Techniques for manufacturing planar patterned transparent contact and/or electronic devices including same

Specific embodiments relate to methods of making patterned, substantially transparent contact films, and contact films and / or electronic devices made by such methods. In certain embodiments, the contact film may be patterned but substantially flat. That is, the contact film can be patterned without the step of deliberately removing any material from the layer and / or film as required by methods such as photolithography.

This application is a partial continuation application (CIP) of U.S. Patent Applications 13 / 174,349 and 13 / 174,362 filed June 30, 2011, the entire contents of which are referenced herein. included.

Electronic devices are known in the art. As one form of the electronic device, examples of the display device include an LCD device, an LED device, an OLED device, a plasma display, a flat panel display device, a touch screen device, and the like. In certain cases, the electronic device may include patterned transparent electrodes, thin films and / or contact materials. Obviously, "patterned" may optionally mean patterned with respect to conductivity and / or resistance. In some cases, such patterned films may be treated (eg, via TFT arrays) and may include grid-type and / or matrix-type patterns of conductive and resistance portions of the film. Good. Provided with electrodes and / or contact materials that include conductive and resistant parts for the display and / or touch screen device to function properly, often as in the case of including an active matrix LCD device. It is preferable to do so.

The production of conventional patterned transparent contact materials for electronic devices involves depositing a continuous transparent conductive oxide layer (TCO) and then removing the portion of TCO by multi-step photolithography. .. For example, indium tin oxide (ITO) is often deposited on a glass substrate as a blanket layer by sputtering. Sputtered blanket layers are often patterned using photolithography methods (typically by spin coating) that include photoresist material application, soft baking, exposure, hard baking, etching, and cleaning. ..

FIG. 1 is a cross-sectional view of a conventional patterned contact material. As can be seen from FIG. 1, TCO (for example, ITO) is arranged as a blanket layer on the substrate 1. The TCO is photolithographically separated and patterned with multiple patterned islands 3 to limit the transparent contact material. It can be seen that there is a step pattern and the contact material is not continuously flat.

Although photolithography is widely used, it has various disadvantages. For example, photolithography involves many steps and many intermediate materials, increasing the time and cost associated with the product. Such methods are generally used while forming patterned layers due to photoresist misalignment, photoresist baking problems, inaccurate exposure and / or etching, and incomplete removal. Can increase the likelihood of defects. Photolithography may generally form sharp steps or "horns" that can affect the next applied layer and / or material. As an example, organic light emitting diodes (OLEDs) may be particularly sensitive to such effects. Further, in some cases, the refractive index of the TCO substance may differ from the refractive index of the substrate on which the TCO substance is deposited. Therefore, if the TCO portion is removed, the appearance of the substrate and / or the coating is partially present in the TCO coating. And it looks non-uniform due to the difference in its refractive index. That is, the refractive index of a general TCO is usually about 2.0, while the refractive index of the supporting glass substrate is usually about 1.5. Therefore, photolithography may make the appearance of the product look non-uniform, which is another disadvantage. ITO itself is expensive, indium itself is a toxic substance, and the supply on the earth is insufficient. In photolithography, ITO itself is a toxic substance, and there is a large amount of waste known to be partially removed by the vapor deposition of the blanket layer. It is known to have potential harmful environmental impacts because it occurs.

<p num="0007"> Therefore, one of ordinary skill in the art can understand that it is desirable to provide an improved method for producing a patterned contact material and / or an electronic device produced by such a method.</p>

