JP2000121825A - Substrate with light shielding layer, its production as well as sputtering target, color filter substrate and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with light shielding layers which has the optical characteristics approximately equal to those of conventional chromium films, excellent in durability and is kind to the environment. SOLUTION: The substrate with the light shielding layers including at least one layer of the light shielding layers 2 and low reflection layers 2 consisting of metals and/or metal compounds which consists essentially of nickel(Ni) and titanium(Ti) on a substrate 1 and in which the composition of Ti is 15 to 70%, more preferably 25 to 65% of the total sum of Ni and Ti in atomic ratios is usable particularly for display elements (for example, liquid crystal display elements), etc., as the substrate with the light shielding layers which solves the problem described above, has the excellent optical characteristics and durability and is kind to the environment. More particularly the substrate with the light shielding layers is preferably formed of the structure obtained by successively forming low reflection layers 3 and light shielding layers 2 having the composition described above on the substrate 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a novel light-shielding layer, its use, that is, a color filter substrate and a display device using the same, for example, a liquid crystal display device, a method of manufacturing the same, and a sputter target used therefor. It is possible to provide a substrate with a light-shielding layer used for a display element or the like having optical performance and durability comparable to those of a metal light-shielding film represented by a chromium film conventionally used.

[0002]

2. Description of the Related Art In recent years, colorization of flat panel displays such as a liquid crystal display (LCD), a plasma display (PDP), and an electroluminescence display (ELD) has been advanced.

In each of these color panels, a light-shielding layer having a light-shielding function is provided between the RGB color filters in order to improve the contrast of the screen and improve the visibility. Examples of the material of the light-shielding layer include a metal film such as chromium and nichrome, and a resin containing a black pigment such as carbon.

As a method of forming a light-shielding layer on a substrate, in the case of a metal film such as chromium, a thin film having a thickness of about 100 nm is formed on the substrate by sputtering or the like, and then a resist pattern is formed by photolithography. Then, using this as a mask, etching is performed to form a desired metal pattern.

[0005] In particular, when it is desired to obtain a light-shielding layer having a low surface reflectance, a metal oxide or oxynitride is formed on a substrate by 50n.
A structure in which a metal film having a thickness of about 100 nm is stacked after forming a metal film having a thickness of about m is also used.

On the other hand, in the case of a resin containing a black pigment, a method in which an ink in which a black pigment powder is dispersed in a resin is printed into a print pattern by a printing method, and then cured by heating to form a light-shielding layer is used. In some cases, an ink in which a black pigment powder is dispersed in a photosensitive resin is applied, and a light-shielding layer having a desired pattern is formed by photolithography.

[0007]

A conventional light-shielding film using a metal such as chromium or nichrome not only has an advantage that a sufficient light-shielding performance can be obtained even with a film thickness of about 100 nm, but also has a very fine pattern formation. Is easy.

The light-shielding layer using these metals, their oxides or their oxynitrides is mainly formed by a vacuum film-forming method such as a sputtering method, and then is subjected to pattern formation by photolithography and etching of a resist. Do. For this reason, there is an advantage that occurrence of pinholes and the like is extremely small, and sufficient light shielding performance can be obtained even with a film thickness of about 100 nm.
On the other hand, there is a disadvantage that productivity is low and production cost is high.

[0009] Furthermore, in recent years, when consideration for the environment is strongly screamed,
The reduction of the load of the chromium etching waste liquid treatment has become a new issue, and a metal material for a light shielding layer instead of chromium has been demanded.

On the other hand, in the case of a resin containing a black pigment, it is not necessary to use a vacuum film forming method, so that the productivity is high,
Although the manufacturing cost is low, the pattern thickness must be extremely thick, about 2 μm, in order to obtain sufficient light-shielding performance, making it difficult to form a fine pattern, or a large step between the substrate and the portion where the light-shielding layer exists. This step may adversely affect, for example, the alignment control of the liquid crystal, and has not yet completely replaced the metal light-shielding film.

In view of the above problems, the present invention has excellent optical performance, durability performance and patterning performance, and particularly preferably fine patterning performance, which are equivalent to those of the metal light-shielding film represented by the chromium film described above. It is an object of the present invention to provide a new substrate with a metal light-shielding layer having less production problems, a color filter substrate thereof, a display device such as a liquid crystal display device, a method of manufacturing the same, and a sputter target used therefor. .

[0012]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that nickel (Ni) and titanium (Ti) are the main components and the composition of the Ti is Ni in atomic ratio. The problem can be solved by a substrate with a light-shielding layer containing at least one of a light-shielding layer and a low-reflection layer made of a metal and / or a metal compound which is 15 to 70% of the total of Ti and Ti. The inventors have found that the performance is comparable to that of the conventional product from both the performance and the durability performance, and have completed the present invention based on this finding.

That is, in the present invention, nickel (Ni) and titanium (Ti) are the main components, and the composition of the Ti is Ni in atomic ratio.
A substrate having a light-shielding layer containing at least one of a light-shielding layer and a low-reflection layer made of a metal and / or a metal compound in an amount of 15 to 70% based on the total of Ti and Ti (a substrate with a light-shielding layer); The following contents are also included in the present invention.

