CN110872687B

CN110872687B - Laminate and target material

Info

Publication number: CN110872687B
Application number: CN201910826773.8A
Authority: CN
Inventors: 木村优太; 胜见昌高; 川岛慎吾; 南和希
Original assignee: Daido Steel Co Ltd
Current assignee: Daido Steel Co Ltd
Priority date: 2018-09-03
Filing date: 2019-09-03
Publication date: 2022-07-19
Anticipated expiration: 2039-09-03
Also published as: CN110872687A

Abstract

Provided is a laminate having a low-reflectance blackened film. The laminate (10) comprises a substrate (18), a metal layer (32) laminated on the substrate (18) and forming electrodes and/or wiring, and a blackening film (35) laminated on the surface of the metal layer (32) on the side opposite to the substrate (18), and/or a blackening film (34) laminated between the metal layer (32) and the substrate (18). These blackened films (34), (35) are composed of (Ti)_1‑xMo_x)_1‑yN_yThe titanium alloy represented by the formula (I) has a nitride and unavoidable impurities, and x and y each represent an atomic ratio and satisfy 0.03 ≦ x ≦ 0.28 and 0.40 ≦ y ≦ 0.60.

Description

Laminate and target material

Technical Field

The present invention relates to a laminate having a blackened film that suppresses reflection at a metal layer, and a target for forming the blackened film.

Background

The liquid crystal panel has a color filter substrate, a TFT (Thin Film Transistor) array substrate, and a liquid crystal layer sandwiched between the two substrates. As for the electrodes formed on the TFT array substrate, ultra-fine metal electrodes are used in addition to transparent ITO (Indium Tin Oxide) electrodes. In the case of a metal electrode, since a metal wire is opaque and has a metallic luster, there are the following problems: when light from the outside is reflected by the metal wire, visibility to the display portion is lowered due to the reflected light.

As a countermeasure, a liquid crystal panel employs a structure in which a black matrix is disposed directly above a metal electrode to shield light reflected from the metal electrode. However, in this case, it is difficult to reduce the width of the black matrix that divides the color filter of each of R (red), G (green), and B (blue) into a lattice, and it is difficult to improve the panel performance such as the aperture ratio of the color filter.

On the other hand, as another means for suppressing the reflection light from the metal electrode, various methods have been proposed in which a blackened film capable of suppressing the reflection to a low level is formed on the metal layer on which the metal electrode is formed (for example, see patent document 1 below). Although these blackened films are considered to have a certain effect of suppressing reflection at the metal layer, in recent years, it is required to have a blackened film having a lower reflectance.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2015-69573

Disclosure of Invention

[ problems to be solved by the invention ]

In view of the above circumstances, an object of the present invention is to provide a laminate including a low-reflectance blackened film, and a target suitable for forming the low-reflectance blackened film.

[ means for solving problems ]

Accordingly, the laminate of the present invention has at least:

a base material,

A metal layer laminated on the substrate to form an electrode and/or a wiring, and

a blackened film laminated on a surface of the metal layer on a side opposite to the substrate and/or laminated between the metal layer and the substrate,

the blackened film is composed of (Ti)_1-xMo_x)_1-yN_yThe nitride of the titanium alloy and inevitable impurities, x and y each represent an atomic ratio and satisfy: x is 0.03 ≦ 0.28, y is 0.40 ≦ 0.60.

As described above, when the laminate of the present invention is configured as a laminate including a base material and a metal layer forming an electrode and/or a wiring, a blackened film made of a nitride of a titanium alloy having a predetermined composition range is formed in a laminated manner at least one of the following positions: a surface of the metal layer on the side opposite to the substrate (that is, an upper surface of the metal layer when the substrate is a lower side and the metal side is an upper side), and between the metal layer and the substrate.

According to the present invention, when the blackening film composed of the nitride of the titanium alloy is formed on the upper surface of the metal layer in a laminated manner, the reflection of light incident from the metal layer side to the base material side at the metal layer can be suppressed to be low.

