JPH1048402A - Optical element or device, their production, and equipment for production therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical element or device excellent in adhesiveness, optical characteristics and economy, and a process for producing the same, and an equipment for production thereof. SOLUTION: A first layer 1 consisting of SiOx (where X is a positive number below 2), a second layer 2 consisting of SiO2 , a third layer 5 consisting of SnO2 and a fourth layer 6 consisting of SiO2 are laminated in this order on a base body 3. At the time of producing the optical element or the device, the first layer 1 is formed by a physical film formation method (sputtering method, vacuum vapor deposition method, etc.) in an atmosphere contg. oxygen. This equipment has a film forming chamber for forming the first layer 1 and the respective film forming chambers respectively forming the second to fourth layers 2, 5, 6 by the physical film formation method in the atmosphere contg. the oxygen used for production of the optical element or the device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical element or device, a method for manufacturing the same, and an apparatus for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, demand for optical elements or devices such as cathode ray tubes (CRTs) and liquid crystal display elements has been remarkably growing.

In these optical elements or devices, an optical element made of silicon oxide, tin oxide, or the like is formed on a substrate such as plastic for the purpose of improving light transmittance, preventing light reflection, and protecting the surface of a display element. A film is provided, and a substrate such as plastic with the optical film is attached to a display element.

The optical film is provided as a plurality of layers having different refractive indexes on a substrate of an optical element or an apparatus mainly for the purpose of preventing reflection of external light.

[0005] However, the substrate used for the above-mentioned optical element or device, in particular, between the plastic substrate and the optical film,
There were problems such as adhesion and durability. Therefore, in an optical element or device such as a cathode ray tube (CRT) or a liquid crystal display device, in order to improve the adhesion between an inorganic optical film and an organic plastic substrate, titanium is generally used as a method. A highly reactive thin film (so-called adhesive film or adhesive layer) of chromium or chromium is provided between the two.

FIG. 10 shows an example of an antireflection structure in a conventional optical element or device. For example, on a substrate 3 made of polyethylene terephthalate (a silicon resin-containing hard coat layer may be provided thereon) or the like, a layer 70 having a thickness of 5 nm or less made of a metal thin film of titanium or the like, and tin dioxide ( a layer 5a having a thickness of 15nm made of SnO ₂₎ transparent electrode layer of oxide, such as, mainly a layer 6a having a thickness of 23nm made of SiO _2, tin dioxide (SnO ₂₎ transparent electrode layer of oxide, such as Thickness 1
A layer 5b of 00nm, thickness 8 consisting mainly of SiO ₂
A layer 6 b of 5 nm is provided as an antireflection film (AR film) 4.

The extremely thin and highly reactive metals such as titanium and chromium are chemically bonded to a base such as plastic to form an inorganic thin film 70.
The optical film, which is an inorganic material having low reactivity, adheres to the surface.

Since the metal thin film 60 is very thin, the influence on the characteristics of the optical film (for example, light absorption or antireflection) is negligibly small.

However, in order to form the adhesive layer made of the metal thin film 70, a film forming system and a film forming process different from those used for forming the optical film must be added and introduced. Including the installation of the additional device, the material for the adhesive layer, the supply and maintenance of the electric power, and the like are costly, and thus cannot be said to be an economically superior method.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of such a conventional situation, and its object is to provide:
While maintaining the optical characteristics of the anti-reflection optical film, an optical element that improves the adhesiveness of the optical film without adding a special adhesive layer such as the above metal thin film, and is economically excellent. Another object of the present invention is to provide an apparatus, a manufacturing method thereof, and an apparatus for manufacturing the same.

[0011]

The present inventors have made intensive studies to achieve the above-mentioned object, and as a result, have found that a structure in which an optical film is laminated on a base of an optical element or apparatus such as a cathode ray tube or the like. In the above, it has been found that by using a layer made of a specific material as a layer (first layer) in contact with the substrate, an optical element or device excellent in adhesiveness, optical characteristics and economy can be obtained, and the present invention has been achieved. did.

That is, the present invention relates to SiO _x (where X is 2
An optical element or device in which a first layer made of a positive number less than 1, a second layer mainly made of SiO ₂ , and another antireflection layer are laminated on a substrate in this order (hereinafter, the present invention) Referred to as an optical element or device).

Here, the above-mentioned "optical element or device" means an element or device capable of transmitting, emitting, and entering a light beam, transmitting, outputting, and inputting information by the light beam. , A cathode ray tube (CRT: cathode ray tube, etc.), an optical lens, an optical prism, and other various elements or devices.

In the optical element or device according to the present invention, _X in SiO x is a positive number less than 2 (ie, 0 <X <
2) It must be.

This is because the ratio of oxygen atoms in SiO _x (where X is a positive number less than ₂ ) is smaller than that of a stable composition (SiO ₂ ), so that SiO _x deficient in oxygen atoms is activated. It is considered that the reactivity is increased and the adhesiveness to a substrate such as plastic is remarkably improved. That is, Si
Adhesion as the ratio of oxygen atoms in the O _X is small is improved. However, when X = 0, SiO _X becomes a simple substance of silicon (Si) and has excellent adhesiveness, but has too much optical absorption and deteriorates optical characteristics. This X is 0.2 ~
It is preferably 1.8, more preferably 0.5 to 1.0.

