TWI492304B - A substrate to which an oxide layer is attached, and a method of manufacturing the same - Google Patents

Description

Substrate with oxide layer and method of manufacturing same

The present invention relates to a substrate with an oxide layer and a method of manufacturing the same.

A transparent conductive film typified by tin-doped indium oxide (ITO) is becoming a flat panel display (FPD, Flat Panel) or a plasma display panel (PDP). Display), and the necessary materials for electronic devices such as solar cells. A general manufacturing method of a transparent conductive film is as follows.

First, a transparent conductive film is formed on the substrate by sputtering, and then unnecessary portions are removed by patterning. There are various methods of patterning, but photolithography is often used.

However, the photolithography method has a potential problem of a large number of steps. In particular, as the size of the substrate in the FPD increases, it is a major cause of deterioration in productivity.

Further, since it is difficult to produce a large-sized photomask, the laser patterning method has been studied as a patterning method for a transparent conductive film instead of the photolithography method (see Patent Documents 1 and 2). The reason is that compared with the photolithography method, the number of steps of the laser patterning method is small, and the stability of the process is high.

Further, due to low resistance characteristics and the like, it is widely used as a potential problem in the depletion of resources of indium metal in ITO such as FPD. Therefore, the development of tin oxide and the like is being carried out in the industry as a transparent conductive film which can replace ITO (Patent Document 3).

However, since tin oxide has high durability against chemical etching, the application of the acid photolithography method is actually difficult. Therefore, the study of laser patterning is also carried out for tin oxide.

Further, a method is also known in which an oxide layer 2 is provided on a glass substrate 1, and then a laser beam is irradiated through a mask to deteriorate an irradiated portion of the object, and thereafter, by wet etching in the groove. (wet etching) The removal portion 4 is removed to obtain a desired pattern at a portion as an electrode (refer to FIG. 5).

Further, as a processing technique using a laser, there is known a method in which a dielectric mask of a dielectric multilayer film having a different refractive index is formed on a synthetic quartz substrate, in advance, a dielectric body A metal layer is formed on the upper surface of the multilayer film, and then the dielectric multilayer film and the metal layer are simultaneously etched by laser light, and then the metal layer is removed (Patent Document 4).

Further, a method of manufacturing an optoelectronic device by patterning by laser ablation is known (Patent Document 5).

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 5: Japanese Patent Special Publication 2007-533091

In the laser patterning method, the workability of the object is roughly determined by the relationship between the laser light and the object (material). Therefore, there is less room for improvement in productivity. Further, since the transparent conductive film is generally low in workability, in order to secure the processing ability of the entire step of patterning the transparent conductive film, it is necessary to take measures such as providing a laser patterning device.

Further, in the processing of the transparent conductive film, an infrared laser is often used in terms of power, stability, and the like necessary for processing. However, in the wavelength region of the infrared laser light, the processability of tin oxide is lower than that of ITO, which is a particularly significant problem.

An object of the present invention is to provide a method for producing a substrate with an oxide layer which is excellent in productivity and excellent in processing quality, and a substrate having an oxide layer.

That is, Aspect 1 of the present invention provides a method of manufacturing a substrate with a patterned oxide layer, comprising the steps of: sequentially forming an oxide layer and a metal layer exhibiting transparent conductivity on a substrate; On the outer surface side of the metal layer, the metal layer is irradiated with pulsed laser light having an energy density of 0.3 to 10 J/cm ² , a repetition frequency of 1 to 100 kHz, and a pulse width of 1 ns to 1 μs, and the irradiated portion of the pulsed laser light is irradiated. The metal layer and the oxide layer are removed; and the metal layer is removed by etching.

Aspect 2 provides a method of fabricating a substrate with an oxide layer as in Aspect 1, wherein the wavelength of the pulsed laser light is 1047 to 1064 nm.

Aspect 3 provides a method of producing a substrate having an oxide layer as in Aspect 1 or 2, wherein the area of the irradiated portion irradiated by the primary pulsed laser light is 1 mm ² or more.

Aspect 4 provides a method of manufacturing a substrate having an oxide layer as in Aspect 1, 2 or 3, wherein each time the pulsed laser light is irradiated, the irradiation site is moved once.

Aspect 5 provides a method of producing a substrate having an oxide layer as in the form 1, 2, 3 or 4, wherein the pulsed laser light is irradiated at an irradiation speed of 15,000 mm ² /s or more.