On the other hand, when the blackening film is formed by laminating between the metal layer and the base material, in the case where the laminate is disposed in a direction in which the base material is the upper side and the metal layer is the lower side, reflection of light incident from the base material side to the metal layer side at the metal layer can be suppressed to be low, and good visibility can be ensured.

The blackened film of the present invention is a nitride containing Ti and Mo as metal components. In the formula (Ti) of defined composition_1- _xMo_x)_1-yN_yIn the above formula, x represents the atomic ratio of Mo in the metal component, and 1-x represents the atomic ratio of Ti in the metal component. In addition, y represents an atomic ratio of N in the blackened film.

Since the blackened film containing Ti and Mo as metal components is excellent in heat resistance, even when heat of 300 ℃ or higher (for example, 10 minutes in a vacuum state or 370 ℃) is applied, such as in a TFT manufacturing process, no color change occurs, and a predetermined effect of reducing the reflectance can be maintained.

In the present invention, the atomic ratio x of Mo in the metal component in the blackened film is set to 0.03 ≦ x ≦ 0.28. When the value of x is small and less than 0.03, it is difficult to form a pattern by wet etching, and thus manufacturability is poor. On the other hand, when the value of x is large and exceeds 0.28, the reflectance becomes high and exceeds 25%, and the effect of reducing the reflectance is reduced. Therefore, in the present invention, x is set to 0.03 ≦ x ≦ 0.28, which can obtain the effect of reducing the reflectance while ensuring the productivity.

Here, in order to obtain the effect of reducing the reflectance while further ensuring the productivity, x is preferably 0.08 ≦ x ≦ 0.25, and more preferably 0.10 ≦ x 0.20.

In addition, the effect of the reflectance reduction also depends on the value of the atomic ratio y of N in the blackened film. Therefore, in the present invention, y is set in the range of 0.40 ≦ y ≦ 0.60, preferably 0.40 ≦ y ≦ 0.50.

The blackened film may contain inevitable impurities in addition to the above elements. For example, oxygen (O) may be contained at less than 3 at% as an inevitable impurity.

In the present invention, the blackened film may be formed by an oxynitride containing Ti and Mo as metal components. In this case, the blackening film is configured of (Ti)_1-xMo_x)_1-y-zN_yO_zThe nitrogen oxides and inevitable impurities of the titanium alloy, x, y and z each represent an atomic ratio and satisfy: x is 0.03 ≦ 0.28, y is 0.10 ≦ 0.60, and z is 0.03 ≦ 0.47. Preferably, x is 0.07 ≦ 0.16, y is 0.10 ≦ 0.15, and z is 0.10 ≦ 0.15.

In the formula (Ti) defining the composition of the blackened film_1-xMo_x)_1-y-zN_yO_zIn the formula, x represents the atomic ratio of Mo in the metal component, and 1-x represents the atomic ratio of Ti in the metal component. In addition, y represents an atomic ratio of N in the black film, and z represents an atomic ratio of O in the black film.

The effect of reducing the reflectance can be further improved by forming the blackening film as an oxynitride film. However, since the effect of reducing the reflectance is rather impaired when the atomic ratio of O in the blackened film is excessively increased, the range of z is set to 0.03. ltoreq. z.ltoreq.0.47 in the present invention.

Further, the target material for forming the blackened film of the present invention is characterized in that: contains 3 to 28 at% of Mo, preferably 7 to 16 at% of Mo, and the balance of Ti and unavoidable impurities. By using the target of the titanium alloy defined in this way, a blackened film of low reflectance can be easily formed by reactive sputtering.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention as described above, it is possible to provide a laminate including a low-reflectance blackened film, and a target suitable for forming a low-reflectance blackened film.

Brief description of the drawings

FIG. 1 is a view showing a laminate according to an embodiment of the present invention.

Fig. 2 is an explanatory view showing a manufacturing process of the laminate.

Fig. 3 is an explanatory view showing a manufacturing process after fig. 2.

Fig. 4 is an explanatory view showing a manufacturing process after fig. 3.

Fig. 5 is an explanatory view showing a manufacturing process subsequent to fig. 4.

FIG. 6 is a view showing a laminate according to another embodiment of the present invention.

FIG. 7 is a graph showing the relationship between the atomic ratio x of Mo in the blackened film and the reflectance.