FIG. 1A illustrates an antireflection structure in an optical element or device according to the present invention. For example, polyethylene terephthalate (a hard coat layer containing a silicon resin may be provided thereon) .) or the like on the substrate 3 made of, SiO _X (where, X of the present invention is 2
A first layer 1 having a thickness of 15 nm and a second layer ₂ mainly consisting of SiO ₂ and having a thickness of 23 nm are sequentially laminated. Thickness 1 made of an oxide-based transparent electrode layer such as SnO ₂ )
A third layer 5 having a thickness of 00 nm and a fourth layer 6 having a thickness of 85 nm mainly composed of SiO ₂ are provided.
R film) 4.

In the structure illustrated in FIG.
Has a function of an adhesive layer for improving the adhesiveness between the base 3 and the layer 2, and the laminated structure of the layer 1 and the layer 2 forms an antireflection structure together with the layers 5 and 6. That is, since the refractive indices are arranged in the order of large-small-large-small in the order of the layers 1-2-5-6,
The reflection of external light is effectively refracted or absorbed, and an antireflection effect is obtained.

FIG. 1B illustrates the structure of the optical element or device of the present invention. The thickness of the anti-reflection film 4 shown in FIG. 1
A top coat layer 8 made of, for example, fluorocarbon is provided with a thickness of 10 nm or less via an adhesive layer 7 of 0 nm or less. It is preferable that the layer 5 made of an oxide-based transparent electrode layer such as tin dioxide (SnO ₂ ) be grounded for preventing static electricity or shielding.

The first layer 1 is preferably formed to a thickness of 2 to 50 nm, more preferably, 5 to 25 nm. If the thickness is too thick, the optical characteristics deteriorate, and if it is too thin, the adhesiveness deteriorates. About 15 nm is preferable. The second layer 2 described above is preferably formed to a thickness of 5 to 50 nm, more preferably 10 to 30 nm.

Here, in FIG. 1, a hard coat layer may be provided on the base 3, or a plastic film layer is provided on the base 3 via an adhesive layer, and the hard coat layer is provided thereon. The anti-reflection structure of FIG.

For example, FIG. 2 is a schematic sectional view of another example of the optical element or device according to the present invention. A plastic film layer such as polyethylene terephthalate is provided on a substrate 3 such as a cathode ray tube via an adhesive layer 9. 10, a first layer 1, a second layer 2, a third layer 5, and a fourth layer 6 are provided thereon via a hard coat layer 11 containing an organic substance such as a silicone resin or a silicone resin. This is a structure in which an antireflection film 4 made of is laminated, and a top coat layer 8 is further laminated via an adhesive layer 7.

The anti-reflection structure of the optical element or device illustrated in FIG. 1 does not use the metal thin film 70 for bonding to the substrate 3 and uses SiO _x compared to the conventional anti-reflection structure shown in FIG.
(However, X is a positive number less than 2), so that it is not necessary to add a metal thin film such as titanium, and therefore it is not necessary to add a new film forming system to the currently used manufacturing apparatus. .

The present invention also relates to an optical element for manufacturing the optical element or the apparatus according to the present invention, wherein the first layer (SiO _x ) is formed by a physical film forming method in an atmosphere containing oxygen. Another object of the present invention is to provide a method for manufacturing an apparatus (hereinafter, referred to as a manufacturing method according to the present invention).

The above-mentioned physical film forming method is a so-called PVD method.
This is a thin film forming technique for forming a thin film mainly using physical phenomena and changes, and examples thereof include a sputtering method, a vacuum deposition method, and an ion plating method.

In addition, the first layer is physically formed in an atmosphere containing oxygen. As described above, the oxygen gas in the first layer is made of oxygen gas such that _X in SiO x is a positive number less than 2. The amount has to be adjusted.

In the production method according to the present invention, for example, a silicon target is reacted with oxygen in an atmosphere containing oxygen gas, and then physically flies to form a SiO _x film. Adjustment is very important. However, the state of SiO _X is not strictly determined solely by the amount of oxygen gas introduced.

Further, the present invention relates to SiO _x (where X is 2
Manufacturing an optical element or device according to the present invention in which a first layer consisting of (a positive number less than), a second layer mainly consisting of SiO ₂ , and other antireflection layers are laminated on a substrate in this order. A film-forming chamber for forming the first layer by a physical film-forming method in an atmosphere containing oxygen;
Another object of the present invention is to provide an apparatus for manufacturing an optical element or an apparatus (hereinafter, referred to as a manufacturing apparatus according to the present invention), which includes a layer and a film forming chamber for forming each of the other layers for preventing reflection.

The manufacturing apparatus according to the present invention can perform physical film formation in this apparatus. The physical film formation method is, as described above, a so-called PVD method, and mainly a physical phenomenon. A thin film forming technique for forming a thin film by utilizing a change in temperature or a change. Examples thereof include a sputtering method, a vacuum deposition method, and an ion plating method. In the manufacturing apparatus according to the present invention, any of the above methods can be used.

The first layer is physically formed in an atmosphere containing oxygen. In the manufacturing apparatus according to the present invention, _X in the first layer SiO x is 2 in the first layer film forming chamber. A system capable of appropriately adjusting the amount of oxygen so as to be a positive number less than is arranged.

Hereinafter, the manufacturing method and the manufacturing apparatus according to the present invention will be described in detail.