Aspect 6 provides a method of fabricating a substrate with an oxide layer as in the aspect 1, 2, 3, 4 or 5, wherein the oxide layer is tin oxide or tin-doped indium oxide.

Aspect 7 provides a method of producing a substrate having an oxide layer as in any one of Aspects 1 to 6, wherein the oxide layer has a film thickness of 10 nm to 1 μm.

Aspect 8 provides the method for producing a substrate with an oxide layer according to any one of Aspects 1 to 7, wherein the metal layer is selected from the group consisting of Ag, Al, Co, Cr, Cu, Fe, Mo, Ni, Sn And a metal composed of at least one of a group consisting of Zn and V.

Aspect 9 provides a method of producing a substrate with an oxide layer according to any one of Aspects 1 to 8, wherein the metal layer is composed of a metal of a non-magnetic body.

Aspect 10 provides a method of producing a substrate having an oxide layer as in any one of Aspects 1 to 9, wherein the metal layer has a film thickness of from 3 to 100 nm.

The aspect 11 provides a substrate to which an oxide layer is attached, which is produced by a method of producing a substrate having an oxide layer as in any one of the aspects 1 to 10.

The aspect 12 provides an electronic device which is formed by using an oxide layer of a substrate with an oxide layer as in the aspect 11 as an electrode.

In each of the above aspects, the case where the metal layer contains oxygen is included.

Further, in the above aspect, it is preferred that a pattern of 100 or more oxide layers is formed on the substrate. Further preferably, a pattern of 200 or more oxide layers is formed on the substrate. Further, when the oxide layer of the substrate with the oxide layer is used as the electrode of the display panel, the number of patterns suitable for displaying the pixels of the screen is preferably, for example, 500 to 2,000. Moreover, it is preferred to implement a short pitch corresponding to the panel of high density display. Highly detailed patterning.

In the above aspect, it is preferred that the oxide layer is composed of one or more materials selected from the group consisting of indium oxide, tin oxide, tin-doped indium oxide, zinc oxide, titanium oxide, and aluminum oxide.

In the above aspect, the film forming method is magnetic control. In the case of sputtering, it is preferred that the material of the metal film is not a magnetic body. That is, it is particularly preferable that the metal layer is composed of at least one metal selected from the group consisting of Ag, Al, Cr, Cu, Mo, Sn, and V.

Among them, even in the case of magnetic Fe, Co, or Ni, a metal layer that can be used can be formed by paying attention to the operation of the target.

Further, in the above aspect, it is preferable that the electronic device is a display panel. Further preferably, the display panel is an LCD or a PDP. Further, it is preferable that the electronic device described above is a solar battery module. In the above aspect, since the metal layer can be easily removed by wet etching or dry etching, the productivity of the entire step is not deteriorated. The present invention can be applied to various electronic devices, among which, it is particularly suitable for the production of a high-definition large-sized display panel having a large number of electrodes. The present invention is suitable, for example, for a screen having a diagonal size of 106 cm or more, or as an electrode of a screen, having 1024 or more rows on the row side and 768 or more columns on the column side. The invention is particularly suitable for the manufacture of display panels for high resolution images.

In the present invention, the productivity and processing quality of the laser patterning process of the oxide layer can be greatly improved. The invention is effective for transparent oxide layers comprising ITO or tin oxide. It is especially suitable for the patterning of tin oxide which has difficulty in etching speed. Further, damage to the oxide layer exhibiting transparent conductivity to be formed can be suppressed.

Further, the present invention can greatly improve the productivity of the substrate with the transparent conductive film for the FPD or the solar cell module, and can reduce the production cost.

In the present invention, in addition to the oxide layer of the object, a metal layer is compositely formed on the substrate. Irradiating the pulsed laser light with the composite laminated structure, and simultaneously removing the oxide layer and the metal layer of the irradiated portion without substantially causing damage to the substrate, thereby obtaining a desired processed object, that is, on the substrate A patterned oxide layer is obtained.

Generally, the metal has good laser workability as compared with the oxide. In the present invention, a metal is used as an auxiliary layer in laser patterning. It is believed that by disposing a metal layer in addition to the oxide layer, the energy absorbed by the metal layer from the pulsed laser light can be transferred to the oxide layer.

