TWI378509B - - Google Patents

Description

1378509 As shown in detail in FIG. 2, the pixel region P of the pixel electrode 19 is composed of a transmission region A and a reflection region C, the transmission region A is provided with a transparent pixel electrode 19a, and the reflection region C is provided with a transparent pixel electrode 19a. And a reflective electrode 19b. Between the transparent pixel electrode 19a and the reflective electrode 19b, a barrier metal layer 51 composed of a high melting point metal such as Mo, Cr, Ti, or W is formed. For example, in Patent Document 1 to Patent Document 3, a barrier metal layer 51 such as molybdenum or chromium is interposed between the aluminum-based alloy film and the oxide transparent conductive film. The operation principle of the transmission mode and the reflection mode will be described with reference to Fig. 2 with respect to the transflective liquid crystal display device 11 shown in Fig. 1 . First, the principle of operation of the transmission mode will be explained. In the transmission mode, the light F of the backlight 41 disposed in the lower portion of the TFT substrate 21 is used as a light source. The light emitted from the backlight 41 is incident on the liquid crystal layer 23 through the transparent pixel electrode 19a and the transmission region A, and is formed by The electric field between the transparent pixel electrode 19a and the common electrode 13 controls the alignment direction of the liquid crystal molecules of the liquid crystal layer 23, and the incident light F from the backlight 41 through the liquid crystal layer 23 is modulated. Thereby, the amount of light transmitted through the counter substrate 15 is controlled to display an image. On the other hand, in the reflection mode, external natural light or artificial light B is utilized as a light source. The light B incident on the counter substrate 15 is reflected by the reflective electrode 19b, and the alignment direction of the liquid crystal molecules of the liquid crystal layer 23 is controlled by the electric field formed between the reflective electrode 19b and the common electrode 13 through the liquid crystal layer 23. The light B is modulated. Thereby, the amount of light transmitted through the counter substrate 15 is controlled to display an image. -7- 1378509 The pixel electrode 19 is composed of a transparent pixel electrode 19a and reflection. Among them, the transparent pixel electrode 19a contains a 10% by mass of tin oxide (indium tin oxide) in a representative indium (Ιη203). (ITO) or an oxide such as indium zinc oxide (IZO) containing 10 mass of zinc oxide in indium oxide is transparently conductive, and the reflective electrode 19b is made of a metal having a high reflectance, and representative aluminum or Aluminum alloys such as Al_Nd (collectively referred to as "aluminum alloys"). Aluminum alloys are extremely useful as wiring materials because of their electrical resistivity. Here, as shown in Fig. 2 or the aforementioned Patent Documents 1 to 3, the aluminum of the emitter electrode 19b. The reason for forming the molybdenum Mo metal barrier metal layer 51 between the alloy film and the oxide transparent conductive film such as ITO or IZO is because galvanic is directly formed by this continuous reflection region. Corrosion causes the contact resistance to rise, causing the display product of the screen to be etched by the Galvania, such as an oxide such as ITO, and an aluminum-based alloy film, such as an electrode potential difference between the dissimilar metals. The electrode potential of the Ag/AgCl standard electrode in the aqueous solution of the photoresist to the alkaline developing solution is not about -0.17V, and the polycrystalline-ITO is about -0.19, while the pure aluminum is very low. Moreover, aluminum alloys are very susceptible to oxidation. Therefore, the alloy film is directly formed on the oxide transparent conductive film, and the aluminum alloy film and the oxidation electrode 19b, which are formed by the film of the percentage of the oxygen SnO) in the immersion of the TMAH aqueous solution, are low in the following. The material that constitutes the reverse 19a is a material that reduces the current quality. The field of the conductive film is very large (TMAH crystal - ITO about 1.93V'. The pattern of the aluminum film is transparent. The interface of the transparent film 1378509 produces an insulating layer of alumina, which produces corrosive liquid, which is produced along the aluminum. When the pinhole of the alloy film or the interface of the granulated transparent conductive film is passed through, the galvanic corrosion occurs at the interface, and the blackening of various non-oxide transparent conductive films occurs, resulting in fine patterns such as fine pixels and broken lines. The formation is poor, the contact resistance of the aluminum alloy film and oxidation increases, and the display caused by it (the point, however, the method of interposing the barrier metal layer, there are problems such as an increase in complicated production costs. Here, the review can be omitted. In addition, it is possible to make contact with the transparent pixel electrode "direct contact technology". The contact resistance of the aluminum alloy film and the transparent pixel electrode in the manner of obtaining a display device with high display quality is better. Also, as described in the invention of the present invention, the method of the proposed document 4, as a related direct contact technique, the aluminum alloy film having the reflective electrode is directly contacted on the oxygen film. The display device of the structure is a target. The patent material includes at least one aluminum alloy film wiring material selected from the group consisting of Au, Ag, Zn, Ge, Sm, and Bi in an atomic percentage of 0 to 6 atomic percent. A precipitate of a conductive element is formed at the interface between the alloy film alloy film and the transparent pixel electrode, and the contact resistance of the insulating material such as alumina is suppressed, and the addition amount of the alloy element is as follows: TMA is dissolved in water and invades to oxygen. Electrochemical corrosion (good conditions, such as blackening, wiring transparent conductive film is bright), etc. The manufacturing process becomes aluminum alloy film directly in direct contact technology, requiring low electrode material, heat resistance is described in the patent although not In the case of a transparent conductive material 4, which reveals Cu, Ni, and Sr' alloying elements, the alloy containing the alloy is born, so that the resistivity of the aluminum alloy itself can be within the above range of -9 - 1378509. The suppression is low. In addition, when the alloy element of at least one of Nd, Y, Fe, and C is further added to the aluminum alloy film, hillocks can be suppressed. The generation of the nodule) increases the heat resistance. The precipitate of the alloying element is formed on the substrate by an aluminum alloy film by sputtering or the like, and is preferably 150-400 ° C (preferably It is obtained by heating (annealing) for a period of 15 minutes to 1 hour. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-144826 [Patent Document 2] Japanese Patent Laid-Open No. 2005- 9 1 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-1961 72 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2004- 2 1606 It is an object of the invention to provide a display device having a structure in which an aluminum alloy film for a reflective electrode is directly connected to an oxide transparent conductive film, which is less likely to cause corrosion in an alkaline developing solution such as a TMAH aqueous solution, and can effectively prevent an aluminum-based alloy film. A method of manufacturing a corrosion display device. [Means for Solving the Problem] The present invention relates to a method of manufacturing a display device having a structure in which an aluminum alloy film for a reflective electrode is directly connected to an oxide transparent conductive film, and a method of manufacturing the display device. The method includes a first step of forming the oxide transparent conductive film on a substrate, a second step of forming the aluminum alloy film on the -10- 1378509 oxide transparent conductive film, and heating the aluminum alloy film 3 steps; the aluminum alloy film is composed of at least one of nickel and cobalt containing 0.1 to 4 atomic percent, and the total amount