FIG. 3 is a schematic sectional view of an example of a manufacturing apparatus that can be used for manufacturing an optical element or apparatus according to the present invention. In the vacuum chamber 20 of this device, a partition plate 21
Film forming chambers (chambers) 61, 62, 6 partitioned by
Each of the film forming chambers 62, 63, and 64 has an exhaust port (not shown), a vacuum pump, a gas inlet such as an argon gas and an oxygen gas, a cooling water inlet, a high frequency power supply, an AC power supply, or a DC power supply. There is a power supply.

In FIG. 3, an unwinding roll 41 rotating at a constant speed in the clockwise direction and a winding roll 42 rotating at a constant speed in the counterclockwise direction in the figure are provided. Unformed plastic film 50
a, plastic film 50b after film formation is sequentially indicated by arrow D
It is made to run in the direction. This plastic film 50a corresponds to the substrate 3 of FIG. 1 or the film layer 10 with the hard coat layer 11 of FIG. 2, and the plastic film 50b has thereon the layers 1 and 2 of FIG.
2, 5, 6 and the like may be sequentially formed. The top coat layer 8 may be formed after winding the film, or may be formed in the vacuum chamber 20 in FIG. 3 before winding the film.

A cooling can 44 is provided at an intermediate portion where the plastic films 50a and 50b sequentially run from the unwind roll 41 to the take-up roll 42. This cooling can 44 is made of plastic films 50a, 50b.
Is pulled out downward in the drawing and then rotated counterclockwise.

The unwinding roll 41 and the winding roll 4
2 and the cooling can 44 have a cylindrical shape with a length corresponding to the width of the plastic films 50a and 50b. A cooling device (not shown) is provided inside the cooling can 44, and the plastic film 50a ,
Deformation or the like due to a temperature rise during sputtering of 50b can be suppressed.

Therefore, the plastic films 50a, 5a
Ob is sequentially sent out from the unwinding roll 41, further passes over the peripheral surface of the cooling can 44, and is wound up by the winding roll 42. It should be noted that guide rolls 43 are provided for transporting the plastic film from the unwinding roll 41 to the winding roll 42 via the cooling can 44 under a predetermined tension. In each of the film forming chambers, each target is set on the electrode plate so as to face the cooling can.

FIG. 3 is suitable for an apparatus for manufacturing the laminated structure shown in FIG. 1. A Si target 51 for the SiO _x layer 1 is formed in the film forming chamber 61, and a silicon dioxide is formed in the film forming chamber 62, for example. 2, an Sn target 53 for tin dioxide 5 is disposed in the film forming chamber 63, and an Si target 54 for silicon dioxide 6 is disposed in the film forming chamber 64.
Then, in each of the film forming chambers, the targets 51, 52, 53, and 54 are sequentially sputtered while supplying oxygen gas, so that each of the layers 1, 2, 5, and 5 shown in FIG.
6 can be stacked.

In the apparatus shown in FIG. 3,
An appropriate number of film formation chambers can be provided depending on the number or thickness of the layers to be stacked. However, since the third layer of SnO ₂ and the fourth layer of SiO ₂ are thick, it is preferable to increase the number of targets and keep the line speed constant for efficient film formation.

In this apparatus, in particular, feedback means for adjusting the supply amount of oxygen gas is provided. That is, in the detection chamber 65 between the film formation chamber 61 and the film formation chamber 62,
An optical monitor 30 for detecting the state of the SiO _X layer 1 formed in the film forming chamber 61 is provided, and information detected here is sent to a controller 32 a provided outside the vacuum chamber 20. The supply amount of oxygen gas to the film formation chamber 61 is adjusted by the oxygen gas adjustment valve 33 according to the control signal of the controller 32a. The oxygen gas 34 is sent to the film forming chamber 61 through the oxygen gas introduction pipe 35. In addition,
The optical monitor 30 may be arranged inside the film forming chamber 61.

At the position after the formation of the four layers or each layer, if the film other than the first layer is transparent after the formation of the first layer, the above-mentioned optical monitor is provided and oxygen gas is introduced. The amount can be controlled. Note that the above-described control of the oxygen gas introduction amount may be performed on layers other than the first layer.

The feedback means is provided for the film 50.
The optical monitor 30 includes an optical monitor 30 for measuring the absorption of light of the SiO _X film formed on the substrate a. The optical monitor 30 optically detects the state (degree of oxidation) of the SiO _X , converts this to a current or voltage value, and The controller 32a outputs a control signal so that a constant amount of oxygen is always supplied as compared with the reference value.

For example, as shown in FIG. 4, the optical monitor 30 converts the light beam emitted from the light emitting
Irradiating the O _X layer 1, the reflected light beam to measure the absorption of light in the SiO _X by incident on the light receiving element 72, is fed back to.

The details will be described later, there is a correlation between the proportion of oxygen atoms in the proportions and in SiO _X absorption of the light beam, the state of SiO _X can be controlled by the flow rate of the oxygen gas.

As a method for detecting the refractive index (n) and the extinction coefficient (k) of SiO _X , a measuring device for light deflection is an Ellipsometer (“AutoEL NIR-3” manufactured by Rudolph Research). ) Etc. for Surface Pr
The refractive index (n) and the extinction coefficient (k) can be determined from these measured values using an ofilometer (“P-10” manufactured by Tencor) or the like.