As a result, the laser processability of the oxide layer is improved. The position of the metal layer is not particularly limited, and it is preferably formed on the surface layer side in terms of easiness of removing the auxiliary layer after laser irradiation. Further, the metal layer may also form a plurality of layers of two or more layers. In this case, a metal layer may also be disposed between the oxide layer and the substrate.

1 is a schematic cross-sectional view showing a configuration of the present invention, in which a substrate 1, an oxide layer 2, a metal layer 3 functioning as an auxiliary layer, a removal portion 4, a laser light source 50, and a laser beam 51 are disclosed. And the mask 7. In this configuration, an oxide layer 2 containing tin oxide having transparent conductivity and a metal layer 3 containing a metal selected from Ag, AlCr, Mo, SnZn alloy or Sn are formed on the substrate (glass substrate) 1. . From the laser light source 50, the pulsating laser light 51 is moved once from the outer surface side of the metal layer 3, and the irradiation position is irradiated through the mask 7, and the metal layer 3 and the oxide layer 2 are removed. Thereby, the removal portion 4 is formed. Thereafter, the metal layer 3 is removed by etching to form a substrate with an oxide layer attached thereto.

Fig. 2 is a schematic plan view of the present invention in which a transparent conductive film is patterned into a line shape. The substrate with the oxide layer obtained in the above manner can be used as a transparent electrode of an LCD or a PDP. The electrode corresponding to the number of pixels of the display screen is subjected to laser patterning processing. 2(A) is a schematic plan view before laser patterning, and FIG. 2(B) is a schematic plan view after laser patterning.

Figure 3 is a flow chart showing the basic steps of a method of manufacturing a substrate with an oxide layer of the present invention.

Figure 4 is a schematic plan view of the present invention in the case of different patterning. 4(A) is a schematic plan view before patterning, and FIG. 4(B) is a schematic plan view after patterning. Figure 5 is a schematic diagram showing the steps of the prior art.

In the present invention, the material of the metal layer is preferably at least one selected from the group consisting of Ag, Al, Co, Cr, Cu, Fe, Mo, Ni, SnZn, Sn, and V. The material of the metal layer may be an alloy as long as it does not form a film, removes by laser irradiation, or obstructs etching.

In particular, it is preferably selected from the group consisting of Ag, Al, Cr, Cu, Mo, and Zn, Sn in terms of ease of formation or workability when the auxiliary layer is removed after laser irradiation. At least one material. When the auxiliary layer is removed, an etching method that removes only the metal layer without damaging the oxide layer is used. Specifically, wet etching or dry etching can be used.

In terms of uniformity or easiness of etching, etc., it is preferred to use wet etching. The chemical liquid used in the wet etching is suitable in view of the etching rate and the like in consideration of the kind of the auxiliary layer or the durability of the oxide layer to the chemical liquid.

For example, when the auxiliary layer is Ag, Al, Cu or Mo, a mixture of phosphoric acid, nitric acid, acetic acid and water is suitable. In the case of an Al, Sn, Zn, or SnZn alloy, an alkaline solution such as a sodium hydroxide solution may be used in addition to the above. When the auxiliary layer is Cr, a mixture of cerium ammonium nitrate, perchloric acid and water, or a mixture of cerium ammonium nitrate, nitric acid and water is suitable. The temperature of the chemical solution can be set to room temperature to 50 ° C, which is good in terms of productivity or management.

In the laser patterning process, by the laser irradiation, the flying matter removed from the workpiece is deposited as debris, resulting in a decrease in processing quality. In the present invention, since the metal layer is located on the surface layer, it is preferable to simultaneously remove the debris deposited on the auxiliary layer when the auxiliary layer is etched and removed. The metal layer is removed corresponding to a specific area in which the oxide layer is to be patterned. In general, from the viewpoint of workability, it is preferred to collectively remove the metal layer by using the patterned oxide layer on the substrate as a specific electrode surface of the transparent electrode.

The metal layer used as the auxiliary layer is preferably formed by sputtering in terms of film thickness or uniformity of film quality. The sputtering pressure is suitably 0.1~2 Pa. Further, the back pressure is preferably 1 × 10 ^-6 to 1 × 10 ^-2 Pa. The substrate temperature is from room temperature to 300 ° C, particularly preferably from 150 to 300 ° C.