of at least one element selected by the group X is 0.1 to 2 atomic percent of aluminum_(nickel/cobalt) _X alloy, the above X is La, Mg, Cr, Mn, Ru, Rh, Pt, Pd, Ir, Ce, Pr, Gd, Tb, Dy, Nd ' Ti ' Zr, Nb, Mo, Hf, Ta And W, Y, Fe, Sm, Eu, Ho, Er, Tm, Yb, and Lu, depending on at least one of the nickel content and the cobalt content of the aforementioned aluminum-(nickel/cobalt)-x alloy film, The substrate temperature in the second step and the heating temperature in the third step are controlled. In a preferred embodiment, the aluminum alloy film contains at least one of 0.5 to 4 atom% of nickel and cobalt. In a preferred embodiment, the aluminum alloy film contains 0.5 to 4 atomic percent of nickel. In a preferred embodiment, the temperature of the substrate of the second step and the heating temperature of the third step are based on the nickel content (atomic percentage, [Ni]) of the aluminum alloy film as follows (1) to (1) 3) The ground is controlled. (1) When the substrate is not heated in the second step, the heating temperature in the third step is controlled to be increased to 200 ° at a temperature of 50 ° C or lower which is set in accordance with a ( 4-[Ni]). (2) In the temperature range of C (2) When the temperature of the substrate is controlled to be 1 〇〇 ° C or more and less than 150 ° C in the second step, the heating temperature of the third step is controlled to correspond to a (4). -[Ni]) is set to 100T: The following temperature is added in the temperature range of -11 - 1378509 to 100 °C. (3) When the temperature of the substrate is controlled to 150 ° C or higher and less than 250 ° C in the second step, the heating temperature in the third step is controlled in accordance with a (4-[Ni]). 10 (the temperature below TC is added to a temperature range of 100 ° C. In a preferred embodiment, the Al-(Ni/Co ) -X alloy film contains 0.1 to 4 atomic percent of nickel and cobalt. At least one of, and at least one of 0.1 to 2 atomic percent of cerium and ammonium. In a preferred embodiment, the aforementioned Al-(Ni/Co)-X alloy film further contains 0.1 to 2 atomic percent of Z (Z) It is at least one element selected from the group consisting of Ge, Cu, and Si. In a preferred embodiment, the Al-(Ni/Co)-X alloy film contains 0.1 to 4 atomic percent of nickel and cobalt. At least one of, and at least one of 0.1 to 2 atomic percent of lanthanum (La) and yttrium (Nd), and at least one of 0.1 to 2 atomic percent of yttrium (Ge) and copper (Cu). Preferably, in the patterning of the aluminum alloy film, it is preferred to use an aqueous solution of tetramethylammonium hydroxide (TMAH). Further, the manufacturing method of the present invention is preferred. The oxide transparent conductive film is indium tin oxide (ITO) or indium zinc oxide (IZO). [Effects of the Invention] According to the present invention, the reflective electrode can be appropriately controlled in accordance with the nickel content and the cobalt content contained in the aluminum alloy film. The thermal history of the aluminum alloy film (in detail, the substrate temperature at the time of film formation and the heating temperature after film formation), so that it is suppressed even when immersed in an alkaline developing solution such as ΤΜAH aqueous solution in the case of Fig. -12-1378509 The corrosion resistance of the aluminum alloy film can reduce the contact resistance between the oxide transparent conductive film and the aluminum alloy film. [Embodiment] The inventors of the present invention have an aluminum alloy for directly connecting a reflective electrode to an oxide transparent conductive film. In the case of a patterned aluminum alloy film, when an alkaline developing solution represented by a TMAH aqueous solution or the like is used, corrosion of an aluminum alloy (electrochemical corrosion) is prevented, and the review is repeated. In view of the nickel content of the aluminum alloy film, the method of controlling the substrate temperature at the time of film formation of the aluminum alloy film and the heating temperature after the film formation of the aluminum alloy is appropriately controlled, in detail, The present invention can be achieved by controlling the heating temperature after film formation in consideration of the nickel content in the aluminum alloy film, and considering the relationship with the substrate temperature at the time of film formation, thereby achieving the desired object. For the aluminum alloy film, cobalt may be used instead of nickel, and it is also recognized that cobalt has the same effect as nickel. Nickel and cobalt may be used alone. That is, the aluminum alloy film contains only cobalt. In the case of the case where the aluminum content of the aluminum alloy film contains nickel and cobalt, the substrate temperature at the time of film formation of the aluminum alloy film and the heating temperature after the film formation of the aluminum alloy are appropriately controlled depending on the content of bismuth and the content of cobalt. Just fine. Further, it has been found that the method of the present invention is further characterized in that the alloy film of the present invention further contains a Z group of at least 1 atomic percent (Z group is at least one selected from the group consisting of Ge, Cu, and Si). The occasion can also be applied. -13- 1378509 Hereinafter, an alloy containing nickel and/or cobalt and at least one of the x groups is referred to as an Al-(Ni/Co)-X alloy. Further, the above-mentioned αι·(Ni/Co)-X alloy is referred to as an Al-(Ni/Co)-X-Z alloy in which at least one type of bismuth group is further included. Further, the respective amounts of nickel, cobalt, and Z group in the aluminum alloy film are represented by [Ni], [Co], and [Z]. [ζ] means that the Z group alone means a single amount, and when two or more Z group elements are contained, it means a total amount. Hereinafter, the production method of the present invention will be described in detail. In the following, for the convenience of explanation, the aluminum alloy film used in the present invention is classified into (i) a case where an Al-(Ni/Co)-X alloy film is used' and (ii) an Al-(Ni/Co) is used. The case of the -xz alloy film will be described. (i) When an Al-(Ni/Co)-X alloy film is used, the manufacturing method of the present invention is a display device having a structure in which an aluminum alloy film for a reflective electrode is directly connected to an oxide transparent conductive film The first step of forming the oxide transparent conductive film on a substrate, the second step of forming the aluminum alloy film on the oxide transparent conductive film, and the third step of heating the aluminum alloy film. The aluminum alloy film contains aluminum and/or cobalt of 4 atomic percent, and aluminum-(nickel/cobalt)-X alloy of at least one element selected from the group X in a total amount of 0.1 to 2 atomic percent. Composition, X is composed of La, Mg, Cr, Mn, Ru, Rh, Pt, Pd, Ir, Ce, Pr, Gd, Tb, Dy, Nd, Ti, Zr, Nb, Mo, Hf, Ta, W, Y , Fe, Sm, Eu, Ho, Er, Tm, 丫1?, and 1^11. -14- 1378509 Next, the characteristic part of the present invention controls the substrate temperature of the second step and the third step in response to the nickel content and/or the cobalt content of the aluminum-(nickel/cobalt)-X alloy film. Heating Temperature First, the above-described characteristic portions will be described. As described above, in the present invention, as a factor to be considered for preventing electrochemical uranium (alkaline corrosion resistance), the temperature of the substrate in the second step (that is, the film formation of the aluminum alloy film) may be mentioned. The substrate temperature), the heating temperature of the third step (that is, the heating temperature after the aluminum alloy is formed), and the nickel content ([Ni]) and/or the cobalt content ([Co]) in the aluminum alloy film. Here, the nickel content and the cobalt content are cited because these elements should all be combined with aluminum to form a fine intermetallic compound which helps prevent electrochemical corrosion. By the generation of the fine intermetallic compound, the number of pinholes or the like penetrating through the aluminum alloy film is reduced, and as a result, the alkali corrosion resistance is improved. Further, by producing a fine intermetallic compound at the interface which contributes to prevention of electrochemical corrosion, the contact resistance between the oxide transparent conductive film and the aluminum