TWI460078B - A multilayer film with hydrophilic, anti-reflection and anti-fog and the method of manufacturing the multilayer film - Google Patents

Description

Multilayer composite film with hydrophilicity, anti-reflection and anti-fog and preparation method thereof

The present invention relates to a multilayer composite film, and more particularly to a multilayer composite film having hydrophilicity, antireflection and antifogging properties and a method for producing the multilayer composite film.

Generally speaking, a hydrophilic film refers to a photocatalyst film layer attached to a substrate. When a water droplet contacts the surface of the hydrophilic film layer, the photocatalyst layer has a self-cleaning property, so that water droplets cannot adhere to the surface of the film layer; The photocatalyst film layer generates an electron hole pair after being irradiated with light, and the electron hole has a redox effect on impurities attached to the surface of the film film, so that the impurities cannot adhere to the surface of the film layer, and the water droplets are caused to generate hydroxyl groups. The water droplets are rendered super-hydrophilic on the surface.

Currently known photocatalyst materials are titanium dioxide, tin dioxide, zinc oxide, cadmium sulfide, zinc sulfide and other materials, but based on environmental impact, cost considerations, sustainability and hydrophilic effects, titanium dioxide is currently the main photocatalyst material; The energy level of titanium dioxide is 3.2eV, and the spectral range of the excited electron hole pair falls within the ultraviolet wavelength range. Therefore, the spectrum of other regions cannot be used, which causes the photocatalytic effect of titanium dioxide to be low. It is proposed to add other The utilization ratio of the spectrum of the region is such that when the titanium dioxide film layer is prepared, the tungsten oxide material is infiltrated into the film layer at a level of 2.7 eV, thereby increasing the absorption spectrum range, and the absorption spectrum of the original titanium dioxide is increased from 387 nm to 460 nm. In order to improve the utilization range of the spectrum, the film of the doped tungsten trioxide has a phenomenon of agglomeration of the tungsten trioxide atomic group, resulting in uneven light absorption of the film and affecting the hydrophilic effect.

In addition, the most commonly used photocatalyst preparation method is a coating method in which a solution in which titanium dioxide is dissolved is sprayed on the surface of a substrate, and then dried by heating to form a photocatalyst film layer having titanium dioxide, but the film layer The adhesion to the substrate is insufficient, so that the film layer is often detached and the photocatalytic effect is lost. At the same time, when the hydrophilic film layer is prepared by the coating method, the film thickness is too thick, so that the light transmittance is too low to be applied to the glass lens. This further limits the range of use of the hydrophilic membrane.

One of the objects of the present invention is to provide a multilayer composite film which can increase the hydrophilicity, antireflection and antifogging properties in the wavelength range of the absorption spectrum.

Another object of the present invention is to provide a multilayer composite film having hydrophilicity, antireflection and antifogging properties with high specific surface area.

Another object of the present invention is to provide a multilayer composite film which is hydrophilic, antireflective and antifogging in a high proportion of titanium dioxide anatase.

The multilayer composite film of the present invention comprises: a substrate and a multi-layer anti-reflection film layer disposed on the substrate for reducing the reflectivity of the light, wherein the multi-layer anti-reflection film layer is made of high refraction The coefficient and the low refractive index material are sequentially stacked; an iron/tungsten composite film layer is disposed on the multilayer reflective film, wherein the iron/tungsten composite film layer is made of tungsten-iron alloy palladium or Formed by tungsten and iron targets respectively; a hydrophilic film layer disposed above the ferric oxide/tungsten oxide composite film layer for providing photocatalytic function; a protective film layer disposed on the hydrophilic layer Above the film layer, the hydrophilic film layer is protected from external damage, and the protective film layer is formed of a material having a low refractive index and a high hardness.