The metal layer may contain oxygen in addition to the metal component. As described below, in the embodiment of the present invention, when an oxide layer is formed, an oxygen-containing gas atmosphere is formed by oxygen introduced from the outside or oxygen generated from the oxide target. The metal layer and the oxide layer can usually be formed by different process methods, but it is preferred to form the metal layer and the oxide layer in series using the same film forming apparatus. That is, it is particularly preferable to carry out the treatment continuously by the same process method using the same film forming apparatus.

In this case, there is a case where oxygen is contained in the metal layer. The oxygen in the metal layer is preferably 0 to 20 atom% with respect to the total composition. When the content of oxygen exceeds 20 atom%, the effect of improving the workability of the oxide is reduced when laser patterning is performed.

In order to make the oxygen in the metal layer 0 to 20 atom% with respect to the total component, a gas containing an oxygen element (for example, a mixed gas of O ₂ or CO ₂ gas and argon gas) may be used for film formation.

Preferably, the thickness of the metal layer is from 3 to 100 nm. If it is less than 3 nm, the effect of improving the workability of the oxide is reduced when laser patterning is performed. If it exceeds 100 nm, the effect of improving the workability of the oxide is rather reduced. Further, when the film thickness is too large, load is generated in the formation of the auxiliary layer and the removal of the auxiliary layer after the laser patterning, which is not preferable.

The oxide layer may also form a plurality of layers of two or more layers. For example, a base/oxide layer 1 / oxide layer 2 / metal layer, a substrate / oxide layer 1 / a metal layer / an oxide layer 2 / a metal layer can be formed.

The oxide layer exhibiting transparent conductivity is preferably at least one selected from the group consisting of indium oxide, tin oxide, zinc oxide, titanium oxide, and aluminum oxide.

Further, in terms of transparency, conductivity, durability in removing the metal layer, and the like, the oxide layer exhibiting transparent conductivity is preferably ITO or tin oxide.

The oxide layer can be formed by an electron beam evaporation method, a sputtering method, an ion plating method, or the like. In the present invention, in terms of film thickness or uniformity of film quality, a sputtering method is preferred.

The sputtering gas is preferably a mixed gas of argon gas and oxygen gas, and the oxygen concentration is preferably 0.2 to 4% by volume. The sputtering pressure is suitably 0.1~2 Pa. Further, the back pressure is preferably 1 × 10 ^-6 to 1 × 10 ^-2 Pa. It is preferred to set the substrate temperature to room temperature to 300 ° C, and particularly preferably to 150 to 300 ° C.

It is preferred that the oxide layer has a film thickness of 10 nm to 1 μm. If it is less than 10 nm, the function as an oxide layer is insufficient. When it exceeds 1 μm, it is practically difficult to remove the auxiliary layer (metal layer) and the oxide layer of the irradiated portion of the pulsed laser light in addition to the impaired transparency. .

In the present invention, it is not particularly necessary to form a base layer (for example, a resin or the like) for improving laser workability between the oxide layer and the substrate.

However, a base layer (such as a ruthenium dioxide film) may be formed between the oxide layer and the substrate for the purpose of different laser processing properties (diffusion barrier of the alkaline component of the substrate). Further, the base layer may be removed together with the oxide layer and the metal layer during laser processing, or may remain without being removed. The base layer is preferably formed by sputtering.

The substrate used in the present invention is not necessarily a flat plate shape, and may be a curved surface or a profiled shape. Examples of the substrate include a transparent or opaque glass substrate, a ceramic substrate, a resin film, and the like.

The substrate is preferably transparent. A glass substrate is particularly preferable in terms of strength and durability. As the glass substrate, a colorless transparent soda lime glass substrate, a quartz glass substrate, a borosilicate glass substrate, or an alkali-free glass substrate can be exemplified. In terms of strength and transmittance, the thickness of the substrate is preferably 0.4 to 3 mm.

The pulsed laser light that can be used in the present invention has a wavelength of 700 to 1500 nm. In the case of this wavelength band, it is preferable that the interaction between the oxide layer exhibiting transparent conductivity and the pulsed laser light is particularly large as compared with the interaction between the substrate and the pulsed laser light. Particularly preferably, the wavelength of the pulsed laser light is from 1047 to 1064 nm. It is also preferable in terms of a general-purpose laser processing machine (YAG, YLF, YVO laser, etc.) capable of high-power oscillation.

