TWI380102B - Layered solid system, its application for electro-optical device and integral system, and manufacturing method thereof - Google Patents

Description

1380102 IX. Description of the Invention: [Technical Field] The present invention relates to the use of a layered solid system as a transparent electrode layer, particularly a board display such as LCDs, PDPs, and ELs, and the manufacture of the system and its structure. [Prior Art], particularly a transparent conductive film, which is used in electro-optical displays, particularly flat, LEDs, FEDs, and OLEDs, and

Layered solid systems, especially in the form of thin films on substrates, are known and used for various purposes such as optical coatings, interference filters, surface finishing, especially for example using transparent conductive films (TCFS) as electrodes for electro-optic displays. And the second is a touch input device such as a touch screen material. Obviously, a number of such systems must be constructed to cover only a portion of the substrate to achieve the desired device. The industry has been studying TCFs for many years (see, for example, "Semiconductor Transparent Films, HL Hartnagel et al., Institute 〇f physics Publishing,

Bristol and Philadelphia, ISBN 0 7503 0322 0, p.l ff). Most • TCFs are coated on a transparent substrate such as glass by a thin film method. These tcf films are etched to form conductive electrodes to fabricate electronic devices, and in particular, electro-optic displays differ from erbium-based semiconductor integrated circuits in that TCF circuits are more suitable for many electro-optic applications because they allow for light transmission. Transparent electronic devices have been widely used in current technologies such as liquid crystal displays (LCDs), plasma display panels (pDp), light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), electroluminescent (le), and electroluminescent displays (FED). ), trigger panel, solar cell, waveguide converter, filter, transparent EMI shutter 985i4.doc 8 1380102

Two: More: He! use. The requirements of its basic characteristics include high transparency, low power, good stability, and #刻 capability. In addition, the TCF film should also be resistant to chemicals, high humidity, and high temperature baking for specific alkaline solutions, and the need for complex processing flows for such electronic devices in various plants. For example, indium tin oxide (ιτο) has excellent light transmittance, good electrical resistance in the visible range of the electromagnetic spectrum, and high hardness for good environmental stability. Therefore, it becomes the most widely used material for all coffee.

However, most of the TCFs are n-type semiconductors (see, for example, "new (iv) transparent conductive oxides" T. Minami, MRS Bulletin, 2000, 8, ρ·38 hearts, so their resistivity cannot be as such Comparable thickness metal film

As low as it is. For example, most of the materials used as TCF, the resistivity of the crystalline indium tin oxide (ITO) film usually has a value of about 2. 1 〇 -4 Ώ · cm. On the contrary, the resistivity of the aluminum film is generally about 5 · 1 〇 -6 Ω · cme The inherent characteristics of KTCFs are indeed difficult to complete the thin electrode of the TCF film having low resistance. On the other hand, improvements in the performance of modern displays require extremely thin conductive electrodes to increase the resolution of the display, i.e., eager for lower TCF sheet resistance.