Fig. 8 is a view showing a structure of a laminate for reflectance evaluation.

[ description of symbols ]

10. 50, 50A, 60A laminate

18. 52 base material

32. 54 metal layer

34. 35, 56 blackened film

Detailed Description

Next, embodiments of the present invention will be described in detail below.

In fig. 1, reference numeral 10 denotes a laminate having a function as a thin film transistor (hereinafter referred to as "TFT"), which includes: a gate electrode layer 20 formed on the substrate 18, a gate insulating layer 22 covering the gate electrode layer 20, a semiconductor layer 24 arranged to overlap with the gate electrode layer 20 with the gate insulating layer 22 interposed therebetween, and a source electrode layer 26 and a drain electrode layer 28 connected to the semiconductor layer 24. The source electrode layer 26 and the drain electrode layer 28 may be collectively referred to as a metal electrode layer 30.

The substrate 18 is made of a transparent base material, and a resin substrate such as polyethylene terephthalate (PET) may be used in addition to a glass substrate such as soda lime glass or alkali-free glass. The thickness of the substrate 18 is preferably set to 300 μm to 1mm from the viewpoint of workability.

Gate electrode layer 20 may be made of a low-resistance metal material such as Al or Cu. However, since Al alone has problems of poor heat resistance, easy corrosion, and the like, it may also be combined with other heat-resistant conductive materials to form the gate electrode layer 20.

The gate insulating layer 22 may be a single layer or two or more layers, and conventionally used ones, such as a silicon oxide film (SiO) may be used_xFilm), silicon nitride film (SiN)_xFilm), etc.

The semiconductor layer 24 may be formed of an oxide semiconductor such as an In — Ga — Zn oxide (also referred to as IGZO). The In-Ga-Zn based oxide refers to an oxide containing In, Ga and Zn as main components, and the proportions of In, Ga and Zn are not limited. In addition, metal elements other than In, Ga, and Zn may also be added.

The semiconductor layer 24 is not limited to an oxide semiconductor, and for example, amorphous silicon (also referred to as a-Si) may be used.

The source electrode layer 26 and the drain electrode layer 28 are connected to the semiconductor layer 24, respectively. Specifically, a recess 29 is provided between the source electrode layer 26 and the drain electrode layer 28, and the source electrode layer 26 and the drain electrode layer 28 are connected to the semiconductor layer 24 in a state where they are separated from each other by the recess 29.

The source electrode layer 26 and the drain electrode layer 28 have a stacked structure including: a metal layer 32 containing Al, Cu, or an alloy thereof, a 1 st blackened film 34 provided on a surface of the metal layer 32 on the semiconductor layer 24 side, and a 2 nd blackened film 35 provided on a surface of the metal layer 32 on the side opposite to the semiconductor layer 24.

The metal layer 32 is preferably composed of Al alone to achieve low resistance. Usually, Cu is used as an electrode material in addition to Al. Both Al and Cu can be processed by wet etching, but Cu cannot be processed by dry etching, so Al has high versatility. In addition, Al is inexpensive in terms of cost, about 1/3 of Cu.

When the metal layer 32 is composed of Al alone, it can be formed by non-reactive sputtering using a pure Al target. In addition, the metal layer 32 may be formed of an Al alloy having an Al content of 90 at% or more, or may be formed by combining with a heat-resistant conductive material. The thickness of the metal layer 32 is preferably 10nm to 1 μm.

The 1 st and 2

nd blackening films

34 and 35 coat the lower and upper surfaces of the metal layer 32 to suppress reflection of light at the surface of the metal layer 32. The 1 st blackened film 34 and the 2 nd blackened film 35 are (Ti)_1-xMo_x)_1-yN_yNitrides of the titanium alloys represented. x and y represent atomic ratios, respectively, and satisfy 0.03. ltoreq. x.ltoreq.0.28, and 0.40. ltoreq. y.ltoreq.0.60. The 1 st blackened film 34 and the 2 nd blackened film 35 can be formed by reactive sputtering in a mixed gas atmosphere of an inert gas such as Ar and nitrogen gas using a target made of a titanium alloy having a predetermined composition (specifically, a target containing 3 to 28 at% of Mo and the balance being Ti and unavoidable impurities).