Further, in a laser processing machine of a type that can output pulsed light, it is preferable to irradiate the patterned pulsed laser light onto the oxide layer via a mask to facilitate patterning of the oxide layer.

In the present invention, the pulse width of the pulsed laser light is 1 ns to 1 μs. If the pulse width of the pulsed laser light is less than 1 ns, it is difficult to use a high-power laser processing machine, and the influence of heat is reduced to make it impossible to form a homogeneous pattern. Moreover, it is not preferable because the effect of the metal layer is lowered. Further, when the pulse width exceeds 1 μs, the influence of heat increases, and the heat-affected layer around the irradiated portion cannot be ignored, and a fine pattern cannot be formed, which is not preferable. Further, in terms of workability, it is more preferable to have a pulse width of 10 ns to 100 ns.

The removal of the oxide layer or the metal layer by irradiation with pulsed laser light is preferably carried out by one irradiation. When a processing method in which the irradiation portion is irradiated with a plurality of times of pulsed laser light having a low energy density is used, since the workability after the second irradiation is lowered as compared with the first irradiation, the processing of homogenization cannot be performed. Poor.

It is preferred that the pulsed laser light irradiated with one shot only removes the pulsed laser light having an energy density higher than the energy density of the oxide layer and the metal layer. Further, even in the case of processing by one irradiation, since the pulse irradiation of the pulsed laser light slightly overlaps, the pulsed laser light is irradiated twice or more on the overlapping portion.

It is preferred that the energy density of the pulsed laser light is 0.3 to 10 J/cm ² . If it is less than 0.3 J/cm ² , the oxide layer of the irradiated portion is not completely removed, and the film remains, which is not preferable. If it exceeds 10 J/cm ² , damage to the substrate cannot be ignored.

Further, the area of the irradiation portion irradiated by the primary pulsed laser light is preferably 1 mm ² or more.

The pulsed laser light is irradiated from the surface side on which the oxide layer or the metal layer is formed. If the irradiation is performed from the side where the oxide layer or the metal layer is not formed, the pulsed laser light propagates in the substrate, the energy loss due to the absorption of the substrate increases, and the workability of the oxide layer decreases, which is not preferable. .

Further, the present invention provides a substrate with an oxide layer formed by the above manufacturing method. Further, the present invention provides an electronic device in which an oxide layer of a substrate to which an oxide layer is attached is used as an electrode. In particular, the present invention provides a display panel or a solar cell module.

Example

Hereinafter, the present invention will be described by way of Examples 1 to 19, but the present invention is not limited to the following examples. Examples 1, 3, 14 and 15 are comparative examples, and Examples 2, 4 to 13, 16 to 19 are examples of the present invention.

(example 1)

A PDP having a thickness of 2.8 mm × a length of 100 mm × a width of 100 mm was cleaned with a high strain point glass (PD200 manufactured by Asahi Glass) substrate, and then placed on a sputtering apparatus as a substrate. By DC magnetron sputtering using ITO (In ₂ O ₃ with respect to the total amount of SnO _2, containing 10% by mass of SnO ₂₎ target, having a thickness of 120 nm on the ITO layer on the substrate, thereby obtaining attached A glass substrate having an ITO layer. As the sputtering gas, an Ar gas containing 2% by volume of O ₂ gas was used. The back pressure was 1 × 10 ^-3 Pa, the sputtering gas pressure was 0.4 Pa, and the power density was 3.5 W/cm ² . Further, the substrate temperature was 250 °C.

The glass substrate with the ITO layer was irradiated with pulsed laser light from the ITO layer side. Pulsed laser light uses pulsed laser light (wavelength of 1064 nm) by pulse type Yb-Fiber Laser. The pulsed laser light has a Gaussian type energy distribution 6, and the power of the illuminating portion is 5 W. Further, the pulse width is 100 ns, the irradiation diameter is 100 μm, the number of irradiations is once, and the frequency is 20 kHz. Then, the pattern diameter 5 formed by the irradiation of the pulsed laser light is measured (see FIG. 6).