There are two different technologies for industrial application development, the first being wet etching and the second being dry etching. The wet etching method is applied to most production routes, and its advantage is that on the one hand, only a machine having a relatively low cost is required, and on the other hand, it has excellent compatibility with mass production. However, several empirical parameters must be carefully considered in the wet etching process, such as composition of the etchant, etching temperature, buttoning time, and surface characteristics of the TCF film. If the etching rate is too high, it is easy to cause the formation of the sub-etching and the improper zigzag pattern. If the etch rate is too low, then the productivity of the surname method is limited. Usually, I prefer a higher meal 98514.doc 1380102 rate to save on processing costs. As described by Mc Bartelt et al., c〇u〇ids and Sutfaces' A'165 (2000) p. 373 ff, usually at the beginning of any wet etching process, whether it is a soaking or spraying method, the etchant is adsorbed to The surface of the TCF film. The chemical reaction then takes place at the interface between the etchant and the TCF film. During the progress of the etching process, the island structure in the TCF is formed by the vacancy nucleation, the occluded atoms of the growth vacancies, and the aggregation of the vacancies to form β. After the etching method is almost completed, most of the vacancies are connected and only a small part is connected. The TCF that is not etched is left behind. The remainder of these residual TCFs is commonly referred to as "tcf island". Regarding practical applications such as in a display, such island structures, the TCF island causes a short circuit of each circuit and then impairs the function of the electrodes. Therefore, its occurrence must be suppressed. The means of limiting the number of TCF islands, or even completely etching the TCF island, is to increase the etching time. However, this measure will reduce productivity and lead to an increase in production costs. Zinc oxide doped with alumina (ΑΖΟ) is considered as a possible material for TCFs (Y. Igasaki et al., Applied Surface Science, 169-170 (2001) p. 508-51 1; T·, K. Ellmer et al. Thin Solid Films, 317 (1998) pp. 413-416; T. Minami et al., Thin Solid Films, 366 (2000) pp. 63-68 and M. Miyazaki et al., J of Non-Crystalline Solid, 218 (1997). ) pp. 323-328). AZO has the characteristics of good light transmittance and is easily coated by sputtering. However, as a single layer of TCF, ruthenium has poor temperature and chemical stability compared to ITO. However, for example, display applications require good temperature and chemical stability. As noted above, TCFs must demonstrate sufficient stability to the chemical for the long-term operation of the device. However, TCFs must also exhibit good etch energy as a polymer material, and the orientation remains in the liquid crystal system. With regard to the composite system, a liquid crystal medium having a relatively high birefringence (?!!) is required, an effective scattering state is achieved, and a good contrast is achieved. Regarding reversed PDLCs, Λ n must be matched to the medium polymer, which is effective Δη for the green polymer in the solidified liquid crystal system. The good compatibility with the precursors of the polymer of the complex system and the ease of phase separation during the formation of the composite system are a clear prerequisite for the liquid crystals of the application. Although there is a system in which spontaneous induced phase separation (SIPS) occurs, in large-scale systems, phase separation does not start spontaneously, and more importantly, in a large P-knife system, it does not completely follow this approach. Instead, the phase separation initiates the polymerization initiation using a cleavage, which can be a thermally activated initiator or a photoinitiator. Regarding the phase separation, the liquid crystal medium must be stable under exposure conditions by exposure to heat or radiation, especially curing with actinic radiation. This retention is especially useful for other preferred compositions, which require the use of a liquid crystal medium which is particularly stable to exposure to uv. This is a challenging requirement, because the birefringence of the medium must be quite two at the same time. The most typical should not be compared to the nematic phase range where the clearing point is not high enough, the unfavorable narrowness, the relatively high temperature of the lower end of the nematic phase stability, too low The electrical anisotropy is thus too high for operating voltage, unsuitable for elastic constants, too high viscosity values, and too low stability for exposure to UV radiation or combinations thereof. Another advantageous electro-optical module for LCDs is an optically compensated bending (〇CB) module. This module is described, for example, in Yamaguchi et al., " Wide viewing angle display module for use with a curved matrix liquid crystal cell active matrix LCD", SID η.", Digest, 98514.doc • 10·1380102 [invention] Providing a layered system, in particular a butyl CFs, which does not exhibit the disadvantages of prior art materials, or at least exhibits the disadvantage of being lighter. Such layered systems, especially TCFs, are introduced into each device, preferably electronically or Provided by a new multi-layer structure in optical devices. In such layered devices, especially g-multilayer TCFs (MTCFs), the ability to engrave is clearly superior to the prior art:,: in the first-like surname layer The lower introduction buffer layer itself has a better etchability than the second surname layer.

Thus, the first aspect of the invention is: a layered solid system comprising: - a substrate, - a first solid etchable layer, and a first - (four) layer, from a modifiable material

a first solid etchable layer, between the solid etchable layers, an etchable material layer, preferably referred to as a buffer layer, located on the substrate and the first etchable layer different from the first layer The material - the second etchable layer (buffer layer) has a substantially greater rate than the first layer, and more preferably, the surname-layered solid system is a structural system of the substrate. The etchable layer covers only a part of the special aspect of the invention: a transparent conductive film characterized by a 98514.doc layered system comprising a substrate, a first solid can be a transparent layer, a material The composition is referred to as a first etchable layer, and the etchable first solid 'is preferably thin and etchable transparent layer, referred to as a buffer layer, between the substrate and the first layer, the etchable material of the material Composition β Another preferred aspect of the present invention is that the composition of the first layer is a layered system comprising a layered system, a substrate, a first solid etchable transparent layer, and a material. A structural transparent conductive film, which is referred to as a first profitable layer, can be etched into a transparent layer by a first solid, preferably thin, called a buffer layer.