Further, in the manufacturing method and the apparatus according to the present invention, information obtained by detecting the state of the SiO _X being formed is input to the feedback means, and the formed SiO _X is inputted.
_By the output of the optical monitor that measures the absorption of _X light,
The set point of the feedback means can be adjusted.

This is because the S film formed by the optical monitor
It detects the state of iO _X, as a set point for the feedback means of the detection value (reference value), SiO during film formation
The amount of oxygen gas is adjusted by the oxygen gas adjusting valve by the controller based on the information compared with the detection information on the state of _X.

To detect the state of SiO _X during the film formation,
As shown in FIG. 5, a plasma intensity sensor 38 is preferably used. Alternatively, as shown in FIG.
1 can be used as oxygen content detection information, but the target voltage is the SiO _x deposited on the target.
This is because it fluctuates due to In this case, since the power supply 39 also serves as the controller, the circuit configuration can be further simplified.

That is, the information obtained by detecting the plasma intensity or the target voltage during the film formation of the SiO _X is input to the controller 32b or the power supply 39, and the light absorption of the formed SiO _X is performed. Is input via the controller 32c or 32d, whereby the controller 32b or the power supply 3
Adjust the 9 set points.

This adjustment method is more effective than the method of adjusting the amount of oxygen gas by feedback means based on information only from the optical monitor 30 illustrated in FIG.
Because it can detect the state of O _X, it is possible to accurately control the amount of actually required oxygen gas into the film forming, it is possible to more accurate film formation.

Also, as shown in FIG. 7, it has been found that in the case of sputtering, the impedance of the plasma depending on the supply amount of oxygen gas causes a hysteresis between the impedance of the plasma in the case of silicon oxide and the plasma in the case of silicon alone. .

That is, in order to form the first layer by utilizing this hysteresis, the film formation is started as indicated by an arrow a ₁ from a stable state (Si) in which the amount of oxygen is smaller than the target value V ₁ ,
The oxygen amount is increased to fix the target value V ₁ and the SiO _X
The Start and method for forming oxygen amount of deposition as shown by the arrow a ₂ from more stable state than the target value V ₂ (SiO _2),
There is a method for forming the SiO _X the amount of oxygen is fixed to the target value V _2, either method, becomes possible to accurately fix the target value of the oxygen amount by the start condition of the deposition. That is,
Si showing impedance corresponding to the desired degree of oxidation
The O _X it is possible to be formed.

The physical film forming method in the manufacturing method and the manufacturing apparatus according to the present invention refers to a so-called PVD method. In the present invention, DC (direct current) sputtering method, RF (high frequency) plasma sputtering method, AC A sputtering method such as a sputtering method is preferable, and a vacuum evaporation method can also be used.

In the present invention, the SiO _x layer as the first layer is a layer having optical absorption. That is, the first layer is not a layer having only an adhesive function to the substrate, and the first layer and the second layer form an antireflection structure together with other antireflection layers. That is, the first layer is a layer having an adhesive function and an optical function.

Here, the other antireflection layer is formed by laminating a layer having a large refractive index (for example, an oxide-based transparent electrode layer) and a layer having a small refractive index (for example, a layer mainly composed of SiO ₂ ) in this order. A layer (film) having a function of reducing the reflectance of a light beam of external light or internal light. The first layer is
The first layer and the second layer form an antireflection structure together with the other antireflection layers described above, and have an antireflection function as an optical film.

FIG. 8 shows polyethylene terephthalate (P
FIG. 4 is a graph showing a change in reflectance depending on an incident wavelength in an example in which the antireflection structure (four layers) shown in FIG. 1A is applied to an (ET) film and an example of a single layer of polyethylene terephthalate (PET). is there.

It can be seen that the example in which an anti-reflection structure is provided on PET has an excellent anti-reflection ability in the wavelength range of 480 to 600 nm, as compared with the example of the PET single layer. The wavelength of 480 to 600 nm is a wavelength range of visible light, and the reflectance in this range is particularly remarkably improved.

FIG. 9 shows an example in which the above-described antireflection film is provided on a face plate 13 of a cathode ray tube 12 as an optical element or device according to the present invention. That is, as shown in FIG. 8, since the reflectance is small in the wavelength range of visible light, the amount of reflected light greatly decreases with respect to incident light. Further, since the SnO ₂ layer is grounded, the amount of electromagnetic waves emitted from the inside of the cathode ray tube to the outside is reduced, and the influence of the electromagnetic waves on other devices and the human body is extremely small. Also, the antistatic effect for preventing dust adhesion is good.

In the present invention, as will be described in detail later,
Since there is a correlation with the ratio of oxygen atoms of proportions and in SiO _X absorption of the light beam, be determined so as to correspond to the preferred components of SiO _X the extinction coefficient (k) and refractive index (n) it can. That is, at a wavelength of 550 nm, SiO _x
Has an extinction coefficient (k) of 0.01 to 0.05,
Further, the refractive index (n) of SiO _{X at} a wavelength of 550 nm is preferably from 1.8 to 2.3. In general, in order to avoid excessive light absorption, the refractive index (n) is 1.7 to 2.3 at any wavelength, and the wavelength 45
At 0 to 650 nm, the extinction coefficient (k) is required to be 0.05 or less on average.

