TW201042059A - Cu alloy film, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Cu alloy film exhibiting high adhesiveness with respect to a semiconductor layer of a thin film transistor and excellent wet etching property. ; SOLUTION: This Cu alloy film is for a display device contacting directly with the semiconductor layer of the thin film transistor, and the Cu alloy film is a Cu alloy film for the display device of an oxygen containing alloy film satisfying required conditions (1), (2) as follows: (1) the Cu alloy film contains 0.10 atom% or more to 5.0 atom% or less as total of at least one selected from the group consisting of Ni, Al, Zn, Mn, Fe, Ge, Hf, Nb, Mo and W, and (2) the Cu alloy film has a base layer and an upper layer different in oxygen contents, wherein the base layer contacts with the semiconductor layer, the oxygen content of the base layer is 0.1 atom% or more to 30 atom% or less, and the oxygen content of the upper layer is less than 0.1 atom% (including 0 atom%). ; COPYRIGHT: (C)2010,JPO&INPIT

Description

[Technical Field] The present invention relates to a copper alloy film for use in a display device such as a liquid crystal display or an organic electroluminescence display device, and a display device including the same, A copper alloy film superior to a transparent substrate such as a glass substrate, and a copper alloy film and a display device which are superior to the semiconductor layer of the thin film transistor. ❹ [Prior Art] For the wiring of the display device represented by the liquid crystal display device, the alloy film of Ming (A1) has been used up to now. However, with the increase in the size and high image quality of display devices, the problem of signal delay and power loss due to large wiring resistance is apparent. Therefore, as a wiring material, copper (Cu) which is lower in resistance than A1 is attracting attention. For the resistivity of A1 is 2 5χ1〇-6 Ω · cm, the resistivity of 'Cu is low ι.6χ1〇-6Ω·cm. However, the adhesion between the Cu system and the glass substrate is low, and there is a problem of peeling. Further, since the adhesion to the glass substrate is low, the Cu is a problem that wet etching for processing into a wiring shape is difficult. Therefore, various techniques for improving the tightness of Cu and a glass substrate have been proposed. Further, the semiconductor layer of the Cu-based film and the thin film transistor (amorphous germanium or 'polycrystalline germanium) has low adhesion and has a problem of peeling. For example, when a Cu wiring film is directly formed as a source-drain electrode wiring on a semiconductor layer of a base plate, Cxi is diffused in the semiconductor layer to form a reaction layer of the semiconductor layer and Cu. In the reaction layer portion, the cu film is peeled off and the problem is -5 - 201042059. Further, the 'Cu type has a problem that wet etching for processing into a wiring shape is difficult. Therefore, various proposals have been made to improve the tightness of Cu and the semiconductor layer. For example, 'Patent Documents 1 to 3 disclose a technique in which a high-melting-point metal layer such as molybdenum (Mo) or chromium (Cr) is interposed between the Cu wiring and the glass substrate to improve the tightness. However, in these technologies, the film forming process of the high melting point metal layer is increased, and the manufacturing cost of the display device is also increased. Further, in order to laminate a dissimilar metal of Cu and a high melting point metal (Mo or the like), there is a possibility of corrosion at the interface between Cu and a high melting point metal during wet etching. Further, in such a dissimilar metal, there is a problem that the wiring cross section cannot be formed into a desired shape (for example, a shape having a taper of about 45 to 60°) because of a difference in etching rate. Further, a high melting point metal such as Cr has a resistivity (12.9 χ 10·6 Ω · cm) which is higher than Cu, and signal delay or power loss via wiring impedance is a problem. Patent Document 4 discloses a technique in which a nickel or a nickel alloy and a polymer resin film are interposed as a dense layer between a Cu wiring and a glass substrate. However, in this technique, in the high-temperature annealing process at the time of manufacture of a display (e.g., a liquid crystal panel), the resin film is deteriorated, and the tightness is lowered. Patent Document 5 discloses a technique in which copper nitride is interposed as a dense layer between a Cu wiring and a glass substrate. However, copper nitride itself is not a stable compound. Therefore, in this technique, in the high-temperature annealing process at the time of manufacture of a display (for example, a liquid crystal panel), N atoms are released as N2 gas, and the wiring film is deteriorated, and the tightness is lowered. -6 - 201042059 Patent Documents 6 and 7 are disclosed by the same applicant at the same time. Patent Document 6 discloses a technique of improving the tightness of the Cu wiring when the Cu wiring includes at least one selected from the group consisting of 'Zr, Zr and Zr, or Zn and Sn. Patent Document 7 discloses that

The Cu wiring includes a first additive metal selected from at least one of the group consisting of Hf, Ta, Nb, and Ti, and a second additive metal selected from the group consisting of Mn, Zn, and Sn, each containing 〇·5 atoms. A technique for improving the tightness of Cu wiring when it is more than %. In the case of the above-mentioned patent documents, it is described that when the cu wiring is formed by sputtering, the oxygen of the reaction gas can be supplied, and the display shows that the Cu resistance (resistivity) can be lowered. Figure. However, there is no indication of any close relationship between oxygen and Cu wiring. Patent Document 8' discloses an oxygen-containing layer obtained as a source-drain electrode wiring material, an oxygen-containing layer obtained by oxidizing the upper portion of the semiconductor layer, and a material formed using a pure Cu or copper alloy film to constitute the oxygen-containing material. At least a part of the argon oxygen of the layer is bonded to Si of the semiconductor layer, and the pure CU or copper alloy film is a thin film transistor substrate which is connected to the semiconductor layer by the oxygen-containing layer. Thus, it is verified that even if the barrier metal layer is omitted , can also get superior TFT characteristics. [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Document 4: Japanese Patent Laid-Open Publication No. JP-A No. 2008-112989 Patent Document No. 5: Japanese Patent Application Laid-Open No. Hei No. Hei. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and its object is to provide transparency and transparency. The high-density of the substrate, the low resistivity, and the superior wet uranium engraving property, and the copper alloy film have a small film thickness, and the copper alloy film is excellent in film thickness controllability. In addition, the other purpose is to provide a copper alloy film for a display device which is in direct contact with a semiconductor layer of a thin film transistor, and has a low resistivity to the semiconductor layer and a superior wet etching property. Alloy film. [Means for Solving the Problem] The gist of the present invention is shown below. [1] A copper alloy film is a copper alloy film for a display device, and the copper alloy film is a copper alloy film for a display device of an oxygen-containing alloy film which satisfies the requirements of (2) and (2) below. . -8- 201042059 (1) The copper alloy film is at least one element selected from the group consisting of Ni, A1, Zn, Μη 'Fe, Ge, Hf, Nb, Mo, W, and Ca, and contains 0.10 atom in total. % or more and 10 atom% or less. (2) The copper alloy film has a base layer and an upper layer having different oxygen contents, and the base layer is in contact with the transparent substrate or the semiconductor layer, and the oxygen content of the underlayer is larger than the oxygen content of the upper layer. . [2] The copper alloy film according to Item [2], wherein the base layer is in direct contact with the transparent substrate. [3] The copper alloy film according to [1], wherein the underlayer is in direct contact with the semiconductor layer. [4] The copper alloy film according to the above [2], wherein, in the above (2), the oxygen content of the underlayer is 0.5 atom% or more and 30 atom% or less, and the oxygen content of the upper layer is The copper alloy film according to the item [2], wherein the elemental system contained in the copper alloy film is 0.10 in the above (1). Atomic % or more and 0.5 atomic % or less. [6] The copper alloy film according to the above [3], wherein, in the above (2), the oxygen content of the underlayer is 1. 1 atom% or more and 30 atom% or less 'the oxygen content of the upper layer. (2) The copper alloy film according to the item [3], wherein the element selected from the copper alloy film is selected in the above (1). From Ni, A1, Ζη, Μη, -9- 201042059