The material is composed of an etchable material. The structured transparent conductive film according to the present invention can be advantageously used as an electrode of an electronic or electro-optical device which is also the object of the present invention. Further, the method of manufacturing a layered system and the apparatus comprising the same are also the subject of the present invention. In a preferred embodiment of the invention, which is applied to all of the above specific examples, the second surname layer (buffer layer) has a etch rate substantially greater than the first etchable layer. The surname rate is usually defined as the layer thickness removed per unit time, usually expressed as 98514.doc -14* 8 microns/sec. Here, the thick second rate of the 材料i material layer is defined by the average etch rate determined by the removal of the ui, and unless otherwise indicated. The thickness of each layer 戸 β, 曰 layer can be conveniently used by a profilometer or an ellipsometer. Preferably, the etch rate of the buffer layer is higher than that of the first etchable layer. When the species and the same etchant are used at the same etch temperature, the amount is preferably in the range of 5% to 丨,000%, more preferably 50% to 500%, preferably 100% to 300/〇. The initial thickness can be measured by an ellipsometer or a profilometer. Then, the etching time to remove the π% layer thickness can be determined by carefully controlling the etching process. The etch rate of the first etchable layer and the buffer layer can be determined as the layer thickness removed per unit time, respectively. A preferred embodiment of the multi-layer system (MTCF) according to the present invention comprising a ruthenium film preferably as the first etchable layer is described in Example 1 below. The preferred temperature is 45 +/- TC unless otherwise noted. The etchant and the etch temperature are also preferably used as a standard for the measurement of the etch rate. Preferably, the first etchable layer is composed of a film selected from the group consisting of ITO, SrO, TiO, VO, NbO, MnO, FeO, CoO, NiO, PdO, Pto, CuO, AgO, ZnO, CdO, Cu20, Ag20, Mn304, Fe304, Co304, Y2O4' Ti2〇3, V2O3, Cr2〇3Mn2〇3, Fe2〇3, Rh2〇3, Ga2〇3, I.n2〇3, Ti02, V02, Nb02, Cr02, Mo02, W02, Mn02, Re02, Ru02, Rn02, 0s02, Ir02, Pt02, Sn02, V2〇5, Nb2〇5, Sb205, W03, Re03, SrTi03, LaTi03, SrZr03, LaV03, KTa03, LaCr03, SrMo03, L1WO3, NaW03, KW03, KW03, LaMn03, LaFe03, LaCo03, LaNi03, SrFe03> SrRu03, LaRh03, LaGa02, 98514.doc 15 1380102

MnV3〇4, CoV2〇4, ΖηΜη2〇3 CoF^ η 广ΖηΜ „J ope2〇4> CoNi2〇4, MnFe204, znMn2〇3^BaIr2〇5 〇 In a preferred embodiment, it is a guide. Preferably, the buffer layer is composed of a material selected from the group consisting of w ^ ^ , m μ , and the I3 is oxidized by an emulsification Narrative (including 4 钿: ΑΖ0), emulsified zinc doped with gallium oxide (abbreviation: GZ〇) or simultaneously doped with oxygen. (abbreviation: AGZO), Ag, Au, etc., oxidation of oxidized gallium Preferably, the zinc etch is selected from the group consisting of AZO and GZO. In a preferred embodiment of the invention, the etchable layer is transparent, preferably a conductive layer. Preferably, the resistivity of the material of the etchable layer is Ω · cm or less, more preferably * ln · 3 ln - 4 is preferably 10 Ω or less, most preferably 2 Ω · cm or less. ^ In another preferred embodiment of the present invention, the buffer layer is Transparency $ conductive layer 1 is better, the resistivity of the material of the buffer layer is ... :: better for the heart - ' one ~ ^ In the special case of the invention, the second layer can be (four) layer, the first - can be described The layer is transparent The first layer of the material, which is preferably a conductive layer, is composed of a material and a material, and the material is preferably used for the resistance of the material for each layer. The first solid-solid layer has a thickness in the range of % nm. Or above to 700 nm or below, more preferably 80 nanometers or more to 420 house micro water or below 'best 1 〇〇 叫 宅 宅 或 或 or above to 300 nm or to 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 16 8 1380102 The under buffer layer has a thickness ranging from 0. 1 nm or more to 5. Lower: more preferably ° 5 nm or more to 4. Nano or more preferably 1 millimeter t m or 5 Ο fV -A* (half μm or less, preferably 4 nanoseconds or more to 26 nanometers or less.) Preferably, the thickness of the buffer layer is less than the first etchable layer. The enthalpy, the ratio of the thickness value is equal to or lower than 1/2, preferably equal to or lower than 1/5, and most preferably equal to or lower than 1/1 〇.

The transmittance of the MTCF, particularly the transmittance of the first decimable layer of 2 Mtcf according to the present invention, depends on the desired sheet resistance. Preferably m is, in particular the layer _ _ _ layer of the MTCF according to the invention is at 55. The nanometer has a transmittance of 70% or more, more preferably 75% or more. Preferably, the buffer layer of the MTCF according to the present invention has a transmittance of 70% or more, more preferably 75% or more at 55 Å. Preferably, the multilayer transparent conductive film according to the present invention has a transmittance of 7〇% or more, more preferably 75% or more at 550 nm.