alloy film is also suppressed to be low. The role of these elements will be explained in detail later. Specifically, as long as the content of nickel and/or cobalt in the aluminum alloy film (in the case where it is contained alone is a single amount and the total amount is contained in both cases), the temperature of the substrate and the subsequent heating temperature are as follows ( 1) ~ (3) can be controlled as described. (1) When the substrate is not heated in the second step, the heating temperature in the third step is controlled to 50° set in accordance with <x{4-([Ni] + [Co]) } The temperature below C is added to the temperature range of 200 °C. (2) In the second step, the temperature of the substrate is controlled to be 〇 (when TC is less than 150 ° C on -15-1378509), the heating temperature of the third step is controlled to be in accordance with a{4-( [Ni] + [Co]) } The temperature below i〇〇°c is set to a temperature range of 100° C. (3) The temperature of the substrate is controlled to be less than i50°c or more in the second step. In the case of 250 ° C, the heating temperature in the third step is controlled to be increased to 100 ° below the temperature set in accordance with a {4-([Ni] + [Co]) }. For example, in the case where the aluminum alloy film contains only nickel (that is, in the case of the A1-Ni-X alloy film), the temperature of the substrate and the subsequent heating temperature are as follows (1 A )~ (3A) The control may be performed as described above. (1A) When the substrate is not heated in the second step, the heating temperature in the third step is controlled in accordance with <x(4-[Ni]) The set temperature of 50 ° C or lower is added to a temperature range of 200 ° C. (2A) When the temperature of the substrate is controlled to 100 ° C or more and 150 ° C or less in the second step, the third step is performed. Heating temperature Controlling the temperature below 100 ° C set to a (4-[Ni]) is added to a temperature range of 10 (TC). (3A) The temperature of the substrate is controlled at 150 ° in the second step described above. When C is less than 250 ° C, the heating temperature in the third step is controlled to be within a temperature range of 100 ° C or lower set to 100 ° C depending on a (4-[Ni]). In the above, (1) to (3), the temperature of the substrate is set to a temperature lower than the room temperature (about 25 ° C) as low as the above (1), and the heating temperature after the formation of the aluminum alloy film is formed. When the film temperature is set to a higher temperature of about 250 ° C as in the above (3), the film can be set to a higher temperature, and the heating temperature after film formation can be set to The setting (adjustment) of the substrate temperature and the heating temperature can be set in consideration of the nickel content contained in the aluminum alloy film. The same applies to the above (1A) to (1C). Here, the substrate temperature is classified as The three types of the above (1) to (3) are because of the increase in the temperature of the substrate (on The manufacturing method (adjustment means) of the present invention for controlling the degree of decrease (decreased) of the heating temperature after film formation) can be roughly classified into the above three forms according to the basic experiment of the inventors of the present invention. The "substrate temperature" means the temperature of the entire substrate, that is, when the substrate temperature is controlled to 20 (TC), the temperature of the entire substrate is 20 ° C or higher, and is maintained at 200 during the film formation step. t can be. In addition, 'the requirement of 'a{4-([Ni] + [Co]) }" in the above (1) to (3) is a simple way to express the substrate temperature and heating temperature for convenience (considering The aluminum content ([Ni]) and/or cobalt content ([Co]) contained in the aluminum alloy film is controlled and adjusted. The coefficient a ' in the above-mentioned requirements can be arbitrarily adjusted depending on the substrate temperature or the heating temperature, even the composition of the aluminum alloy film to be used and the like. Further, "4" in the above-mentioned requirements means an upper limit (4 atomic percent) of the amount of nickel and/or cobalt which may be contained in the above aluminum alloy film, and in the range of 4 atomic percent, it means that it may be in the range of 4 atomic percent. Control the amount of these elements internally. In reality, how to control better is based on the creative ability of the industry. If you are familiar with the art of -17-1378509, you can refer to the results of the examples described later, considering the direct connection of oxide transparent conductive film and aluminum. The degree of contact resistance or alkali corrosion resistance of the alloy film is determined as appropriate. Hereinafter, the manufacturing method of the present invention will be described in more detail with reference to Figs. 10 to 12 . (Figs. 10 to 12) Figs. 10 to 12 are the results of the examples described later, and the relationship between the nickel content and the heating temperature at the respective substrate temperatures specified in the above (1) to (3) is examined, and these pairs are investigated. The effect of alkali corrosion resistance. Here, an aluminum-X atomic percentage of nickel-0.35 atomic percent of a ruthenium alloy film is used, and the nickel content (X) is in the range of 0 to 3 atom% as shown in Figs. Fig. 10 is a result of forming a film at a substrate temperature of room temperature [corresponding to the above (1)], and Fig. 11 is a result of forming a film at a substrate temperature of 100 ° C [corresponding to the above (2)], Fig. 0 is a result of forming a film when the substrate temperature is further increased to 150 ° C and 25 ° C [corresponding to the above (3)]. In the figure, 〇 means excellent alkali corrosion resistance, and ▲ means poor alkali corrosion resistance. The details of the evaluation method are detailed later. In comparison with Figs. 10 to 12, it is understood that when the substrate temperature is low, if the heating temperature is not increased, alkaline corrosion cannot be effectively prevented. However, when the substrate temperature is high, even if the heating temperature is lowered, alkaline corrosion can be suppressed. Further, it can be seen that the substrate temperature and the heating temperature adjustment width (for example, when the substrate temperature is raised, the increase in the substrate temperature and the decrease in the heating temperature when the heating temperature is lowered) are determined by the nickel content in the aluminum alloy film. - 1378509. For example, when the nickel content in the aluminum alloy film is 2 atomic percent, when the substrate temperature is room temperature, the heating temperature is preferably controlled at 250 ° C or higher, but the substrate temperature is controlled at iOOt. At the time, the preferred lower limit of the heating temperature can be lowered, and the alkali corrosion resistance can be improved by heating to substantially 150 ° C or more. Further, when the substrate temperature is controlled to 15 0 to 250 ° C, the preferred lower limit of the heating temperature can be further lowered, and as long as it is heated to 10 (TC or higher), good alkali corrosion resistance can be obtained. As described above, the present invention does not control the heating temperature after film formation to be uniform as in the above-described Patent Document 4, and the technical idea is to adopt a relationship between the temperature of the substrate at the time of film formation and the nickel content in the aluminum alloy film. The above-mentioned Patent Document 4 is different from the present invention in that the present invention differs in the configuration of the display device, but the direct contact technique of heating after forming the aluminum alloy film is common to the present invention. Patent Document 4 does not have any consideration for the substrate temperature at the time of film formation. The idea of controlling the heating temperature after film formation by the relationship with the substrate temperature, and the idea of controlling the heating temperature or the substrate temperature without considering the nickel content. And the like is different from the present invention. Further, FIGS. 10 to 12 show the results of using an aluminum-nickel-niobium alloy film as an aluminum alloy film, but when cobalt