According to the present invention, there is provided a substrate provided with a light-shielding layer, and Ni and Ti are used as the light-shielding layer formed on the substrate.
And a light-shielding layer composed of a metal and / or a metal compound in which the composition of Ti is 15 to 70% by atomic ratio with respect to the sum of Ni and Ti,
Alternatively, there is a case of a light-shielding layer not formed of a metal compound.

The substrate of the present invention is a substrate having at least a substrate such as glass, a light-shielding layer and a low-reflection layer if necessary. A light-shielding layer composed of a metal and / or a metal compound containing Ni and Ti as main components and having a composition of Ti in an atomic ratio of 15 to 70% with respect to the total of Ni and Ti; and / or b. A light-shielding layer-containing substrate including a low-reflection layer made of a metal compound containing Ni and Ti as main components and having a composition of Ti in an atomic ratio of 15 to 70% with respect to the total of Ni and Ti.

The light-shielding layer is a layer having a light-shielding performance, and may include at least one thin film layer having a light-shielding performance. In the case of being composed of a plurality of thin films, at least one thin film may be included in the above numerical range for the calculation of the composition of Ti, but it is preferable to include it as an entire layer in terms of etching control. .

The above composition ratio of Ti is defined by the atomic ratio of Ti to the sum of Ni and Ti. The present invention relates to a substrate with a light-shielding layer. In the present invention, the light-shielding layer contains Ni and Ti as main components, and the composition of the Ti is Ni and T in an atomic ratio.
Firstly, the case of a metal and / or a metal compound which is 15 to 70% of the total of i is included. In this case, a low-reflection layer may or may not be provided. When the low-reflection layer is provided, Ni and Ti are used as main components and the T
The composition of i is 15 to 7 with respect to the sum of Ni and Ti in atomic ratio.
One or more low-reflection layers made of a metal compound having a concentration of 0% may be contained, or one or more low-reflection layers made of a material other than such a metal compound, for example, one or more low-reflection layers formed by a known method may be contained. Is also good. Each of these layers can also include one or more layers.

The low reflection layer is a layer having a low reflection performance, that is, a layer having a reflection suppressing function, and it is sufficient that the low reflection layer includes a thin film having a low reflection performance. In the case of being composed of a plurality of thin films, at least one thin film may be included in the above numerical range for the calculation of the composition of Ti, but it is preferable to include it as an entire layer in terms of etching control. .

Further, as a structure of the light-shielding layer in the substrate of the present invention, the light-shielding layer contains Ni and Ti as main components, and the composition of the Ti is an atomic ratio of 15 to the total of Ni and Ti.
When the composition does not include a metal and / or metal compound composition of up to 70%, that is, as described above, this layer may be composed of a plurality of thin films. There are cases where it is not included. In this case, as the light-shielding layer, for example, a known method can be employed. As the low-reflection layer, the low-reflection layer used in the present invention described above is used.
And a low reflection layer made of a metal compound having a composition of Ti in an atomic ratio of 15 to 70% with respect to the sum of Ni and Ti.

The present invention comprises a metal and / or a metal compound containing Ni and Ti as main components and having a Ti composition of 15 to 70% or 25 to 65% by atomic ratio with respect to the total of Ni and Ti. For the light-shielding layer and / or the low-reflection layer,
As long as Ni and Ti are the main components, they may be in a simple substance, a compound, or any other form. For example, various metals and / or metal compounds are included, such as in the case of only metal (including the form of alloy) and in the case of metal compound, both of them. included. Ni and Ti are the main components as metal components. Although it is desirable to use only these two metals (including the form of an alloy), other metal components may be further included as subcomponents. In the case where other metal components are contained, the content of the other metal components is 5 at an atomic ratio to the total of all metal components including the two metal components of the main component and the other metal components as subcomponents. Do not exceed%. In this case, it may be contained in the form of an alloy or a metal compound, in which case,
The above metal composition may be calculated by dividing into Ni component and Ti component and other metal components, and when present in the form of a compound, distinguishing the components of each metal portion.

In the present invention, the term “metal compound” includes, in addition to those in which a certain metal and another element are completely bonded by a chemical bond, such as a covalent bond, for example, a metal and another element. For example, those in the broadest sense of bonding, such as those in which oxygen is in a molecular or atomic state or other physical bonding, are also included. Naturally, the embodiment in which various gases react and react at the stage of film formation in the following embodiments of the present invention is also included.

On the other hand, when employing a light-shielding layer or a low-reflection layer which is not composed of a metal and / or a metal compound having the above-mentioned Ni and Ti as main components and the above-mentioned predetermined composition, the two metals are mainly used as the components. It may be a component, but as long as it does not have the above composition of Ti, Ni and / or
Alternatively, various metals including Ti can be selected at various contents. Furthermore, those metal compounds can be variously selected.