The multilayer composite film of the present invention is prepared by first placing a substrate in a vacuum chamber, and depositing materials of different refractive indexes on the substrate in a sputtering manner to form a multilayer anti-reflection film layer; Forming an iron/tungsten composite film layer on the anti-reflective film layer by sputtering, wherein the iron/tungsten composite film layer may be formed by depositing a tungsten-iron alloy target, or may be formed by simultaneously depositing a tungsten target and an iron target, respectively. Iron/tungsten The composite film layer is formed on the multilayer anti-reflection film layer, and the roughness of the surface of the iron/tungsten composite film layer is increased due to the difference in size of the iron atoms and the tungsten atoms, and then the photocatalyst material is deposited on the iron by sputtering. /Tungsten composite film layer forms a hydrophilic film layer, wherein the photocatalyst material may be titanium dioxide, cadmium sulfide, zinc oxide, zinc sulfide, tin dioxide, etc., when the hydrophilic film layer is deposited, due to the roughness of the surface of the iron/tungsten composite film layer When the size is increased, the surface area of the hydrophilic film layer is also increased, thereby increasing the specific surface area of the hydrophilic film layer; then depositing a protective film layer on the hydrophilic film layer, the protective film layer is made of high hardness It is formed of a highly transparent material.

After the preparation of the hydrophilic, anti-reflective and anti-fogging multilayer film, the hydrophilic, anti-reflective and anti-fogging multilayer film is annealed to increase the proportion of the anatase structure of the titanium dioxide, thereby improving The hydrophilic membrane has a hydrophilic and defogging effect.

The multilayer film of hydrophilicity, anti-reflection and anti-fog prepared according to the invention can absorb different wavelengths of the spectrum by the iron/tungsten composite film layer, and generate more electron hole pairs to prolong the photocatalytic effect, and has an expanded use. The wavelength range increases the solar light utilization rate; after the film formation of the hydrophilic film layer by the atomic particle size of the iron/tungsten composite film layer, the specific surface area of the hydrophilic film layer can be increased, and the effective area of the electron hole is increased. Extend the hydrophilic life.

However, those of ordinary skill in the art should be able to understand the detailed description and the specific embodiments set forth in the present disclosure are merely illustrative of the present invention and are not intended to limit the scope of the patent application.

1‧‧‧Multilayer film

10‧‧‧Substrate

20‧‧‧Multilayer anti-reflective coating

201‧‧‧High refractive index film

202‧‧‧Low-refractive-index film

30‧‧‧ iron/tungsten composite film

40‧‧‧Hydrophilic film

50‧‧‧Protective film

S1‧‧‧Substrate pre-cleaning process

S2‧‧‧Multilayer anti-reflection film formation process

S3‧‧‧Iron/Tungsten Composite Film Formation Process

S4‧‧‧Hydrophilic film formation process

S5‧‧‧Protective film formation process

S6‧‧‧Multilayer film annealing process

FIG. 1 is a schematic view showing the stacking of the multilayer composite film.

Figure 2 is a structure of a multilayer antireflection film layer.

3 is a schematic view showing the preparation process of the multilayer composite film

Referring to FIG. 1, a multilayer composite film 1 having hydrophilicity, anti-reflection and anti-fogging properties according to the present invention comprises: a substrate 10, which may be a glass substrate or An optical plastic substrate; a multilayer anti-reflective film layer 20 deposited on one side of the substrate 10, the multilayer anti-reflective film layer 20 comprising a plurality of layers of high refractive index film 201 and a plurality of layers of low refractive index The high-refractive-index film 201 may be a titanium dioxide film, and the low-refractive-index film 202 may be a ceria film, and the multi-layer anti-reflective film layer 20 is used to reduce light reflectance and improve light transmittance; An iron/tungsten composite film layer 30 is deposited on the side of the multilayer anti-reflective film layer 20 with respect to the substrate 10, and the iron/tungsten composite film layer 30 can absorb energy at a wavelength of 460 nm to 563 nm. The electro-optical pair is generated; a hydrophilic film layer 40 is deposited on the side of the opposite iron/tungsten composite film layer 30, and the hydrophilic film layer 40 is deposited from a photocatalytic material. It is titanium dioxide, cadmium sulfide, zinc oxide, zinc sulfide, tin dioxide, etc.; a protective film layer 50 deposited on one side of the hydrophilic film layer 40 with respect to the iron/tungsten composite film layer 30, the protective film The layer 50 is deposited from a material having high hardness and high light transmittance. Wherein the material of the protective layer may be silicon dioxide.

