

By forming the siloxane chain as described above, the inorganic layer 3 and the antifouling layer 4 are more firmly bonded, and the adhesion can be improved.

In this case, if water vapor is used when OH is bonded to the surface of the inorganic layer 3, the treatment can be performed easily and inexpensively.

For example, the same effect can be obtained when a cerium oxide (SiO ₂ ) layer is formed by reactive sputtering using oxygen as a reactive gas, and OH is bonded to the surface of the cerium oxide (SiO ₂ ) layer. .

On the other hand, by forming the inorganic layer 3 by reactive sputtering using water vapor as a reactive gas as in the present embodiment, one step can be reduced, and the station time can be reduced.

In the present embodiment, reactivity is performed using only steam as a reactive gas. Sputtering, but it is also possible to introduce other reactive gases. Examples of the other reactive gas are an oxygen-containing gas such as oxygen or a hydrogen-containing gas such as hydrogen.

Thereafter, an antifouling layer 4 is formed on the inorganic layer 3. Examples of the method for forming the antifouling layer 4 include a coating method, a vapor deposition method, and the like, and in the present embodiment, a vapor deposition method is used.

Examples of the vapor deposition method include a vacuum vapor deposition method, an ion beam evaporation method, and a resistance heating vapor deposition method. In the present embodiment, resistance heating deposition is performed by heating a vapor deposition source under a specific pressure state and performing vapor deposition. law. The specific pressure state means 1 × 10 ^-4 to 1 × 10 ^-2 Pa.

In the present embodiment, the product name is OPTOOL DSX (DAIKIN INDUSTRIES) which is held as a vapor deposition source by a heating mechanism while maintaining the size of 2 × 10 ^-3 to 4 × 10 ^-4 Pa. , manufactured by heating) to 220 ° C to form a vapor deposited film having a thickness of 2 to 4 nm (2 nm).

Next, the film thickness of the formed vapor deposition film was measured. Specifically, the film thickness can be measured by a non-contact optical system measurement method such as ellipsometry.

In the ellipsometry method, the surface of the substance is irradiated (incident) light by an evaluation system such as an ellipsometer, and the reflected light is measured, and the change in the polarization state (incident and reflection) of the light reflected from the surface is observed. Information related to the substance (film thickness, etc.).

Then, in the determination step, feedback of the supply amount of the vapor deposition source and the heating state of the heating means is performed based on the measurement result of the film thickness, and the film thickness control of the vapor deposition layer is performed.

Specifically, when the allowable value of the film thickness is smaller than the specific range, the amount of vapor deposition is increased to increase the amount of vapor deposition, or the temperature of the heating means is increased. On the other hand, when the film thickness is measured to be larger than the allowable value, control for reducing the amount of supply of the vapor deposition source or lowering the set temperature of the heating means is performed in order to reduce the amount of vapor deposition.

The parameters fed back in the determination step include a heating temperature, a heating time, and a material supply amount.

Thereafter, as a final processing step, constant temperature and humidity treatment or final heat treatment is performed to stabilize and immobilize the vapor deposition film.

Here, the constant temperature and humidity treatment can be carried out under the treatment conditions of a treatment temperature of about 30 to 60 ° C, a humidity of about 60 to 90%, and a time of about 2 hours. The final heat treatment can be carried out under the treatment conditions of a treatment temperature of about 150 to 250 ° C and a time of about 1 to 5 minutes.

As shown in FIG. 2, the laminated structure 1 of the cover glass which becomes the outermost surface of the touch panel in this embodiment is manufactured by the film formation method as follows, that is, the film formation method includes the pretreatment step S01, which is Prepared to form a transparent substrate (glass substrate) 2 for covering glass, O ₂ ashing, etc.; inorganic layer forming step S02 (insulating layer forming step), which comprises forming SiO of inorganic layer 3 containing SiO ₂ film by sputtering method _{2 a} sputtering step and a water vapor sputtering step of forming an OH group on the surface; a vapor deposition film forming step S03 for forming a vapor deposition film containing a fluorine resin as the antifouling layer 4 as an antifouling layer forming step; S04, which measures the film thickness of the vapor-deposited organic material (vapor-deposited film), and determines step S05, based on the measurement result of the film thickness, determines a parameter for giving feedback by correcting the condition of the vapor-deposited film forming step S03, and The evaporation conditions in the batch after the next batch or several times are controlled; and the final processing step S06 is used to stabilize and immobilize the vapor deposition film.