At least one element of the group formed by Fe, Ge, Hf, Nb, M〇, and w, in total, contains 0. 10 atom% or more 5. 0 atom% or less. [8] The copper alloy film according to any one of [1], wherein the copper alloy film of the above (2) has a depth from the base layer toward the upper layer Concentration curve. [1] The copper alloy film according to any one of [1], wherein, in the above (1), the copper alloy film has at least one of an element type and an element amount. In the first layer and the second layer, the first layer is in contact with the transparent substrate or the semiconductor layer, and the element content specified in the above (1) contained in the first layer is contained in the first layer. The element content (% by atom) specified in the above (!) of the second layer of the upper layer is large. [10] The copper alloy film according to any one of [1], wherein the upper layer is pure Cu. [1] A display device comprising the copper alloy film according to any one of [1] to [3]. [Effects of the Invention] In the present invention, 'a copper alloy film for a display device which is in direct contact with a transparent substrate' employs an oxygen amount such as a base layer containing a suitable alloying element and in direct contact with the transparent substrate. In addition to the multilayer structure (ideally, the base layer contains an appropriate amount of oxygen, the upper layer on the base layer contains substantially no oxygen), in addition to obtaining high tightness with a transparent substrate, low electrical resistivity, and superior wetness In addition to etchability, it can also reduce the thickness distribution of the film. -10- 201042059 Both. If such a copper alloy film is used in a display device, the number of engineering and cost of the manufacturing process can be reduced. The oxygen-containing copper alloy film of the present invention is used for a wiring or an electrode which is in direct contact with a transparent substrate, and is typically used for a gate wiring or a gate electrode. Further, in the present invention, as the copper alloy film for a display device which is in direct contact with the semiconductor layer of the thin film transistor, a substrate layer containing a suitable alloying element and in direct contact with the semiconductor layer contains appropriate oxygen, and the base layer is used. The upper layer on the bottom layer does not substantially contain a layered structure of oxygen, and has high tightness with the semiconductor layer, low resistivity, and superior wet etching properties. Such a copper alloy film can reduce the number of manufacturing processes and the cost according to the display device. The oxygen-containing copper alloy film of the present invention is used for wiring or electric pole which is in direct contact with a semiconductor layer (amorphous germanium or polycrystalline germanium) of a thin film transistor, and is representatively used for source-drainage Wiring or source-drain electrodes.实施Embodiment The present inventors have provided a film having a high degree of closeness to a semiconductor layer of a transparent substrate or a thin film transistor, a low resistivity and superior wet etching property, and more preferably a film of a copper alloy film. Repeated review is carried out on copper alloy films that are not thick for display devices. As a result, the oxygen contained in the alloy element containing Ni or the like contains a copper alloy film, and the copper alloy film is a base having a different amount of oxygen.  The layer is formed with the upper layer, such as (i) containing a specific amount of oxygen in the base layer in direct contact with the substrate or the semiconductor layer and (u) the layer above the base layer is substantially free of oxygen' even if at most The layered product of the amount of oxygen contained in the underlayer -11 - 201042059 was found to have a copper alloy film having all of the above characteristics, and the present invention has been completed. According to the present invention, at the interface where the transparent substrate or the semiconductor layer is in contact with the copper alloy film (hereinafter, simply referred to as an interface), a layer (base layer) containing at least a specific oxygen amount is formed, or the interface system contains It is composed of a certain amount of specific elements. As a result, in combination with the tightness improving effect formed by the base layer and the tightness improving effect by the specific element addition, a strong chemical bond is formed at the interface between the transparent substrate or the semiconductor layer and the base layer, and it is considered that Should be able to get superior tightness. In the following, in the convenience of explanation, there is a case where the alloying element of Ni or the like used in the present invention is referred to as a tightness promoting element. First, the base layer and the upper layer constituting the copper alloy film of the present invention will be described. As described above, in the present invention, the relationship between the underlayer and the upper layer of the oxygen layer is different, and the laminated structure having a different oxygen content is used, whereby both the adhesion to the transparent substrate and the decrease in the resistivity are obtained. In the present specification, "base layer" means a layer in direct contact with a transparent substrate or a semiconductor layer, and "upper layer" means a layer directly above the base layer. The base layer and the upper layer are distinguished by the difference in oxygen amount. When the base layer is in contact with the transparent substrate, the amount of oxygen is preferably about 0. 5 atom% is distinguished as a boundary, and the above-mentioned underlayer is in contact with a semiconductor, and it is preferable that the amount of oxygen is distinguished by a boundary of about 0.1 atom%. When the base layer is in contact with the transparent substrate, the ratio is 0. 5 atom% or more 30 atom% or less of the range containing oxygen is preferred, in contact with the semiconductor layer -12 - 201042059 condition, to 〇.  It is preferred that oxygen is contained in a range of 1 atom% or more and 30 atom% or less. As shown in the embodiment to be described later, the case where the base layer is in contact with the transparent substrate contains 0. When the base layer of oxygen is 5 atom% or more, the tightness of the copper alloy film and the transparent substrate is improved. Similarly, as shown in the later-described embodiment, the case where the underlayer is in contact with the semiconductor layer is contained via the setting. When the base layer of oxygen is 1 atom% or more, the tightness of the copper alloy film and the semiconductor layer is improved. Although the structure is not clear in detail, Q forms a strong bond between the substrate or the semiconductor layer due to the presence of a substrate layer containing a specific amount of oxygen due to the interface between the substrate or the semiconductor layer (chemical property) Combined), it is believed that the tightness should be improved. In order to sufficiently exhibit the above-described effects, the underlayer is in contact with the transparent substrate, and the oxygen content of the underlayer is preferably 5% by atom or more, more preferably 1% by atom or more, and more preferably 2 The atomic % or more is most preferably 4 atom% or more. When the basal layer is in contact with the semiconductor layer, the oxygen content of the basal layer is taken as 〇.  1 atom% or more, Q is better, more preferably 0. 5 atom% or more, more preferably as 1. 0 atomic % or more. On the other hand, when the oxygen content is excessive and the tightness is too high, the residue remains after wet etching, and the wet etching property is lowered. Further, when the oxygen content of the underlayer is excessive, the electrical resistance of the entire copper alloy film is increased. Further, when the oxygen content is excessive, it is difficult to uniformly control the film thickness of the copper alloy film (see the examples described later). In view of the above, the oxygen content of the underlayer is preferably 30% by atom or less, more preferably 20% by atom or less, in the case where the underlying layer is in contact with the transparent substrate and in contact with the semiconductor layer. More ideally as 1 5 original -13 - 201042059 sub% below, and more ideal as 13. 5 atom% or less is particularly preferably 10 atom% or less. On the other hand, when the base layer is in contact with the transparent substrate, the oxygen content of the upper layer is less than 0. 5 atom% is better. The oxygen contained in the upper layer is preferably as small as possible from the viewpoint of reducing the electric resistance, and does not exceed the lower limit of the amount of oxygen in the underlayer (0.5 atom%). The optimum oxygen content of the upper layer is 0 · 3 atom% or less, more preferably 〇.  2 atom% or less is most preferably 〇 atom%. In addition, when the base layer is in contact with the semiconductor layer, the oxygen content of the upper layer is less than 〇. 1 atom%. The oxygen contained in the upper layer is reduced from the viewpoint of electric resistance, and as small as possible, even if it does not exceed the lower limit of the amount of oxygen in the basal layer (0.  1 atom%). The optimal oxygen content of the upper layer is 0. 05 atom% or less, more preferably 0. 02 atom% or less is most preferably 0 atom%. It is preferable that the oxygen-containing copper alloy film composed of the underlayer and the upper layer has a depth-direction concentration curve in which oxygen is reduced from the basal layer toward the upper layer. Hereinafter, the oxygen-containing copper alloy film of the present invention is preferably formed by a sputtering method, and a layer having a different oxygen concentration curve in the depth direction is easily obtained by the amount of oxygen introduced. For example, it is also possible to have a concentration curve from the interface of the transparent substrate or the semiconductor layer to the copper alloy film toward the upper layer, and the amount of oxygen is slowly (both continuous or discontinuous), or vice versa. In other words, when the underlayer is in contact with the transparent substrate, the underlayer is in a range of "oxygen amount: 〇·5 atom% or more" less than 30 atom%, and a form having a different oxygen concentration curve in the depth direction is obtained. The upper layer is in the "oxygen amount: not reached."  In the range of 5 atoms, a form having a different oxygen concentration curve from the depth of -14 to 201042059 is obtained. Further, the case where the underlying layer is in contact with the semiconductor layer is described above. In the range of 1 atom% or more and 3 〇 'atomic % or less", the oxygen concentration curve including the depth direction is obtained. • The upper layer is in the range of "oxygen amount: not 〇·ι atom", and the depth is included. The shape of the oxygen concentration curve in the direction is different. In the case where the base layer is in contact with the transparent substrate, the preferred embodiment of the present invention is an oxygen average of the base layer from the interface of the transparent substrate to the copper alloy film 'to the surface of the copper alloy film' Q in the depth direction to a depth of about 10 nm. The content is 0. 5 atom% or more and 30 atom% or less' and the average content of oxygen contained in the upper layer of the base layer is less than 0. 5 atom% (including 0 atom%), from the interface to the upper layer, the oxygen concentration in the depth direction in which the oxygen content continuity is reduced. ^ In the case where the base layer is in contact with the transparent substrate, another preferred embodiment of the present invention is from the interface of the transparent substrate and the copper alloy film to the surface of the copper alloy film, and the oxygen contained in the base layer at a position to a depth of about 50 nm. The average cerium content is 〇·5 atom% or more and 30 atom% or less' and the average oxygen content of the basal layer contained in the upper layer is less than 原子5 atom% (including 0 atom%), from the interface to the upper layer. A depth-direction oxygen concentration curve having a reduced oxygen content continuity. In the case where the base layer is in contact with the semiconductor layer, the ideal shape of the present invention is from the interface between the semiconductor layer and the copper alloy film toward the surface of the copper alloy film, and the base layer is contained in the depth direction to about 1 Onm. The average oxygen content is 0. 1 atom% or more and 30 atom% or less, and the average content of oxygen contained in the upper layer of the base layer is less than 0. 1 atom% (including 0 atoms. /.), from the boundary -15- 201042059 face up, with a decrease in oxygen content continuity in the depth direction oxygen concentration curve. In the case where the underlying layer is in contact with the semiconductor layer, the other preferred embodiment of the present invention is an average of oxygen from the interface of the semiconductor layer to the copper alloy film toward the surface of the copper alloy film, and the basal layer at a depth direction of about 50 nm. The content is 0. 1 atom% or more and 30 atom% or less 'the average content of oxygen contained in the upper layer of the underlayer is less than ι·1 atom% (% of yttrium containing atoms)' From the interface toward the upper layer, the oxygen content is continuously reduced. Depth direction oxygen concentration curve. Next, the composition of the copper alloy film according to the present invention will be described. The copper alloy film of the present invention is a combination of at least one selected from the group consisting of Ni, A1, Zn, Mn, Fe, Ge, Hf, Nb, Mo, W, and Ca, and has a total of 0. 10 atom% or more and 10 atom% or less. These elements are easy to form an element which is chemically bonded to the transparent substrate or the semiconductor layer, and are combined with the aforementioned adhesion improving effect of the underlying layer to further improve the tightness of the copper alloy film or the transparent substrate or the semiconductor layer. In other words, when the above-mentioned tightness-improving element is added in a specific amount, the crystal grain of the copper alloy film is finely reduced, and the adhesion enhancement effect of the oxygen introduction through the base layer is promoted to form an interface with the transparent substrate or the semiconductor layer, which is easy to form. The gradual strengthening of the chemical combination 'is considered to be very high tightness. In order to achieve high adhesion to a transparent substrate or a semiconductor layer, the content of the above-mentioned elements in the copper alloy film (the amount of the above-mentioned elements in the case of being separately contained is two or more) is taken as 0. 10 atom% or more. However, even if the content of the above element becomes too high, the above-mentioned compact -16 - 201042059 is also saturated (for example, referring to Figs. 1 to 4 which will be described later), and the upper limit is made 10% by atom. When the base layer is in contact with the transparent substrate, the upper limit of the content of the above element is preferably 5% or less, more preferably 2% or less. The content of the above elements is preferably determined from the viewpoint of the high tightness to the transparent substrate and the balance of the low resistivity, and is 0 as a viewpoint of low resistivity. Less than 5 % is better. 0 When the underlayer is in contact with the semiconductor layer, the upper limit of the content of the above element is from the viewpoint of the resistivity of the copper alloy film, as 5. 0 atom% is preferred. Here, the above element amount means the amount contained in the entire copper alloy film. As described above, the copper alloy film of the present invention has a base layer and an upper layer having different amounts of oxygen.  The composition (type and/or content) of the elements contained in each layer may be different, but in any case, the total content of the elements contained in the copper alloy film (base layer + upper layer) must be in the above range. Insider. When considering the production of bismuth, etc., the types of elements contained in the basal layer and the upper layer are preferably the same. The desirable content of the above alloying elements is strictly different depending on the kind of the alloying elements. The load (impact) of the resistance varies depending on the type of the alloying element. When the underlayer is in contact with the transparent substrate, for example, an element selected from the group consisting of Ni, A1, Zn, Μ, Fe, and Ca is a combination of 0. 12 atom% or more 0. 4 atom% or less is preferable, and more desirably 0. 15 atom% or more 0. 3 atom% or less. On the other hand, an element selected from at least one of the group consisting of Ge, Hf, Nb, Mo, and W is a total of -17-201042059 〇 12 atoms. / 〇 〇 〇 25 25 atom% or less is better ‘ more ideally to § ten 0. 1 5 atom% or more _ 2 atom% or less. When the underlayer is in contact with the semiconductor layer, for example, at least one element selected from the group consisting of Ni, Α1, Ζη, Μη, and Fe is preferably 〇15 at% or more and 4 at% or less. In order to total 〇·2 atomic ❶/. Above 2 atom% or less. On the other hand, an element of at least one selected from the group consisting of Ge, Hf, Nb, Mo, and W is preferably 15 atom% or more and 3 atom% or less in total, and more preferably 1 atom% in total. Above 2 atom% or less. The above-mentioned tightness enhancing elements may be contained alone or in combination of two or more. When the underlying layer is in contact with the transparent substrate, among the above elements, Ni, Al, Zn, Mn, Ge, and Ca are preferable, and Ni, A1, Ζη, Μη, C a 〇 the underlying layer and the semiconductor layer are more preferable. In the case of contact, among the above elements, Ni, Al ' Zn, Mn, and Ge ' are preferably Ni, Α1, Ζη, Μη. The present invention also includes a copper alloy film having a layer having a different composition (type and/or content) of elements. In such a form, for example, 'the content of the element contained in the layer in contact with the transparent substrate or the semiconductor layer' is more than that contained in the layer (layer having different composition (type and/or content) of the element). The content of the element of the layer (% by atomic atom) is a copper alloy film. However, the layer in which the composition (type and/or content) of the elements is different is defined as the first layer (layer in contact with the transparent substrate or the semiconductor layer) and the second layer (layer on the first layer). In the case of the above-mentioned form -18-201042059, the content of the element contained in the first layer is a copper alloy film having a larger content of the element (the ytterbium atom-containing content) contained in the second layer. The layer on the 'square side' may also be pure Cu which does not substantially contain an alloying element. As described above, in order to ensure good adhesion to the transparent substrate or the semiconductor layer, it is preferable that at least the specific amount of the above element is positively contained in the vicinity of the interface between the transparent substrate or the semiconductor layer, and on the other hand, in order to implement low resistance, At least the vicinity of the surface of the copper alloy film is preferably controlled to a specific amount or less (0% of yttrium atoms, and further contains pure Cu), and the copper alloy film of the above form is used to ensure such a "transparent substrate" A preferred example of the high tightness of the semiconductor layer and the decrease in the resistance of the copper alloy film. The specific content of each layer is the elemental amount of the entire copper alloy film (0. 10 atom% or more 10 .  Within the range of atomic % or less, it can be appropriately controlled. When the underlying layer is in contact with the transparent substrate, the elemental amount of the entire copper alloy film is controlled to a more desirable range in order to achieve high tightness with the transparent substrate and lower resistance of the copper alloy film. 1 0 atom% or more 0. After 5 atom% or less (〇, the content of the element contained in the layer in contact with the transparent substrate is taken as a total of 0. 1 〇 atom% or more 4. 0 atom% or less is preferred. Further, from the viewpoint of lowering the overall resistivity of the copper alloy film, it is preferable to use the upper layer as pure Cu. Further, in the case where the underlayer is in contact with the semiconductor layer, in order to achieve high tightness with the semiconductor layer and decrease in resistance of the copper alloy film, for example, the element amount of the entire copper alloy film is controlled to a more desirable range of 0. 10 original - sub% above 5. 0 atom% or less. Further, from the viewpoint of lowering the overall resistivity of the copper alloy film, it is preferable to use the upper layer as pure Cu. Here, the layer having different elemental compositions (types and/or contents) may be identical to or different from the depth direction of the layer having a different oxygen content of -19 - 201042059. For example, Table 2 of the examples to be described later specifically discloses an example of the composition (type and/or content) of the elements which are various copper alloy films. For example, No. The amount of the 36-series element (here, Ni) contained in the layer from the interface to 50 nm is 2. 0 atom%, the amount of the element (here, N i ) of the layer above it is less.  3 atom% copper alloy film. Further, Tables 6 to 7 of the examples described below specifically disclose examples in which the composition (type and/or content) of the elements are various copper alloy films. For example, No. in Table 6. The amount of the 56-series element (here, Ni) contained in the layer from the interface to 50 nm is 2. 2 atom%, the amount of the element (here, N i ) of the layer above it is 0. 3 atom% copper alloy film. However, the types of elements of each layer may be the same or different. For example, No. in Table 2. The amount of element 43 contained in the layer from the interface to 50 nm (here, A1) is 2. 0 atom%, the element of the layer above it (here, Ni) is less. 4 atom% copper alloy film. In addition, the total amount of the element No. 44 contained in the layer from the interface to 5 〇 nm (here, Ni & A1) is 2. 3 atom%, the amount of the element (here, N i ) of the layer above it is less.  4 atom% copper alloy film. Any of these copper alloy films' is also included as an example of the present invention. In addition, the No. of Table 6. The amount of element 65 contained in the layer from the interface to 50 nm (here, A1) is 2 . The atomic %, the element of the layer above it (in this case, Ni) is 0. 4 atom% copper alloy film. In addition, the total amount of No. 66 element (from Ni& A1) contained in the layer from the interface to 5 〇 nm is 1. 9 atoms. /. The element contained in the layer above it (this is Ni in -20- 201042059) is 0. 4 atom% copper alloy film. Any of these copper alloy films is also included as an example of the present invention. " The copper alloy film of the present invention contains the above-mentioned tightness-improving element, residual portion: Cu and unavoidable impurities. Further, other elements may be added for the purpose of not impairing the effect of the present invention, and other elements may be added. The copper alloy film of the present invention exhibits its characteristics and is used for wiring or electrodes which are in direct contact with the semiconductor layer 0 of a transparent substrate or a thin film transistor. However, the copper alloy film is applied to, for example, a TFT having a bottom gate type structure. As for the characteristics of the gate electrode and the scanning line, the adhesion to the glass substrate is required to be excellent in oxidation resistance (contact stability with an ITO film) or corrosion resistance. In addition, there are also cases where it is required to lower the resistance. Moreover, the copper of the present invention.  The alloy film system can also be applied to the source electrode and/or the drain electrode of the TFT and the signal line. In this case, the characteristics of the oxidation resistance (contact stability with the ITO film) and the like are also required. Insulating film (SiN film) The tightness of the crucible is superior. Further, the copper alloy film 'of the present invention can be applied to the gate electrode and the signal line. In this case, it is also required to be superior to the transparent substrate. In addition, in addition to the above-mentioned tightness-improving element, the well-known alloying element which contributes to the above-mentioned various characteristics is added to the range which does not impair the effect of the present invention, and can also be used as a multi-layered copper alloy film. • The above description has been made on the copper alloy film of the present invention for the most characteristic oxygen content and composition. Furthermore, it is better to increase the above characteristics and to control it as follows -21 - 201042059. First, it is preferable that the thickness of the underlayer is 2 nm or more and less than 150 nm. When the underlayer is too thin, there is a possibility that a good tightness with a transparent substrate or a semiconductor layer cannot be achieved. The other side 'when the base layer is too thick' has an increase in the electrical resistance of the copper alloy film. Further, when the underlayer is in contact with the transparent substrate, the thickness unevenness of the place (the portion) passing through the underlayer becomes large. As a result, there is a possibility that the copper alloy film cannot be obtained uniformly. Therefore, the thickness of the underlying layer is 2 nm or more (when the underlying layer is in contact with the transparent substrate, it is preferably 1 〇 nm or more, more preferably 30 nm or more; and the underlying layer is in contact with the semiconductor layer) is preferably 5 nm or more, more preferably 1 Onm or more), less than 1 50 nm (the base layer is in contact with the transparent substrate, preferably 13 〇 nm or less 'more preferably 100 nm or less; the base layer is in contact with the semiconductor layer' ideally 130 nm or less, Ideally below 100 nm). Further, it is preferable that the thickness of the upper layer is appropriately defined in relation to the base layer. When the underlayer is too thick compared to the upper layer, the low resistivity cannot be maintained because of the presence of the entire copper alloy film. The ratio of the thickness of the upper layer to the thickness of the base layer (i.e., the thickness of the upper layer / the thickness of the base layer) is preferably 2. 5 or more, more preferably 4 or more, and still more preferably 5 or more. On the other hand, when the upper layer is too thick compared to the base layer, it becomes difficult to ensure sufficient tightness. Therefore, the ratio of the thickness of the upper layer to the thickness of the underlayer is preferably 400 or less, more preferably 100 or less, still more preferably 5 or less. The copper alloy film of the present invention is preferably about 2 Å nm or more and 700 nm or less, more preferably -22 - 201042059 is 250 nm or more and 500 nm or less, in consideration of the desired thickness of the underlying layer and the upper layer. If the copper alloy film of the present invention is used, it has high adhesion to a transparent substrate (especially a 'glass substrate), low resistivity, superior wet etching property, and excellent film thickness controllability, and is excellent in efficiency. A display device that produces superior characteristics. Further, the copper alloy film of the present invention is excellent not only for the adhesion to a transparent substrate or a semiconductor layer, but also has a low contact resistance even when it is in direct contact with the transparent conductive film, and is not only used as a gate wiring. It can also be used for source/drain wiring. When the gate wiring and the source/drain wiring of the display device are all fabricated by the copper alloy film of the present invention, it is possible to obtain a manufacturing engineering advantage that the same sputtering target can be used. It is preferable that the copper alloy film described above is formed by a sputtering method. Sputtering • The method refers to the introduction of an inert gas such as Ar in a vacuum, and a plasma discharge is formed between the substrate and the sputtering target (in the case where there is also a target), and the ion is discharged through the plasma. The method in which the Ar is in conflict with the above target, and the atom of the target is forced to be deposited on the substrate to form a thin film.薄膜 can be formed by ion plating or electron beam evaporation, and the film formed by vacuum evaporation can easily form a film which is superior in uniformity in film surface of component or film thickness and can form alloying elements in a freshly deposited state. The solid solution film can effectively find high temperature oxidation resistance. As the sputtering method, for example, DC sputtering method, "RF sputtering method", magnetron sputtering method, reactive sputtering method, etc., can be used, and any sputtering method can be formed as appropriate. . - Oxygen is introduced into the underlayer or the like by sputtering, and a copper alloy film is formed into a film by a specific oxygen. When the film is formed, oxygen may be supplied. As the oxygen supply source 'except oxygen (?2), an oxidizing gas containing an oxygen atom can be used -23- 201042059 (for example, 〇3, etc.). Specifically, in the case of film formation of the underlayer, a mixed gas in which oxygen is added to the processing gas which is usually used in the sputtering method is used, and when the upper layer is formed, if the oxygen is not added, the processing gas is used for the sputtering method. A copper alloy film having a base layer containing oxygen and an upper layer containing no oxygen is formed into a film. The processing gas is exemplified by a rare gas (for example, helium or argon), and is preferably argon. At the time of film formation of the underlayer, if the amount of oxygen in the process gas is changed, a plurality of underlayers having different oxygen contents can be formed. The amount of oxygen in the underlayer may be changed by the mixing ratio of oxygen in the processing gas, and the mixing ratio may be appropriately changed as appropriate in accordance with the amount of oxygen to be introduced. For example, when the underlayer is formed, the concentration of ruthenium 2 in the treatment gas (argon gas or the like) is preferably 1% by volume or more and 50% by volume or less, and more preferably 20% by volume or less. In addition, in the case where 1 atomic % of oxygen is to be introduced into the base layer, the large amount of oxygen is mixed into the processing gas by about 2 times, and the ratio of oxygen in the processing gas is preferably about 2% by volume. . In the sputtering method, a copper alloy film having a composition slightly the same as that of the sputtering target can be formed into a film. Therefore, the composition of the copper alloy film can be adjusted by adjusting the composition of the sputtering target. The composition of the sputter target can also be adjusted by using a copper alloy target of a different composition, or by adjusting the metal of the alloy element by a pure Cu target. However, in the sputtering method, there is only a slight offset between the composition of the film-formed copper alloy film and the composition of the sputtering target. However, its offset is within a few atomic %. Therefore, if the composition of the sputtering target is within the range of ± 1 〇 atomic % even if it is controlled to the maximum, the copper alloy film of the desired composition can be formed into a film. When each of the copper alloy film of the underlayer or the copper alloy film of the upper layer is formed, when the sputtering target is changed, a plurality of underlayers or a plurality of upper layers having different alloying elements may be formed. Further, when the film is formed in the underlayer and the film is formed on the upper layer, the underlayer and the upper copper alloy film having different alloying elements can be formed by changing the sputtering target. However, from the viewpoint of production efficiency, the same sputtering target is used for the underlayer and the upper layer to form a copper alloy film having a base layer and an upper layer having the same ratio of the alloy elements of oxygen. [Examples] The present invention will be more specifically described by way of examples, but the present invention is not limited by the following examples, and may be adapted to the above-mentioned and the following contents. The implementation is changed, and these are all included in the technical scope of the present invention. Example 1-1 (Production of sample) In this example, a DC magnetron sputtering method was applied to a glass substrate (#1737, manufactured by Japan Corning Co., Ltd., and a diameter of 100 mmx. A sample (having a film thickness of 5 〇〇 nm) having a pure Cu film or a copper alloy film (hereinafter, also represented by a copper alloy film) was produced on 7 mm). The copper alloy film of the present embodiment is composed of a base layer and an upper layer (a layer from the base layer to the surface of the copper alloy film of -25-201042059), and the amount of oxygen and the alloy composition contained in the base layer and the upper layer are as follows. 1 and Table 2. Among them, the sample No. of Table i. The alloy composition (type and content) of the upper layer and the base layer of the 1 to 3 2 is the same example, and the composition of the composition (upper layer = lower layer) shows the composition of the entire copper alloy film. For example, in Table 1, No. 5 (upper layer = lower layer = Cu-0. 05Ni) is attached to the entire copper alloy film and contains Cu-0. The meaning of 05 atom%... On the other hand, Sample Nos. 33 to 44 in Table 2 have different alloy compositions (types and/or contents) of the upper layer and the underlayer. The film formation system of the above-mentioned copper alloy film was carried out by using a sputtering apparatus (trade name: HSR 542) manufactured by Shimadzu Corporation, Japan. First, the composition of the copper alloy film (i) uses a Cu sputtering target for the film formation of the pure Cu film, and (ii) the film formation of the copper alloy film containing various alloy elements on the Cu sputtering target. It is controlled by using a sputtering target that is provided with a wafer containing an element other than Cu. When a copper alloy film having the same composition as the base layer and the upper layer is formed into a film, the same sputtering target is used, and a copper alloy film having a different composition or content of the underlying layer and the upper layer is formed. Sputter targets with different compositions were used to obtain a specific film. Further, the oxygen content of the copper alloy film is in the film formation of the underlayer, and a mixed gas of Ar and 〇2 is used as the processing gas, and in the film formation of the upper layer, it is controlled by using only the Ar gas. The oxygen content in the underlayer is adjusted by changing the ratio of oxygen in the mixed gas. For example, the ratio of 〇2 in the treatment gas is taken as 1 〇 vol% for the case where 5 atom% of oxygen is contained in the underlayer. -26- 201042059 Other film forming conditions are as follows. . Back pressure: 1. 0x1 (less than T6Torr • Process air pressure: 2. 0x1 (Γ3 Tor r • • Process gas flow: 30sccm • Sputter power: 3. 2W/cm2 • Distance between poles: 50 mm • Substrate temperature: room temperature Q • Film formation temperature: room temperature The ICP emission spectroscopic analyzer is used as the composition of the copper alloy film formed as described above (manufactured by Shimadzu Corporation, Japan) The ICP emission spectroscopic analyzer "ICP-8 000" was quantitatively analyzed and confirmed.  (Oxygen content in the underlayer and the upper layer) The oxygen content in each of the underlayer and the upper layer was measured by a high-frequency glow discharge spectrometer (GD-OES). The cerium (oxygen) content of each of the underlayer and the upper layer described in Tables 1 and 2 is based on the depth-direction concentration curve obtained by the above analysis, and the average of the film thicknesses of the underlying layers and the upper layer is calculated. Concentration content. As the sample according to the present invention, the oxygen content of the upper layer is less than 0. 05 atom% (refer to Tables 1 and 2) does not substantially contain oxygen. • (Measurement of the thickness of the upper layer and the base layer) The thickness of the upper layer and the base layer of the copper alloy film is such that the film surface direction (depth direction) of Cu can be observed perpendicularly to the surface 'other thickness -27- 201042059 degrees The measurement sample was measured by a Hitachi, Ltd., liberation-type transmission electron microscope, and the film thickness of each layer was measured from observation (magnification of 150,000 times) and projection of an arbitrary measurement field of view. The composition of the copper alloy film (the composition of the upper layer and the base layer, the oxygen content and the thickness) are shown in Tables 1 and 2. (Evaluation of Characteristics of Copper Alloy Film) Next, the sample obtained as described above was used as the measurement (1) the tightness of the copper alloy film and the glass substrate, and (2) the wet etching property. In addition, when measuring (3) film thickness unevenness (film thickness controllability) and (4) the resistivity of the copper alloy film, each characteristic measurement sample was produced and measured by the method described later. (1) Evaluation of the tightness with the glass substrate. Before and after the heat treatment (under vacuum, at 305 °C).  The tightness of the copper alloy film of 5 hours was evaluated by a peel test through a tape. Specifically, the film-forming surface of the copper alloy is cut into a checkerboard shape of a lmm interval by a milling cutter. Next, a black polyester tape (product number 8422B) made by Sumitomo 3M was firmly attached to the film-forming surface, and the tape was peeled off at 60 ° while the tape was peeled off. The ratio of the entire compartment (membrane residual ratio) was determined without the number of compartments of the checkerboard stripped by the above tape. In the present embodiment, the peeling rate of the tape was determined to be less than 10%, and 10% or more was judged as X. -28- 201042059 (2) Evaluation of wet etching property" For the above samples, a copper alloy film was formed by photolithography, and a pattern of line and space having a width of 1 Ομηι was used, and a mixed acid etching solution was used ( Phosphoric acid: nitric acid: water volume ratio = 75 : 5 : 20 ) etching was performed, and the presence or absence of the residue was confirmed by observation with an optical microscope (observation magnification: 400 times). In the present embodiment, the residue was not observed by the optical microscope observation, and the residue was judged to be X. (3) Film thickness controllability In the present embodiment, the thickness of the copper alloy film is measured as follows (referred to as film thickness control property). First, a glass substrate was formed by using a polyimide film (5412 manufactured by Sumitomo 3, Ltd.) to cover a portion of the substrate, and then formed into a film by the above method to produce a film on the glass substrate. A copper alloy film of a portion of the copper alloy film and an unformed portion. Then, the polyimide film was peeled off, and a copper alloy film having a step was formed in the film as a sample for film thickness control measurement. For the sample (diameter: 100 mm), the thickness d (nm) from the center of the sample (thickness: 500 nm) at 25 mm was measured with a stylus type step ("DEKTAK II" manufactured by VEECO), and the film was calculated from the following formula. Thickness-distribution (%): film thickness distribution = { (500-d) / 5 00} χ 1 〇〇 -29 - 201042059 In the present embodiment, the thickness distribution is ±10. Those who are within 0% are evaluated as 〇, and those who exceed the range are evaluated as X. (4) Evaluation of electrical resistivity The electrical resistivity of the copper alloy film was calculated by the following formula. In the following formula, "film thickness" is a ruthenium measured by the above-described method, and "sheet resistance" is a ruthenium measured by a four-terminal needle method by cutting the sample into a size of 2 inches. Resistivity p = (sheet resistance 値) / (film thickness) In the present embodiment, a resistance of less than 40 μ Ω / cm was judged as ’ '4. 0 μ Q / c m or more is judged as X. However, as a total evaluation, the evaluation of the tightness of (1) with the glass substrate, (2) evaluation of wet etching property, (3) film thickness controllability, and (4) evaluation of resistivity are all judged as Hey, it is not the case that X is judged as X. The results are shown in Tables 3 and 4. -30- 201042059 [Table 1]