In a preferred embodiment of the present invention, the buffer layer is composed of a material selected from the group consisting of zinc oxide doped with alumina (abbreviation: AZ〇), zinc oxide doped with gallium oxide. (abbreviation: GZ〇) or zinc oxide (abbreviation: AGZO) doped with both aluminum oxide and gallium oxide. Preferably, according to the present invention, AZO, GZO or AGZO is coated by sputtering. Preferably, 'using AZO' is preferably doped with 0.5 atom% or more to 8 atom% or less, preferably 1 atom% or more to 4 atom% or less, and most preferably about 2 atom% of gossip. The composition of 2 〇 3 ZnO is used as a buffer layer to improve the etching ability of the TCF film. Alternatively, it is also preferred to use gz〇, preferably by mixing 1380102 with 0.5 atoms. /. Or above 8 atom% or less, preferably argon% or more to 4 atom% or less, most preferably about 2 atom%, consisting of 2 〇 3 of Zn ,, used as a buffer layer to improve the TCF film. Etching ability. In another embodiment, AGZO is used, preferably from 2 atom% or more to 6 atom% or less, preferably 0.5 atom% or more to 3 atom% or less, most preferably 0 to about 1 atom. % consists of eight 〇12〇3 and Ga203 ZnO. As described above, if a suitable buffer layer according to the present invention is applied between the surface of the substrate and the first (four) layer before the first etchable layer is deposited on the surface of the substrate, the '(4) material cannot be removed from the surface. The first - can be (four) layer. In addition, the first etchable layer is etched into the island structure through vacancy nucleation and growth. In a particular location, the 'first-like surname layer is faster than the other position (four). Therefore, in these locations, the first surname is faster and it is first removed there. However, the current (four) material is in contact with the buffer layer, wherein the first etchable layer is first removed' rather than in contact with its own substrate, as in the prior art. Now, by contacting the buffer layer, the meal inscription reacts with the material of the slow (4) and the money is removed. Since the buffer layer has a faster engraving rate than the first modigate layer, the buffer layer is faster (four) than the remaining portion of the first surname layer. Therefore, the buffer layer is also engraved from the portion between the portion of the first edible layer that has not been completely surnamed and the substrate, thereby effectively increasing the number of the first layer that can be accessed. The rest of the surface allows the money = to reach between the surface and the rest of the first-axis engraved layer and from the back side of it. Therefore, all of the time required for the MTCF's money is significantly reduced compared to the TCF consisting only of the first money layer. However, it must be emphasized that the basic characteristics of the 'th-(four) layer are maintained by the method of forming the structured electrode of the present invention, as described above, and thus the characteristics of the MTCF can be dominated. Therefore, the rest]y[TCF is in the structural region, where it is covered by a protective layer such as a photoresist material, and thus has not been removed by the etching process, and the electrical properties of the combined layered structure can be governed. The combined layered structure has the same or at least nearly the same characteristics as chemical resistance, hardness, reliability and stability, and only improves the etching of this force. Through the island-name, the silver engraving can directly react with the buffer layer to enhance the etching ability. If any, the presence of a buffer layer within the multilayer structure has only a slight effect on the optical characteristics of the structure. The theory of transparent thin layers of optics (for example, "Thin Film Filters" H. Macleod, Institute of Physics Publishing,

Bristol and Philadelphia, ISBN 0 7503 0688 2 (2001) p. 86 ff.) 'The effect of the refractive index of each multilayer optical film layer is expected. It can be tested by experience or by software. In the case where the refractive index of the buffer layer is lower than the coverage of the first surnamed layer, the transmittance is increased as compared with the same first profitable layer without the buffer layer. This feature is widely used in typical anti-reflective coatings. Generally, however, the transmittance of the layer system according to the present invention is controllable by optimizing the refractive index and the film thickness of the system layer. The transmission spectrum through the wavelength of visible light is very similar to the case where the thickness of the buffer layer is small relative to the thickness of the first etchable layer. The color interference of the layer system is not significantly altered and can be controlled by known measures. In the case where AZ0 is used as the buffer layer and IT is used as the first etchable layer, it is relatively easy to control the transmittance of the layered system (ΙΤ0/ΑΖ0) because the refractive index of the buffer layer of the crucible is only slightly smaller than that. Layered glass. Specifically, the average sheet resistance of the first moorable layer by, for example, 985l4, doc • 19·1380102 is preferably in the range of 〇ιω/□ or more to 60 Ω /□ or less, more preferably! Ω / □ or more to 3 〇◦ / □ or less, particularly preferably 3 Ω / □ or more to 20 Ω / □ or less, preferably 5 Ω / [□ or more to 15 Ω / □ or less, Good to 丨〇Ω / □ or below. The average time of the MTCFs according to the present invention is removed at 45 ° C and under the conditions provided in Example 1 below, preferably in the range of seconds or more to 8 seconds or less, more preferably 5 seconds or more to 300 seconds. Or less, still more preferably 1 second or more to 300 seconds or less, and most preferably 2 seconds or more to 15 seconds or less. The surname velocity of the first-scratch layer used in accordance with the present invention is preferably in the range of 0.1 nm/sec or more to 10 nm/sec or less, more preferably 〇2 nm/sec or more to 3 nm. /second or less, preferably 〇3 nm/sec or more to 1 nm/sec or less. . The etching rate of the buffer layer used in accordance with the present invention is preferably in the range of 0.15 nm/sec or more to 15 nm/sec or less, more preferably 025 nm/sec or more to 8 nm/sec or less. Preferably, it is 毫35 nm/sec or more to 2 nm/sec or less. The range of parameters provided in this case includes all limits unless otherwise indicated. Unless otherwise indicated, throughout this case, all concentrations are expressed in mass % and are associated with each complete complex. 'All temperatures are expressed in degrees Celsius and all temperature differences are in Celsius. All physical systems are based on "Me(10) liquid crystal, liquid crystal The physicality of "Status Nov.1997, Merck KGaA, Germany and at a temperature of 2 ° C means 'unless otherwise specified. The optical anisotropy (?n) was measured at a wavelength of 3 nm. The dielectric anisotropy (Λε) is measured at a frequency of 丄k Hz. For the measurement of transmittance, a commercially available photoelectric spectrometer 98514.doc, 21 · 8 1380102 is used. Example 1 A multilayer system is formed by depositing a Si 2 film, an AZO film, and a conventional ITO film in a thickness of Prepared on a substrate of 1.1 cm soda lime glass. The thickness of the three-layer film is 25 nm, 6 nm, and 120 nm, respectively. The parameters of these layered structures are summarized in Table 1. Table 1: Overview of the layered structure of Example 1 and the results:

Example 1 Comparative Example 1-1 Comparative Example 1-1 Structure Layer Thickness (Layer) ΙΤΟ 120 nm 125 nm 0 nm ΑΖΟ * 6 nm 〇 nm 120 纳米 SiO 2 25 nm Glass: Sodium Calcium 1.1 cm Characteristic Average resistivity / Ω / Π 14.6 13.4 63.8 Transmittance at 550 nm /% 87.27 89.58 90.13 Etch rate / nm / sec ΝΑ 0.79 2.85 Clearance time (45 ° 〇 / sec 90 500 55 and stripping clearance time (30 °C) / sec 240 > 1,500 90 and stripped of the micro-grid grid on the ΑΖΟ (30 seconds) The shape of the small name cracked open micro-structure grid local + unstated failure (120 seconds) shape engraved area (stripping) micro Structure flawless - island failure (360 seconds) (stripping) Good adhesion of rubber Good chemical stability in NaOH: ΔΙΙ /% Resistivity / Ω / 〇 2.0 14.8-15.1 1.5 13.5-13.7 Failure (stripping) Temperature stability :AR/% Resistivity / Ω / Π 6.7 15.0-16.0 7.9 13.9-15.0 149% 580-1, 420 Humidity stability: ΔΙΙ /% Resistivity / Ω / 〇 0.0 14.8-14.8 0.1 13.5-13.6 Stripping ^ 580 Note: * : ΑΖΟ : With 2 atom% eight 1203 ΖηΟ, ΝΑ : Cannot apply 98514.doc -23 - 8 1380102 The change in sheet resistance after the temperature cycle in the ambient air is completed. Fifth, the determination of humidity stability is defined as the temperature at 6〇+/_2. (: and change in sheet resistance after 24 hours of treatment at 90 +/- 5% RH. The sheet prepared according to this example passed all five stability tests, and the results are shown in Table 1. Comparative Example 1-1 The multilayer system was prepared as in Example 1, but no AZO film was deposited under the ITO film. The thickness values of this multilayer system are also shown in Table 1. This multilayer system is available through Taiwan Merck Display Technology. The company of the Merck Group obtained a film called "MDT #3 00 fully oxidized ITO glass", a typical ITO coated glass for STN displays. The film obtained at nine points of the typical sheet of Comparative Example 1-1. The results of the material resistance are not shown in Table 3. Table 3: Sheet resistance (Ω/Π) of Comparative Example 1-1: 13.2 13.6 13.4 13.3 13.4 13.6 13.2 13.3 13.2 Note: Sheet resistance: Ω /□ The results are in comparison with the results of Table 2, and the sheet resistance of Example 1 is clearly known. Very similar to this comparative example, Comparative Example 1_丨. Secondly, study the optical role of the sheet. The transmittance of the sheet was measured as the transmittance with respect to air at 550 nm. This comparative example, the transmittance of 550 nm of Comparative Example 1, is shown in Table 1, very similar to Example 1. The purge time is at (45 +/- 1). (: measured as 500 seconds and measured at a temperature of 98,514.doc -26- 8 1380102 at (30 +/- 1 ) ° C for more than i, 5 〇〇 seconds. Second, during the etching, the formation of microstructure The sheet was studied, as described in Example 1. After 12 G seconds, it was clear that the ITQ zone was not visible by the photoresist material.