is used instead of nickel, In other words, when an aluminum-cobalt-niobium alloy film was used, the same tendency as described above was confirmed by experiments. In addition, when nickel and cobalt were used instead of nickel, that is, aluminum-(nickel+cobalt)_χ-19 was used. - 1378509 In the case of a gold film, it was confirmed by experiments that the same results as described above were obtained. Further, the upper limit of the heating temperature is not particularly limited from the viewpoint of alkali corrosion resistance, but if it is too high, it will be in the aluminum alloy film. A hillock or the like is produced, so that it is preferably 350 ° C or less, more preferably 300 ° C or less. Specifically, the aforementioned heat treatment is preferably performed under a vacuum atmosphere or an inactive environment. (For example, in a nitrogen atmosphere), the specific heating conditions of the respective substrate temperatures of the above (1) to (3) are as described in the following (I) to (melon). Actually, the aluminum alloy film is applied. In the case of the nickel content and/or the cobalt content (0.5 to 4 atomic percent), the heating temperature may be appropriately adjusted. (I) When the heating temperature is room temperature as described in the above (1), the preferred heating temperature is about 200~25 0 °C, the preferred heating time is about 30~60 minutes (Π) When the heating temperature is 100 ° C or more and 150 ° C or less as described in the above (2), the heating temperature is preferably about 100 to 200 ° C, and the preferred heating time is about 30 to 60 minutes. (Dish) If the heating temperature is 150 ° C or higher and 250 ° C or less as described in the above (3), the heating temperature is preferably about 1 〇〇 to 200 ° C, and the preferred heating time is about 30. ~60 minutes. The details of the mechanism for preventing the alkaline corrosion of the aluminum alloy film according to the method of the present invention are not clear, and it is inferred that the aluminum, and the fine intermetallic compound of nickel and/or cobalt are aggregated by heating. At the interface between the oxide transparent conductive film such as the IT0 film and the aluminum alloy film, the concentration of nickel which is small at the interface ionization tendency -20 - 1378509 is increased, so the electrode potential of the aluminum alloy film is shifted to the positive side, so that ITO is bonded The contact potential difference of the oxide transparent conductive film such as a film is reduced. As a result, electrochemical etching due to a developing solution or an etching solution does not easily occur when an etching method is used. In particular, according to the experiments of the inventors of the present invention, it is possible to infer the generation of the above-mentioned "aluminum, a fine intermetallic compound of nickel and/or cobalt" which contributes to prevention of electrochemical corrosion, which is affected not only by the heating temperature after film formation. It is also affected by the substrate temperature at the time of film formation. According to the production method of the present invention, the electrode potential difference between the aluminum alloy film and the oxide transparent conductive film can be substantially suppressed to 1.55 V or less, preferably to 1.5 V or less. For reference, the relationship between the immersion time and the immersion potential when immersed in an aqueous TMAH solution is shown in Fig. 3. Here, an aluminum alloy film of aluminum-2 atomic percent nickel - 0.35 atomic percent is used, so that the substrate temperature at the time of film formation is from room temperature - the sample without heating, and the substrate temperature at the time of film formation is from room temperature - Two kinds of samples, such as a sample heated at 200 °C. • As can be seen from Fig. 3, the sample subjected to heating after film formation has an immersion potential of about 1 00 mV (0.1 V) after immersion (about 0.1 min) compared with the sample which is not heated after film formation. ), and this state is maintained until about 0.7 minutes after immersion. This result suggests that the heating can be carried out for a long period of time, and the difference between the immersion potential of the ITO film and the ITO film can be suppressed to a small extent, and the electrochemical corrosion can be effectively suppressed. The aluminum alloy film used in the present invention contains 0.1 to 4 atomic percent of nickel and/or cobalt, and a total amount of 0.1 to 2 atomic percent of aluminum selected from the group X of at least one element - (nickel/cobalt -X alloy, -21 - 1378509 The above X system is composed of La, Mg, Cr, Μη, Ru, Rh, Pt, Pd' Ir, Ce, Pr, Gd, Tb, Dy, Nd, Ti, Zr, Nb , Mo, Hf, Ta, W, Y, Fe, Sm, Eu, Ho' Er, Tm, Yb, and Lu. Here, in addition to the effect of reducing the contact resistance with the oxide transparent conductive film, nickel and cobalt also have an effect of improving alkali corrosion resistance (refer to Examples described later). The reason for reducing the contact resistance with the oxide transparent conductive film by adding nickel and/or cobalt to the aluminum alloy film is not clear in detail, but it should be at the interface between the aluminum alloy film and the oxide transparent conductive film (contact interface). A nickel- and/or cobalt-containing precipitate or a nickel and/or cobalt-concentrated layer that prevents diffusion of aluminum is formed. It can be contained in the aluminum alloy film alone or in combination with either nickel or nickel. The content of (nickel/cobalt) in the aluminum-(nickel/cobalt)-X alloy film (in the case of a single amount, which is a single amount, and the total amount of both of them), in order to effectively reduce the contact resistance and improve the contact resistance The effect of alkali corrosion resistance is necessary to reach 0.1 atomic percent or more. On the other hand, as shown in Fig. 4 which will be described later, when the content of (nickel/cobalt) exceeds 4 atom%, the reflectance and specific resistance of the aluminum alloy film are increased, and it becomes impossible to be practically used. The (nickel/cobalt) content in the aluminum alloy film is set to be 0.1 atomic percent or more (preferably 0 to 5 atom% or more, more preferably 1 atomic percent or more) of '4 atomic percent or less (preferably 3 atomic percent) the following). In addition, the elements of the X group (especially yttrium and yttrium) are elements that contribute to the improvement of heat resistance of the aluminum alloy film (elements that improve heat resistance). In particular, by including at least one of the X groups, it is possible to effectively prevent the occurrence of hillocks (nodule-like protrusions) on the surface of the aluminum alloy film when -22-1378509 is heated. These elements may be added alone or in combination of two or more. When two or more elements are contained, the total amount of each element may be controlled so as to satisfy the following range. In order to sufficiently exert such an effect of improving heat resistance, the content of the element belonging to the X group is 0.1 atom% or more, preferably 0.2 atom% or more. However, if the content of these elements is excessive, the electrical resistivity of the octa-(Ni/Co)-X alloy film itself increases. Here, the content of these elements is preferably 2 atomic percent or less, preferably 8% by weight or less. In view of characteristics such as heat resistance and electrical resistivity, elements belonging to the X group are preferably La, Nd, Gd, Tb and Μη, particularly preferably lanthanum (La) and ammonium (Nd). In the present invention, the remaining components of the Al-(Ni/Co)-X alloy film are substantially composed of aluminum and unavoidable impurities. (ii) When an Al-(Ni/Co)-X-Z alloy film is used Next, a manufacturing method in which an Al-(Ni/Co)-X-Z alloy film is used as the aluminum alloy film will be described. The aluminum alloy film is the A1-(Ni/Co)-X alloy film of the above (i) and further contains a z group element of 0. 2 atomic percent (in the group consisting of Ge, Cu, and Si). At least one element selected), whereby the contact resistance can be further reduced and the heat resistance can be further improved. Among the aforementioned Z, from the viewpoint of improving the contact resistance with the transparent conductive film and improving the alkali resistance, it is preferably bismuth (Ge) and copper (-23-1378509).