As metal components used in the light-shielding layer or the low-reflection layer of the present invention, Ni and Ti are typical metal components. Other metal components usable other than Ni and Ti, for example, tantalum, zirconium, Examples include elements such as niobium, silicon, tungsten, molybdenum, iron, vanadium, antimony, phosphorus, and boron. Further, a compound (oxide, nitride, etc.) of the metal can be contained.

In particular, when a metal compound of the same element is used for the light-shielding layer and the low-reflection layer, the light-shielding layer has a lower degree of compounding of the element than the low-reflection layer. This is preferable in that sufficient light-shielding properties are ensured. For example, an oxide of the metal having a lower oxidation degree, a nitride of the metal having a lower nitridation degree, a carbide of the metal having a lower carbonization degree, and an oxynitride of the metal having a lower oxidation degree and nitriding degree than the low reflection layer. And mixtures thereof and these metals themselves can be used for the light-shielding layer. As will be described later, the light-shielding layer or the low-reflection layer may be formed by appropriately selecting the mutual transmittance.

Regarding the above calculation of the composition of Ti, the calculation targets are Ni metal and Ti metal (including the form of alloy).
It is a requirement that the calculation formula: Ti / Ni + Ti (atomic ratio) for the metal component be included in the numerical range in the present invention.

In the above substrate, a light-shielding layer made of a metal and / or a metal compound containing Ni and Ti as main components and having a composition of Ti in an atomic ratio of 15 to 70% with respect to the total of Ni and Ti, and a low reflection layer In at least one of the layers, the Ti composition has an atomic ratio of 15 to the sum of Ni and Ti.
The content is more preferably 25% to 65% from the viewpoint of enabling fine processing (fine patterning).

In the above substrate, the metal compound containing Ni and Ti as main components includes, for example, oxides, nitrides, carbides, oxynitrides, oxycarbides of metals containing Ni and Ti as main components. A mixture of two or more of them is preferably used.

In the above substrate, a substrate provided with a low-reflection layer on at least one of an upper portion and a lower portion of the light-shielding layer containing Ni and Ti as a main component, or a low-reflection layer containing Ni and Ti as a main component. A substrate provided with a light-blocking layer on one of the upper and lower portions is preferably used.

In the above substrate, a low-reflection layer mainly containing Ni and Ti is provided on at least one of an upper portion and a lower portion of the light shielding layer mainly containing Ni and Ti, and the light shielding layer is made of Ni and Ti. And / or an oxide of the metal, a nitride thereof, a carbide thereof or an oxynitride thereof, and the low reflection layer is made of Ni and Ti having a higher transmittance than the light shielding layer. A structure composed of a metal oxide, its nitride, its carbide or its oxynitride as a main component is preferably used.

In the substrate of the present invention, Ni
It is preferable that the light-shielding layer and the low-reflection layer have the same metal composition within the above-mentioned composition range and have a structure of two or more layers including the low-reflection layer. In this case, it is more preferable that a first low-reflection layer is provided from the substrate side, and a second layer of a light-shielding layer having light-shielding performance is laminated thereon.
A compound of the metal having a lower degree of oxidation, nitridation or carbonization, and also a lower degree of oxidation and nitridation, as compared to the metal compound used in the layer, such as its oxides, nitrides, carbides and acids. The light-shielding layer may include nitride or the metal, that is, Ni and Ti, and the low-reflection layer may have a higher transmittance than the light-shielding layer (see FIG. 1).

When a structure of a plurality of layers such as a low reflection layer other than the light-shielding layer is formed, if these are formed of the same material, there are many advantages such that only one type of sputter target is required at the time of fabrication.

Therefore, in the manufacture of the substrate, Ni and Ti are the main components, and the composition of the Ti is 15 to 70%, more preferably 25%, in terms of atomic ratio to the total of Ni and Ti.
A sputter target having a metal composition of about 65% can be preferably employed, and such a sputter target is also included in the present invention.

As a method of manufacturing a sputtering target, there is a casting method by vacuum melting or electron beam melting, or a method of sintering powders of Ni, Ti, and additional elements. However, the most preferable manufacturing method is to obtain an NiTi-based alloy powder using an Ar gas atomizing method or the like and sinter the powder using a hot isostatic press or the like. Since this target has less segregation and less defects and higher density, a film having a uniform chemical composition can be obtained at the time of film formation, and the generation of foreign matter is reduced. When magnetron sputtering is performed, alloying can increase leakage magnetic flux and improve film productivity.

In particular, as described above, when preparing a sputter target for magnetron sputtering for forming a light-shielding layer and / or a low-reflection layer, the composition of Ni and Ti in the sputter target material, which is the main component, is as described above. What is necessary is just to manufacture so that it may be a composition ratio. In particular, when a low reflection layer is provided, it is preferable to select a material having the same metal composition as this, particularly from the viewpoint of productivity.

The present invention also includes a color filter substrate having a color filter layer on any of the above substrates provided with a light-shielding layer. According to a conventional method, a color filter layer can be formed on any one of the above substrates with a light-shielding layer, and an electrode can be further formed on the substrate with an insulating layer if necessary.