<p num="0008"> One aspect of a particular embodiment relates to a thin, transparent conductive contact material that is a natural plane, selectively patterned by radiant heat or the like.</p><p num="0009"> Yet another aspect of a particular embodiment relates to the use of ultraviolet (UV) radiation that supplies energy to the target layer to cause oxygen transfer. The stack of exemplary layers that can be used in connection with certain embodiments may not include layers that have good absorption in the infrared (IR) spectrum. That is, in an exemplary coating stack that can be used in connection with the particular embodiments described herein, the layer does not have to be highly absorbent to IR radiant heat. Redistributing the energy into the Ag and oxygen infusion layers after heating the glass can reduce the resolution of the patterned contacts and the efficiency of the method. Therefore, certain embodiments may supply energy to the target layer via UV light exposure (eg, by a UV laser). The target layer of a particular embodiment contains a Zn and / or Sn oxide that can be redistributed into Ag "injection layer" bonds after absorbing UV, or a Zn and / or Sn "seed" semiconductor. It may be a layer. In other embodiments, the Ag-based layer may itself be the target layer.</p><p num="0010"> In yet another embodiment of the particular embodiment, with respect to a transparent contact material which can include at least two adjacent layers, the first layer is highly conductive, transparent (at least in the visible spectrum) and conductive. The nature is strongly dependent on the oxidation state, and the second layer is a transparent layer capable of exchanging ionic or atomic form of oxygen with the first layer at elevated temperatures.</p><p num="0011"> In certain embodiments, the first layer is sub-oxidized and the second layer is oxidized during deposition; substantially conductive during the next heat, IR, UV, or other exposure. Oxygen is transferred from the second layer to the first layer to suppress it. In certain embodiments, the first layer is oxidized and the second layer is sub-oxidized during deposition; oxygen is transferred from the first layer to the second layer during the next heat, IR, UV, or other exposure. Be done.</p><p num="0012"> In some cases, the vapor-deposited film stack is non-conductive in the entire region and conductive only in regions exposed to heat or other energy. In some cases, the vapor-deposited film stack is conductive in the entire region and non-conductive only in regions exposed to heat or other energy.</p><p num="0013"> In certain embodiments, the selective change in conductivity has a significant effect on the optical variables of the layer only in the NIR spectral region, which is not the visible region, and the difference in appearance between the conductive and non-conductive regions is Almost none or none at all.</p><p num="0014"> In certain embodiments, two layers may be deposited on the substrate. In certain embodiments, one layer is substantially conductive and the other layer is at least partially (and optionally totally) oxidized. In certain different examples, the two layers may be at least partially oxidized. Between layers, layers may be selectively exposed to heat, radiation, and / or energy to facilitate the transfer of oxygen atoms. In some cases, oxygen atoms may flow from a layer of high enthalpy of formation to a layer of low enthalpy of formation. In certain cases, such oxygen transfer may alter the conductivity of the selective portion of the film. This may produce a planar contact film that is appropriately patterned for conductivity and / or resistance.</p><p num="0015"> A particular embodiment is a transparent planar contact material in displays, flat panels, touch screens, and / or other electronic devices, for example as an alternative to universally used non-planar contact materials manufactured by photolithography. Regarding the use of. In some cases, the planar patterned contact material and the method for producing the planar patterned contact material described herein are based on selective conductivity changes at specific locations in the planar thin film layer. In certain embodiments, this may be achieved by applying heat, radiation, and / or energy (eg, infrared radiation) to at least two thin films and / or thin films. Optionally, the application of heat, radiation, and / or energy may also activate and / or facilitate the transfer of atoms (eg, oxygen atoms) that affect conductivity between layers. Optionally, it may form a matrix of conductive and non-conductive regions from the original composition of the deposited and / or heat, radiation, and / or energy-applied layers.</p><p num="0016"> Specific embodiments of the present invention relate to methods of making coated products that include a multilayer thin film coating supported by a substrate. The conductive layer is arranged on the substrate. A lower oxide buffer layer is placed on top of the conductive layer. An upper-oxidized layer is placed on top of the lower oxidation buffer layer. Energy is selectively applied to one or more portions of the coating to move oxygen downward from the upper oxide layer to the conductive layer, increasing resistance at one or more portions of the conductive layer. After selectively applying energy, the multilayer thin film coating is substantially planar and patterned for conductivity and / or resistance.</p><p num="0017"> Specific embodiments of the present invention relate to methods of manufacturing electronic devices. A coating containing a glass substrate supporting a multilayer thin film coating including a seed layer containing Zn, Sn and / or an oxide thereof, a vapor-deposited Ag-containing conductive layer, a lower oxidation buffer layer, and an upper oxide dielectric layer in this order from the glass substrate. The product is offered. The first set of the Ag-containing layer portion that becomes the conductive portion is limited, and the second set of the Ag-containing layer portion that becomes the non-conductive portion is limited. The coating in the second set of regions is exposed to energy from the energy source, moving oxygen ions or atoms from the upper dielectric oxide layer to the Ag-containing layer and patterning the Ag-containing layer against conductivity and / or resistance. To become. A coated product having a patterned Ag-containing layer is attached to the electronic device.