In the optical element or device according to the present invention, the substrate may be an inorganic substance such as glass or silicon.
It is preferably made of an organic substance such as ET. When the substrate is an organic substance, the SiO _{x of} the first layer exhibits extremely excellent adhesion. Here, the “substrate” refers to an optical element or device including a main body of the optical element or device.

Further, the above-mentioned organic substance is more preferably a resin. As the resin, a synthetic resin such as polyethylene terephthalate (PET) is particularly preferable, and any conventionally known resin can be used.

As shown in FIG. 2, it is preferable that the substrate has a structure in which a hard coat layer made of an organic substance is provided on the substrate, and the first layer of SiO _X is provided on the hard coat layer. By providing the hard coat layer, the mechanical strength of the optical element or the device is improved, and the durability is excellent. As the material of the hard coat layer, conventionally known materials used for the hard coat layer such as plastic can be used.

Even if the hard coat layer is a layer containing a silicone resin, the adhesion to the first layer of the present invention is good.

The second layer preferably has a lower refractive index than SiO _x and SnO ₂ and is made of a material that does not alter SnO ₂ , and SiO ₂ is preferred.

The anti-reflection film provided on the second layer is
It is preferably formed of a third layer composed of an oxide-based transparent electrode layer such as SnO ₂ or ITO (indium tin oxide) and a fourth layer composed mainly of SiO ₂ . That is, since the third layer has a large refractive index and the fourth layer has a small refractive index, the first layer, the second layer, the third layer, and the fourth layer can form an antireflection film.

It is preferable that a top coat layer is formed on the antireflection film via an adhesive layer made of titanium, silicon, or the like to protect the surface. It is possible.

As the top coat layer, it is preferable to use a fluorocarbon, and a conventionally known fluorocarbon having excellent printing durability can be used. In particular, polytetrafluoroethylene (PTFE), perfluoropolyether (PFPE) or It is preferred to use these mixtures. When silicon (silicon) is used as the adhesive layer below the top coat layer, the adhesive strength is improved.

[0066]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples.

1. Single layer coated sample peeling
Test (1) Preparation of Sample Coated with Single Layer As a substrate, a 0.188 mm-thick polyethylene terephthalate (manufactured by Toray Industries, Inc.) provided with a 6 μm-thick hard coat layer (Toughtop: manufactured by Toray Industries, Inc.) was 5 cm square. And washed with ethanol and dried.

Thereafter, in a sputtering apparatus (R & D manufactured by MRC), pressure reduction (degassing) was performed for 30 minutes, and a layer of a material shown in Table 1 below (the first layer described above) was formed in a film formation chamber adjusted to a pressure of 2 mTorr. Was formed).

However, before sputtering, the target was covered with a shutter for one minute, pre-sputtering was performed, and M
Film formation was performed for 1 minute using a DC (direct current) sputtering method by a sputtering apparatus “R & D” (hereinafter the same) made by RC Corporation. At this time, the film thickness was 100 to 200 nm. Further, the gas introduced when forming the SiO _X (Ar + O
The total amount of ₂ ) was 60 sccm. Table 2 below shows argon gas, oxygen gas, nitrogen gas at the time of film formation, and electric power at the time of DC (direct current) sputtering.

In the materials shown in Table 1 below, ()
In the figure, the amount (unit: sccm) of oxygen gas in the total amount of gas of 60 sccm is shown (the same applies hereinafter).
TiN _x (W) is the material of the first layer doped with W.

(2) Peeling Test of Sample The following peeling test was performed in the order of Test 1, Test 2, Test 3, and Test 4 (these tests were similarly performed in the following other examples).

In "Test 1," four layers of cloth were covered with a spherical weight having a radius of about 30 mm, impregnated with ethanol, and subjected to a force of 2 kg for 40 times (20 reciprocations). Rub the surface of. In this test, a sample in which the surface of the sample did not change in appearance was marked with “○”, a sample in which a slight peeling of the film occurred in a streak state was marked with “△”, and a sample in which the film peeled was marked with “×”.

In "Test 2", the one obtained in Test 1 by covering one layer of cloth with a spherical weight having a radius of about 30 mm was used. In this case as well, as in Test 1, a sample whose surface did not change in appearance was marked with “」 ”, a sample in which some peeling of the film occurred in a streak shape was marked with“ △ ”, and a sample in which the film peeled was marked with“ 「”. X ".

In “Test 3”, the sample was immersed in boiling water for 10 minutes, and then a film peel test and its evaluation were performed in the same manner as in Test 1.

In “Test 4”, the sample was immersed in boiling water for 10 minutes, and then a film peel test and its evaluation were performed in the same manner as in Test 2.

However, in the case of a single-layered cloth, the peeling of the film is more likely to occur, and the test is more severe than a cloth of four layers. Also, by dipping the sample in boiling water for 10 minutes, the heat resistance and moisture resistance of the sample can be evaluated.

[0077] *: A sample having a refractive index (n) and an extinction coefficient (k) that can be used optically when used for the first layer on a four-layer coating type cathode ray tube.

[0078] *: It was introduced optimum amount of oxygen gas to deposit a SnO _X having electrical conductivity for the antireflection film of four layers on a cathode ray tube.

(3) Results From Table 1, the samples of each example can be classified into three ranks based on their peeling resistance. Examples 1 to 6 are easy to peel off,
Samples that are difficult to withstand in practical use, Examples 7 to 13 are difficult to peel off, but samples that are easy to peel off in a severe environment, Examples 14 to
The sample No. 19 is hard to peel off and has excellent mechanical durability (however, Si of Example 19 has a disadvantage of too much light absorption).