The compositions of the 1 st blackened film 34 and the 2 nd blackened film 35 may be the same as or different from each other. If the composition is the same, a common target material may be used.

The thickness of the 1 st blackened film 34 and the 2 nd blackened film 35 is preferably 15 to 200 nm.

The interlayer insulating layer 14 is provided so as to cover the source electrode layer 26 and the drain electrode layer 28, and is provided so as to be in contact with the channel region 43 of the semiconductor layer 24 in the recess 29 between the source electrode layer 26 and the drain electrode layer 28. As the gate insulating layer 22, a silicon oxide film (SiO) can be used as the interlayer insulating layer 14_xFilm), silicon nitride film (SiN)_xFilm), etc.

The oxide conductive layer 16 is made of ITO, ZnO or SnO₂And IZO, etc., and is provided on the interlayer insulating layer 14. In the case where the laminate 10 of the present example is used as a TFT array substrate constituting a liquid crystal panel, the oxide conductive layer 16 constitutes a structure not shown in the drawingThe pixel electrode in the liquid crystal display portion is shown. The oxide conductive layer 16 is electrically connected to the drain electrode layer 28 via a connection hole 36 formed in the interlayer insulating layer 14, and application of voltage to the oxide conductive layer 16 is started/ended by turning on/off the TFT.

In the multilayer body 10 configured in this way, since the source electrode layer 26 and the drain electrode layer 28 are configured by the metal layer 32 and the blackening

films

34 and 35 laminated with the metal layer 32 interposed therebetween, reflection of light from the outside in the metal layer 32 can be suppressed.

Next, a manufacturing process of the laminate 10 will be described.

First, a 1 st conductive film is formed on the substrate 18 by a vacuum thin film forming method such as a sputtering method or a vapor deposition method, and the 1 st conductive film is patterned to form a gate electrode layer 20 made of Al or the like as shown in fig. 2 (a).

When the gate electrode layer 20 is formed by patterning the 1 st conductive film, the surface of the substrate 18 is exposed except for the portion where the gate electrode layer 20 is located. As shown in FIG. 2(B), SiO is formed on the surfaces of the substrate 18 and the gate electrode layer 20₂、SiN_xEtc. the gate insulating layer 22.

Then, as shown in fig. 2(C), a semiconductor thin film is formed on the gate insulating layer 22, followed by patterning, to form a semiconductor layer 24 composed of the patterned semiconductor thin film. For example, an oxide semiconductor layer is formed of an In-Ga-Zn oxide containing In, Ga, and Zn at a predetermined ratio.

Next, as shown in fig. 3(a), (B), and (C), the 1 st blackened film 34a, the 2 nd conductive film 32a, and the 2 nd blackened film 35a are sequentially laminated in a film form on the surface of the semiconductor layer 24 and the surface of the gate insulating layer 22 exposed at a position other than the portion where the semiconductor layer 24 is present.

The 1 st blackened film 34a is formed by: the laminate produced up to the state of fig. 2(C) was subjected to reactive sputtering using a target of a titanium alloy of a predetermined composition and a mixed gas containing nitrogen as a sputtering gas.

Then, by non-reactive sputtering using a target containing Al as a main component and a gas that is non-reactive with the target as a sputtering gas, as shown in fig. 3(B), the 2 nd conductive film 32a is formed on the surface of the 1 st blackened film 34 a.

Next, by reactive sputtering using a target made of a titanium alloy of a predetermined composition and using a mixed gas containing nitrogen as a sputtering gas, as shown in fig. 3(C), the 2 nd blackened film 35a is formed on the surface of the 2 nd conductive film 32 a. In this manner, the laminated film 30a including the 1 st blackened film 34a, the 2 nd conductive film 32a, and the 2 nd blackened film 35a is formed.