Covered and it is not etched or only partially etched. After 36 seconds, no unetched or only partially etched areas are seen. However, there are still a few remaining IT〇• islands left behind. The sheets were passed through all five stability tests as described in the Examples. The results are not shown in Table 1. Comparative Example 1-2

In this comparative example, the multilayer system was prepared as in the example, but only the ruthenium film was deposited without depositing any ruthenium film. The thickness values of this multilayer system are also shown in Table 1 for comparison. The results of sheet resistance obtained at nine points of the typical sheet of Comparative Example 1-2 are not shown in Table 4. ^Comparative Example 1 · 2 material resistance (Ω / Γμ: 58.9 61.4 67.2 56.8 67.2 70.6 60.0 64.9 67.1 Note: Sheet resistance: Q / port Table 4:

It is apparent from the table that the sheet resistance of the example is obviously lower than that of the comparative example, and the sheet of the example is more suitable for practical use than the sheet of the comparative example. Second, study the optical effects of the sheet. The transmittance of the sheet of this comparative example was measured to be relative to air at 550 nm, and the results were very similar to those of Example 1 and Comparative Example 1-1, and are also included in Table i. The purge time is measured at 45 +/- 0^ for 6 sec and at a temperature of 98514.doc • 27-8 1380102 (30 +/- 1) C for 45 seconds 蚀刻 during etching, AZ〇 Membrane stripping and stripping of the film can be observed in the engraved solution by unassisted visual inspection. Next, the sheet was investigated for the formation of microstructure during etching, as described in Example 1. Shown in Table i. Sheet material to the five-time stability test described in Example 1 above, which passed the second stability test, but the other three stability tests failed significantly. Example 1 and Comparative Examples 1-1 and I· Summary of Comparison of 2 In the comparison of the IT0 glass of Comparative Example 1.1, the standard IT glass used for the STN obtained by the company Merck Display Technology of Merck Group, Taiwan, the multilayer & system according to Example 1 of the present invention has similar Electrical and optical properties. The film of the life U and the ratio (4) was passed through all five reliability tests. However, the name of the multi-layer system according to the example i of the present invention clearly shows that the money is changed and improved. Clear time. It can be etched into frequent occurrences in a short time. In addition, the semi-etched layer can be quickly moved from the surface of the substrate under the typical conditions of the manufacture of the electro-optical display. The multi-layer system according to the first embodiment of the present invention can save the wet etching compared to the system of the comparative example W. The time required for the law does not even leave the island of ιτ〇. Although the system of Comparative Example 1-2 has a more example! Compared with the comparative example, it is larger and better, and the shorter and better clearing time, but It cannot be easily applied to devices, for example, the actual manufacture of STN displays. It has a failure of three-fifths of the reliability tests performed with higher and worse sheet resistance than other systems. Example 2 98514.doc •28· 1380102 As in Example 1, a multi-layer system was prepared by depositing a SiO 2 film, an AZO film, and a conventional ITO film on a substrate having a thickness of 1.1 cm of soda lime glass by sputtering. However, the thickness of the three-layer film was The parameters are 35 nm, 24 nm, and 145 nm. The parameters of these layered structures are summarized in Table 5.

Table 5: Layered structure of Example 2 and Comparative Example 2: Example 2 Comparative Example 2 Structural layer thickness (layer) ΙΤΟ 145 nm 145 nm ΑΖΟ* 24 nm 〇 nano SiO 2 35 nm glass: sodium calcium 1.1 cm Characteristic average resistivity / Ω / Π 13.3 11.5 550 nm selection luminosity /% 78.64 86.75 etch rate / nm / sec NA 0.70 removal time (45 ° C) / sec 100 580 good adhesion of rubber good chemical stability in NaOH :AR/% 2.2 -2.6 Resistivity / Ω / 〇 13.3-13.5 11.6-11.3 Temperature stability: △! (/% 6.0 8.8 Resistivity / Ω / 〇 13.4-14.2 11.4-12.4 Humidity stability: 0.1 2.7 Resistivity /Ω/〇13.2-13.3 11.1-11.4 Notes·· * ·· AZO: ZnO having 2 atom% 八1203, ΝΑ: The area where the glass substrate cannot be applied is the same as that used in Example 1. The sheet is processed as in Example 1. The same studies and tests were carried out in the same manner. The results of these tests are included in Table 5. The results of the sheet resistance obtained from the nine points of the general sheet of Example 2. Table 6: Sheet resistance (Ω/CI) of Example 2. : I 13Τ4 ϊΌ Γ3Τό 98514.doc -29- 8 1380102 13.5 13.2 13.2 13.6 13.1 13.6 Remarks: Sheet resistance: Ω / □ Next, study the optical action, etching action and removal time of the sheet. The results of these tests are contained in Table 5. Second, during the etching, the microstructure The study sheets were formed. The results of these tests are also included in Table 5. Finally, the sheets were subjected to five reliability tests as described in Example 1. The sheets passed all five stability tests. The results of these tests were also It is contained in Table 5. Comparative Example 2 A multilayer system was prepared as in Example 1, using the same ιτο film and sich film as used in Example 2, but as in the comparative example, no ruthenium film was deposited on the ιτ〇 film. Below, the thickness values of this multi-layer system are also shown in Table 5. This multi-layer system can be accessed through Taiwan Merck DispUy Techn〇1〇gy.