Pure Cu film or Cu alloy film sample composition 轲 upper layer base layer No. 0 content film thickness 0 film thickness (upper layer = lower layer) (atomic %) (nm) (atomic %) (nm) 1 pure Cu (500 nm) 1 layer (0 contains J 1 &lt; 0.05) 2 pure Cu &lt; 0. 05 450 5 50 3 pure Cu &lt; 0. 05 450 20 50 4 pure Cu &lt; 0. 05 450 40 50 5 Cu-0.05Ni &lt; 0. 05 450 5 50 6 Cu-0.2Ni &lt;0. 05 450 5 50 7 Cu-0.4Ni &lt; 0. 05 450 5 50 8 Cu-2_0Ni &lt; 0. 05 450 5 50 9 Cu-0.2Ni &lt ;0. 05 499 5 1 10 Cu-0.2Ni &lt;0. 05 495 5 5 11 Cu-0.2Ni &lt; 0. 05 400 5 100 12 Cu-0.2Ni &lt;0· 05 350 5 150 13 Cu-0.2 Ni &lt; 0. 05 450 0.1 50 14 Cu-0.2Ni &lt; 0. 05 450 0.5 50 15 Cu-0.2Ni &lt; 0. 05 450 4 50 16 Cu-0.2Ni &lt; 0. 05 450 40 50 17 Cu -0.2A1 &lt;0. 05 450 5 50 18 Cu~0.2Zn &lt; 0. 05 450 5 50 19 Cu-0.2Mn &lt;0· 05 450 5 50 20 Cu-〇.2Fe &lt; 0. 05 450 5 50 21 Cu - 0.2Ge &lt; 0. 05 450 5 50 22 Cu-0.2Hf &lt; 0. 05 450 5 50 23 Cu~0.2W &lt; 0. 05 450 5 50 24 Cu-0.2Nb &lt; 0. 05 450 5 50 25 Cu - 0.2M 〇 &lt; 0. 05 450 5 50 26 Cu-0.1Ni-0.1Al &lt; 0. 05 450 5 5 0 27 Cu-O.IN 卜O.lZn &lt;0. 05 450 5 50 28 Cu-0.1Ni-0.1Hf &lt;0· 05 450 5 50 29 Cu-0.1Ni-0.1Ge &lt; 0. 05 450 5 50 30 Cu-0_lZnH3.1Hf &lt;0_ 05 450 5 50 31 Cu-0.1M〇-0.1W &lt;0. 05 450 5 50 32 Cu-〇.5Bi &lt;0· 05 450 5 50 Component unit: atomic % -31 - 201042059 [Table 2] Sample No. Pure Cu film or Cu alloy film Upper layer base layer composition Ben 10 content (atomic %) Film thickness (4) Composition w 0 content (atomic %) Film thickness (4) 33 Pure Cu &lt 0_ 05 450 Cu-2.0Ni 5 50 34 Pure Cu &lt; 0. 05 450 Cu-2.0A1 5 50 35 Pure Cu <0. 05 450 Cu-2.0Mn 5 50 36 Cu-0.3Ni <0. 05 450 Cu -2.0Ni 5 50 37 Cu-0.2A1 &lt; 0. 05 450 Cu-2.0A1 5 50 38 Cu-〇.2Mn &lt; 05. 05 450 Cu - 2·0Μη 5 50 39 Cu-〇.2Ge &lt;0 05 450 Cu-2.0Ge 5 50 40 Cu-0.1Ni-0.1Al &lt; 0. 05 450 Cu-0.8Ni-l.5Al 5 50 41 Cu-O.IN Bu O.lGe &lt; 0. 05 450 Cu -l.lNi-l.5Ge 5 50 42 Cu-0.1Ni-0.1Zn &lt; 0. 05 450 Cu-l.2Ni-l.4Zn 5 50 43 Cu-0.4Ni &lt;0· 05 450 Cu-2.0A1 5 50 44 Cu-0.4Ni &lt; 0. 05 450 Cu-0.8Ni-l.5Al 5 50 Component unit: Atomic % -32- 201042059 【table 3】