Further, a cathode ray tube (CR) as shown in FIG.
The use of T) also requires optical characteristics, and those satisfying this are Example 14 (material: SiO _X (17)), Example 15 (Material: SiO _X (16)), and Example 16 (Material: SiO _X). (1
5)).

However, the above optical characteristics are the characteristics of the refractive index (n) and the extinction coefficient (k) of the sample. In the measurement, the above-mentioned layer is formed on a silicon substrate, and the light deflection is performed.
Ellipsometer (“AutoEL NIR-
3)), the film thickness was measured with a SurfaceProfilometer (“P-10” manufactured by Tencor), and the refractive index (n) and extinction coefficient (k) were determined from these (the same applies hereinafter).

[0082] 2. Stripping of multi-layer coated sample
Test (1) Preparation of Multilayer Coated Sample A sample for a cathode ray tube (CRT) coated with the above “R & D” on the same substrate was prepared on the same substrate as in the preparation of the single layer coated sample. The materials of the prepared samples are shown in Table 3 below.

(2) Peeling test of sample Like the peeling test of the sample coated with a single layer,
A peeling test was performed on the outermost layer of each sample, and the results of this test are shown in Table 3 below. Best first layer in a structure (CRT specification) for a cathode ray tube (CRT) shown in FIG. 9: SiO _x (15), SiO _x (16), SiO _x
(17) The film formation rate and wavelength of 405.0 nm and 546.
The refractive index (n) and the extinction coefficient (k) at 1 nm and 632.8 nm are shown in Table 4 below.

[0084] *: If the substrate was previously subjected to the plasma discharge treatment, the result was ○ in Test 4.

[0085]

(3) Results From Table 3, it can be seen that even when four layers are laminated on the substrate, the sample using SiO _X for the first layer is hard to peel off and has excellent mechanical durability.

From Table 4, it can be seen that Example 24 (material: SiO _X
(15)), Example 25 (material: SiO _x (16)), Example 2
All samples of 6 (material: SiO _X (17)) have a wavelength of 546.1 nm, n of 1.8 to 2.3, and k of 0.01.
It is in the range of -0.05, which indicates that the optical characteristics are excellent.

[0088] 3. Transmittance of the antireflection film of the CRT specifications (1) Example was prepared by making the above-described method of sample 24 (Material: SiO _X
(15)), Example 25 (material: SiO _x (16)), Example 2
In addition to the sample of No. 6 (material: SiO _X (17)), a sample of Example 27 using SnO _X for the first layer was produced.

(2) Measurement of transmittance of sample The transmittance of light of the above four samples was measured. However,
The measuring instrument used was Lambda 19 manufactured by PerkinElmer.
It is a spectrophotometer. Table 5 below shows the results. The measured values were obtained by measuring the light transmittance of the antireflection film of the CRT specification with respect to the minimum transmittance and the average transmittance (however, the numerical values are in the wavelength range of 450 to 650 nm).

[0090]

(3) Results The transmittance of the sample using SiO _X for the first layer is slightly lower than that of the sample using SnO _X for the first layer. It is not enough to degrade the performance of. Then, the transmittance of the samples using SiO _X is large, it can be seen that sufficient.

[0092] 4. Evaluation In this example, the DC sputtering method was used, and the cleaning of the substrate by plasma was not performed before sputtering, and the above-described examples were performed under poor conditions such that the deaeration of the film formation chamber was not sufficient. The sample of Example 24, Example 25, or Example 26 has extremely excellent adhesion and optical characteristics even under such conditions. Therefore, it is clear that when these samples are formed under other conditions, they are formed under better conditions than under poor conditions, so that the obtained performance is further improved.

Regarding Adhesion As can be seen from Table 1 above, in SiO _X , the smaller the amount of oxygen gas, that is, the smaller the amount of oxygen atoms in SiO _X , the better the adhesion. This is thought to be due to the lack of oxygen atoms improving the adhesion. The supply amount of oxygen is preferably 17 sccm or less.

From the above Table 4, it can be seen from Table 4 that, in SiO _X , as the amount of oxygen gas increases, that is, as the amount of oxygen atoms in SiO _X increases, the refractive index decreases. In the first layer of the CRT specification,
Since the larger the refractive index, the better the optical characteristics, the smaller the amount of oxygen gas, the better.However, if the amount of oxygen gas is too small, k increases, and the absorption of light becomes too large. There is a problem. Conversely, if the amount of oxygen gas is large, k becomes small, light absorption is small, and reflection is likely to occur. The samples of Examples 24, 25 and 26 all show excellent optical properties.

Although the present invention has been described with reference to the embodiment, the above-described embodiment can be further modified based on the technical idea of the present invention.

For example, the layer structure, material, shape, and the like of the above-described optical element or device can be variously changed. In particular, in addition to the cathode ray tube, various optical systems and light sources such as an optical lens, an optical prism, a semiconductor, and a liquid crystal element. The present invention can be applied to a device and an optical information processing device.

As the method of forming each layer, an appropriate method can be adopted for each type, and a sputtering method, a vacuum deposition method, a coating method, and the like can be appropriately combined.