Cu). The alkali resistance is improved by the addition of bismuth and copper, and is shown in Fig. 13 to Fig. 15 (an example of adding copper) and Fig. 16 to Fig. 18 (an example of adding bismuth) which will be described later. In these figures, in the case of 〇 (good alkali corrosion resistance), the contact resistance was 1 500 Q/cm 2 or less, and it was suppressed to be low (not shown). Therefore, in the present invention, as the Al-(Ni/Co)-XZ alloy layer, it is preferable to use 0.1 to 2 atomic percent of nickel and/or cobalt, and 0.1 to 2 atomic percent of La and/or Nd, and 0.1 to 2 atomic percent of the alloy layer of Ge and/or Cu. When the content of Z is less than 0.1 atomic percent, the above effects cannot be effectively exerted. On the other hand, when the content of Z described above exceeds 2 atom%, the above-mentioned effects are enhanced, and a decrease in reflectance or an increase in resistivity is also caused. The content of Z is preferably 0.2 atomic percent or more and 0.8 atomic percent or less. Each element such as Ge, Cu, and Si belonging to Z may be added alone or in combination of two. When two or more elements are added, the total content of each element may be controlled so as to satisfy the above range. The design policy (basic consideration) of the manufacturing method using the above-described Al-(Ni/Co)-XZ alloy film is the same when using the aluminum alloy film of the above (i), as long as it is in the aluminum alloy film The nickel content ([Ni] ) and/or cobalt content ([Co]) ' and the element content ([z]) of the Z group can appropriately control the substrate temperature and the heating temperature thereafter. Specifically, when the substrate temperature is set to a room temperature lower than the above (1) (about 25 (in the vicinity), when the film formation is performed, the heating temperature after the formation of the aluminum alloy film can be set to be higher] When the substrate temperature is set to a high temperature of about 250 ° C as described above, the film formation temperature can be set to be lower after the film formation - 24 - 1378509 heating temperature, and the substrate temperature and heating temperature are set. (Adjustment) It can be set in consideration of the (nickel/cobalt) content and the amount of Z group contained in the aluminum alloy film. When the aluminum alloy film is used, it is used as a means for preventing electrochemical corrosion (alkaline corrosion resistance). Factors to be considered, in addition to the above-mentioned nickel and cobalt contents, the elements of the Z group are also mentioned, because the Z group elements should also be combined with aluminum as described above to form a fine layer to help prevent electrochemical corrosion. In the intermetallic compound, the pinholes and the like which penetrate the aluminum alloy film are reduced by the generation of the fine intermetallic compound, and as a result, the alkali corrosion resistance is improved. The contact resistance of the fine intermetallic compound, the oxide transparent conductive film and the aluminum alloy film is also suppressed to be low. Thus, when an Al-(Ni/Co)-XZ alloy film containing a Z group element is used, the most It is preferable to set (adjust) the substrate temperature and the heating temperature, and consider not only the nickel content and/or the cobalt content in the aluminum alloy film but also the amount of the elements of the Z group (individual amount or total amount). 13 to 15 (containing copper as the Z group element) and FIG. 16 to FIG. 18 (containing yttrium as the Z group element) are explained in detail. Again, as in FIGS. 10 to 12, in the figures, 〇 also means alkali resistance. Excellent uranium, ▲ indicates poor alkali corrosion resistance (Refer to Figure 13 to Figure 15) First, refer to Figure 13 to Figure 15. Here, aluminum-X atomic percent nickel - 0.35 atomic percent 镧 - 0.5 is used. Atomic percentage copper alloy film [nickel contains -25 - 1378509 (x) as shown in Fig. 13 to Fig. 15 in the range of 0 to 3 atomic percent], and is arranged in the above (1) to (3) The relationship between the nickel content and the heating temperature at each substrate temperature, investigate these resistance to alkaline corrosion Fig. 13 shows the result when the substrate temperature is formed at room temperature [corresponding to the above (1)], and Fig. 14 is a result of increasing the substrate temperature to 10 (the result of TC film formation [equivalent In the above (2)], FIG. 15 is a result of forming a film when the substrate temperature is further increased to 150 ° C and 250 ° C [corresponding to the above (3)]. In order to show the effect of adding copper, these FIG. 13 Fig. 14 and Fig. 15 ' together with the results (▲, 〇) when the aluminum alloy film is used, the results (▲, 〇) of the above-mentioned Fig. 10, Fig. 11, and Fig. 12 (both without copper) are described. Fig. 13 to Fig. 15 show the case where the two are not overlapped, and the same nickel content, the right side of the ▲, the lanthanum is added to the copper, the left side of the ▲, the lanthanum is not added with copper. Further, in a way that makes it easier to distinguish the difference between the two, the size of the drawn mark is changed, ▲, the case where the larger size is added is the case of adding copper ▲, and the case where the size is smaller is the case where copper is not added. Further, in FIG. 14 and FIG. 15', as a result of not adding copper, a result of adding a nickel content of 1 atomic percent and a case of adding copper, a result of adding a nickel content of 1 atomic percent * from FIG. 13 to FIG. 15 In addition, when the aluminum alloy film further contains a Z-group copper Al-Ni-La-Cu alloy film, the same tendency as in the case of using the above-described Al-(Wi/C〇)-La alloy film is also known. That is, it is understood that when the substrate temperature is low, if the heating temperature is not increased, the alkaline corrosion can not be effectively prevented. However, when the substrate temperature is high, the temperature can be suppressed even if the heating temperature is lowered. Moreover, it can be seen that the substrate temperature and the heating temperature adjustment range -26 - 1378509 (for example, when the substrate temperature is raised, the increase in the substrate temperature when the heating temperature is lowered and the heating temperature decrease) is determined by the nickel content in the aluminum alloy film. Or the copper content is determined. Further, as a result of comparing the addition of copper with the addition of copper, it is understood that the addition of copper improves the alkali corrosion resistance. Therefore, when the nickel content is the same as the substrate temperature, the lower limit of the heating temperature can be further lowered. In detail, first, in Fig. 13 (substrate temperature = room temperature), the case where the nickel content in the aluminum alloy film is 2 atomic percent is examined. When the substrate temperature is room temperature, when an alloy film containing copper-free aluminum-2 atomic percent nickel-0.35 atomic percent ruthenium is used, the heating temperature is preferably controlled to be substantially 250 ° C or higher, but aluminum-2 containing copper is used. When an alloy film of atomic percentage nickel - 0.35 atomic percent 镧 - 0.5 atomic percent copper is used, the lower limit of the heating temperature can be lowered, and the alkali corrosion resistance can be improved by heating only to 150 ° C or more. The same tendency is also seen in the case where the nickel content is 3 atom%, and the case where the nickel content is 1 atomic percent. Therefore, when the substrate temperature is room temperature, when a copper-containing aluminum alloy film is used, a lower limit which can lower the heating temperature is actually confirmed as compared with the aluminum alloy film not containing copper. Fig. 13 shows the results when the substrate temperature is room temperature, and the same tendency is also seen in Fig. 14 (substrate temperature = 1 〇〇 ° C) for changing the substrate temperature and Fig. 15 (substrate temperature = 150) t and 2 50 °C). From the above results, it can be inferred that the adjustment range of the substrate temperature and the heating temperature is not only affected by the nickel content in the aluminum alloy film, but also the copper content is affected -27-1378509 (refer to FIG. 16 to FIG. 18). Next, referring to FIG. 16 to FIG. 18 (as a group Z element containing 锗). Here, an alloy film of aluminum-X atomic percentage nickel-0.2 atomic percent atomic percent yttrium is used [nickel content (X) as shown in FIGS. 16 to 18 in the range of 0 to 1 atomic percent, nickel = 0.2 atomic percent, 0 The percentage of the sub-portion, the atomic percentage of 1 atom%, and the relationship between the nickel content and the heating temperature at the respective substrate temperatures (1) to (3), and the influence of the alkali corrosion resistance. Fig. 16 is a result of forming a substrate at a film temperature [corresponding to the above (1)], and Fig. 17 is a substrate.