</p><p num="0018"> Specific embodiments of the present invention relate to methods of making coated products that include a multilayer thin film coating supported by a substrate. An Ag and O-containing first layer, which is non-conductive at least initially, is placed on the substrate. The lower oxidation buffer layer is placed on top of the first layer. Energy is selectively applied to the coating adjacent to one or more portions of the first layer to move oxygen upward from one or more portions of the first layer to the lower oxidation buffer layer of the first layer. Increase conductivity in one or more portions. After selectively applying energy, the multilayer thin film coating is substantially planar and patterned for conductivity and / or resistance.</p><p num="0019"> Specific embodiments of the present invention relate to methods of manufacturing electronic devices. A coated product containing a glass substrate supporting a multilayer thin film coating including a seed layer containing Zn, Sn, and / or an oxide thereof, a vapor-deposited Ag and O-containing non-conductive layer, and a lower oxidation buffer layer in order from the glass substrate. Provided. The first set of Ag and O-containing layer portions that become conductive portions is limited, and the second set of Ag and O-containing layer portions that become non-conductive portions is limited. In the first set of regions, the coating containing the Ag and O-containing layers is exposed to energy from the energy source, moving oxygen ions or atoms from the Ag and O-containing layers to the lower oxidation buffer layer, making them conductive and / or The Ag and O-containing layers are patterned against resistance. A coated product having a patterned Ag-containing layer is attached to the electronic device.</p><p num="0020"> Specific embodiments of the present invention relate to methods of making coated products that include a multilayer thin film coating supported by a substrate. A seed layer is placed on the substrate. A silver-containing conductive layer is placed on top of the seed layer. The upper oxide layer is placed on top of the conductive layer. A selected area of the coating is exposed to radiant energy, at which the layer of interest absorbs radiant energy, at least in part. Photons are absorbed by the target layer and transmitted to the upper oxide layer, causing (a) exchange of ions and / or atoms between the upper oxide layer and the conductive layer and / or (b) silver aggregation in the conductive layer. .. The conductivity of the conductive layer is changed at the conductive layer portion corresponding to the selected region by ion and / or atomic exchange and / or silver aggregation.</p><p num="0021"> According to the specific embodiment, the target layer may be a seed layer (including, for example, an oxide of Zn and / or Sn), a conductive layer, or a part of other layers.</p><p num="0022"> According to a particular embodiment, the exposure process is carried out by supplying an average output per unit area with a coating below the ablation threshold of the top layer. Therefore, according to certain embodiments, the coating is not significantly peeled off by exposure and / or the coating may be flat before the exposure process, such as after the exposure process.</p><p num="0023"> Specific embodiments of the present invention relate to methods of manufacturing electronic devices. Coating products are provided that include a multilayer thin film coating supported by a glass substrate. The multilayer thin film coating includes a seed layer containing an oxide of Zn and / or Sn, a vapor-deposited silver-containing conductive layer, and an upper dielectric oxide layer in order from the glass substrate. The selected area of the coating is exposed to radiant energy and the target layer absorbs radiant energy at least partially in the coating. Photons absorbed by the target layer are transmitted to the upper oxide layer, causing (a) exchange of ions and / or atoms between the upper oxide layer and the conductive layer and / or (b) silver aggregation in the conductive layer. Therefore, the conductivity of the conductive layer is changed at the conductive layer portion corresponding to the selected region. After the exposure process, the coated product is attached to the electronic device.</p><p num="0024"> Specific embodiments of the present invention relate to methods of manufacturing electronic devices. Coating products are provided that include a multilayer thin film coating supported by a glass substrate. The multilayer thin film coating includes a seed layer containing an oxide of Zn and / or Sn, a vapor-deposited silver-containing conductive layer, and an upper dielectric oxide layer in this order from the glass substrate. The selected area of the coating product is exposed to radiant energy, and the target layer absorbs radiant energy at least partially in the coating, and the photons absorbed by the target layer are transmitted to the upper oxide layer, and (a) with the upper oxide layer. Exchange of ions and / or atoms with the conductive layer and / or (b) silver aggregation in the conductive layer causes the conductivity of the conductive layer to change at the conductive layer portion corresponding to the selected region. After the exposure process, the coated product is attached to the electronic device.</p><p num="0025"> These and other embodiments, features, embodiments, and advantages can be made into further embodiments by any suitable combination, or subcombination.</p><p num="0026"> These and other features and advantages can be fully understood by reference to the embodiments described in detail below along with the drawings.</p>