Compact Resistivity Wet Etching Film Thickness Controlled General Test Sample Heat Treatment Before Heat Treatment After Judging Heat Treatment, Judgment of Residue Thickness Distribution No. Peel Rate of Peel Rate Determined Resistivity (%) Deviation (%) ) 定 (%) (μ U/cm) 1 100 X 100 X 2.0 Dirty /»»' 〇2.0 〇X 2 68 X 63 X 2.4 〇値〇4.2 〇X 3 8 〇9 〇3.6 〇X 10.2 XX 4 86 X 92 X 4.2 X with X 12.4 XX 5 80 X 81 X 2.4 〇Μ ..., 〇 4.4 〇 X 6 2 〇 0 〇 2.6 〇Μ /,,, 〇4.3 〇〇7 5 〇0 〇2.8 〇 〇 4.4 〇〇8 3 〇0 〇4.2 X Sister 〇4.5 〇X 9 18 X 13 X 2.3 〇No 〇2.2 〇X 10 2 〇0 〇2.3 〇Sister 〇2.3 〇〇11 4 〇0 〇2.8 〇No 6.7 〇 〇12 3 〇0 〇4.3 X Dirty y»,, 〇10.2 XX 13 31 X 23 X 2.2 〇钲〇3.6 〇X 14 7 〇8 〇2.4 〇 〇 4.4 〇〇15 4 〇0 〇3.2 〇车川· ' 〇 4.5 〇〇 16 3 〇 0 〇 4.9 X with X 1L9 XX 17 7 〇 5 〇 3.0 〇Μ /», ' 〇 4.5 〇〇 18 7 〇 6 〇 3.2 〇4.6 〇〇19 3 〇0 〇2.9 〇钿/*\χ 〇4.1 〇〇20 5 〇0 〇3.1 〇钿〇4.9 〇〇21 4 〇0 〇3.2 〇No 〇4.6 〇〇22 4 〇2 〇3.3 〇姐八'·» 〇4.3 〇〇23 5 〇3 〇3.1 〇〇4.6 〇〇24 4 〇2 〇3.2 〇赃•M,, 〇4.8 〇〇25 6 〇4 〇3.1 〇无〇4.5 〇〇26 4 〇2 〇2.8 〇无〇4.4 〇〇27 5 〇2 〇2.7 〇魅〇4.9 〇〇28 2 〇3 〇2.9 〇〇4.6 〇〇29 3 〇2 〇3.0 〇No 〇4.3 〇〇30 5 〇3 〇3.1 〇无〇4.7 〇〇31 3 〇2 〇3.2 〇无〇4.5 〇〇32 92 X 100 X 3.3 X i X 5.1 XX -33- 201042059 [Table 4] Tight part resistivity wet etching film thickness control heat treatment After the heat treatment, the thickness of the film is judged by the heat treatment, and the thickness of the film is determined. (%) Evaluation (%) 33 4 〇0 0 2.6 〇无〇3.9 〇〇34 3 〇0 〇2.7 〇无〇4.2 〇〇35 3 〇0 0 2.9 〇无〇4.3 〇〇36 2 〇0 0 2.8 〇4&amp; Sichuan, 〇4.1 〇〇37 4 〇0 〇3.2 〇无〇4.2 〇〇38 3 〇0 〇3.3 〇No 〇 4.1 〇〇39 3 〇0 〇3.3 〇无〇4.4 〇〇40 3 〇0 0 3.3 〇Μ 〇4.3 〇〇41 4 〇0 〇3.4 〇No 〇4.3 〇〇42 5 〇0 〇3.2 〇No 〇4.1 〇 〇43 4 〇0 〇3.2 〇无〇4.2 〇〇44 4 〇0 〇3.3 〇赃〇4.3 Table No.6, 7, 1〇, 11, I4, 15, I7~31, Table 4