Subsequently, as shown in fig. 4(a), a resist material 38 is formed at a non-removed portion of the laminated film 30a, and in this state, a portion of the laminated film 30a not masked by the resist material 38 is partially removed by immersing the laminated body including the laminated film 30a in an etching solution. Thereafter, when the resist material 38 is removed, as shown in fig. 4(B), the source electrode layer 26 and the drain electrode layer 28 having the 1 st blackened film 34, the metal layer 32, and the 2 nd blackened film 35 are formed.

As described above, the 1 st blackened film 34 and the 2 nd blackened film 35 of the present example can be patterned together with the metal layer 32 by conventional wet etching or dry etching.

In fig. 4(B), a channel region 43 is formed between the source region 41 and the drain region 42 in the semiconductor layer 24, and the gate electrode layer 20 is located at a position facing the channel region 43 with the gate insulating layer 22 interposed therebetween. In this state, the TFT is constituted by the semiconductor layer 24, the gate insulating layer 22, and the respective electrode layers 20, 26, and 28 of the gate/source/drain.

Next, as shown in FIG. 5(A), SiN is formed_x、SiO₂And the like. Meanwhile, a connection hole 36 (refer to fig. 1) is formed at a predetermined position of the interlayer insulating layer 14. Thereafter, as shown in fig. 5(B), a 3 rd conductive film such as ITO is formed on the surface of the interlayer insulating layer 14, and then patterned to form an oxide conductive layer 16.

Although the structure of the laminate 10 and the method for manufacturing the same according to one embodiment of the present invention have been described above, the structure of the laminate 10 and the method for manufacturing the same may be appropriately modified. For example, although the blackening film is provided on the source/

drain electrodes

26 and 28 in the stacked body 10, the blackening film may be formed above and below the gate electrode 20 shown in fig. 1 in some cases. The black film may be formed only on the upper side of the gate electrode 20 and the source/

drain electrodes

26 and 28, or may be formed only under the gate electrode 20 and the source/

drain electrodes

26 and 28.

In the above embodiment, the 1 st blackened film 34 and the 2 nd blackened film 35 are made of nitride of titanium alloy, but the blackened

films

34 and 35 may be made of (Ti)_1-xMo_x)_1-y-zN_yO_zThe oxynitride composition of the titanium alloy. x, y and z represent atomic ratios, respectively, and satisfy: x is 0.03 ≦ 0.28, y is 0.10 ≦ 0.60, and z is 0.03 ≦ 0.47. Such an oxynitride can be formed by reactive sputtering using a target made of a titanium alloy having a predetermined composition in a mixed gas atmosphere containing nitrogen and oxygen.

Fig. 6 shows a laminate according to another embodiment of the present invention.

In fig. 6(a), 50A shows an example of a laminated body used as a touch panel sensor. In the figure, 52 is a transparent base material, and a metal layer 54 forming an electrode is laminated in a film shape on one surface (upper surface in the figure) of the base material 52 over the entire surface of the base material 52. Then, a blackening film 56 is formed in a laminated manner on the surface (i.e., the upper surface in the drawing) of the metal layer 54 on the side opposite to the base material 52. The blackening film 56 is also formed by film-like lamination over the entire surface of the metal layer 54.

The blackened film 56 in this example is made of (Ti)_1-xMo_x)_1-yN_yThe nitride of the titanium alloy shown. Here, x and y represent atomic ratios, respectively, and satisfy: x is more than or equal to 0.03 and less than or equal to 0.28, and y is more than or equal to 0.40 and less than or equal to 0.60. The blackening film 56 may be made of (Ti)_1- _xMo_x)_1-y-zN_yO_zThe oxynitride composition of the titanium alloy. Here, x, y, and z represent atomic ratios, respectively, and satisfy: x is more than or equal to 0.03 and less than or equal to 0.28、0.10≤y≤0.60、0.03≤z≤0.47。

The laminated body 50A is actually processed to be used as an element of a touch panel sensor. And 50 denotes a processed laminate.

In the processed laminate 50, the unnecessary portions of the film-like metal layers 54 in the pre-processed laminate 50A are removed, leaving only a number of ultra-fine lines S1 as the metal layers 54, and these remaining ultra-fine lines S1 are parallel to each other to form the stripe-pattern electrodes 54D.