Next, a film forming apparatus of this embodiment will be described with reference to Fig. 3 .

The film forming apparatus 10 is a so-called inline film forming apparatus in which a plurality of processing chambers for performing specific processing on a substrate are connected. The film forming apparatus 10 sequentially includes a carrier chamber 11, an inorganic layer forming chamber 12, a vapor deposition chamber 13 which is a vapor deposition film of the antifouling layer 4 as an antifouling layer forming chamber, a film thickness measuring chamber 14, and final processing. Finally, the processing chamber 15 is processed.

Further, in the film forming apparatus 10, the transparent substrate 2 is carried by the transfer tray as a transport mechanism. Furthermore, in the present embodiment, the transport mechanism includes a transport tray on which the transparent substrate 2 is placed, and a moving mechanism that moves the transport tray.

In the carrier chamber 11, the transparent substrate 2 is carried into the atmosphere. In the carrying room 11, provided with A vacuum pump (not shown) is configured to be evacuated to a predetermined degree of vacuum in the load-bearing chamber 11 and to maintain the degree of vacuum. Further, although not shown, a vacuum pump may be provided in each processing chamber to set a desired degree of vacuum for each processing chamber.

The inorganic layer forming chamber 12 is for forming the inorganic layer 3 (see FIG. 1) on the transparent substrate 2 by a sputtering method. The transparent substrate 2 conveyed to the inorganic layer forming chamber 12 is provided at the substrate installation position 121 by a transport mechanism (not shown).

In the inorganic layer forming chamber 12, the sputtering target 122 is supported by the target supporting portion 123 so as to face the transparent substrate 2 provided at the substrate mounting position 121. A high-frequency power source 124 is connected to the target supporting portion 123, and is configured to apply a voltage to the sputtering target 122.

The sputtering target 122 is appropriately set in accordance with the inorganic layer. In the present embodiment, in order to form an SiO ₂ film as an inorganic layer, a metal tantalum target is provided as the sputtering target 122.

Further, in the inorganic layer forming chamber 12, a first gas filling portion 125 filled with an inert gas is provided through the first valve 126. By adjusting the opening degree of the first valve 126, a required amount of inert gas can be introduced into the inorganic layer forming chamber 12 from the first gas filling portion 125.

In the present embodiment, the first gas filling portion 125 is filled with an Ar gas as an inert gas. Further, in the inorganic layer forming chamber 12, a second gas filling portion 127 filled with a reactive gas is provided through the second valve 128.

By adjusting the opening degree of the second valve 128, a required amount of the reactive gas can be introduced into the inorganic layer forming chamber 12 from the second gas filling portion 127. The second gas filling portion 127 is filled with H ₂ O gas as a reactive gas.

In the vapor deposition chamber 13 as the antifouling layer forming chamber, a vapor deposition film to be the antifouling layer 4 (see FIG. 1) is formed on the inorganic layer of the transparent substrate 2 by a vapor deposition method. The transparent substrate 2 conveyed to the vapor deposition chamber (antifouling layer forming chamber) 13 is provided at the substrate installation position 131 by a transport mechanism (not shown).

In the vapor deposition chamber 13, steam is disposed opposite to the transparent substrate 2 provided. Plating mechanism 132. Although the vapor deposition mechanism 132 depends on the vapor deposition method, in the present embodiment, a vapor deposition source (not shown) is provided in a crucible provided with a heating mechanism.

The film thickness measurement chamber 14 as the antifouling layer forming chamber measures the film thickness of the vapor deposition film formed on the transparent substrate 2 in the film thickness measurement step S04 shown in FIG. 2 . An ellipsometer is included in the film thickness measurement chamber 14 , and the ellipsometer includes a measurement light irradiation unit 142 that illuminates the surface of the transparent substrate 2 provided on the substrate installation position 141 with the vapor deposition film formed thereon; and detects Mechanism 143 observes the reflected light and measures the change in the polarization state.