The No. 3 3 to 44 series completely satisfy the requirements of the present invention. In particular, the content of the tightness-improving element is from the viewpoint of lowering the resistivity, and the copper alloy film satisfying the ideal requirements, for the tightness, the resistivity and the wetness Excellent etchability and good film thickness controllability. Among them, N 〇 . 3 3 to 4 4 of Table 4 are different examples of the alloy composition of the upper layer and the base layer, but both satisfy the requirements of the present invention to obtain desired characteristics. On the other hand, No. 1 to 4, 5, 8, 9, 12, 13, 16, 32 are examples which do not satisfy any of the requirements specified in the present invention, or examples which do not satisfy the ideal of the present invention. Examples of Nos. 1 to 4 in Table 3 are examples in which pure Cu is used. Specifically, the No. 1 peeling rate of the single-layer pure Cu film was 100%, and the adhesion to the glass substrate was not good. N 〇 . 2 is an example in which the underlying layer contains 5 at% of oxygen. However, since it does not contain a specific alloying element, the adhesion to the glass substrate is not good. On the other hand, N 〇·4 is an example in which the base layer contains a large amount of 40% by atom of oxygen, even if it does not contain a specific alloying element, compared with No. 2, except for the peeling rate increase of -34 to 201042059, wet etching Sex or film thickness control also decreased. No. 3 does not contain a specific alloying element, and has poor wet etching characteristics and film thickness controllability. 'No. 5 is an example in which the amount of Ni is small, and the adhesion to the glass substrate is not good. On the other hand, in the case of No. 8 which has a large amount of Ni, the electrical resistivity after heat treatment becomes high.