Increasingly, it is a result of the film formation of TC (corresponding to the above (2)], and the result of film formation is further increased to 150 °C and 250 °C [corresponding to the above (3)]. The results of the addition of copper are shown in Fig. 16, Fig. 17, and β (all containing 锗), together with the results of the above-mentioned Fig. 10, Fig. 11, and Fig. 12, but the cerium content is 0.35 atomic percent) (▲, In Fig. 16 to Fig. 18, the drawing is described in the horizontal direction of the same nickel content, the right side of the ▲, the side of the 〇 锗 added 锗, the 〇 system is not added 锗. It is easier to distinguish the two ways, change the size of the drawn mark, ▲, the case of the larger size of the 锗, ▲, 〇, the smaller size is not added 锗. In addition, 16, in addition to the drawing of Figure 1 Outside the 'additional nickel content is 〇2 original ratio, 0.5 atomic percent of the result without adding yttrium, and the first one shown in the 1-0.5 shows the room temperature Β 18 when the graph 18 ( Uniform) Move, the left difference is added to the picture of Baiyingzhi -28- 1378509 when adding 锗. Figure 17, in addition to the result of adding a nickel content of 0.2 atomic percent, 1 atomic percent in Figure 11 and the corresponding addition of yttrium. In addition to the plot of Figure 12, the additional nickel content is 〇. 2 atomic percent. In the case of the percentage, there is no result of adding ruthenium, and the corresponding addition is added. Further, in Fig. 16 to Fig. 18, only the result of the nickel content being 〇~1 is described. From Fig. 16 to Fig. 18, it is understood that the aluminum alloy film is further included. When the Al-Ni-La-Ge alloy film is used, it has almost the same tendency as when the above-mentioned (no ruthenium) alloy film is used. That is, when the temperature is low, the heating temperature is not corroded if it is not increased, but on the substrate. When the temperature is high, the heating temperature suppresses alkaline corrosion. Moreover, it is known that the substrate temperature and the heating range are determined depending on the nickel content or the niobium content. Moreover, it is known that the addition and the addition of antimony are combined to improve the addition. Alkaline corrosion resistance, so in the case of nickel content and the same, the lower limit of the heating temperature can be more effective in reducing the enthalpy, can not be organized into a uniform law, but the content is about 1 When the low concentration is below the sub-percentage, it is remarkable. First, in the case where the substrate temperature is 1 atomic percent in the substrate temperature = room temperature alloy film, when the substrate temperature is room temperature, the use of ruthenium-free is used. When the aluminum alloy is an alloy film of 0.2 atomic percent bismuth, the alkali corrosion resistance cannot be obtained without the heating temperature °C, and it is also added without the addition of 锗1 8 ^ In addition to the graph ratio, 1 As a result of the atomic error, the atomic percentage is Al-Ni-La of the Z group, and it is understood that the substrate can be effectively prevented from lowering the temperature and the temperature can be adjusted, and the substrate temperature of the crucible is relatively low. ), for aluminum inspection. It can be seen that the F percentage nickel is set at 250 when an alloy film containing -1 1378509 of aluminum-1 atomic percent nickel - 0.2 atomic percent 镧 -0.5 atomic percent 锗 is used, and the alkali corrosion resistance can be improved only by heating to 200 ° C or more. The same tendency is also observed in the case where the nickel content in the aluminum alloy film is 0.5 atomic percent, and the heating temperature is not set to 2 when an alloy film containing bismuth-free aluminum-0.5 atomic percent nickel-0.2 atomic percent ruthenium is used. Good alkali corrosion resistance can also be obtained at 50 ° C. When an alloy film containing yttrium aluminum - 0.5 atomic percent nickel - 0.2 atomic percent 镧 - 0.5 atomic percent 锗 is used, heating to 25 ° C can be improved. Alkaline corrosion resistance. Next, in the case of Fig. 17 (substrate temperature = 100 °C), the case where the nickel content in the aluminum alloy film was 1 atomic percent was examined. It can be seen that when an alloy film containing yttrium-containing aluminum-1 atomic percent nickel-0.2 atomic percent ruthenium is used at a substrate temperature of 10 Torr, the heating temperature is not set to 20 (TC cannot obtain good alkali corrosion resistance). When an alloy film containing yttrium aluminum-1 atomic percent nickel-0.2 atomic percent 镧-0.5 atomic percent 相对 is used, heating to only 15 (TC or more improves alkali corrosion resistance. The same tendency, It can also be seen that the nickel content is 0.5 atomic percent and 0.2 atomic percent, and it is understood that when the aluminum alloy film containing ruthenium is used, the lower limit of the heating temperature can be lowered as compared with the aluminum alloy film containing no ruthenium. 18 (substrate temperature = 150 ° C and 250 ° C), as in the above, when the nickel content is 1 atomic percent and 0.2 atomic percent, the effect of adding cerium is observed, and it is known that when using an aluminum alloy film containing cerium, The lower limit of the heating temperature can be lowered as compared with the aluminum alloy film containing ruthenium. Reviewing the results of the above-mentioned FIGS. 16 to 18, (1) the adjustment range of the substrate temperature and the heating temperature should not only be nickel in the aluminum alloy film. content Effect -30- 1378509, bismuth content should also have an effect, (2) 添加 addition effect, with nickel content or substrate temperature, there are some differences, generally a low concentration of nickel content of about 1 atomic percent or less, roughly The present invention is described above with respect to the features. The present invention suitably controls the substrate temperature in response to the amount of nickel and/or cobalt (including the Z group element, including the amount of Z) as described above. The heating temperature is the maximum characteristic, and the film forming step other than the above is not particularly limited. A commonly used means can be employed. That is, the first step of forming an oxide transparent conductive film on a substrate, or an oxide transparent conductive film. In the second step of forming the aluminum alloy film (excluding the substrate temperature), a conventional method may be appropriately selected. As a film forming method of the aluminum alloy film, a sputtering method using a sputtering target is exemplified. The sputtering method is to form a plasma discharge between a film to be formed and a sputtering target (target) composed of the same material, and ionize the gas and the target by plasma discharge. The method by which the conflict strikes the atoms of the target and is laminated on the substrate to form a thin film. The sputtering method is different from the vacuum evaporation method or the Arc Ion Plating method, but has the ability to form and target In particular, an aluminum alloy film formed by a sputtering method can dissolve an alloying element such as ruthenium which does not solidify in an equilibrium state, and has an advantage that it can exhibit excellent characteristics as a film, etc. However, The gist of the present invention is not limited to the above, and a method generally used for film formation of an aluminum alloy film can be suitably employed. In the present invention, the order of patterning is not particularly limited. For example, sputtering is sequentially performed on a substrate. After the oxide transparent conductive film and the aluminum alloy film -31 - 1378509 are formed, the oxide transparent conductive film and the aluminum alloy film may be patterned by a lithography method or an etching method. Alternatively, an oxide transparent conductive film is formed on the substrate, and after patterning, an aluminum alloy film is formed and patterned. In addition, the ITO film constituting the oxide transparent conductive film is in an amorphous state before being heated, and is dissolved in an etching solution for aluminum containing phosphoric acid as a main component. However, when crystallization is performed by applying heat of 200 ° C, it is used for aluminum. The etchant is selective. Therefore, an aluminum alloy film is formed after patterning the oxide transparent conductive film, and when etching is performed, it is possible to prevent the oxide transparent conductive film which has been formed from being unnecessarily etched away. However, when the uranium selectivity of aluminum is not required, an IZO film may be used as the oxide transparent conductive film. Further, the oxide transparent conductive film which is selective between the aluminum etchant and the aluminum etchant can be used without any problem. The