When the light-shielding layer and / or the low-reflection layer of any of the above-mentioned substrate and color substrate is formed by a sputtering method, particularly preferably a magnetron sputtering method, a substrate with a light-shielding layer and a color filter substrate can be manufactured.
This method is also included in the present invention.

In the case of having a structure of two or more layers such as a low reflection layer other than the light-shielding layer, it is preferable that at least one layer is formed by a sputtering method, in particular, a magnetron sputtering method, so that uniform coating, foreign matter, and This is preferable in that a dense film having few hole defects can be formed.

A display element having any of the above substrates or having the above color filter substrate is also included in the present invention. When used as a liquid crystal display element, it is preferable to provide a liquid crystal layer on the liquid crystal display element. Usually, when the liquid crystal layer is sandwiched between the color filter substrate and another substrate with electrodes, the liquid crystal display element is manufactured. Is done.

[0039]

Next, an embodiment of the present invention will be described. FIG. 1 is a cross-sectional view of a typical example showing a substrate with a light-shielding layer of the present invention, which has a two-layer structure of a light-shielding layer and a low-reflection layer. FIG. 2 is a cross-sectional view of an example showing a substrate with a light-shielding layer of the present invention, which is an example of one light-shielding layer having no low-reflection layer. 1 to 3, reference numeral 1 denotes a substrate such as glass;
Represents a light shielding layer, and 3 represents a low reflection layer. In the example of FIG. 1, the light-shielding layer 2 (second layer) and the low-reflection layer 3 (first layer) constitute two layers.

Hereinafter, the present invention will be described mainly with reference to FIG. 1 which is a typical example showing a substrate with a light-shielding layer of the present invention, but the present invention is of course not limited to this.

The light-shielding layer 2 and / or the low-reflection layer 3 according to the present invention contain Ni and Ti as main components, and the composition of the Ti with respect to the atomic total of Ni and Ti is 15 to 70% by atomic ratio.
It is good to form with the material which consists of a metal and / or a metal compound which is preferably 25 to 65%.

Specifically, the light-shielding layer and / or the low-reflection layer are made of Ni and Ti having a composition containing Ni and Ti as main components.
The composition (proportion) of the Ti with respect to the atomic sum of N is in the range of 15 to 70%, preferably 25 to 65% by atomic ratio.
A metal film containing i and Ti as main components and / or a compound film of the metal, for example, an oxide film, a nitride film, a carbide film, and an oxynitride film can be suitably used.

Also, because the durability is improved,
For the light-shielding layer and / or the low-reflection layer, besides Ni and Ti, zirconium, niobium, tantalum, silicon, tungsten, molybdenum, iron, vanadium, antimony,
Any one or more of phosphorus and boron may be additionally contained. In this case, it is preferable to appropriately select the elements to be contained and their contents, particularly the contents, in consideration of durability and patterning performance. In consideration of this point, when the additional element is present, the content of the additional element is 5 atomic% with respect to the atomic total of all metal components including Ni and Ti. Do not exceed. If it exceeds 5 atomic%, fine patterning performance is often impaired. in this case,
It may be present in the form of an alloy or a compound, in which case N
In the case of the i and Ti components and other components or compounds, it is necessary to calculate the above content separately for each metal part.

Further, from the viewpoint that the reflection on the substrate side can be suppressed, it is preferable to use the light shielding layer in a two-layer structure by adding a low reflection layer as shown in FIG. in this case,
As a preferred embodiment, the first layer 3 is formed as a layer for suppressing reflection on the substrate 1 side by making the metal composition of Ni and Ti the same, that is, a low reflection layer such as a film having low reflection performance. Then, a second layer 2 having a high light shielding degree is formed thereon as a light shielding layer. There is no particular difficulty in manufacturing the low-reflection layer of the first layer 3, and those skilled in the art can easily reflect light based on conventional techniques, for example, techniques used for metal films such as Cr and the embodiments of the present invention. A suppression film can be formed. As the film of the low reflection layer, a metal compound film containing Ni and Ti as main components is preferably used, and the effect of comparing the transmittances with each other and easily suppressing reflection can be imparted.

As the second layer 2, a metal film mainly composed of Ni and Ti or a compound film of the above-mentioned metal is preferably used with the same metal composition as the first layer. At this time, the first layer 3 and the second layer 2 are formed because the durability is improved.
May contain the same or the above-mentioned other elements independently in the above-mentioned content. However, the above-mentioned other elements may preferably be contained, but as described above, the first element may be contained.
It is also preferable in terms of productivity that the metal composition be the same between the layer and the second layer.