The No. 9-based underlayer is thin, and the adhesion to the glass substrate is not good. On the other hand, the No. 12-based underlayer was thick, and the controllability of resistivity and film thickness was poor. The Q No. 13-based base layer has a low oxygen content and is inferior to the glass substrate. On the other hand, in the case where the No. 16-based underlayer has a large oxygen content, the resistivity, the wet etching property, and the film thickness controllability are not good. Νο·32 is an example of Bi containing an alloying element not defined in the present invention, and contains a specific amount of oxygen content in the underlying layer, and appropriately controls the thickness thereof. For the tightness to the glass substrate, the resistivity The wet etching property and the film thickness controllability are not good. [Example 1-2] In this example, the influence of the kind and amount of alloying elements in the underlayer on the tightness was examined. In the present Example, a copper alloy underlayer (film thickness: 5 Å) was produced in the same manner as in Example 1-1, and a copper alloy upper layer (film thickness: 25 〇 nm) having the same composition as the underlying layer was produced. A sample of a copper alloy film of ', and a sample of a pure Cu-film having a thickness of 300 ππι for comparison. In the same manner as in Example 1-1, the film formation system of the copper alloy film was used for a sputtering target of a wafer containing elements other than Cu (Ni, A1, Μ, W, Zn) on a pure Cu sputtering target. For the Ca system, a pendulum plating plate of a C u -C a alloy having a specific composition is prepared by dissolving -35- 201042059. Further, the addition of oxygen to the copper alloy film is carried out by controlling the sputtering gas used in the film formation described above. More specifically, for the film formation of the underlayer portion, an Ar + 5 vol% 02 mixed gas containing 5 vol% of 02 in Ar was used, and a pure Ar gas was used for film formation of the upper layer. However, the mixing ratio of the Ar gas to the 〇2 gas is set by the partial pressure of the Ar gas and the 02 gas, and the partial pressure is controlled by adjusting the flow ratio of these. In the same manner as in Example 1-1, the concentration of 02 in the present example was measured by a high-frequency glow discharge luminescence spectrometer (GD - Ο ES ), and the concentration of 上 2 in the upper layer was 0.02 at%. The concentration of 02 in the basal layer was 2.9 atom%. The sample after the film formation (as-depo state) and the sample subjected to heat treatment at 350 °C × 30 μm in a vacuum atmosphere after film formation were evaluated for tightness in the same manner as in Example 1-1. However, the angle at which the tape is peeled off only for Ζη is 90°. The results are shown in Figures 1 to 3 (after film formation) and Figures 4 to 6 (after heat treatment). From Figs. 1 to 6, it is understood that as the amount of the alloying element added to the underlayer increases, the tightness of the copper alloy film to the glass substrate increases. Further, the heat resistance is further improved. In particular, in the case of adding Ni, Α1, Μη, Ca, and Zn, a slight 100% tightness ratio can be achieved after the heat treatment. Example 1-3 In this example, the effect of the film thickness of the underlayer on the tightness was examined. In the preparation of the sample, the base layer and the upper layer were both made of Cu-2 -36-201042059 atom% Zn, and the thickness of the base layer was changed to be outside the range of 1 〇 to 2 〇〇 nm, which was the same as in Example 1-2. As. Further, for comparison, when a film of the underlayer was formed, a sample in which pure Ar gas was used and oxygen was not contained in the underlayer was also produced. Thereafter, the sample after film formation was evaluated as tightness as in Example 丨_i. The results are shown in Fig. 7. It is understood from Fig. 7' that as the film thickness of the basal layer increases, there is a tendency to increase tightness. In addition, it has been found that the effect of improving the tightness is saturated at a film thickness of 〇100 nm, and the tightness is hardly changed even if it is increased to 丨〇〇nm or more. Embodiment 1-4 - In the present embodiment, 'the effect of the oxygen concentration in the process gas on the tightness and the oxygen concentration in the process gas and the oxygen concentration in the underlayer are evaluated. In the production of the sample, the base layer and the upper layer were treated in the same manner as in Example 1-2 except that Cu-2 atomic % Zn ' was used to form a film in the base layer portion. For the sample after film formation, the evaluation was as similar as in Example 1-1. Further, in the case where the concentration of 〇2 in Ar in the formation of the underlayer portion was changed, the concentration of ruthenium 2 in the underlayer was analyzed by a high-frequency glow discharge luminescence spectrometer in the same manner as in Example 1-1. . The results are shown in FIGS. 8 and 9. Through FIG. 9, it is understood that the content of 〇2 in the basal layer increases with an increase in the concentration of 〇2' in Ar when the underlayer is formed, and it is understood that the film formation of the basal layer is accompanied by FIG. The increase in the concentration of ruthenium 2 in Ar increases the tightness of the copper alloy film to the glass substrate. -37-201042059 Example 2 -1 (Production of sample) In the present embodiment, it was produced on a semiconductor layer and had various pure Cu films or copper alloy films shown in Tables 5 to 7 (hereinafter, there is a copper alloy film). The sample represented by the case). In detail, the copper alloy film of the present embodiment has an oxygen content of 〇. 1 atom% as a boundary line from the base layer (from the interface between the semiconductor layer and the copper alloy film to the surface of the copper alloy film l〇nm). a layer or a layer up to 50 nm), an upper layer (a layer from the base layer to the surface of the copper alloy film), and oxygen content and alloy composition contained in the underlayer and the upper layer are as shown in Tables 5 to 7. . Here, Table 5 shows an example in which the alloy composition (type and content) of the upper layer and the base layer are the same, and the composition of the composition (upper layer = lower layer) shows the composition of the entire copper alloy film. For example, in Table 5, N 〇 _ 4 (upper layer = lower layer = Cu-0.05Ni) is based on the entire copper alloy film and contains Cu - 0.05 atomic % Ni. Tables 6 and 7 show examples in which the alloy composition (type and/or content) of the upper layer and the base layer are different (except Table No. 53). [Table 7 is the composition of the layers of the upper layer and the base layer. (Type and/or content) are more different examples. For Table 7, the layer structure from the rightmost column (base layer) to the leftmost column (upper layer) and from the interface to the surface of the copper alloy film is shown. For example, the N 〇 · 7 1 of Table 7 is from the interface toward the copper alloy. On the surface of the film, 5 atom% of oxygen in this order contains Cu-2_2 atomic % (l 〇 nm) -&gt; 5 atoms. /. Oxygen contains a layered composition of Cu-0.3 at% (1 〇 11111) (above, basal layer) - Cu-0.3 at% Ni (300 nm). -38- 201042059 The detailed production method of the sample is as follows. First, the semiconductor layer is formed into a film as 'on the glass substrate' as follows. First, a tantalum nitride film having a film thickness of about 200 nm was formed on a glass substrate (manufactured by Japan Corning Corporation #1737, diameter: 100 mm, thickness: 77 mm) by a plasma CVD method using a cluster CVD apparatus manufactured by ULVAC Corporation. SiN) acts as a gate insulating film. The film formation temperature of the plasma CVD method is about 3 50 °C. Next, an undoped amorphous ruthenium film [a-Si(i)] having a film thickness of about 200 nm and an impurity having a doped film thickness of about 40 nm are sequentially passed through a 0-plasma CVD method using the same CVD apparatus as described above. The low-impedance amorphous ruthenium film [a-Si ( η )] of (P) is formed into a film. The low-impedance amorphous ruthenium film [a-Si ( η)] is formed by plasma CVD when SiH4 and yttrium 3 are used as raw materials. Then, a sputtering apparatus (trade name: HSR 542) manufactured by Shimadzu Corporation of Japan was used to form a copper alloy film of various compositions shown in Tables 5 to 7 on the semiconductor layer as follows. 〇 First, the composition of the copper alloy film (i) uses a Cu sputtering target for the film formation of the pure CU film, (ii) the film formation of the copper alloy film containing various alloying elements, and is attached to the Cu splash target. In the above, it is controlled by using a spatter target which is provided with a wafer containing an element other than Cu. When a copper alloy film having the same composition of the base layer and the upper layer is formed into a film, the same sputtering target is used, and the other side is formed by forming a copper alloy film having a different composition or content of the base layer and the upper layer. , to obtain a specific film, using a different composition of the sputtering target. In addition, the oxygen content of the copper alloy film is in the film formation of the base layer, and will be -39- 201042059