The irradiated portion irradiated with the laser was observed with an optical microscope, and the diameter of the patterned portion was measured, and then the pattern diameter 5 was evaluated. Since the pulsed laser light has a Gaussian-type energy distribution, the energy of the pulsed laser light is more absorbed and is easily removed, and the pattern diameter 5 becomes larger. Therefore, by processing the pattern diameter 5, the laser processing object can be processed. The processability of the material was evaluated. In addition, it can be seen from other evaluations that the sample having a pattern diameter of 5 up to 50 μm in the above evaluation has a processable minimum energy density of 6.6 J/cm ² when using homogenized pulsed laser light, and the pattern diameter of 5 is reached. The 56 μm sample was 2.4 J/cm ² . That is, in the case of the evaluation, when the pattern diameter 5 was 56 μm from 50 μm, the laser workability was equivalent to an increase of about 2.8 times. Further, the pattern diameter 5 herein means a removal portion of an oxide layer which can be formed on a substrate with respect to one irradiation. The pulsed laser light may be irradiated as long as it corresponds to the gap size necessary for the transparent electrode of the electronic device to be formed. In order to pattern the lines between one part, that is, to pattern the lines between adjacent transparent electrodes, the pulsed laser light is sequentially irradiated to a specific position in accordance with the pattern diameter which can be formed by one irradiation. can. Further, it is also possible to arbitrarily perform patterning in a non-linear manner in accordance with the arrangement configuration of the complicated pixel electrodes. Fig. 6 is a view schematically showing the case of continuous and linear patterning.

The homogenized pulsed light is used in actual laser patterning at the mass production level. Also, the patterned gap size becomes important. Therefore, a mask is disposed between the laser light source and the workpiece, and the gap size is controlled to be defined. In other words, in order to correspond to a specific pattern, laser irradiation is performed so that the laser light cut by the mask is marked on the workpiece (see FIG. 1). In this case, since sufficient light source power can be utilized, the area of the irradiation portion irradiated by the primary pulsed laser light can be set to 1 mm ² or more.

(Example 2)

On the ITO layer of the glass substrate with the ITO layer of Example 1, after exhausting the residual gas, a Cr metal target was used, and a thickness of 11 nm was formed in an Ar gas atmosphere by DC magnetron sputtering. Auxiliary layer. The back pressure was 1 × 10 ^-3 Pa, the sputtering gas pressure was 0.3 Pa, and the input power density was 1 W/cm ² . Further, the substrate temperature was 250 °C.

For the glass substrate with the auxiliary layer attached in this example, the same pulsed laser light as in Example 1 was irradiated from the film surface side. Then, in order to evaluate the pattern diameter of the ITO layer, the auxiliary layer of the entire surface of the substrate was removed by an etching solution. The etching solution used a mixture of ammonium cerium nitrate, perchloric acid and water. No damage was substantially observed on the ITO layer by the treatment of the etching solution.

The pattern diameter of the ITO layer of this example was evaluated by an optical microscope in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3)

On the glass substrate used in Example 1, a SnO ₂ target containing Ta ₂ O ₅ and ZnO (containing 9.6 mass % of Ta ₂ O ₅ with respect to the total amount) was used by DC magnetron sputtering. 0.5% by mass of ZnO) was formed to form a SnO ₂ layer having a thickness of 140 nm, thereby obtaining a glass substrate with a SnO ₂ layer.

As the sputtering gas, an Ar gas containing 2% by volume of O ₂ gas was used. The back pressure was 1 × 10 ^-3 Pa, the sputtering gas pressure was 0.4 Pa, and the power density was 3.5 W/cm ² . Further, the substrate temperature was 250 °C.

With respect to the glass substrate with the SnO ₂ layer of this example, the pulse laser light of the same manner as in Example 1 was irradiated from the film surface side, and the pattern diameter was measured by the same method as in Example 1, and the results are shown in Table 1.

(Examples 4~15)

On the SnO ₂ layer of the glass substrate with the SnO ₂ layer attached to Example 3, after the residual gas is exhausted, an Ag metal target, an Al metal target, a Cr metal target, a Mo metal target or an ITO target is used. The material was formed by DC magnetron sputtering to form the film thickness and the auxiliary layer shown in Table 1.

The sputtering gas used was an Ar gas atmosphere (in the case of forming Ag, Al, Cr, and Mo) or an Ar gas containing 2% by volume of O ₂ gas (in the case of forming ITO). The back pressure was 1 × 10 ^-3 Pa, the sputtering gas pressure was 0.3 Pa, and the input power density was 1 W/cm ² . Further, the substrate temperature was 250 °C.