The blackening film 56 is also removed of an unnecessary portion, leaving only a portion of the upper surface in the drawing covering the ultrafine wires S1 as ultrafine wires S2, which function to reduce reflection of incident light from the upper surface in the drawing by the ultrafine wires S1.

In this embodiment, the

laminated bodies

50A and 50 shown in fig. 6(a) are also included in the concept of the laminated body of the present invention.

The

laminates

60A and 60 shown in fig. 6(B) are another embodiment of the laminate in the present embodiment. In the

laminated bodies

60A and 60, the blackening film 56 is laminated between the metal layer 54 and the transparent substrate 52. In this way, light incident from the lower side upward can be suppressed from being reflected downward in the electrode 54D (metal layer 54).

[ example 1]

Next, embodiments of the present invention will be described in detail below.

In example 1, (Ti) was produced as follows_1-xMo_x)_1-yN_yThe reflectance and etching properties of each laminate obtained by changing the atomic ratio x of Mo in the black film shown in table 1 were measured and evaluated by the following methods.

(preparation of a laminate of a blackened film/Metal film/blackened film/substrate)

Using a glass substrate of 100mm × 100mm × 1.1mm as a transparent base material, reactive sputtering was first performed to form a 1 st blackened film on the base material. Reactive sputtering was performed as follows: sputtering targets made of TiMo alloys having different Mo ratios were used, and the degree of vacuum was set to 5X 10^-4To 5X 10^-5Pa, ratio of nitrogen gas introduced into the chamberThe ratio of the mixed gas (the balance being Ar gas and unavoidable impurities) is 80% or more, the sputtering pressure is 0.1 to 1.5Pa, and the power is 100 to 500W. Thus, a blackened film having a thickness of 100nm was formed.

Next, non-reactive sputtering is performed to form a metal film composed of Cu in a stacked manner on the blackened film. The non-reactive sputtering for forming the metal film was performed as follows: the degree of vacuum was set to 5X 10^-4To 5X 10^-5Pa, introducing Ar gas (inert gas) into the chamber. The sputtering pressure was set to 0.1 to 1.5Pa, and the power was set to 100 to 500W. Thus, a metal film having a thickness of 200nm and made of Cu was formed.

Then, reactive sputtering is performed to form a 2 nd blackened film on the metal film. The film formation conditions were the same as those of the 1 st black film.

In this manner, a structure in which the 1 st black film, the metal film, and the 2 nd black film were sequentially stacked on the transparent substrate, that is, a laminate of the 2 nd black film/the metal film/the 1 st black film/the substrate shown in fig. 8 was obtained.

[ Table 1]

(evaluation of reflectance)

The reflectance was measured according to JIS K7105 using the laminate of the 2 nd blackened film/metal film/1 st blackened film/substrate prepared as described above. Specifically, the reflectance per 1nm wavelength of visible light (wavelength 400 to 780nm) was measured using an ultraviolet-visible spectrophotometer, and the average value thereof was calculated. In the measurement of the reflectance, as shown by the arrow in fig. 8, the reflected light when the base material side is viewed from the metal film side, that is, the reflected light when the light enters the base material side from the metal film side is measured, and the evaluation is performed according to the following evaluation criteria. The results are shown in table 1.

O: the reflectivity is less than 25%

X: a reflectance of 25% or more

(evaluation of Wet etching Property)

In the evaluation of wet etching properties, a 5cm square sample was cut out from the blackened film/base material laminate before the metal film was formed, the sample was immersed in Pure Etch TE, an etching solution prepared by "pen and drug ", the time required for the blackened film formed on the substrate to be completely dissolved was measured, the etching rate (nm/min) was determined, and the evaluation was performed according to the following evaluation criteria. The results are shown in table 1.

O: the etching rate is more than 70 nm/min

X: the etching rate is less than 70 nm/min

In the results of Table 1, the laminate of No.1 contained no Mo, and the blackened film was formed of TiN. The laminate of No.1 was x in both the evaluation of reflectance and the evaluation of wet etching property.

On the other hand, the laminate of nos. 6 and 7 containing 32 at% or more of Mo in the blackened film was o in the wet etching evaluation, but the reflectance was high and exceeded 25%, and the reflectance was x.