The mixed gas of Ar and 〇2 is used as a processing gas, and is controlled by the time when only Ar gas is used in the film formation of the upper layer. The oxygen content in the underlayer is adjusted by changing the ratio of oxygen in the mixed gas. For example, when 5 atom% of oxygen is contained in the underlayer, the ratio of 02 in the processing gas is taken as 0% by volume. Other film forming conditions are as follows. • Back pressure: 1.0x1 〇 '6 Torr or less • Process air pressure: 2.0x1 (T3Torr • Flow rate of process gas: 30sccm. Sputter power: 3.2W/cm2 • Distance between poles: 50 mm • Substrate temperature: room temperature • Film temperature: room temperature The ICP emission spectroscopic analyzer (ICP-8 000 type ICP emission spectrometer manufactured by Shimadzu Corporation) was used for the quantitative analysis of the composition of the copper alloy film to be formed. (Oxygen content in the underlayer and the upper layer) The oxygen content in each of the underlayer and the upper layer is measured by a high-frequency glow discharge luminescence spectrometer (GD-OES), and is described in Tables 5 to 7. The amount of cerium (oxygen) in the underlayer and the upper layer is calculated based on the depth-divided concentration curve obtained by the above analysis, and the average concentration of the film contained in each of the underlayer and the upper layer is calculated. For any sample, the oxygen content of the upper layer is less than 〇·0 5 atoms./ (Refer to Table 5~7) -40 - 201042059, which does not contain oxygen. ' (Measurement of thickness of upper layer and base layer) • Copper Upper layer of alloy film and The thickness of the underlayer is a surface that can be observed perpendicularly to the film surface direction (depth direction) of Cu, and a sample for thickness measurement is prepared, and a liberation-type transmission electron microscope is used. (magnification: 150,000 times) · Projection arbitrary measurement 0 Field of view photo, and measuring the film thickness of each layer. The composition of the copper alloy film (the composition of the upper layer and the underlying layer, the oxygen content and the thickness) are shown in Table 5~ (Evaluation of Characteristics of Copper Alloy Film) Next, the sample obtained as described above was used as the measurement (1) tightness of the copper alloy film and the semiconductor layer, and (2) wet etching property (1) Evaluation of the tightness of the semiconductor layer The tightness of the copper alloy film before and after the heat treatment (in a vacuum atmosphere at 350 ° C for 5 hours) was evaluated by a peel test by a tape. On the film-forming surface of the copper alloy, cut into a checkerboard shape of 1 tnm by a milling cutter. Then, a black polyester-tape (product number 8422Β) made by Sumitomo 3 of Japan was firmly attached to the above. On the film-forming surface, 'the peeling angle of the above-mentioned tape is maintained at 60. At the same time, the tape is peeled off at the same time', and the number of the checkerboards which are not peeled off by the above-mentioned tape is calculated - 41 - 201042059, and the whole area is obtained. The ratio (membrane residual ratio). However, the average enthalpy of the result of the 3-part implementation including the unevenness of the film formation by Cu should be performed. In the present embodiment, the peeling rate via the tape is not determined as 〇, 20% or more was judged as X. (2) Evaluation of wet etching property For the above-mentioned sample, copper was used as a pattern of line and space having a width of 1 μm by photolithography, and (phosphoric acid: The volume ratio of nitric acid:water = 7 5 : 5 : 2 0 ) was observed by an optical microscope (observation magnification: 400 times). In the present embodiment, the observer of the optical microscope described above was judged to be ◦, and the person who saw the residue was judged to be χ. The results are shown in Tables 8 and 9. According to the evaluation of the knot, it is shown that up to 20% of the alloy film is formed. The mixed acid uranium engraving is etched, and the residual residue is not seen. -42 - 201042059 [Table 5] Ο

Pure Cu film or Cu alloy film sample composition 纣 upper layer base layer No. 0 content film thickness 0 content film thickness (upper 僧 - dip) (atomic %) (nm) (atomic %) (nm) 1 pure Cu ( 300 nm) 1 layer (0 content &lt; 〇 · 〇 5) 2 pure Cu &lt; 0.05 250 10 50 3 pure Cu &lt; 0.05 250 33 50 4 Cu-0.05Ni &lt; 0.05 250 10 50 5 Cu-4Ni &lt; 0.05 260 10 50 6 Cu-6.9Ni &lt;0.05 260 10 50 7 Cu-0.2Ni &lt;0.05 450 0.1 50 8 Cu-0.2Ni &lt;0.05 450 0.5 50 9 Cu-0.2Ni &lt;0.05 450 4 50 10 Cu -0.2Ni &lt;0.05 450 20 50 11 Cu-0.2Ni &lt;0.05 495 15 10 12 Cu~0.05Mn &lt;0.05 250 10 50 13 Cu-〇.4Mn &lt;0.05 300 10 50 14 Cu - 4Mn &lt;0.05 260 10 50 15 Cu-7.1Mn &lt;0.05 260 10 50 16 Cu~0.2Mn &lt;0.05 450 0.1 50 17 Cu-〇.2Mn &lt;0.05 450 0.5 50 18 Cu - 0.2Mn &lt;0.05 450 4 50 19 Cu - 〇.2Mn &lt;0.05 450 20 50 20 Cu-〇.2Mn &lt;0.05 495 15 10 21 Cu-0.05A1 &lt;0.05 250 10 50 22 Cu-0.4A1 &lt;0.05 300 10 50 23 Cu_4Al &lt;0.05 260 10 50 24 Cu-7.1A1 &lt;0.05 260 10 50 25 Cu-0.2AI &lt;0.05 450 0.1 50 26 Cu-0.2A1 &lt;0.05 450 0.5 50 27 Cu-0.2A1 &lt;0.05 450 4 50 28 Cu-0.2A1 &lt;0.05 450 20 50 29 Cu-0.2A1 &lt;0.05 495 15 10 30 Cu-〇.2Zn &lt;0.05 450 5 50 31 Cu~0.2Fe &lt;0.05 450 5 50 32 Cu-〇.2Ge &lt;0.05 450 5 50 33 Cu - 0.2Hf &lt;0.05 450 5 50 34 Cu-0.2W &lt;0.05 450 5 50 35 Cu-0.2Nb &lt;0.05 450 5 50 36 Cu-〇.2Mo &lt;0.05 450 5 50 37 Cu-0.1Ni-0.1Al &lt;0.05 450 5 50 38 Cu-0.1Ni-0.1Zn &lt;0.05 450 5 50 39 Cu-0.1Ni-0.1Hf &lt ; 0.05 450 5 50 40 Cu-0.1Ni-0.1Ge &lt;0.05 450 5 50 41 Cu-0.1Zn-0.1Hf &lt;0.05 450 5 50 42 Cu-0.1M〇-0.1W &lt;0.05 450 5 50 43 Cu -0.5Bi &lt;0.05 450 5 50 Component unit: Atomic % -43- 201042059 [Table 6] Sample No. Pure Cu film or Cu alloy film upper layer base layer composition about 0 content (atomic %) film thickness (run) composition μ 0 content (atomic %) film thickness (nm) 51 Cu-0.3Ni &lt; 0.05 300 Cu-0.2Ni 10 50 52 pure Cu &lt; 0.05 300 Cu-0.2Ni 10 50 53 Cu-0.2Ni &lt; 0.05 500 - - a 54 pure Cu &lt; 0.05 300 Cu-〇.4Mn 10 50 55 pure Cu &lt; 0.05 300 Cu-0.4A1 10 50 56 Cu-0.3Ni &lt; 0.05 300 Cu-2.2Ni 5 50 57 Cu-0.2A1 &lt;0.05 450 Cu-2.5A1 5 50 58 Cu-〇.2Mn &lt;0.05 450 Cu-2.1Mn 5 50 59 Cu-〇.2Ge &lt;0.05 450 Cu_2.3Ge 5 50 60 Cu - 0.3 Ni &lt;0.05 300 Cu-0.5A1 5 50 61 Cu-0.2Ni &lt;0.05 450 Cu-〇.5Mn 5 50 62 Cu-0.1Ni-0.1Al &lt;0.05 450 Cu-0.6Ni-l.9Al 5 50 63 Cu-0.1Ni-0.1Ge &lt;0.05 450 Cu-l.0Ni-l.2Ge 5 50 64 Cu-0.1Ni-0.1Zn &lt;0.05 450 Cu-1.5N Bu l_5Zn 5 50 65 Cu-0.4Ni &lt;0.05 450 Cu-2.1A1 5 50 66 Cu-0.4Ni &lt;0.05 450 Cu-l.lNi-0.8Al 5 50 Component unit: atomic % -44 - 201042059

[Pu Shu] 1 pure Cu film or Cu alloy film] base film thickness (then) 〇1—H 1 o 1 o γΉ 1 〇1 0 content (atomic %) LO 1 LT3 1 LO 1 LO 1 composition μ Cu -2.2Ni 1 CU-2.2A1 1 Cu-2.2Mn 1 Cu-2.2Ni-0.8Mn 1 Base layer film thickness (nm) o § o § o § o 0 content (atomic %) LO LO l〇lO ΙΛ LO LO composition μ Cu-0.3Ni Cu-2.2Ni Cu-0.3A1 Cu-2.2A1 Cu-〇.3Mn Cu-2.2Mn Cu-0.3Ni-0.3Mn Cu-2.2Ni-0.8Mn Upper film thickness (nm) 1 § 1 .1 § 1 § 0 content (atomic %) ι &lt; 0.05 1 &lt; 0.05 1 &lt; 0.05 1 &lt; 0.05 Composition "1 Cu-2.2Ni 1 Cu-2.2A1 1 Cu~2.2Mn 1 Cu-2.2 Ni-0.8Mr I Upper film thickness (nm) 300 "300 1 "300 1 1 300 1 o % Γ^ο^Ί "300 I o 0 content (atomic %) &lt;0,05 &lt;0.05 1 &lt; 0.05 1 &lt; 0.05 1 &lt; 0.05 1 &lt; 0.05 &lt; 0.05 &lt; 0.05 Composition d Cu-0.3Ni Cu-0.3Ni Cu-0.3Ni Cu-0.3A1 Cu - 0.3Mn Cu-0.3Mn Cu-0.3Ni- 0.3Mn Cu-0.3Ni-0.3Mn sample No. tH go LO CD 00 -45- 201042059

[Table 8] After the heat treatment of the compact wet etching sample, the total Ή* No. is determined by the evaluation of the peeling rate. (1) 1 100 X No X 2 38 X Μ &lt;m, 〇X 3 29 X XX 4 23 X 〇X 5 0 〇无〇〇6 0 〇有XX 7 12 〇无〇〇8 8 〇无〇〇9 5 〇4bp /,,,〇〇10 0 〇Μ 〇〇11 0 〇Μ &gt ;,,,〇〇12 35 X New/w\ 〇X 13 7 〇Μ 〇〇14 0 〇Μ y\s\ 〇〇15 0 〇 XX 16 13 〇Μ , , , , 〇〇 17 12 〇Μ 〆,,, 〇〇18 7 〇Μ 〇〇19 0 〇4βρ /ν\&gt; 〇〇20 0 〇Μ Μ,, 〇〇21 41 X group 〇X 22 8 〇Μ /w\ 〇〇23 0 〇 〇〇24 0 〇 XX 25 14 〇Μ vwv 〇〇26 12 〇铿〇〇27 6 〇Μ 〇〇28 0 〇无〇〇29 0 〇Μ 〇〇30 8 〇无〇31 7 〇Μ &gt; , , , 〇〇 32 8 〇 〆 , , , 〇〇 33 9 〇Μ &gt;, ν» 〇〇 34 7 〇Μ /\w 〇〇 35 6 〇 sister 〇〇 36 8 〇 no 〇〇 37 6 〆 、,,, 〇〇38 7 〇Μ 〇〇39 7 〇鈒y», 〇〇40 6 〇姐Μ', 〇〇41 8 〇Sister V», 〇〇42 8 〇 sister/, V« 〇〇43 100 X has XX -46- 201042059