Further, in the method and apparatus for manufacturing each layer, in addition to the above-described feedback means, the temperature, pressure, voltage, oxygen gas,
Various parameters such as argon gas are set appropriately,
Feedback means for optimizing the state can be employed. The feedback means may be automatic,
It may be manual.

[0099]

According to the present invention, SiO _x (however,
X is a positive number less than 2) and SiO 2
_Since the second layer made of 2 and the other anti-reflection layer are laminated on the substrate in this order, an optical element having excellent adhesiveness, optical properties and economical efficiency without adding a special adhesive layer. An element or device can be provided.

Further, according to the manufacturing method of the present invention, since the first layer is formed by a physical film forming method in an atmosphere containing oxygen, the above excellent optical element or apparatus can be efficiently and economically manufactured. It can be manufactured in a special way.

Further, according to the manufacturing apparatus of the present invention, a film forming chamber for forming the first layer by a physical film forming method in an atmosphere containing oxygen, the second layer and the other anti-reflection film are formed. Since each of the above-described layers has a film forming chamber for forming each layer, the above-described excellent optical element or apparatus can be manufactured using the manufacturing apparatus of the present invention.

[Brief description of the drawings]

FIG. 1A is a schematic sectional view of a structural example I of an antireflection film of the present invention, and FIG. 1B is a structural example I of an optical element of the present invention.
FIG.

FIG. 2 is a schematic sectional view of a structural example II of the optical element of the present invention.

FIG. 3 is a schematic cross-sectional view of an example of the manufacturing method and the manufacturing apparatus.

FIG. 4 is a schematic sectional view of an optical sensor that can be used in the manufacturing method and the manufacturing apparatus.

FIG. 5 is a schematic diagram including feedback means that can be used in the manufacturing method and the manufacturing apparatus.

FIG. 6 is a schematic diagram including feedback means that can be used in the manufacturing method and the manufacturing apparatus.

FIG. 7 is a hysteresis curve diagram showing a change in plasma impedance depending on the amount of oxygen during sputtering in the manufacturing method and the manufacturing apparatus.

FIG. 8 is a graph showing changes in reflectance depending on wavelength when polyethylene terephthalate and an antireflection film are applied on polyethylene terephthalate.

FIG. 9 is a schematic cross-sectional view showing an external light reflection prevention and an inner electromagnetic wave shield in a structural example of the optical device of the present invention.

FIG. 10 is a schematic sectional view of a structure example of a conventional antireflection film.

[Explanation of symbols]

1: SiO _X layer, 2, 6, 6a, 6b: SiO ₂ layer, 3
... Base, 4 ... Anti-reflection film, 5, 5a, 5b ... SnO
₂ layers, 7, 9 adhesive layer, 8 top coat layer, 10 plastic layer, 11 hard coat layer, 12 cathode ray tube (CRT), 20 vacuum chamber, 21 partition plate, 30 optical sensor, 32a, 32b, 32c, 32d: controller, 33: oxygen gas control valve, 34: oxygen gas supply source, 35: oxygen gas inlet tube, 38: plasma intensity sensor, 39: power supply (voltage), 41: unwinding roll , 4
2: winding roll, 44: cooling can 50a, 50b: plastic film, 51, 52,
54: silicon target, 53: Sn target, 6
1 ... SiO _X layer forming chamber, 62, 64 ... SiO ₂ layer forming chamber, 63 ... SnO ₂ layer forming chamber, 65 ... detection chamber, 71 ... light emitting element, 72 ... light-receiving element

Claims (51)