In order to provide light-shielding performance or low-reflection performance, a gas such as oxygen, nitrogen, or a carbonized material is produced in a production stage of a metal material based on the prior art and the description of the present invention. The reaction may be appropriately performed using

When materials used for these layers, particularly materials having the same metal composition, are used, the contents of oxygen, nitrogen, carbon and the like suitable for each layer are selected. That is, the first
Both the second layer and the second layer can be used as a metal oxide film or a nitride film containing Ni and Ti as main components. In this case, the first layer of Ni and Ti is mainly used. The oxide or nitride film used as the component has an oxygen or nitrogen content such that the reflection gloss is smaller than the light blocking degree, and the second layer Ni
It is preferable that the oxide or nitride film containing Ti and Ti as main components has an oxygen or nitrogen content that increases the degree of light shielding.

In this case, the light-shielding layer is made of a material mainly composed of Ni and Ti. The reason is that Ni, which is the first main component of the light-shielding layer used here, has low durability. In addition to the above, colored oxides, nitrides, oxynitrides, and the like are easily formed, which is suitable for precisely controlling the transparency and the refractive index.
That is, it is because a reflection suppressing layer (first layer) which is a low reflection layer having excellent reflection suppressing performance can be easily provided. In addition, the use of Ni also facilitates etching with an acidic solution.

On the other hand, Ti as the other main component has excellent properties such as chemical resistance and heat resistance, and can provide a light-shielding layer having high light-shielding properties and excellent durability. However, Ti is very easily oxidized and easily becomes a colorless and transparent oxide, and it is very difficult to precisely control the transparency and the refractive index. It is difficult to provide a layer (first layer).
Therefore, by using the material containing Ni and Ti as the main components of the present invention for the constitution of the layer of the present invention, excellent optical performance such as light-shielding properties and anti-reflection performance and excellent durability such as chemical resistance and heat resistance are obtained. In the composition of the light-shielding layer, the ratio of Ti to the atomic total of Ni and Ti in the atomic ratio is in the range of 15 to 70%, preferably 25 to 65%. Patterning becomes possible. Ti is 1
If it is less than 5 atomic%, it is difficult to obtain fine patterning performance, and durability such as heat resistance and acid resistance tends to decrease. If it exceeds 70 atomic%, it is difficult to obtain sufficient reflection suppressing performance and fine patterning performance.

Further, a durable layer or the like made of the above-mentioned metal oxide film or the like may be provided above or below the light-shielding layer to form a three-layer structure. And a two-layer structure. In this case, the durable layer can be provided to improve the durability of the light shielding layer. Thereby, in a process such as cleaning or photolithography during the color filter forming process, it is possible to suppress the performance of the light-shielding layer from deteriorating and the occurrence of pinholes.

On the other hand, as for the low reflection layer, not only one layer but also a plurality of layers can be provided if necessary. In this case, two layers can be provided on both sides of the light-shielding layer or below it.

The thickness of the light-shielding layer 2 is about 50 to 1000 nm, preferably about 80 to 300 nm. That is, if the thickness is less than 80 nm, it is difficult to obtain high light-shielding performance. If the thickness exceeds 300 nm, the internal stress of the film increases, the film is peeled off, and the film formation time and the etching time are unnecessarily long.

When the light-shielding layer 2 has a two-layer structure by adding a low-reflection layer to the first layer as shown in FIG. 1, the thickness of the first layer should be about 10 to 100 nm. preferable.
If it is less than 10 nm, it is difficult to obtain sufficient reflection suppression performance,
If it exceeds 100 nm, the reflection suppressing performance hardly increases and the film formation time and the etching time are required. Therefore, a film thickness that satisfies the required reflection suppression performance may be selected within such a range. The thickness of the second layer is about 50 to 1000 nm, and preferably about 80 to 300 nm. That is, if the thickness is less than 80 nm, it is difficult to obtain high light-shielding performance. If the thickness exceeds 300 nm, the internal stress of the film increases, the film is peeled off, and the film formation time and the etching time are unnecessarily long.

The light-shielding layer may have at least one light-shielding film. For example, a plurality of the above-mentioned films may be provided.

For a film containing Ni and Ti as the main components, the light-shielding property increases as the metal components such as Ni and Ti increase with respect to the contained oxygen, nitrogen, and carbon. The more, the higher the transparency. Also, as with oxygen, the higher the content of nitrogen, the higher the transparency. However, compared to oxygen, the effect is small, and it is suitable for precisely controlling the transparency and the refractive index. On the other hand, the feature is that the etching rate increases as the content of carbon increases.

Therefore, by utilizing these characteristics, oxygen, nitrogen, carbon, and the like for the metal components such as Ni and Ti, which are the materials of the light-shielding layer, are satisfied so as to satisfy the desired light-shielding properties and patterning properties, and further, the reflection suppression performance. May be selected.

As a method for forming a black matrix pattern, a light-shielding film having a desired composition and film thickness is formed on a substrate by a sputtering method or the like, and then a resist pattern is formed by photolithography. Etching is performed with a system etchant to form a desired black matrix pattern. At this time, the hydrochloric acid-based etchant is preferably a hydrochloric acid aqueous solution of 3 M or more hydrochloric acid. If it is desired to increase the etching rate but not increase the concentration of hydrochloric acid, an acid such as sulfuric acid may be added. It is believed that the reason why the hydrochloric acid-based etchant is preferable is that Ti is easily complexed with Cl in addition to the fact that Ni is soluble in acid.