The detecting unit 143 is configured to be connected to the control unit C and can output a measurement result. The control mechanism C is configured to be connected to the vapor deposition mechanism 132 to control the operating conditions thereof, and can determine whether or not the film thickness output by the detecting mechanism 143 is controlled within a specific range.

The measurement light irradiation means 142 and the detection means 143 may be provided in the film thickness measurement chamber 14, or may be provided outside the film thickness measurement chamber 14. When it is provided outside the film thickness measurement chamber 14, a measurement window portion (not shown) is provided, and the measurement light and the reflected light are transmitted through the window portion.

Further, the film thickness measuring chamber 14 is set to a specific vacuum environment, and may be set to a condition such as atmospheric pressure equivalent to the environment outside the device.

The final processing chamber 15 as the antifouling layer forming chamber performs the final processing in the final processing step S06 shown in Fig. 2. The final processing chamber 15 includes a temperature setting mechanism 152 that sets the temperature conditions in the final processing chamber 15, or a processing environment control mechanism (not shown).

The film formation in the film forming apparatus 10 will be described.

When the transparent substrate 2 is conveyed to the carrier chamber 11, the exhaust is performed in the carrier chamber 11, and the carrier chamber 11 is in a vacuum state. After the desired vacuum state is reached, the transparent substrate 2 is transferred to the inorganic layer forming chamber 12.

In the processing chamber (not shown) before the inorganic layer forming chamber 12 or the inorganic layer forming chamber 12, a pretreatment such as O ₂ ashing is performed as the pretreatment step S01 in Fig. 2 .

Then, in the inorganic layer forming chamber 12, as the inorganic layer forming step S02 in Fig. 2, an inorganic layer is formed on the transparent substrate 2.

Specifically, the opening degree of the first valve 126 and the second valve 128 is adjusted, and the inert gas and the reactive gas are introduced into the inorganic layer forming chamber 12 from the first gas filling portion 125 and the second gas filling portion 127, respectively. The voltage is applied from the high frequency power source 124 to the sputtering target 122 to start reactive sputtering, thereby forming the inorganic layer 3.

Then, the transparent substrate 2 is transferred from the inorganic layer forming chamber 12 to the vapor deposition chamber 13 which is an antifouling layer forming chamber. In the vapor deposition chamber 13, as the vapor deposition film forming step S03 in Fig. 2, a vapor deposition film to be the antifouling layer 4 is formed on the inorganic layer 3.

Specifically, a material (vapor deposition source) such as a perfluoropolyether stored in a crucible as the vapor deposition mechanism 132 is heated by a heating means to adhere to the surface of the inorganic layer 3 of the transparent substrate 2 to be transported. The material which is heated and evaporated is formed into a vapor deposition film which becomes the antifouling layer 4.

Then, the transparent substrate 2 is transferred to the film thickness measurement chamber 14. In the film thickness measuring chamber 14, as the film thickness measuring step S04 in Fig. 2, the film thickness is measured by an ellipsometry using an ellipsometer. The ellipsometer measures the thickness of the measurement by irradiating the surface of the transparent substrate 2 with the measurement light from the measurement light irradiation means 142, observing the reflected light by the detecting means 143, and measuring the change in the polarization state of the incident light and the reflected light.

As a result of the film thickness measurement step S04, in the determination step S05, the control means C determines whether or not the film thickness of the vapor deposition film formed in the vapor deposition chamber 13 is within a tolerance of a specific range, and whether it is necessary to change the vapor deposition chamber 13 Feedback is provided in the manner in which the evaporation conditions are controlled.

When the control unit C determines that feedback is required, the supply amount of the vapor deposition source in the vapor deposition mechanism 132, the heating state of the heating mechanism, the processing time of the transparent substrate 2 in the vapor deposition chamber 13, and the like are changed.

Specifically, when the measurement mechanism C measures the film thickness to be smaller than the allowable value, the amount of vapor deposition in the vapor deposition chamber 13 is increased to increase the supply amount of the vapor deposition source or set the temperature of the heating mechanism. The output signal is controlled in such a manner as to rise or extend the processing time.

On the other hand, when the measurement mechanism C measures the film thickness to be larger than the allowable value, the amount of vapor deposition in the vapor deposition chamber 13 is reduced to reduce the supply amount of the vapor deposition source or to lower the set temperature of the heating mechanism. Output signals by means of control such as shortening of processing time.