The preparation process of the multilayer film 1 having hydrophilicity, anti-reflection and anti-fog property according to the present invention is as follows; the substrate 10 pre-cleaning process S1: first pumping the pressure of the sputtering machine chamber to 8×10 ^-6 Torr, An argon gas is introduced, a bias voltage is applied to generate an argon plasma, and the substrate 10 is pre-bombard by the plasma to clean the surface of the substrate 10, and then the argon gas is stopped, the oxygen is turned on, and the oxygen plasma is generated to activate the surface of the substrate 10. Multi-layer anti-reflection film layer forming process S2: oxygen and argon gas are introduced into the cavity, and the ratio of the flow rate to the flow rate is 1/4 of oxygen/argon gas, and the temperature of the susceptor is controlled at 150 ° C, the cavity The vacuum degree is controlled at 4 × 10 ^-2 Torr, and the high refractive index film 201 and the low refractive index film 201 are sequentially sputtered to form a multilayer antireflection film layer 20 in which the high refractive index film 201 and the low refractive index film 202 are alternately overlapped. The multi-layer anti-reflection film layer 20 is deposited on one side of the substrate 10, wherein the high-refractive-index film 201 may be a titanium dioxide film, and the target may be a titanium metal target or a titanium dioxide target, and the low-refractive-index film 202 is cerium oxide. a film whose target can be a ruthenium target or a ruthenium dioxide target, and the multilayer anti-reflection The number of layers of the film layer 20 is not particularly limited, depending on the required light transmittance; the iron/tungsten composite film layer is formed into a film flow S3: oxygen and argon are introduced into the cavity, and the flow rate of the flow is oxygen. / argon gas is 1/2, and sputtering is performed to form an iron/tungsten composite film layer 30 deposited on one side of the multilayer anti-reflection film layer with respect to the substrate 10, wherein the iron/tungsten composite film The layer 30 utilizes an iron-tungsten target 30 for depositing an iron/tungsten film 30, wherein the iron/tungsten film 30 is a ferric oxide/tungsten trioxide film having a film thickness of 30 nm and iron The tungsten target is not limited to the iron-tungsten mixed target, and may be an iron target and a tungsten target, respectively, or a ferric oxide target and a tungsten oxide target respectively; a hydrophilic film forming process S4: passing through the cavity Oxygen and argon are introduced, and the ratio of the flow rate is 1/4 of that of oxygen/argon. Titanium dioxide is used as a target to deposit titanium dioxide film. The thickness of the hydrophilic film 40 is between 70 nm and 120 nm, but 100 nm. Good film thickness; protective film layer forming process S5: oxygen and argon gas are introduced into the cavity, and the flow rate of the flow is 1/4 of oxygen/argon gas. The ruthenium dioxide film is deposited on the ruthenium material or the ruthenium dioxide as a target, and the thickness of the protective film layer 50 is less than 15 nm; the multilayer film annealing process S6: placing the coated substrate 10 in an annealing furnace at 350 ° C to 450 ° C Annealing, the film atoms of the ferric oxide/tungsten oxide composite film layer 30 are diffused into the hydrophilic film layer 40 in the annealing process, and the atomic grain growth of the titanium dioxide film of the hydrophilic film layer 40 is suppressed, and the anatase in the titanium dioxide is increased. The ratio is also due to the diffusion of the film atoms of the ferric oxide/tungsten oxide composite film layer 30 into the hydrophilic film layer 40. Since the particle size of the film atoms is different, the roughness of the surface of the hydrophilic film layer 40 is increased, thereby increasing the hydrophilic film layer. 40 specific surface area.

The specific embodiments of the present invention are intended to be illustrative, and are not intended to limit the scope of the invention.