<figref num="1">FIG. 5 is a cross-sectional view of a conventional patterned contact material.</figref><figref num="2">FIG. 5 is a cross-sectional view of an intermediate product used to produce a planar patterned contact material according to a particular embodiment.</figref><figref num="3">FIG. 5 is a cross-sectional view illustrating that the intermediate product of FIG. 2 can be used to produce a planar patterned contact material according to a particular embodiment.</figref><figref num="4A">It is a detailed cross-sectional view of the Example of Embodiment of FIG.</figref><figref num="4B">FIG. 2 is another cross-sectional view illustrating that the intermediate product of FIG. 2 can be used to produce a planar patterned contact material according to a particular embodiment.</figref><figref num="5">FIG. 5 is a plan view showing an example of a grid-type matrix containing a plane-patterned contact material according to the embodiment of FIG. 4A or 4B.</figref><figref num="6">FIG. 5 is a cross-sectional view of another intermediate product used to produce a planar patterned contact material according to a particular embodiment.</figref><figref num="7">FIG. 5 is a cross-sectional view illustrating that the intermediate product of FIG. 6 can be used to produce a planar patterned contact material according to a particular embodiment.</figref><figref num="8">FIG. 5 is a plan view showing an example of a grid-type matrix containing a planar patterned contact substance of the embodiment of FIG. 7.</figref><figref num="9">FIG. 5 is a plan view showing an example of a diamond-shaped array containing a planar patterned contact material according to a specific embodiment.</figref><figref num="10">It is an exemplary cross-sectional view illustrating that a planar patterned contact material can be used in connection with the contact material formed by the photolithography method according to a particular embodiment.</figref><figref num="11">FIG. 5 is a cross-sectional view illustrating that a planar patterned contact material can be used in connection with the contact material formed by the photolithography method according to a particular embodiment and showing another example.</figref><figref num="12">3 is a graph showing the transmittance of a vapor-deposited electrode and a heat-activated electrode manufactured according to a specific embodiment.</figref><figref num="13">FIG. 5 is a graph showing the difference in reflected color between a vapor-deposited electrode and a heat-activated electrode manufactured according to a specific embodiment of the present invention, together with the ITO shift and glass substrate shown for comparison.</figref><figref num="14">FIG. 5 is a graph showing the difference in transmitted color between a vapor-deposited electrode and a heat-activated electrode manufactured according to a specific embodiment of the present invention, together with the ITO shift and glass substrate shown for comparison.</figref><figref num="15">FIG. 5 is a cross-sectional view showing an example of an OLED including one or more planar patterned contact material layers according to an embodiment.</figref><figref num="16">FIG. 5 is a cross-sectional view of an LCD display device including one or more planar patterned contact material layers according to an embodiment.</figref><figref num="17">FIG. 5 is a schematic cross-sectional view of a touch screen comprising one or more planar patterned contact material layers according to an embodiment.</figref><figref num="18">6 is a graph plotting the transmittance, reflectance, and absorptance of a general silver layer with respect to a wavelength.</figref><figref num="19">FIG. 5 is a schematic representation of laser patterning of a particular embodiment in which the laser leaves undamaged conductivity-imprints.</figref>