When the control unit C determines that there is no need for feedback, the transparent substrate 2 is transported to the final processing chamber 15. In the final processing chamber 15, as the final processing step S06 in FIG. 2, in order to stabilize and fix the vapor deposition film, a constant temperature and humidity treatment or a final heat treatment is performed to form the antifouling layer 4.

When the constant temperature and humidity treatment is performed as the processing step S06, which is a treatment temperature of about 30 to 60 ° C, a humidity of about 60 to 90%, and a time of about 2 hours, as shown in FIG. 4, Hydrolysis (dealcoholation) reaction to form an OH group at the end of the molecule to be a vapor deposited film (Fig. 4 (a)), and the OH group is hydrogen-bonded to the H group on the inorganic layer 3 (Fig. 4 (b)), Thereafter, a strong decane bond (Si-O-Si) is formed by a dehydration condensation reaction (Fig. 4(c)).

Thereafter, a removal step of removing the remaining amount of the unbonded material by wiping or the like may be performed.

When the final heat treatment is carried out at a treatment temperature of about 150 to 250 ° C for a period of about 1 to 5 minutes, as the final processing step S06, the hydrolysis (dealcoholation) reaction and the dehydration condensation reaction shown in FIG. 4 can be carried out. A strong siloxane chain (Si-O-Si) is formed, and the excess liquid is removed by heating.

In this case, it is necessary to appropriately control the processing conditions, and to set the film thickness of the vapor deposition film to an appropriate range to the extent that there is almost no remaining. Thus, the final heating step also serves as a removal step for removing excess liquid.

After the antifouling layer 4 is formed in this manner, the transparent substrate 2 is transferred to the carrier chamber 11, and the atmosphere is opened in the carrier chamber 11 and then carried out from the film forming apparatus 10.

In this manner, in the present embodiment, the laminated structure (the cover glass for touch panel with the antifouling layer) 1 including the antifouling layer 4 having a uniform film thickness and excellent film properties can be formed at a low cost and in a short time.

Hereinafter, a second embodiment of the film forming method and film forming apparatus of the present invention will be described based on the drawings.

Fig. 5 is a schematic view showing a film forming apparatus in the embodiment, in which reference numeral 1A is a laminated structure.

The laminated structure of this embodiment will be described with reference to Fig. 5 . In the laminated structure 1A of the present embodiment, as shown in FIG. 5, the inorganic layer 3A includes a plurality of layers different from the inorganic layer 3 shown in FIG. 1 in the first embodiment. The components that are the same as the other components are denoted by the same reference numerals, and the description thereof will be omitted.

In the inorganic layer 3A of the present embodiment, the first inorganic layer 31 and the second inorganic layer 32 are formed in order. The inorganic layer 3A in the present embodiment also functions as an antireflection layer.

The inorganic layer 3A contains the third inorganic layer 33 having the same function as the inorganic layer 3 described in the first embodiment on the inorganic layers 3A and 3B formed plural times. The third inorganic layer is formed by reactive sputtering using water vapor as a reactive gas.

As the material of the inorganic layer 3A, the same material as the above inorganic layer 3 can be used. Specific examples of the material are Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In. The material of the inorganic layer 3A contains one or more of them, and the first inorganic layer 31 is made of a material different from the second inorganic layer 32.

As the first inorganic layer 31, cerium oxide, cerium nitride, cerium oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, magnesium oxide, indium oxide, tin oxide, zinc oxide, cerium oxide, cerium oxide, or the like may be used. Zirconium oxide and the like. The first inorganic layer is composed of one type or the like, or two or more types are mixed.

In particular, as the first inorganic layer 31, tantalum oxide (Ta ₂ O ₅ ), niobium oxide (Nb ₂ O ₅ ), or titanium oxide (TiO ₂ ) can be used. The first inorganic layer 31 is preferably a Ta ₂ O ₅ film.

The material of the third inorganic layer 33 formed by using water vapor as a reactive gas may be any of the above materials, but it is preferably SiO ₂ .

In the present embodiment, the inorganic layer 3A is formed by laminating two types of films in this order. However, the present invention is not limited thereto, and three or more types of films may be stacked in this order.