For the glass substrates with the auxiliary layers of Examples 4 to 15, pulsed laser light of the same conditions as in Example 1 was irradiated from the outer surface side. Then, in order to evaluate the pattern diameter of the tin oxide layer, the auxiliary layer of the entire surface of the substrate was removed by an etching solution.

The etching solution uses a mixture of phosphoric acid, nitric acid, acetic acid and water (in the case of removing Ag, Al and Mo), a mixture of ammonium cerium nitrate, perchloric acid and water (in the case of removing Cr), or hydrochloric acid or iron (III) chloride. And a mixture of water (in the case of removing ITO).

No damage was substantially observed on the SnO ₂ layer by the treatment of the etching solution. The pattern diameters of the SnO ₂ layers of Examples 4 to 15 were evaluated in the same manner as in Example 1 by an optical microscope. The results are shown in Table 1.

Further, in the evaluation of the fragments shown in the above Table 1, the case where no film (oxide) remained was evaluated as "○", and the case where a small amount of film (oxide) remained was evaluated as "Δ". Further, in the comprehensive evaluation, in the case of using ITO in the oxide layer, the case where the pattern diameter is larger than 58 μm and no film (oxide) remains is evaluated as "○", and the pattern diameter is 58 μm or less or a small amount. The film (oxide) residue was evaluated as "△". Further, in the case of using SnO ₂ in the oxide layer, the case where the pattern diameter is larger than 46 μm and no film (oxide) remains is evaluated as "○", and the pattern diameter is 46 μm or less or a small amount of film (oxide) The case of the residue was evaluated as "△".

As is apparent from Table 1 above, when Ag, Al, Cr or Mo is used as the auxiliary layer, the pattern diameter of the oxide is greatly increased. On the other hand, it can be seen that the pattern diameter is small in the case of no auxiliary layer.

Further, when ITO is used as an auxiliary layer instead of the metal layer, an increase in pattern diameter hardly occurs. From the above, it can be seen that by using a metal as an auxiliary layer, the pattern diameter of the oxide can be greatly increased.

In other words, correspondingly, by accelerating the beat of the production steps, the overall productivity can be improved. Alternatively, it can be seen that by reducing the load of each laser processing apparatus, the production cost of the entire step can be greatly reduced.

Further, the degree of the debris around the irradiated portion of the irradiation laser light of Examples 1 to 15 was observed by an optical microscope and a scanning electron microscope. Example 2 and Examples 4 to 15 were observed after removing the auxiliary layer. Examples 1 and 3 were observed by immersing in a mixture of phosphoric acid, nitric acid, acetic acid and water at room temperature for 5 minutes.

From this, it was confirmed that the fragments of Example 2 and Examples 4 to 15 were reduced as compared with Examples 1 and 3. The reason is presumed to be that when the auxiliary layer is removed, the debris deposited on the auxiliary layer is removed.

(Examples 16~19)

For the case where Sn is used, and Mo in which the pattern diameter of SnO _{2 in} the above Examples 4 to 15 is improved as the auxiliary layer, the homogenized pulsed light used for laser patterning at the mass production level is used. Evaluation. Specifically, a mask is disposed between the laser light source and the workpiece, and the gap size is controlled so that the laser light that is masked and cut is marked on the workpiece to perform laser irradiation (refer to FIG. 1). ). In this case, since sufficient light source power can be utilized, the area of the irradiation portion irradiated by the primary pulsed laser light can be set to 1 mm ² or more. Further, the energy density, the number of times of repetition, and the pulse width of the pulsed laser light during processing were set to 3.3 J/cm ² , 6 kHz, and 50 ns, respectively.

On the glass substrate with the SnO ₂ layer attached to Example 3, after the residual gas was exhausted, the Sn metal target was used, and the DC magnetron sputtering method was used to form the surface shown in Table 2 on the SnO ₂ layer. The film thickness and the auxiliary layer of the composition.

The sputtering gas used was an Ar gas atmosphere (in the case of forming Mo) or an Ar gas containing 2% by volume of O ₂ gas (in the case of forming Sn). The back pressure was 1 × 10 ^-3 Pa, the sputtering gas pressure was 0.3 Pa, and the input power density was 1 W/cm ² . Further, the substrate temperature was 250 °C.