Since the composition of the light-shielding film exhibiting good optical characteristics, durability and fine patterning characteristics and the composition of the sputter target used for producing the same are almost the same, the results of X-ray fluorescence analysis are almost the same. In order to form a light-shielding film, the composition of Ni and Ti is mainly composed of Ni and Ti having a ratio of Ti to the atomic total of Ni and Ti of 15 to 70 atomic%, preferably 25 to 65 atomic%. A sputter target having the following metal composition is preferably used.

The light-shielding layer of the substrate with a light-shielding layer of the present invention can be manufactured by various manufacturing methods such as an evaporation method and a plating method. The sputtering method, in particular, the sputtering method adjusted to the alloy composition of Ni and Ti described above by the magnetron sputtering method. Forming with a target is preferable in that it enables uniform coating in a large area and formation of a dense film with less foreign matter and pinhole defects.

At this time, an oxide film, a nitride film, a carbide film,
When obtaining an oxynitride film, oxygen,
It can be produced by adding an appropriate amount of nitrogen, methane, carbon dioxide gas or the like. Specifically, the flow rate of oxygen, nitrogen, methane, carbon dioxide gas, or the like may be changed experimentally so that the light-shielding layer obtains desired performance.

Depending on the manufacturing conditions at this time, for example, the entire film is not a uniform film having the same composition, but, for example, the degree of oxidation or the degree of nitridation is finely adjusted or changed stepwise or partially to form a light-shielding layer or a low reflection layer. Films with better performance as layers for the purposes of the present invention can be produced.

In the substrate with a light-shielding layer according to the present invention, as described above, the light-shielding layer having high light-shielding performance is provided as a second layer on the first layer having a reflection suppressing function, which is a low reflection layer provided on the substrate. Those having two layers or a structure of two or more layers including this structure are preferable. In addition to these two layers, other layers can be added. For example, a low-reflection layer that suppresses reflection and a layer (durable layer) that protects the second layer are further formed on the second layer, or the adhesion between the first and second layers is further increased. Layers can be added.

FIG. 3 is a cross-sectional view of an example showing a color filter substrate using the substrate with a light shielding layer of the present invention. In FIG. 1, the thickness of the light-shielding layer 2 is extremely large in order to explain the light-shielding layer, whereas in FIG. 3, the thickness of the light-shielding layer 2 is thin in order to show a relationship with other members. are doing.

The color filter layer 4 may be manufactured by a known color filter manufacturing method, and includes a pigment dispersion method, a printing method,
It can be manufactured by employing a manufacturing method such as an electrodeposition method and an inkjet method. In the figure, the light-shielding layer is formed so as to partially overlap with the light-shielding layer. However, the light-shielding layer may be in close contact with each other, or the color filters may be in close contact with each other. Usually, color filter layers of three colors of RGB are arranged, but the present invention is not limited to this.

Although the insulating layer 5 on the color filter layer may not be provided, it is preferable that the insulating layer 5 is provided for protecting the color filter. Usually, the insulating layer 5 also serves as a flattening layer for smoothing the unevenness of the color filter layer. Specifically, resins such as acrylic resin, epoxy resin, silicone resin, polyimide, and polyamide are used. Further, an inorganic film such as SiO ₂ , Si ₃ N ₄ , TiO _2, etc. may be formed on this layer for the purpose of improving the bonding property with the electrode.

The electrode 6 was made of ITO (In ₂ O ₃ --Sn
O _2), it may be used transparent electrodes of SnO _2, ZnO and the like. Further, if necessary, a Si
An overcoat layer of an inorganic substance such as O ₂ or TiO ₂ or a resin such as an acrylic resin, an epoxy resin, a silicone resin, a polyimide, or a polyamide can be formed.

Further, when used as a liquid crystal display element, an alignment film such as polyimide or polyamide may be applied on the electrode and the insulating layer, dried, and subjected to an alignment treatment by rubbing or the like. In the case of a liquid crystal display device, the color filter substrate thus formed and the separately manufactured electrode substrate may be arranged so that the electrode surfaces face each other, and a liquid crystal layer may be sandwiched between them.

As the liquid crystal layer sandwiched between the electrodes,
Nematic liquid crystals are used for ordinary twisted nematic (TN) type liquid crystal display devices, STN type liquid crystal display devices, and the like. In addition to liquid crystal liquids such as guest-host liquid crystal, cholesteric liquid crystal, and ferroelectric liquid crystal using a dichroic dye, solid polymer liquid crystal, and dispersed liquid crystal in which liquid crystal is dispersed in a resin matrix. Can also be used.

In the above description, an example in which the present invention is applied to a liquid crystal display element has been described. However, the substrate with a light shielding layer of the present invention can be used for other elements with a light shielding layer, especially display elements such as PDP and EL.
The present invention is also applicable to flat panel displays such as D and electrochromic display elements (ECD).