In the case of forming the inorganic layer 3A in the present embodiment, examples of the film formation method of each layer include a CVD method, a plasma CVD method, a sputtering method, and an ion plating method. Examples of the sputtering method include an ECR sputtering method, a reactive sputtering method, a bias sputtering method, and an AC/DC electromagnetic field sputtering method.

In the present embodiment, each layer is formed by a reactive sputtering method.

In the case of forming the inorganic layer 3A, for example, the formation conditions of the first inorganic layer 31 are a sputtering target: a Ta target, a sputtering gas: Ar+O ₂ , an Ar gas flow rate: 50 to 500 sccm, and an O ₂ gas flow rate: 50 ~500sccm, input power: 1~10kW.

The formation conditions of the second inorganic layer 32 are, for example, a sputtering target: a Si target, a sputtering gas: Ar+O ₂ , an Ar gas flow rate: 50 to 500 sccm, an O ₂ gas flow rate: 50 to 500 sccm, and an input power: 1 to 10 kW.

The formation conditions of the third inorganic layer 33 formed by using water vapor as a reactive gas are, for example, a sputtering target: Si target, sputtering gas: Ar + H ₂ O, Ar gas flow rate: 10 to 200 sccm, H ₂ O gas flow rate : 100~400sccm, input power: 1~12kW.

In the present embodiment, the formation conditions of the first inorganic layer 31 are a sputtering target: a Ta target, a sputtering gas: Ar+O ₂ , an Ar gas flow rate: 100 sccm, an O ₂ gas flow rate: 300 sccm, and an input power: 8 kW.

The formation conditions of the second inorganic layer 32 are a sputtering target: Si target, sputtering gas: Ar+O ₂ , Ar gas flow rate: 50 sccm, O ₂ gas flow rate: 200 sccm, and input power: 8 kW.

The formation conditions of the third inorganic layer 33 are a sputtering target: Si target, sputtering gas: Ar+H ₂ O, Ar gas flow rate: 30 sccm, H ₂ O gas flow rate: 300 sccm, and input power: 8 kW.

A film forming apparatus that forms such a laminated structure 1A will be described with reference to Fig. 6 .

The film forming apparatus 20 of the present embodiment is provided with a rotating drum 21 at the center. In this rotation The cartridge 21 is provided with a plurality of transparent substrates 2. In other words, in the film forming apparatus 20 of the present embodiment, the rotary cylinder 21 is configured to function as a substrate installation portion. The rotary cylinder 21 is rotatable, and each of the plurality of transparent substrates 2 provided on the surface of the rotary cylinder 21 is subjected to respective processes.

The film forming apparatus 20 is provided with a vacuum pump (not shown), whereby the inside of the film forming apparatus 20 can be set to a desired degree of vacuum.

The interior of film forming apparatus 20 is in turn divided into a plurality of processing chambers. In the present embodiment, the film forming apparatus 20 is partitioned into a first layer forming chamber 22, a second layer forming chamber 23, a vapor deposition chamber 24 as an antifouling layer forming chamber, and a film thickness measuring chamber 25 in the circumferential direction. .

The first layer forming chamber 22 and the second layer forming chamber 23 are located at positions facing each other. The vapor deposition chamber 24 and the film thickness measurement chamber 25 are located at positions facing each other. The vapor deposition chamber (antifouling layer forming chamber) 24 is located between the first layer forming chamber 22 and the second layer forming chamber 23. The film thickness measuring chamber 25 is located between the first layer forming chamber 22 and the second layer forming chamber 23.

Each of the first layer forming chamber 22 and the second layer forming chamber 23 is configured such that the first inorganic layer 31 and the second inorganic layer 32 (see FIG. 5) can be formed by sputtering. That is, the first inorganic layer 31 is formed by sputtering in the first layer forming chamber 22, and the second inorganic layer 32 is formed by sputtering in the second layer forming chamber 23.

In the first layer forming chamber 22, a pair of first layer sputtering targets 221 are respectively supported by a pair of target supporting portions 222. A high frequency power supply 223 is connected to the target support portion 222. Thereby, a voltage opposite to each other is applied to the pair of first layer sputtering targets 221, respectively.

In the first layer forming chamber 22, a third gas filling portion 224 filled with an inert gas is connected to the third valve 225. In the first layer forming chamber 22, a fourth gas filling portion 226 filled with a reactive gas is connected via the fourth valve 227.