1‧‧‧Multilayer composite film

10‧‧‧Substrate

20‧‧‧Multilayer anti-reflective film

30‧‧‧Composite film

40‧‧‧Hydrophilic film

50‧‧‧Protective film

Claims (11)

A multilayer composite film having hydrophilicity, anti-reflection and anti-fog, the film comprising at least: a substrate; a multilayer anti-reflection film layer deposited on one side of the substrate, the multilayer anti-reflection film The layer is formed by sequentially depositing a plurality of layers of a high refractive index material and a low refractive index material; an iron/tungsten composite film layer deposited on the side of the multilayer antireflection film layer opposite to the substrate; a hydrophilic film layer deposited on a side of the iron/tungsten composite film layer opposite to the multilayer anti-reflective film layer; a protective film layer deposited on the hydrophilic film layer with respect to the iron/tungsten composite One side of the membrane layer. The multi-layer composite film having hydrophilicity, anti-reflection and anti-fog as described in claim 1, the multi-layer anti-reflection film layer, the high refractive index material is titanium dioxide, and the low refractive index material is ceria. The multi-layer composite film having hydrophilicity, anti-reflection and anti-fog as described in claim 1, wherein the material of the iron/tungsten composite film layer is an iron/tungsten mixed target, and the film thickness of the iron/tungsten composite film layer is between 15 nm~ 50nm. The multilayer composite film having hydrophilicity, anti-reflection and anti-fog as described in claim 1, wherein the material of the iron/tungsten composite film layer is an iron target and a tungsten target, respectively, and the thickness of the iron/tungsten composite film layer is between 15 nm. ~50nm. The multilayer composite film having hydrophilicity, anti-reflection and anti-fogging according to claim 1, wherein the hydrophilic film layer is titanium dioxide, and the film thickness of the hydrophilic film layer is 70 nm to 120 nm. a multilayer composite film having hydrophilicity, anti-reflection and anti-fog as described in claim 1 The protective film layer is cerium oxide, and the protective film layer has a film thickness of 10 nm to 15 nm. A method for producing a multilayer, composite film having hydrophilicity, anti-reflection and anti-fog as claimed in claim 1, the method comprising at least the following process: a cleaning process: pumping a pressure in a chamber of the sputtering machine to a vacuum, and introducing argon gas, Applying a bias voltage to generate an argon plasma, pre-bombard the substrate with a plasma to clean the surface of the substrate, and then introducing oxygen to generate an oxygen plasma to activate the surface of the substrate; a multilayer anti-reflective film layer forming process: on the substrate One side surface is sputtered to form a multi-layer anti-reflection film layer formed of a plurality of layers of a material having a high refractive index material and a low refractive index; a film forming process of the iron/tungsten composite film layer: The anti-reflective film layer forms an iron/tungsten composite film layer on the side of the substrate; the hydrophilic film layer is formed into a film: a hydrophilic film layer is formed on the side of the iron/tungsten composite film layer relative to the multilayer anti-reflective film layer; Protective film formation process: a protective film layer is formed on the side of the hydrophilic film layer relative to the iron/tungsten composite film layer, and the material used is an iron-tungsten target; the multilayer film annealing process: the substrate is placed in an annealing furnace Annealing is performed. The multi-layer composite film method according to claim 7, wherein the high refractive index material of the multi-layer anti-reflection film layer forming process is titanium dioxide, and the low refractive index material is ceria. The multi-layer composite film method of hydrophilicity, anti-reflection and anti-fog according to claim 7, wherein the iron-tungsten target of the iron/tungsten composite film formation process is a mixed target of iron metal and tungsten metal. The multi-layer composite film method according to claim 7, wherein the iron-tungsten target of the iron/tungsten composite film formation process is a separate iron metal target and a tungsten metal target. The multi-layer composite film method of the hydrophilic, anti-reflective and anti-fog method according to claim 7, wherein the annealing temperature of the multilayer film annealing process is 350 ° C to 450 ° C.