The Merck Group's company is known as "M(10)37〇 fully oxidized ιτ〇 glass", a typical enamel coated glass for STN displays. The results of the sheet resistance obtained at nine points of the typical sheet of Comparative Example 2 are shown in Table 7. Table 7: Film of Comparative Example 1, Lightning Door) 11.3 11.7 11.4 11 ll.i 11. 11.5ΓΓ6ΤΤΤό Note: Sheet resistance: Ω / port This table clearly shows the sheet of K φ k worm J 2 of Example 2. The resistance was very similar to this comparative example, Comparative Example 2. 985l4.doc, 30-8 1380102 Second, study the optical effects of the sheet. The transmittance of the sheet of Example 2 was slightly different from that of Comparative Example 2 in this comparative example. The purge time was determined to be 580 seconds at a temperature of 45 °C. For this comparative example, the sheet of Comparative Example 2 was carried out as described in Example 1 by all five stability tests. The results are shown in Table 5 for comparison. - Summary of comparison of Example 2 with Comparative Example 2 In comparing the ITO glass of Comparative Example 2, the multilayered system according to Example 2 of the present invention has similar electrical and optical characteristics. The sheets of Example 2 and Comparative Example 2 passed all five reliability tests. However, the etching action of the multi-layer system according to Example 2 of the present invention clearly shows that the etching machine is rotated and the cleaning time is improved a lot. Under typical conditions for the manufacture of electro-optic displays, the multilayer system according to Example 2 of the present invention can save 83% of the time required for the wet etching process, even without leaving ITO-islands, compared to the system of Comparative Example 2. Example 3

As in Example 1, the multilayer system was prepared by sequentially depositing Si 2 , Gz film and ITO film on a glass having a thickness of 丨] cm by sputtering. However, the thickness of the three-layer film is 25 nm, (9): and 120 nm, respectively. The parameters of these layered structures are summarized in Table 8. 〇 Ginger 8 : ! Example 3 and the layered example of Comparative Example 3 ~~[ r

ΙΤΟ GZO* Si02 Structure 6 nm Glass: Sodium Calcium Resistivity / Ω Ο 15.2 125 nm Features

98514.doc 8 • 31 - 1380102 at 550 nm Transmittance /% 87,50 89.58 Etch rate / nm / s ΝΑ 0.79 Clearance time (45 ° C) / sec 85 500 __ Good adhesive rubber Good chemistry in NaOH Stability: AR/% 2.0 1.5 _ Resistivity / Ω / Π 15-15.3 13.5-13.7 Temperature stability: Δϋ /% 4.6 7.9 _ Resistivity / Ω / Ρ 15.2-15.9 13.9-15.0 Humidity stability: ΔΙΙ /% 0.1 0.1 Resistivity / Ω 〇 15.2-15.3 13.5-13.6 Remarks:: GZO: ZnO having 2 at% Ga203, ΝΑ : The sheet could not be applied and studied as described in Example 1. The results of the sheet resistance obtained at nine points of the typical sheet of Example 8 are shown in Table 9. Table 9: Sheet resistance of y Example 3 (Ω/ΓΜ : 15.2 15.2 15.4 15.0 15.1 15.3 15.3 15.1 15.4 Note: Sheet resistance: Ω / □

The transmittance of the sheet was measured as shown in Table 8 at a light transmittance of 550 nm with respect to air. The observed etching rate and removal time were also determined in Table 8 at a temperature of (45 + / _1) <> Second, the sheet is studied for the formation of microstructures during etching. The same etching solution was used for the determination of the surname rate and the determination of the removal time. Conventional lithography techniques are used to etch patterns. Photoresist material (AZ VIII?? 75〇£丨| of Clariant, Switzerland) is coated on the surface of one of the sheets by 旋11(!〇-86丨111丨1811 spinner. Heating at 10〇1 for 90 seconds (prebaking), by 98514.doc

*32- 8 1380102 MA-5 601-ML exposure machine exposed to a radiant flux of 70 mJ at a radiation power output of 35 mw/cm 2 , Japan DNK, at 23 ° C by dipping at 2.38% hydrogenated tetra After 60 seconds of development of the ammonium internal calendar, the sheet is now heated for a second time to 220 C for 70 minutes (post-baking). Then, the wet etching process is carried out at a temperature of (45 +/- 1)C. After 120 seconds, I no longer see the rest of IT〇• Island. Finally, the sheet was subjected to the five-time reliability test described in Example 1. The results of these tests are contained in Table 8. The sheet passed all five stability tests. Comparative example 3

The multilayer system was prepared as in Example 3, but without GZ tantalum deposition. The thickness values of this multilayer system are also shown in Table 8 for comparison. This multi-layer system is available from Merck Display Technology, Taiwan, and is called μ〇τ#3〇〇 fully oxidized ιτο glass, a typical IT0 coated glass for STN displays.