In the present embodiment, the third gas filling portion 224 is filled with Ar gas as an inert gas, and the fourth gas filling portion is filled with O ₂ gas as a reactive gas.

In the second layer forming chamber 23, a pair of second layer sputtering targets 231 are respectively supported by a pair of target supporting portions 232. A high frequency power source 233 is connected to the target support portion 232.

In the second layer forming chamber 23, a fifth gas filling portion 234 filled with an inert gas is connected via the fifth valve 235. In the second layer forming chamber 23, a sixth gas filling portion 236 filled with a reactive gas is connected via the sixth valve 237. In the second layer forming chamber 23, a seventh gas filling portion 238 filled with a reactive gas is connected via the seventh valve 239.

In the present embodiment, the fifth gas filling portion 234 is filled with Ar gas as an inert gas, and the sixth gas filling portion 236 is filled with O ₂ gas as a reactive gas.

The seventh gas filling portion 238 is filled with steam H ₂ O gas as a reactive gas or a water vapor generating source. The seventh gas filling portion 238 and the seventh valve 239, which are configured as a steam H ₂ O gas supply unit, are provided on the Si target side.

A vapor deposition mechanism 241 is provided in the vapor deposition chamber (antifouling layer forming chamber) 24. In the present embodiment, the vapor deposition mechanism 241 corresponds to the vapor deposition chamber 13 of the first embodiment, and a vapor deposition source (not shown) is provided in a crucible provided with a heating mechanism.

The film thickness measurement chamber 25 as the antifouling layer forming chamber measures the film thickness of the vapor deposition film formed on the transparent substrate 2. An ellipsometer is included in the film thickness measuring chamber 25, and the ellipsometer includes a measuring light irradiation unit 252 that illuminates the surface of the transparent substrate 2 on which the vapor deposited film is formed, and a detecting mechanism 253 that observes the reflected light and The change in the polarization state was measured.

The detecting means 253 is configured to be connected to the control means C1 and can output the measurement result to the control means C1. The control mechanism C1 is configured to be connected to the vapor deposition mechanism 241 to control the operating conditions thereof, and can determine whether or not the film thickness output by the detecting mechanism 253 is controlled within a specific range.

The film thickness measuring chamber 25 can also serve as a carrying chamber.

In this case, the measurement light irradiation means 252 and the detection means 253 may be provided outside the film thickness measurement chamber 25. In this case, the measurement can be performed by opening the load-bearing chamber 25, or a measurement window portion (not shown) can be provided, and the measurement light reflected light can be transmitted through the window portion to measure.

Thus, the film thickness measuring chamber 25 is set to a specific vacuum environment, but may be set to Conditions such as atmospheric pressure equivalent to the environment outside the device.

Further, in the vapor deposition chamber (antifouling layer forming chamber) 24, a configuration in which the final processing can be performed in accordance with the last processing chamber 15 in the first embodiment, although not shown, may include setting steaming. A temperature setting mechanism for temperature conditions in the plating chamber (final processing chamber) 24 or a processing environment control mechanism. Further, as the final processing chamber (antifouling layer forming chamber), an independent processing chamber may be provided separately from the vapor deposition chamber 24.

The film formation in the film forming apparatus 20 will be described. The plurality of transparent substrates 2 are transported to the film forming apparatus 20, and the transported transparent substrates 2 are provided in the rotating drum 21 at predetermined intervals.

Thereafter, the inside of the film forming apparatus 20 is exhausted to have a desired vacuum state. After the vacuum state is reached, the rotation of the rotating cylinder 21 is started. The rotating cylinder 21 is continuously rotated in one direction until the film formation of all the films is completed for all the transparent substrates 2.

First, the first inorganic layer 31 formed of a Ta ₂ O ₅ film on the transparent substrate 2 is subjected to reactive sputtering using oxygen in the first layer forming chamber 22. Next, the formation of the second inorganic layer 32 (see FIG. 5) is started. In other words, the second inorganic layer 32 is formed on the transparent substrate 2 by a reactive sputtering method using O ₂ gas in the second layer forming chamber 23 .