[Table 9] Sample No. — Tightness wetness _ total evaluation evaluation Heat treatment of the peeling rate (%) Determination of the presence or absence of residue 51 3 〇 no 〇〇 52 5 〇 Ό 〇〇, 〇〇 53 67 X Μ &gt;, , 〇X 54 10 〇无〇〇55 12 〇无〇〇56 &quot;〇〇无〇〇57 0 〇无〇〇58 0 〇无〇〇59 0 〇无〇〇60 2 〇V»,, 〇 61 3 〇车〇~〇~ 62 0 〇Jnt Λν» 〇~δ~~ 63 0 〇ΛνΓ 〇〇64 0 〇dte 〇〇65 0 〇无〇〇_ 66 0 〇Μ &lt;*,,, 〇〇 71 0 〇Μ 〇〇72 0 〇〇〇73 0 〇Μ &gt;,,,〇〇74 0 〇 &&gt;ν\\ 〇〇75 0 〇te 〇〇76 0 〇te 〇〇_ 77 0 dirty 〇〇78 0 〇/,,, 〇〇8 Ν5·7,11~11,13,14,16~20, 22, 23' 25~42, Table 9, No.51, 52 and 54~78 The copper alloy film which completely satisfies the requirements of the present invention is superior in tightness and wet etching property. Among them, No. 51, 52 and 54 to 78 of Table 9 are different examples of the alloy composition of the upper layer and the base layer, but both satisfy the requirements of the present invention to obtain the desired characteristics, although not shown in the table. However, these copper alloy film systems have a completely low resistivity (less than 4·〇μΩ/cm). Here, the resistivity is calculated by the following formula -47- 201042059. Resistivity p = (thin film resistance 値) / (film thickness) In the above, "thin film resistance 値" is obtained by cutting the sample into a size of 2 inches, and the 値 and "film thickness" measured by the four-terminal method are as follows. As a measure of enthalpy. For the glass substrate, a polyimide tape (5412 manufactured by Sumitomo 3M) was used to cover a portion of the substrate, and then a film was formed by the above method, and a portion having a film formed of a copper alloy film was formed on the glass substrate. A copper alloy film with an unformed portion. Then, the polyimide film was peeled off, and a copper alloy film having a step was formed in the film as a sample for film thickness control measurement. With respect to the above-mentioned sample (diameter: 1 mm), the thickness d (nm) which was separated from the sample center (thickness: 500 nm) by 25 mm was measured with a stylus type step ("DEKTAK II" manufactured by VEECO). In this regard, the case in which any of the requirements specified by the present invention are not satisfied has the following problems. Ν 〇 · 1 to 3 are examples of pure c u. Specifically, the No. 1-based peeling ratio of the single-layer pure Cu film was 1%, and the adhesion to the semiconductor layer was not good. No. 2 is an example in which the underlayer contains 1 〇 atomic % of oxygen. However, since it does not contain a specific alloying element, the adhesion to the semiconductor layer is not good. On the other hand, No. 3 is an example in which 33% by atom of oxygen is contained in the underlayer, and the adhesion to the semiconductor layer is not good, and the wet etching property is also lowered. N 〇. 4, 1, 2, 2 1 The examples of the amount of N i, the amount of Μ η, and the amount of A1 are small, and the tightness of the semiconductor layer is not good with -48- 201042059. On the other hand, No. 6, 15, and 24 are examples in which the amount of Ni, the amount of Μη, and the amount of A1 are large, and the wet etching property is lowered. Νο.43 is an example of Bi containing an alloying element not defined in the present invention, and contains a specific oxygen content in the underlying layer, appropriately controls the thickness thereof, and is close to the semiconductor layer, and wet etching Poor sex.

In the case where the No. 43-based underlayer has a small oxygen content, the adhesion to the glass substrate is not good. On the other hand, in the case where the No. 16-based underlayer has a large oxygen content, the wet etching property is not good. Νο·53 is an example in which a base layer (^-0.2 atom% Ni monolayer is not provided, and the tightness of the semiconductor layer is lowered. The present patent application has been described in detail with reference to a specific embodiment, and the manufacturer Various changes or various modifications may be made without departing from the spirit and scope of the invention. The present patent application is based on a Japanese patent application filed on January 16, 2009 (Japanese Patent Application No. 2009-008265), January 16, 2009 Japanese Patent Application No. 2009-008266, the entire contents of which is incorporated herein by reference. The copper alloy film adopts a base layer containing a suitable alloying element and in direct contact with the transparent substrate, and the amount of oxygen is higher than that of the upper layer (ideally, the base layer contains an appropriate amount of oxygen, and the upper layer on the base layer is substantially The layered structure of oxygen is not contained. In addition to the high tightness with the transparent substrate, the low resistance of -49-201042059, and the superior wet etching property, the unevenness of the film thickness distribution can be reduced. .Such as The use of such a copper alloy film in a display device can reduce the number of manufacturing processes and the cost. The oxygen-containing copper alloy film of the present invention is used for wiring or electrodes in direct contact with a transparent substrate, and is typically used for a gate. Further, in the present invention, as the copper alloy film for a display device which is in direct contact with the semiconductor layer of the thin film transistor, a base layer which contains an appropriate alloying element and is in direct contact with the semiconductor layer is used. Containing an appropriate oxygen 'group f| The upper layer on the underlayer is substantially free of oxygen. The layer is formed to have high tightness with the semiconductor layer, low resistivity, and superior wet etching properties. The alloy film can reduce the number of manufacturing processes and the cost according to the display device. The oxygen-containing copper alloy film of the present invention is used for wiring or electrode which is in direct contact with the semiconductor layer (amorphous germanium or polycrystalline germanium) of the thin film transistor. Typically, it is used for source-drain wiring or source-drain electrodes. υ [Simplified illustration] Figure 1 shows the structure of Example 1-2. The relationship between the subsequent tightness ratio and the content of the tightness-enhancing element (Ni, Al, Mn, Ca). Fig. 2 shows the compaction ratio and the adhesion-improving element after the film formation of Example 1-2 ( Fig. 3 is a graph showing the relationship between the tightness ratio after the film formation of Example 1-2 and the content of the compactness-enhancing element (Zn). Fig. 4 is shown in the example. The tightness rate after heat treatment of 1-2, and the tightness of -50-420,420,519 tightness enhancement elements (Ni, ο Figure 5 is shown in the solidity enhancement element (W) Figure 6 is shown in the solidity enhancement element (Ζη) Fig. 7 is a graph showing the relationship between the film thicknesses in the real 0 layer. Fig. 8 shows the Cu·oxygen concentration, and the compact ratio is shown in Fig. 9 which shows the oxygen concentration in the gas.

Relationship chart between the contents of Al, Mn, and Ca) The relationship between the tightness ratio after heat treatment of Example 1-2 and the tight content. A graph showing the relationship between the tightness ratio after heat treatment of Example 1-2 and the tight content. The tightness ratio after film formation of Example 1-3, and the relationship between the argon gas at the time of film formation of the substrate 〇 2 atom% Zn alloy film. Fig. 2 is a graph showing the relationship between the oxygen concentration in the argon base layer at the time of film formation of the atomic layer of the Zn alloy film. 〇 -51 -

Claims (1)

201042059 VII. Patent application scope: 1. A copper alloy film which is a copper alloy film for a display device, characterized in that the copper alloy film is a display device for an oxygen-containing alloy film which satisfies the requirements of the following (1) and (2) (2) The copper alloy film is at least one element selected from the group consisting of Ni, Al, Zn ' Mn, Fe, Ge, Hf, Nb, Mo, W, and Ca, and is contained in total. (0) The copper alloy film has a base layer and an upper layer having different oxygen contents, and the base layer is in contact with the transparent substrate or the semiconductor layer, and the oxygen of the base layer is 0. 10 atom% or more and 10 atom% or less. The content is more than the oxygen content of the above upper layer. The copper alloy film according to the first aspect of the invention, wherein the base layer is in direct contact with the transparent substrate. 3. The copper alloy film according to claim 1, wherein the underlying layer is in direct contact with the semiconductor layer. 4. The copper alloy film according to the second aspect of the patent application, wherein the oxygen content of the underlayer in the item (2) of the first item is in the range of 〇5 atom% or more and 3 atom%. Hereinafter, the oxygen content of the upper layer is less than 5 atom% (% by atom). 5. The copper alloy film according to the second aspect of the invention, wherein the element contained in the copper alloy film in the first item (1) is 0. 10 atom% or more and 0. 5 atom. %the following. 6. The copper alloy film according to the third aspect of the invention, wherein the oxygen content of the underlayer is from 0.1 atom% to 30 atom% or less in the above-mentioned item (2) of -52-201042059. The oxygen content of the upper layer is less than 0.1 'atomic % (including yttrium atom%). 7. The copper alloy film according to claim 3, wherein in the first item (1), the element contained in the copper alloy film is selected from the group consisting of Ni, Al, Zn, Mn, Fe, and Ge. At least one element of the group of Hf, Nb, Mo, and W is contained in an amount of 0.10 atom% or more and 5.0 atom% or less. The copper alloy film according to any one of the items 1 to 3, wherein the copper alloy film has a decrease in oxygen from the base layer toward the upper layer. The copper alloy film of any one of the above-mentioned item (1), wherein the copper alloy film has an element. At least one of the type and the element amount is different from the first layer and the second layer, and the first layer is in contact with the transparent substrate or the semiconductor layer, and is contained in the first item (1) of the first layer. The element content specified in the above is more than the element content (including 0 atom/%) specified in the first item of the second layer of the layer contained in the first layer. The copper-gold film according to any one of claims 1 to 3, wherein the upper layer is pure Cu. 1 1. A display device comprising the copper alloy film according to any one of claims 1 to 3. -53-