present invention does not limit the type of the oxide transparent conductive film. [Examples] Hereinafter, the present invention will be specifically described by way of Examples. However, the present invention is not limited to the following examples, and it is a matter of course that the following is intended to be appropriately modified. All are included in the technical scope of the present invention. The first embodiment is formed on a substrate (without a glass plate having a thickness of 0.7 mm and a size of 4 inches) as an oxide transparent conductive film (transparent pixel electrode) by sputtering to form about 1 Å by mass. The ITO film of SnO (film thickness: about -32 - 1378509 5 〇 nm) was patterned by photolithography. At this time, the sputtering conditions were in an argon atmosphere at a pressure of about 3 mTorr. On the ITO film patterned as described above, a pure aluminum film and an aluminum-nickel-niobium alloy film (hereinafter referred to as "aluminum alloy film"; film thickness: 100 nm) were formed as a reflective electrode by sputtering. . The substrate temperature during sputtering is as shown in Table 1 and Table 2 below. The sputtering conditions are in an argon atmosphere. The pressure is about 2 m T 〇 rr 〇 Next, in a nitrogen atmosphere, as shown in Table 1 and Table 2. The heating temperature was heat treated for 30 minutes. Also, for comparison, a person who has not been subjected to heat treatment is also prepared. Thereafter, the aluminum alloy film was coated with a photoresist and exposed to a 2.38 mass% aqueous TMAH solution (20 ° C) for 1 minute to develop. Further, in the present embodiment, the heat treatment is carried out under a nitrogen atmosphere, but it is not limited thereto, and it can be carried out under a known environmental condition (for example, a vacuum degree S3xl (in a vacuum atmosphere of a degree of T4Pa). Alkaline corrosion resistance) The alkaline corrosion resistance of each aluminum alloy film is determined by a voltmeter by short-circuiting the electrode of the aluminum-based alloy film to be measured with the silver-silver chloride reference electrode in the TMAH aqueous solution described above. The potential difference was evaluated. For comparison, the electrode potential of the polycrystalline ITO film was also measured. In the present example, the optical microscope observation after the immersion of the TMAH aqueous solution and the observation by the electron microscope were carried out as shown in Figs. 7 to 8 which will be described later. When corrosion is observed, and the electrode potential difference of amorphous ITO is 1.55 V or less, it is evaluated as 〇 (excellent alkali corrosion resistance), and those who do not satisfy any of the above requirements are evaluated as x ( -33-1378509 alkali corrosion resistance). Inferior. (Contact resistance) Use a four-terminal method to measure aluminum using a Kelvin pattern (TEG pattern) (contact hole sizes of 20, 40, and 80 #m square) as shown in Figure 9. Contact resistance in the case where the alloy film is directly connected to the ITO film. The contact resistance is investigated by flowing a current between the aluminum alloy film and the IT 0 film and measuring the voltage drop between the ITO-aluminum alloy by other terminals. Specifically, the current I between the h-I2 in Fig. 9 can be obtained by [R^V^VO/h] by monitoring the voltage between ν and -Vz. In the examples, the contact resistance was evaluated as being low (qualified) at 150 〇n/cm 2 . In addition, the alloying element content of the aluminum-based alloy film was determined by ICP luminescence analysis (induction combined with plasma luminescence analysis). These results are shown in Tables 1 and 2. In addition, for No. 1 (pure aluminum film) and No. 19 (aluminum - 2 atomic percent nickel - 0.35 atomic percent) of Table 1, as before The results of the measured electrode potentials are shown in Table 3 » -34 1378509 mi]

No. Substrate brewing (°C) Heating temperature (0〇Ni/LaM source %) Alkaline corrosion resistance contact resistance u (u Q/cm2) 1 Room temperature 250 (pure A1) X > 3000 2 Room temperature — 3/0.35 X >3000 3 Room temperature 100 3/0.35 X > 3000 4 Room temperature 150 3/0.35 X > 3000 5 Room temperature 200 3/0.35 〇700^1500 6 Room temperature 250 3/0.35 〇7 〇〇~t2〇〇7 100一3/0.35 X >3000 8 100 100 3/0.35 〇600-1100 9 100 150 3/0.35 〇400~900 10 100 200 3/0.35 〇200^700 1t 150 — 3 /0.35 X >3000 12 150 100 3/0.35 〇5〇〇^1〇〇〇13 150 150 3/0.35 〇300-700 14 150 200 3/0.35 3/0.35 X 200~600 15 200 One >3000 Te 200 100 3/0.35 〇400~900 17 200 150 3/0.35 〇100-400 18 200 200 3/0.35 〇50-300 19 room temperature one 2/0.35 X >3000 20 room temperature 100 2/0.35 X &gt ; 3000 21 room temperature 150 2/0.35 X > 3000 22 room temperature 200 2/0.35 X > 3000 23 room temperature 250 2/0.35 〇800^1500 24 100 — 2/0*35 X >3000 25 100 100 2/0.35 X >3000 26 100 150 2/0.35 〇500-1000 27 100 200 2/0.35 〇300~800 28 150 — 2/0. 35 X >3000 29 150 100 2/0,35 〇800~1500 30 150 150 2/0.35 〇400-800 3t 150 200 2/0.35 〇100~500 32 200 one 2/0.35 X >$000 33 200 100 2/0.35 〇500~1000 34 200 150 2/0.35 〇200-500 35 200 200 2/0.35 〇50~400 -35- 1378509 [Table 2] No. Substrate stuffing (°C) Heating degree (°C) Ni/LaM formation (atomic %) Alkali corrosion resistance contact resistance u (u Q/cm2) 36 Room temperature 1/0.35 X > 3000 37 Room temperature 100 1/0.35 X > 3000 36 Room temperature 150 1/ 0.35 X > 3000 39 i temperature 200 1/0.35 X > 3000 40 room temperature 250 1/0.35 〇1000-1500 41 room temperature 250 0.5/Λ35 X >3000 42 100 —— 0.5/0.35 X >3000 43 100 100 0.5/0.35 X >3000 44 100 150 0.5/α35 X >3000 45 100 200 0.5/0.35 〇500~1000 46 150 — 0.5/0.35 X >3000 47 150 100 0.5/0.35 X >3000 4S 150 150 0.5/0.35 〇500-0000 49 150 20C □ 5/0.35 Ω 300^800 50 200 a 0.5/0.35 X >3000 51 200 100 0.5/0.35 X >3000 52 200 150 0.5/0.35 〇300-800 53 200 200 0.5/0.35 〇200-700 [Table 3] Sample potential (V) Pure A1 -1, 93 八1-2原子%1^-0.35 Original %La -1 26 ρΗΤΟ -0.19 a-rro -0.17 IZO -D.57 The results of Tables 1 and 2 can be produced by the method of the present invention. Aluminum alloy film (No. 5' 6, 8 to 10, 12 to 14, 16 to 18, 23 ' 26 ' 27 ' 29 to 31 ' 33 to 35 in Table 1 and N to · 40, 45 in Table 2 48, 49, 52, and 53) are excellent in alkali corrosion resistance, and the contact resistance of the aluminum alloy film and the ITO film is also low. Further, as is also understood from Table 3, when the Al-Ni-X-36- 1378509 gold film used in the present invention is used, the electrode potential difference from the ITO film is suppressed to be small as compared with the pure aluminum (No. 1). . For reference, an aluminum-2 atomic percent nickel-0.35 atomic percent bismuth alloy is used to make the substrate temperature to room temperature - No. 19 (comparative example) without heating, and the same alloy is used to make the substrate temperature from room temperature - The corrosion condition of No. 23 (inventive example) heated at 250 ° C is shown in Fig. 5 to Fig. 8» in detail, and Fig. 5 and Fig. 6 are for sample No. 19 of Table 1, after impregnating the TMAH aqueous solution. An optical microscope photograph and a transmission electron microscope cross-section photograph (FE-TEM, a machine of the model "HF2000" manufactured by Hitachi, Ltd.). Further, Fig. 7 and Fig. 8 are an optical microscope photograph and a transmission electron microscope cross-sectional photograph of Sample No. 23, after impregnating the TMAH aqueous solution. Further, the film composition was measured by electron-excitation X-ray analysis according to observation by a transmission electron microscope. Comparing these figures, it can be seen that the sample No. 19 which is not heated can see the corrosion caused by the TMAH immersion (refer to Figs. 5 and 6), and the specific heating No. 23 which is subjected to the specific heating is not observed to be corroded. (See Figures 7 and 8). Further, the influence of the nickel content in the aluminum alloy film on the reflectance was investigated. Specifically, an aluminum alloy having a nickel-x atomic percentage of aluminum-x·35 atomic percent (X is 1 to 5.5 atomic percent) is used, and the substrate temperature at the time of film formation is room temperature, and the heating temperature after film formation The reflectance of the film-formed sample was controlled at about 25 ° C by controlling the heating time to about 30 minutes. The reflectance was measured by using the visible/ultraviolet spectrophotometer -37- 1378509 "V-5 70" manufactured by Japan Spectrophotometer, and the spectroscopic reflectance was measured at a measurement wavelength of 1 000 to 2 50 nm. Specifically, the intensity of the reflected light of the reference mirror and the intensity of the reflected light of the sample are measured as "spectral reflectance". Fig. 4 is a view showing a change in reflection (wavelength: 850 to 250 nm) of each sample. From the viewpoint of the reflectance of 550 nm, a sample having a nickel content of 1 to 4 atom% satisfying the range of the present