The results of the sheet resistance obtained at nine points of the typical sheet of Comparative Example 1 are shown in Table 10. : The sheet resistance of this Comparative Example 3 (Q / gate, . 13.2 13.6 13 4 13.3 13.4 _ __13.6 13.2 13.^~~~—L—J3.2 — .丨Note: Sheet resistance: Ω /□ From this table, it is apparent that the sheet of Example 3 is very similar to the comparative example in the case of Example 3, and the optical effect of the sheet is studied. The transmittance of the sheet is determined to be relatively transparent to air at 55 〇 nm. The luminosity. The transmittance at 55 〇 nm is very similar to that of this comparative example, the transmittance of Comparative Example 3. 985I4.doc 8 • 33 - 1380102 The removal time is at (45 +/- 1) °C. The measurement was 500 seconds. The sheet was passed through all five stability tests as described in Example 3. The results are also shown in Table 8 »

Summary of Comparison of Example 3 with Comparative Example 3 Comparative ICP glass available from Merck Display Technology, Inc. of Comparative Example 3 The multilayered system according to Example 3 of the present invention has similar electrical and optical characteristics. - Shen also, μ„—The examples pass all five reliability tests. However, according to the example of the third layer

Turning and improving even, the effect of 彳 clearly shows that under the different conditions of the money, the typical 83% wet etching method used in the manufacture of electro-optic display of Example 3 can save, compared with the system of Comparative Example 3, and See the residual IT〇• island. 98514.doc

-34 1380102 In comparison with the ITO glass available from Merck Display Technology, Inc. of Comparative Example 3, the multilayered system according to Example 3 of the present invention has similar electrical and optical properties. Both examples passed all five reliability tests. However, the etching effect of the multilayer system according to Example 3 clearly shows the time required for the 83% wet etching method of the multilayer of Example 3 under the conditions of different etching machines and improved cleaning time. In the system for the manufacture of electro-optical displays, the system of Comparative Example 3 was saved and the residual ΙΤΟ-island was not seen. 98514.doc •35- 8

Claims (1)

1380102, the scope of application for patents: Patent application No. 094105264, application for replacement of Chinese patents (August, 2011) / annihilation • layered solid system, characterized by: - substrate, called first An etchable layer consisting of an etchable material - a first solid etchable layer, and a buffer layer, the substrate and the first etchable material - a solid-like layer The buffer layer between layers has a real rate. An etch rate greater than the first etchable layer. 2. The system of claim 1, wherein - the etch rate of the buffer layer ranges from 5 / (> or above to 1,000% or less) In the system of claim 1, the system of claim 1, wherein at least one layer of the buffer layer of the first layer is a transparent layer. The system of claim 1, wherein the first etchable layer and the buffer layer are both transparent layers. 5. The system of claim 1, wherein the first etchable layer and the buffer layer are at least one conductive layer. The system of claim 5, wherein the first etchable layer and the buffer layer are both conductive layers. 7. The system of claim 1, wherein - the first etchable layer is comprised of IT 。. The system of claim 1, wherein the buffer layer is comprised of a material selected from the group consisting of materials AZ〇, GZ〇, and AGZ〇, 98514-1010810.doc 1380102. 9. 10. 11. 12. 13. 14. 15 16. The system of claim 1 wherein the thickness of the δ layer is between 0.1 nm or more and 50 nm below the fire. The system of claim 1, wherein the conductive layer has a sheet resistance range of 〇·1 Ω /□ or more to □ or below at 20 ° C. The system of claim 1 wherein the system has a transmittance of 550 nm 7〇% or more. As in the system of claim 1, each section is formed as an area that is not covered by the __ and the second _ layer without being covered by the layer. The electro-optical device includes the request item丨冬系统. A knowing system. The use of the system 1 is for electro-optical devices. A method of manufacturing a junction-construction system using a layered system as claimed in claim i. A method of apparatus, characterized by using a system such as a request item. A method of fabricating a structural system, characterized in that a second layer of an etchable layer is covered. First, a buffer layer composed of an etchable material is covered and - secondly, covered by a so-called first layer on top of the buffer layer, a < U 骽 - the buffer layer has substantially greater than the first rate. j etching rate of the etching layer 985I4-I0l0810.doc