As described above, according to the present invention, a light-shielding layer is provided which satisfies excellent optical performance such as light-shielding properties and anti-reflection properties and excellent durability such as chemical resistance and heat resistance, and enables fine patterning. In addition to providing a substrate, it is possible to provide a color filter substrate having these excellent light-shielding layers as shown in FIG.

[0071]

The present invention will be described below in detail with reference to Examples (Examples 1 to 6) and Comparative Examples (Examples 7 and 8).

(Example) A substrate of the present invention was manufactured based on FIG. The used sputtering target was manufactured by sintering an alloy powder having a predetermined chemical composition using a hot isostatic press.

Glass substrate (“AN glass” manufactured by Asahi Glass Co., Ltd.)
A layer having a two-layer structure of a low-reflection layer and a light-shielding layer having the composition and configuration shown in Table 1 above was formed. These layers were formed by a magnetron sputtering method. Table 1 shows the sputter targets used.

An alloy target of Ti and Ni and an alloy target of Ti and Ni containing Ta were used. At this time, the first layer for suppressing reflection was formed as a low reflection layer at a flow rate ratio of 3
Examples 1 and 2 and 6 to 8 show examples where the second layer as a light-shielding layer for light-shielding was formed in an atmosphere of 3 mTorr of an argon: oxygen mixed gas of 0:70 and an atmosphere of 3 mTorr of only argon gas. , The first layer at a flow ratio of 10:90
Example 3 shows a case where the second layer was formed in an atmosphere of a mixed gas of argon and carbon dioxide at 3 mTorr, and the second layer was formed in an atmosphere of only 3 mTorr of argon gas. The first layer has a flow ratio of 30:
20:50 argon: nitrogen: oxygen mixed gas 3mTo
In an atmosphere of rr, the second layer was formed of only argon gas at 3 mTorr.
r in Example 4, and the first layer was a mixed gas of 3 mTorr of argon: oxygen at a flow rate ratio of 30:70.
Example 5 shows a case where the second layer was formed in an atmosphere of 3 mTorr in a mixed gas of argon and nitrogen at a flow rate ratio of 90:10 in an atmosphere of r. Further, the thicknesses of the first layer and the second layer were set to 50 and 150 nm, respectively, and adjusted by the sputtering power and the film formation time.

The composition column in Table 1 shows the composition of the sputter target used at the time of film formation, and the gas column shows the film formation gas conditions for the first layer and the second layer. For example, 34TiNi described as Example 1 in the composition column indicates that the ratio of Ti to the total atomic amount of Ni and Ti is 34 atomic%. In Example 6, 3Ta26TiNi indicates that the ratio of Ti to the atomic total of Ni and Ti is 2%.
T at 6 atomic% and the sum of Ni, Ti and Ta atoms
a represents 3 atomic%. In the column of Ar: O _{2 in} the gas column, “30:70” indicates the flow ratio of argon to oxygen during film formation.

The evaluation was performed as follows. Table 1
Regarding the patterning performance in the medium, the case where the side etching amount is 1.5 μm or less when patterning with hydrochloric acid: 6M aqueous solution at a liquid temperature of 50 ° C. is ◎, exceeding 1.5 μm3
場合 for the case of μm or less, × for the case of exceeding 3 μm and 5 μm or less
Was evaluated.

Regarding the alkali resistance in the durability column, 50
The results of the alkali resistance test when immersed in a 5% by weight aqueous solution of NaOH for 30 minutes and the results of the acid resistance test when immersed in a 5% by weight aqueous solution of HCl for 30 minutes at room temperature are shown. The heat resistance shows the results of a heat resistance test when fired in the air at 250 ° C. for 1 hour. At this time, ◎ indicates no change in appearance, ○ indicates almost no change, and × indicates change in appearance.
Was evaluated.

As is clear from the results in Table 1, Examples 1 to 8
Although the film having the composition shown in (1) had a sharp pattern edge shape, the films having the compositions shown in Examples 1 to 6 showed very fine patterning performance with a side etching amount of 3 μm or less. In addition, good performance was also exhibited in durability such as alkali resistance, acid resistance and heat resistance. The film having the composition shown in Example 6 was improved in durability such as alkali resistance, acid resistance, heat resistance and the like as compared with the film having the composition shown in Examples 1 to 5, and exhibited excellent durability. In the film having the composition shown in Example 7, N
Since the i content was too large, fine patterning performance as small as the films having the compositions shown in Examples 1 to 6 could not be obtained, and the side etching amount exceeded 3 μm. In the film having the composition shown in Example 8,
Since the Ti content was too large, the performances such as the films having the compositions shown in Examples 1 to 6 could not be obtained in durability such as alkali resistance and heat resistance. In all of Examples 1 to 6 of the present invention, fine patterning performance and durability performance almost equivalent to those of the conventional Cr film were obtained. Further, in addition to the film having the composition containing Ni and Ti as the main components of Example 6 and containing Ta, the composition also contains Ni and Ti as the main components, zirconium, niobium, silicon, tungsten, molybdenum, iron, vanadium, antimony, phosphorus,
When a film containing at least one element of boron was examined, good results equivalent to those of Example 6 were shown. Patterning the light-shielding films of Examples 1 to 6 with predetermined dimensions,
After forming a resin pattern of each color of red, green, and blue by photolithography and coating an overcoat resin, there was no particular problem in the production process, and a color filter similar to conventional Cr could be obtained. Also, there was no particular problem in the optical properties of the product of the present invention.