When the second inorganic layer 32 is formed on the first inorganic layer 31 of each of the transparent substrates 2 in this manner, sputtering is started again in the first layer forming chamber 22, and the first inorganic layer is formed on the second inorganic layer 32. 31. Then, the first inorganic layer 31 and the second inorganic layer 32 are sequentially laminated in this order, and are repeated a certain number of times.

When the formation of the first inorganic layer 31 and the second inorganic layer 32 is completed, the third inorganic layer 33 using water vapor as a reactive gas is formed thereafter, whereby the inorganic layer 3A is formed (see FIG. 5).

Thereafter, an antifouling layer 4 is formed on the inorganic layer 3A (see FIG. 5). Specifically, in the vapor deposition chamber (antifouling layer forming chamber) 24, heating of the material (vapor deposition source) of the vapor deposition mechanism 241 is started, and the material evaporated by heating on the inorganic layer 3A of the transparent substrate 2 is started. Attached as a vapor deposition film With.

Thereafter, the rotating cylinder is stopped, and the surface of the transparent substrate 2 is irradiated with measurement light from the measurement light irradiation unit 252 using the ellipsometer in the film thickness measurement chamber 25, and the surface from the transparent substrate 2 is observed by the detecting mechanism 253. The film thickness of the vapor deposited film was measured by reflecting the light and measuring the change in the polarization state.

As a result of the film thickness measurement step S04, in the determination step S05, the control means C1 determines whether or not the film thickness of the vapor deposition film formed in the vapor deposition chamber 24 is within a tolerance of a specific range. In other words, the control unit C1 determines whether or not it is necessary to perform feedback so as to change the control of the vapor deposition conditions in the vapor deposition chamber 24.

When the control means C1 determines that feedback is required, the supply amount of the vapor deposition source in the vapor deposition mechanism 241, the heating state of the heating means, the processing time of the transparent substrate 2 in the vapor deposition chamber 24, and the like are changed. Specifically, the control unit C1 is configured to correspond to the control unit C in the first embodiment.

When the control unit C1 determines that feedback is unnecessary, the transparent substrate 2 is transported to the vapor deposition chamber (final processing chamber) 24. In the vapor deposition chamber (final processing chamber) 24, as the final processing step S06, in order to stabilize and fix the vapor deposition film, the final heat treatment is performed to form the antifouling layer 4.

After the antifouling layer 4 is formed, the film forming apparatus 20 is opened to the atmosphere, and the transparent substrate 2 on which the antifouling layer 4 is formed is carried out from the film forming apparatus 20.

In this manner, in the film forming apparatus 20 of the present embodiment, reactive sputtering is performed by using water vapor as a reactive gas in the second layer forming chamber 23, whereby the OH in the water vapor can be easily adhered to The surface of the inorganic layer 33. Thereby, the adhesion between the inorganic layer 3A and the antifouling layer 4 can be improved.

Hereinafter, embodiments of the present invention will be described in more detail by way of experimental examples.

(Experimental Example 1)

According to the film forming apparatus of the first embodiment, the film thickness of the vapor deposition film which becomes the antifouling layer 4 is After vapor deposition was performed for 5 nm, the laminated structure 1 was formed without performing the final processing step. In addition, the conditions which are not described are the conditions corresponding to those described in the first embodiment.

(Experimental Example 2)

In the same manner as in Experimental Example 1, a laminated structure was formed under the same conditions except that the temperature in the constant temperature and humidity furnace was 40 ° C, humidity: 80%, and time: 2 hours as the final processing step.

(Experimental Example 3)

In comparison with Experimental Example 1, except for the final processing step, the temperature in the constant temperature and humidity furnace was 40 ° C, the humidity was 80%, and the time was 2 hours. Thereafter, as a removal step, the laminated structure 1 was cleaned. The laminated structure 1 is formed under the same conditions except for the surface.

(Experimental Example 4)

In the same manner as in Experimental Example 1, a laminated structure was formed under the same conditions except that the final processing step was carried out in a vacuum at a temperature of 170 ° C for a period of 4 minutes as a heat treatment for the removal step.

(Experimental Example 5)

In the same manner as in Experimental Example 1, a layered structure was formed under the same conditions except that the vapor deposition film was deposited to a thickness of 3 nm.