invention can obtain a high reflectance of about 88% to 92%, and a nickel content of 5 to 5 atoms. For samples having a percentage exceeding the scope of the present invention, the reflectance was substantially reduced to 8 4%. The present application has been described in detail with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes or modifications may be made without departing from the spirit and scope of the invention. It is within the scope of the invention. This application is based on a Japanese application filed on December 26, 2007 (Japanese Patent Application No. 2007-3 3 5 004), and a Japanese application filed on December 19, 2008 (Japanese Patent Application No. 2008-3243 74) And the presenter has incorporated this content with reference to its contents. [Industrial Applicability] The present invention relates to a method of manufacturing a display device typified by a liquid crystal display or an organic electroluminescence (EL) display. In particular, the present invention relates to a method of manufacturing a display device having a structure in which an oxide transparent conductive film and an aluminum alloy film for a reflective electrode are directly connected, and is capable of effectively preventing alkali corrosion of the aluminum alloy film during patterning. According to the present invention, it is possible to appropriately control the heat history of the aluminum alloy film of the reflective electrode in accordance with the nickel content and the cobalt content contained in the aluminum alloy film (in detail, film formation) In the case of the substrate, the temperature of the substrate and the heating temperature after the film formation are controlled, so that even if it is immersed in an alkaline developing solution such as a TMAH aqueous solution during patterning, the corrosion of the aluminum alloy film is suppressed, and the contact between the oxide transparent conductive film and the aluminum alloy film can be reduced. resistance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an exploded perspective view showing the configuration of a representative transflective liquid crystal display device. Fig. 2 is a cross-sectional view showing a typical transflective liquid crystal display device. Fig. 3 is a view showing the impregnation potential of an aluminum alloy film (aluminum-2 atomic percent nickel - 0.35 atomic percent 镧) which is formed by changing the substrate temperature at the time of sputtering. Fig. 4 is a graph showing the reflectance of a pure aluminum film and an aluminum-nickel-niobium alloy film (reflective electrode) which changes the amount of nickel (the unit of the figure is atomic percentage). Fig. 5 shows the immersion in an aqueous solution of TMAH in the examples. An optical microscope photograph of the subsequent sample No. 9 (aluminum-2 atomic percent nickel - 0.35 atomic percent ruthenium film, substrate temperature = room temperature, no heat treatment). Fig. 6 is a transmission electron micrograph of the 19th sample after the embodiment was immersed in an aqueous TMAH solution. Figure 7 is a graph showing the sample No. 23 - 39-1378509 (aluminum-2 atomic percent nickel - 0.3 5 atomic percent ruthenium film, substrate temperature = room temperature, heat treatment temperature = 2 50 ° after the embodiment was immersed in the TMAH aqueous solution). Optical microscope photo of C). Fig. 8 is a transmission electron micrograph of the sample No. 23 after the embodiment was immersed in an aqueous TMAH solution. Fig. 9 is a view showing a Kelvin pattern (TEG pattern) used for measurement of contact resistance between an aluminum alloy film and an oxide transparent conductive film (ITO film). The figure is a graph showing the influence of the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance when the substrate temperature is formed at room temperature in an aluminum-nickel-niobium alloy film. Fig. 表示 is a diagram showing the effect of the heating temperature after film formation and the amount of nickel on the resistance to alkaline uranium when the substrate is heated to 100 °C in an aluminum-nickel-bismuth alloy film. 12 series is shown in the aluminum-nickel-bismuth alloy film, when the substrate temperature is raised to 150 ° C and 250 ° C film formation, the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance Picture. Fig. 13 is a view showing the influence of the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance when the substrate temperature is formed at room temperature in an aluminum-nickel-yttrium-copper alloy film. Fig. 14 is a view showing the effect of the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance when the substrate temperature is increased to 10 ° C in an aluminum-nickel-yttrium-copper alloy film. Figure. Figure 15 is a diagram showing the aluminum-nickel-yttrium-copper alloy film, when the substrate temperature is raised to 150 ° C and 250 ° c film formation, the heating temperature after film formation and the amount of nickel-40-1378509 for alkali corrosion resistance A map of the effects of sex. Fig. 16 is a view showing the influence of the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance when the substrate temperature is formed at room temperature in an aluminum-nickel-niobium-niobium alloy film. Fig. 17 is a graph showing the effect of the heating temperature after film formation and the amount of nickel on the alkali corrosion resistance when the substrate temperature is raised to 100 °C in an aluminum-nickel-niobium-niobium alloy film. • Figure 18 shows the aluminum-nickel-niobium-niobium alloy film, which increases the substrate temperature to 15 °C and 25 (when TC is formed, the heating temperature after film formation and the amount of nickel are resistant to alkaline corrosion). Fig. [Description of main component symbols] 5: Gate wiring 7: Data wiring 1 1 : Semi-transmissive liquid crystal display device # I3 : Common electrode 1 5 · _ Counter substrate 16 : Black matrix 1 7 : Color Filter • 19: pixel electrode. 19a: transparent pixel electrode 19b: reflective electrode 21: TFT substrate 23: liquid crystal layer -41 - 1378509 41: backlight 51: barrier metal layer T: switching element (TFT) P: drawing Element area A: transmission area B: ambient light (artificial light source) C: reflection area F: light from backlight - 42

Claims (1)

1378509 X. Patent Application No. 1. A manufacturing method of a display device, comprising a method for manufacturing a structure in which an alloy film for a reflective electrode is directly connected to an oxide transparent conductive film, characterized in that it comprises: forming on a substrate a first step of the oxygen transparent conductive film, a step of forming the aluminum alloy film on the oxide transparent conductive film, and a third step of heating the aluminum alloy film; the aluminum alloy film is made of at least nickel and cobalt A total of at least one element selected from the group X and having an atomic percentage of aluminum-(nickel/cobalt)-X alloy, the former being L a, Mg, Cr, η η, R u, R h, P t, P d, I r, C e, P r , Tb, Dy, Nd, Ti, Zr, Nb, Mo, Hf, Ta, W, Y, Sm, Eu, Ho, Er, Tm, Yb, and Lu are formed, and the substrate temperature and the third step of the second step are controlled in accordance with at least one of the nickel content and the amount of the aluminum (nickel/cobalt)-X alloy film. The heating temperature of the step 2. The manufacturer of the display device as claimed in claim 1 The above aluminum alloy film contains at least one of 0.5 to 4 atomic percent of nickel and cobalt. 3. The aluminum alloy film according to the manufacturing method of the display device of claim 1 containing 0.5 to 4 atomic percent of nickel. The display device of any one of the first to third aspects of the patent application of the present invention, wherein the aluminum atom is represented by a second atom, K 1 to 2, and X, Gd Fe, and cobalt are contained in the above-mentioned, and -43-1378509. The manufacturing method, wherein the Al-(Ni/C〇)-X alloy film contains 0.1 to 4 atomic percent of at least one of nickel and cobalt, and 0.1 to 2 atomic percent of lanthanum (La) and ammonium (Nd) A method of manufacturing a display device according to any one of claims 1 to 3, wherein the A (Ni/C0) · bismuth alloy film further contains from 0.1 to 2 atomic percent Z (Z is at least one element selected from the group consisting of Ge, Cu', and Si). 6 The manufacturing method of the display device of the fifth aspect of the invention, wherein the aforementioned Ai_(Ni/C〇)-X The alloy film contains 〇·1 to 4 atomic percent of nickel and at least one of the original 'and 〇.1~2 original At least one of the percentages of steel (La) and sharp (Nd) "species' and 1.1~2 atomic percent of the error (Ge) and at least one of copper (Cu). 7. As claimed in the patent scope The manufacturing method of the display device of the first aspect, wherein the oxide transparent conductive film is an indium tin oxide (ITO) or an indium zinc oxide (IZO).