[0079]

[Table 1]

[0080]

According to the present invention, a metal containing nickel (Ni) and titanium (Ti) as main components and having a Ti composition of 15 to 70%, preferably 25 to 65% by atomic ratio with respect to the sum of Ni and Ti, The substrate with a light-shielding layer of the present invention containing at least one of a light-shielding layer made of a metal compound and a low-reflection layer has excellent optical performance, durability, and patterning equivalent to those of a conventional Cr-based metal light-shielding layer. Has performance and productivity.

In particular, it is preferable to form a two-layer structure of a low-reflection layer and a light-shielding layer sequentially on the substrate as described above. Further, the low-reflection layer preferably contains Ni and Ti as main components and a compound of these metals. Are preferably oxides, nitrides, carbides and oxynitrides.

The substrate with a light-shielding layer of the present invention can be used, for example, as a display element of the above-mentioned light-shielding layer material for a flat panel display. By using the substrate of the present invention, the substrate having the conventional Cr-based light-shielding layer can be used. The effect of the light-shielding layer having performance comparable to optical characteristics, durability, and patterning properties can be easily obtained. The present invention can be applied to various applications within a range that does not impair the effects of the present invention.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a typical example showing a substrate with a light-shielding layer of the present invention.

FIG. 2 is a cross-sectional view of an example showing a substrate with a light-shielding layer of the present invention.

FIG. 3 is a sectional view of an example showing a color filter substrate of the present invention.

[Explanation of symbols]

 1: substrate 2: light shielding layer 3: low reflection layer 4: color filter layer 5: insulating layer 6: electrode

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoru Takagi 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Atsushi Shiroyama 4-2837, Yawatahara, Yonezawa-shi, Yamagata 11 shares Asahi Glass Fine Techno Co., Ltd. Fine Techno (72) Inventor Takeshi Kuboi 2107-2 Yasugi-cho, Yasugi-shi, Shimane Prefecture F-term in Hitachi Metals, Ltd. 2H042 AA06 AA08 AA26 2H048 BA00 BA11 BB02 BB14 BB37 BB44 2H091 FA02Y FA34Y FA35Y FA37Y FB06 FC02 FC06 FC26 FD06 GA03 GA16 HA07 HA08 HA10 HA12 JA01 JA02 LA12 4K029 AA24 BA50 BA55 BA5 8 BA64 BB02 BC07 BD00 BD09 CA06

Claims (10)

[Claims] 1. A metal and / or metal compound containing nickel (Ni) and titanium (Ti) as main components and having a composition of Ti in an atomic ratio of 15 to 70% of the total of Ni and Ti. A substrate with a light-shielding layer, comprising at least one layer of a light-shielding layer and a low reflection layer. 2. The substrate with a light-shielding layer according to claim 1, wherein the composition of Ti is 25 to 65% by atomic ratio with respect to the sum of Ni and Ti. 3. The metal compound mainly composed of Ni and Ti is an oxide, nitride, carbide or a mixture of two or more of metals mainly composed of Ni and Ti. 2. The substrate with a light-shielding layer according to 2. 4. A substrate with a light-shielding layer, wherein a low-reflection layer is provided on at least one of an upper part and a lower part of the light-shielding layer containing Ni and Ti as main components according to claim 1. 5. A substrate with a light-shielding layer, wherein a light-shielding layer is provided on one of the upper and lower parts of the low-reflection layer containing Ni and Ti as the main components according to claim 1. 6. A light shielding layer mainly composed of Ni and Ti, and a low reflection layer mainly composed of Ni and Ti on at least one of an upper part and a lower part of the light shielding layer, wherein the light shielding layer is provided. , N
a metal mainly composed of i and Ti and / or an oxide of the metal, a nitride thereof, a carbide thereof or an oxynitride thereof, wherein the low-reflection layer has a higher transmittance than the light-shielding layer.
The substrate with a light-shielding layer according to any one of claims 1 to 5, comprising an oxide, a nitride, a carbide, or an oxynitride of a metal containing Ti and Ti as main components. 7. A sputter target comprising Ni and Ti as main components, wherein the composition of Ti has a metal composition in an atomic ratio of 15 to 70% with respect to the sum of Ni and Ti. 8. A color filter substrate, comprising a color filter layer on the substrate according to claim 1. 9. A light-shielding layer according to claim 1, wherein said light-shielding layer and / or low-reflection layer containing Ni and Ti as main components is formed by magnetron sputtering. Substrate manufacturing method. 10. A display element comprising the substrate according to claim 1 or the color filter substrate according to claim 8.