[Claims] 1. A first layer made of SiO _X (where X is a positive number less than 2), a second layer mainly made of SiO ₂ ,
An optical element or device in which another antireflection layer is laminated on the base in this order. 2. The method of claim 1, wherein the first layer is optically absorbing.
An optical element or device according to item 1. 3. The optical element or device according to claim 1, wherein the first layer and the second layer together with another antireflection layer form an antireflection structure. 4. The extinction coefficient (k) of SiO _{X at} a wavelength of 550 nm is from 0.01 to 0.05.
An optical element or device according to item 1. 5. The optical element or device according to claim 1, wherein at a wavelength of 550 nm, the refractive index (n) of SiO _X is from 1.8 to 2.3. 6. The optical element or device according to claim 1, wherein the substrate is made of an organic substance. 7. The optical element or device according to claim 6, wherein the organic substance comprises a resin. 8. The optical element or device according to claim 1, wherein a hard coat layer containing an organic substance is provided on the substrate, and the first layer is provided on the hard coat layer. 9. The optical element or device according to claim 8, wherein the hard coat layer contains a silicone resin. 10. The optical device according to claim 1, wherein the other antireflection layer is formed by a third layer composed of an oxide-based transparent electrode layer and a fourth layer composed mainly of SiO _2. Element or device. 11. The optical element or device according to claim 1, wherein a topcoat layer is formed on another antireflection layer via an adhesive layer. 12. SiO _x (where X is a positive number less than 2)
When manufacturing an optical element or device in which a first layer made of SiO ₂ , a second layer mainly made of SiO ₂ , and another antireflection layer are laminated in this order on a substrate, an atmosphere containing oxygen is used. A method of manufacturing an optical element or an apparatus, wherein the first layer is formed by a physical film forming method. 13. The method according to claim 12, wherein the amount of oxygen in the atmosphere containing oxygen is controlled by feedback means. 14. The production method according to claim 13, wherein the amount of oxygen is controlled by feedback means including an optical monitor for measuring light absorption of the deposited SiO _X. 15. Enter the information obtained by detecting a state during the formation of the SiO _X to the feedback means, the output of the optical monitor that measures the absorption of light of the deposited SiO _X, the feedback means The method according to claim 14, wherein the set point is adjusted. 16. The manufacturing method according to claim 15, wherein a state of plasma during film formation is detected by a plasma intensity sensor. 17. The manufacturing method according to claim 15, wherein a target voltage for SiO _X during film formation is detected. 18. The method according to claim 12, wherein film formation is started from a stable state in which the amount of oxygen is smaller than a target value, and the SiO _x film is formed with the amount of oxygen fixed at the target value. 19. The method according to claim 12, wherein film formation is started from a stable state in which the amount of oxygen is larger than a target value, and the SiO _x film is formed with the amount of oxygen fixed at the target value. 20. The manufacturing method according to claim 12, wherein a sputtering method is used as the physical film forming method. 21. The manufacturing method according to claim 12, wherein a vacuum deposition method is used as a physical film forming method. 22. The method according to claim 12, wherein a first layer having optical absorption is formed. 23. The method according to claim 12, wherein an anti-reflection structure is formed by the first layer, the second layer, and another anti-reflection layer. 24. The method according to claim 12, wherein SiO _x having an extinction coefficient (k) at a wavelength of 550 nm of 0.01 to 0.05 is formed. 25. A refractive index (n) at a wavelength of 550 nm
The method according to claim 12, wherein a SiO _x film having a thickness of 1.8 to 2.3 is formed. 26. The substrate according to claim 12, wherein the substrate is formed of an organic substance.
Production method described in 1. 27. The method according to claim 2, wherein a resin is used as the organic substance.
6. The production method described in 6. 28. The method according to claim 12, wherein a hard coat layer containing an organic substance is provided on the substrate, and a first layer is provided on the hard coat layer. 29. The method according to claim 28, wherein a hard coat layer containing a silicone resin is formed. 30. The method according to claim 12, wherein the other antireflection layer is formed by a third layer made of an oxide-based transparent electrode layer and a fourth layer mainly made of SiO ₂ . 31. The manufacturing method according to claim 12, wherein a top coat layer is formed on another antireflection layer via an adhesive layer. 32. SiO _X (where X is a positive number less than 2)
Is used to manufacture an optical element or device in which a first layer made of, a second layer mainly made of SiO ₂ , and other antireflection layers are laminated in this order on a substrate, and oxygen is removed. The first method is performed by a physical film formation method in an atmosphere containing
A film formation chamber for forming a layer, and a film formation chamber for forming the second layer and the other antireflection layer, respectively.
An apparatus for manufacturing an optical element or device. 33. The manufacturing apparatus according to claim 32, wherein the amount of oxygen in the atmosphere containing oxygen is controlled by feedback means. 34. The manufacturing apparatus according to claim 33, wherein the amount of oxygen is controlled by feedback means including an optical monitor for measuring light absorption of the formed SiO _X. 35. Information obtained by detecting the state of the SiO _X being formed during film formation is input to the feedback means, and the output of the optical monitor for measuring the absorption of light of the formed SiO _X is output from the feedback means. The manufacturing apparatus according to claim 34, wherein the set point is adjusted. 36. The manufacturing apparatus according to claim 35, wherein the state of the plasma during the film formation is detected by a plasma intensity sensor. 37. The manufacturing apparatus according to claim 35, wherein a target voltage for SiO _X during film formation is detected. 38. The manufacturing apparatus according to claim 32, wherein the film formation is started from a stable state in which the oxygen amount is smaller than the target value, and the SiO _x film is formed with the oxygen amount fixed at the target value. . 39. The manufacturing apparatus according to claim 32, wherein film formation is started from a stable state in which the oxygen amount is larger than a target value, and the SiO _x film is formed with the oxygen amount fixed at the target value. . 40. The manufacturing apparatus according to claim 32, wherein the physical film forming method is a sputtering method. 41. The manufacturing apparatus according to claim 32, wherein the physical film forming method is a vacuum deposition method. 42. The manufacturing apparatus according to claim 32, wherein the first layer has optical absorption. 43. The first layer and the second layer together with another antireflection layer form an antireflection structure.
2. The manufacturing apparatus according to 2. 44. The manufacturing apparatus according to claim 32, wherein the extinction coefficient (k) of SiO _x is 0.01 to 0.05 at a wavelength of 550 nm. 45. The manufacturing apparatus according to claim 32, wherein the refractive index (n) of SiO _X is 1.8 to 2.3 at a wavelength of 550 nm. 46. The manufacturing apparatus according to claim 32, wherein the base is made of an organic substance. 47. The manufacturing apparatus according to claim 46, wherein the organic substance comprises a resin. 48. The manufacturing apparatus according to claim 32, wherein a hard coat layer containing an organic substance is provided on the substrate, and the first layer is provided on the hard coat layer. 49. The manufacturing apparatus according to claim 48, wherein the hard coat layer contains a silicone resin. 50. The manufacturing apparatus according to claim 32, wherein the other antireflection layer is formed by a third layer made of an oxide-based transparent electrode layer and a fourth layer mainly made of SiO _2. . 51. The manufacturing apparatus according to claim 32, wherein a top coat layer is formed on another antireflection layer via an adhesive layer.