(Experimental Example 6)

In comparison with Experimental Example 1, the vapor deposition film was vapor-deposited so as to have a film thickness of 3 nm, and the temperature in the constant temperature and humidity furnace was 40 ° C, humidity: 80%, and time: 2 as the final processing step. The laminated structure was formed under the same conditions except for the treatment of the hour.

(Experimental Example 7)

Compared with Experimental Example 1, the vapor deposition film was deposited to a thickness of 3 nm, and the final processing step was carried out in a constant temperature and humidity furnace at a temperature of 40 ° C and wet. Degree: 80%, time: 2 hours of treatment, and thereafter, the laminated structure 1 was formed under the same conditions except that the removal step was to clean the surface of the laminated structure 1.

(Experimental Example 8)

In comparison with Experimental Example 1, the vapor deposition film was deposited to have a thickness of 3 nm, and the final processing step was carried out in a vacuum at a temperature of 170 ° C for a period of 4 minutes. In addition to the above, the laminated structure is formed under the same conditions.

The surfaces thereof were observed, and the following sliding test was conducted as an endurance test.

In the endurance test, the steel wool to which the load (1000 g/cm ² ) is applied is slid on the surface of the antifouling layer of each laminated structure, and after the abrasion, the water droplets are dropped onto the surface of the antifouling layer, and the contact angle of the water droplet is determined to be 105°. The number of slides in the following cases. That is, the more the number of slides, the more the antifouling layer is less likely to be peeled off, and the adhesion is higher.

Experimental Example 1: 0 times

Experimental Example 2: 3000 times

Experimental Example 3: 3000 times

Experimental Example 4: 3000 times

Experimental Example 5: 0 times

Experimental Example 6: 3000 times

Experimental Example 7: 3000 times

Experimental Example 8: 3000 times

According to the results, it is found that the final processing is performed by setting the film thickness of the vapor-deposited film to a target film thickness of about 3 nm, whereby film properties such as slidability can be improved. Moreover, it is understood from these results that the film properties such as the sliding resistance can be improved in a very short time by performing the heat treatment as the final processing.

The present invention is not limited to the above embodiment. For example, the film forming apparatus is not limited to those described in the first embodiment and the second embodiment, and any embodiment can be implemented. The film formation method is sufficient.

For example, the plasma processing mechanism and the vapor deposition mechanism provided in the plasma processing chamber of the present embodiment may be provided in one film forming apparatus, and the substrate may be disposed to face the substrate.

Further, in the film forming apparatus 20 of the second embodiment, the first layer forming chamber 22 and the second layer forming chamber 23 are disposed to face each other. However, the present invention is not limited thereto, and for example, it may be arranged adjacent to each other. .

Further, in the second embodiment, a high-frequency voltage is applied between the two sputtering targets, but the present invention is not limited to the so-called double sputtering method.

In the second embodiment, a film that functions as an antireflection layer as the inorganic layer 3A is exemplified, but the film is not limited thereto, and may be another optical functional film.

In the above embodiment, the antifouling layer is formed as an organic layer, but the function as an organic layer is not limited to the antifouling property.

1‧‧‧Laminated structure

2‧‧‧Transparent substrate

3‧‧‧Inorganic layer

4‧‧‧Antifouling layer

Claims (7)

A film forming method comprising: forming an organic layer containing a fluorine-containing resin on a substrate; and comprising: a vapor deposition film forming step of forming the organic layer as a vapor deposition film; and a film thickness measuring step of measuring the steaming a film thickness of the plating film; and a determining step of determining a parameter for feedback in such a manner as to correct the condition of the vapor deposition film forming step based on the measurement result of the film thickness. The film forming method of claim 1, wherein an inorganic layer is previously formed on the substrate. The film forming method of claim 2, wherein the inorganic layer is exposed to the plasma before the formation of the organic layer. The film forming method of claim 3, further comprising an insulating layer forming step of forming the inorganic layer on the substrate by reactive sputtering using water vapor as a reactive gas. The film forming method according to any one of claims 1 to 4, further comprising a final processing step for realizing stabilization and immobilization of the vapor deposited film. The film forming method according to any one of claims 1 to 4, wherein the film thickness is optically measured in the film thickness measuring step. The film forming method of claim 5, wherein the film thickness is optically measured in the film thickness measuring step.