On the other hand, the laminates of nos. 2 to 5 having the blackened film of the composition defined in the present invention showed good results in both reflectance and wet etching properties. Fig. 7 shows the relationship between the atomic ratio x of Mo in the blackened film and the reflectance.

In addition, the evaluation on dry etching property is also shown in table 1 for reference. The blackened films shown in table 1 were all dry etchable.

[ example 2]

Using Ti_0.92Mo_0.08The same procedure as in example 1 was repeated except for using the titanium alloy of (1) as a target material for a blackened film to prepare a laminate of 2 nd blackened film/metal film/1 st blackened film/substrate. However, here, the amount of nitrogen in the mixed gas at the time of forming the black film was changed as shown in table 2 to produce a laminate, and the composition of the black film was examined and the reflectance was measured. The results are shown in table 2.

[ Table 2]

From the results in table 2, it is found that in order to achieve a reflectance of less than 25%, N needs to be contained in the black film at 40 at% or more. In this example, the amount of nitrogen in the mixed gas at the time of film formation was set to 80% or more, whereby N in the blackened film could be set to 40 at% or more.

[ example 3]

A 2 nd blackened film/metal film/1 st blackened film/substrate laminate was produced by the same procedure as in example 1 above, using a target material of Ti or a titanium alloy alone as the target material for the blackened film. However, here, the ratio of the amount of nitrogen to the amount of oxygen in the mixed gas at the time of forming the blackened film was changed as shown in tables 3 and 4 to manufacture a laminate, and the composition of the blackened film was examined and the reflectance was measured. In addition, wet etching and dry etching were also evaluated. The results are shown in tables 3 and 4.

In Table 3, the description of Ti-4Mo shows that the composition of the target material is Ti_0.96Mo_0.04The description of Ti-8Mo indicates that the composition of the target material is Ti_0.92Mo_0.08。

[ Table 3]

[ Table 4]

From the results of tables 3 and 4, the target (reflectance less than 25%) was not achieved in the case of using the target composed of only Ti (see nos. 21 and 22) and in the case of using the target having a high Mo ratio (Ti-32Mo) (see nos. 57 to 62).

On the other hand, focusing on the laminated body produced using the common target (for example, see nos. 2 to 29 in table 3), it is considered that the reflectance decreases as the amount of O contained in the blackened film increases, which is an effect of containing O in the blackened film. However, when the content exceeds the appropriate amount, the reflectance rather increases, and it is found that it is effective to set O to 47 at% or less (and N to 10 at% to 60 at%) in order to achieve the target reflectance of less than 25%.

Although the embodiments and examples of the present invention have been described in detail, they are merely examples. For example, the laminate of the present invention may be used for a display device including an organic EL, in addition to a liquid crystal panel and a touch panel, and the present invention may be implemented in various modified forms without departing from the scope of the invention.

The present application is based on japanese patent application 2018-.

Claims

1. A laminate characterized by comprising at least:

a base material,

A metal layer laminated on the substrate to form an electrode and/or wiring, and

a blackening film laminated on a face of the metal layer on a side opposite to the substrate and/or laminated between the metal layer and the substrate,

the blackening film is composed of (Ti)_1-xMo_x)_1-yN_yThe titanium alloy represented by the formula (I) has a nitride and unavoidable impurities, and x and y each represent an atomic ratio and satisfy 0.04 ≦ x ≦ 0.24 and 0.40 ≦ y ≦ 0.60.

2. A laminate characterized by comprising at least:

a base material,

the blackening film consists of (Ti)_1-xMo_x)_1-y-zN_yO_zThe nitrogen oxides and the unavoidable impurities of the titanium alloy are expressed, and x, y and z respectively represent atomic ratios and satisfy 0.045 ≦ x ≦ 0.275, 0.10 ≦ y ≦ 0.60, and 0.03 ≦ z ≦ 0.47.

3. The laminate according to claim 1 or claim 2, wherein the blackening film is formed by using a target,

the target material contains 3 at% to 28 at% of Mo, and the balance is Ti and unavoidable impurities.