For the glass substrates with the auxiliary layers of the examples 16 to 19, the homogenized pulsed laser light was irradiated from the outer surface side. Then, in order to evaluate the pattern diameter of the tin oxide layer, the auxiliary layer of the entire surface of the substrate was removed by an etching solution. The etching solution uses phosphoric acid, nitric acid, a mixture of acetic acid and water (in the case of removing Mo), or a mixture of sodium hydroxide solution and water (in the case of removing Sn). In order to confirm the state of the tin oxide layer in the peripheral portion of the laser etching, it was evaluated by an optical microscope. The results are shown in Table 2.

In addition, in the case of "the presence or absence of the reaction layer" shown in the above Table 2, the case where the reaction layer was not observed was evaluated as "○", and the case where a small amount of the reaction layer was observed was evaluated as "△". In the comprehensive evaluation, the reaction layer was not observed, and the overall evaluation in Table 1 was evaluated as "○", and the reaction layer was not observed or the comprehensive evaluation in Table 1 was "○". The situation was evaluated as "○".

When Mo is used as the auxiliary layer, there is a reaction layer of the SnO ₂ layer and the Mo layer. On the other hand, when Sn was used as the auxiliary layer, no reaction layer was observed. It is generally considered that the reason is that Sn is less reactive with the SnO ₂ layer than Mo, and therefore Sn is generally considered to be more suitable as an auxiliary layer.

The present invention has been described in detail above with reference to the specific embodiments thereof, and it is understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2008-126026, filed on Jan.

[Industrial availability]

The present invention can be applied to the manufacture of display panels of large PDPs, LCDs, etc. or the manufacture of solar cell modules.

1. . . Matrix

2. . . Oxide layer

3. . . Metal layer

4. . . Removal department

5. . . Pattern diameter

6. . . Energy distribution

7. . . Mask

50. . . Laser source

51. . . Laser light

Fig. 1 is a schematic cross-sectional view showing the constitution of the present invention.

2(A) and 2(B) are schematic plan views showing the configuration of the present invention, and Fig. 2(A) is a schematic plan view before laser patterning, and Fig. 2(B) is laser patterning. Schematic plan view.

Figure 3 is a flow chart of the present invention.

4(A) and 4(B) are schematic plan views showing other configurations of the present invention, and FIG. 4(A) is a schematic plan view before patterning, and FIG. 4(B) is a schematic view after patterning. Sexual floor plan.

5(A) to 5(E) are explanatory views of the previous example.

Figure 6 is an explanatory view of the present invention.

1. . . Matrix

2. . . Oxide layer

3. . . Metal layer

4. . . Removal department

7. . . Mask

50. . . Laser source

51. . . Laser light

Claims (10)

A method for fabricating a substrate with a patterned oxide layer, comprising the steps of: sequentially forming an oxide layer having a transparent conductivity and a metal layer on a substrate; from the outer surface side of the metal layer to the metal layer a pulsed laser light having an irradiation energy density of 0.3 to 10 J/cm ² , a repetition frequency of 1 to 100 kHz, and a pulse width of 1 ns to 1 μs, removing the metal layer and the oxide layer of the irradiated portion of the pulsed laser light; and etching The metal layer of the entire surface of the substrate is removed. The manufacturing method of claim 1, wherein the wavelength of the pulsed laser light is 1047 to 1064 nm. The manufacturing method of claim 1 or 2, wherein an area of the irradiation portion irradiated by the primary pulsed laser light is 1 mm ² or more. The manufacturing method of claim 1, wherein each time the pulsed laser light is irradiated, the irradiation portion is moved once. The manufacturing method of claim 1, wherein the pulsed laser light is irradiated at an irradiation speed of 15,000 mm ² /s or more. The method of claim 1, wherein the oxide layer is tin oxide or tin-doped indium oxide. The method of claim 1, wherein the oxide layer has a film thickness of 10 nm to 1 μm. The manufacturing method of claim 1, wherein the metal layer is composed of a group selected from the group consisting of Ag, Al, Co, Cr, Cu, Fe, Mo, Ni, Sn, Zn, and V. At least one or more of the metals are formed. The manufacturing method of claim 1, wherein the metal layer is composed of a metal of a non-magnetic body. The method of claim 1, wherein the metal layer has a film thickness of 3 to 100 nm.