Specific embodiments of the present invention relate to techniques for producing planar, multilayer transparent contact materials without the use of photolithography. The selective conductivity change of the thin film material applies energy to the combination of at least two thin films (eg, using one or more infrared (IR) or UV sources, heating, laser through a proximity mask, etc.). It may be achieved by. The application of such energy selectively forms a region with high conductivity and high resistance by activating the transfer of ions or atoms (eg, oxygen ions) that affect conductivity between the two layers.

In a particular embodiment, for example, under IR irradiation, the conductive layer and the upper oxide layer are combined so that oxygen is transmitted from the upper oxide layer to the conductive layer, and the conductive layer is selectively non-conductive in a desired region. Manufactured to have. In certain embodiments, Ag may be used as the conductive layer in connection with upper oxidized TiOx, ZrOx and the like. In addition, a substantially very thin lower oxidation buffer layer is introduced between the conductive layer and the upper oxidation layer to help reduce the potential for oxidation of the conductive layer during deposition. Particularly in other embodiments, by moving ions or atoms (including, for example, Ag) from the non-conductive layer upwards to a thin lower oxidation buffer layer and / or protective layer, the original non-conductive layer is highly conductive. Can help form the region.

Certain embodiments provide a transparent contact material that is advantageously low cost and is a natural flat surface. Further or instead, certain embodiments reduce the possibility of detectable visual differences between the conductive and non-conductive regions.

The exemplary techniques described herein are conventional found in flat panel displays (eg, LCD displays, plasma display panels, OLED displays, OLED lighting, etc.), touch panel screens and / or other popular electronic devices. May be used with or in place of the ITO-based non-planar contact material.

FIG. 2 is a cross-sectional view of an intermediate product used to produce a plane-patterned contact material according to a particular embodiment, and FIG. 3 is a plane-patterned contact according to a particular embodiment. FIG. 5 is a cross-sectional view illustrating that the intermediate product of FIG. 2 can be used to produce a contact material. As shown in the embodiment of FIG. 2, the highly conductive and transparent metal layer 13 (including, for example, Ag) and the dielectric layer 17 (including, for example, ZrOx, TiOx, etc.) are provided adjacent to each other. Will be done. When exposed to an energy source, the dielectric layer 17 can relatively easily exchange oxygen with metal in the conductive layer 13 during irradiation with, for example, heat treatment, laser exposure, IR and / or UV energy. Due to such activity, oxygen is controlledly transferred from the dielectric layer 17 to the region of the conductive layer 13 to selectively form a region of high resistance. In certain embodiments, the dielectric layer 17 may be top-oxidized to facilitate such methods. In certain other embodiments, the dielectric layer 17 may be fully or partially oxidized.

For example, the layer 17 may be any transparent material, such as a dielectric, a transparent semiconductor, a transparent metal, or a combination of the above. For example, TiOx, metal Zr, ZrOx, ZrTiOx, ZrAlOx, InSnOx, ZrNbOx, ITO and the like can be mentioned. The thickness of the layer 17 may be about 10 to 400 nm, preferably about 30 to 300 nm, more preferably about 5 to 250 nm. The layer 17 may be sputter-deposited from a metal target or a ceramic target, and / or sputter-deposited by reactive sputtering. In certain embodiments, layer 17 may be deposited via a zirconium target at an oxygen flow rate of about 3 to 25 sccm. The ratio of argon to oxygen may be from about 50: 1 to about 2: 1. If layer 17 contains more than one material, layer 17 may be deposited from alloy targets and / or by co-sputtering (from more than one target).

In another embodiment of the invention, for example, one or more optional undercoats 11 may be provided between the substrate 1 and the conductive layer 13. The undercoat layer 11 contains or is a seed layer for promoting good quality Ag (eg, stoichiometric zinc oxide, tin oxide, or any suitable TCO material). Alternatively, it may be another metal layer arranged on the metal layer. The undercoat layer 11 can help serve as an alternative or even a barrier layer (eg, help reduce sodium transfer when the substrate 1 is a soda lime silica glass substrate). In certain embodiments, a silicon-containing layer (eg, containing silicon or an oxide and / or nitride of silicon) may be used for this purpose. Also, in other embodiments, one or more index matching layers may be provided to improve the optical properties of the layer stack system. For example, a stack of one or more high index / low index layers may be provided because a high / low / intermediate index stack and the like can be provided. Index matching, color matching and / or in other embodiments of the invention, tin oxides, titanium oxides, silicon oxides, silicon nitrides, silicon oxynitrides, and / or other substances for other purposes. May be used.

In other embodiments of the invention, one or more optional overcoats 19 may also be provided. The optional overcoat 19 serves as a cap layer encapsulated on top of the layer stack to reduce or reduce the likelihood of long-term degradation. Suitable substances include, for example, TiOx, ZrOx, SiOx, SixNy, SiOxNy and the like.

As shown in FIGS. 2 and 3, in a specific embodiment, the lower oxidation buffer layer 15 may be interposed between the conductive layer 13 and the dielectric layer 17. It can be seen that such a buffer layer reduces (and in some cases prevents) oxidation of the conductive layer 15 during vapor deposition. In certain embodiments of the invention, such layers may be under-oxidized. Suitable substances include, for example, lower oxidized ZrOx, metal Zr, ZrTiOx, ZrAlOx, ITO, ZrNbOx, TiOx, SnOx, TiOx and the like. In certain embodiments, the thickness of the buffer layer 15 may be 0.1 to 30 nm, more preferably 0.3 to 20 nm, more preferably 0.5 to 15 nm. It may be about 2 nm.

As shown in FIGS. 2 and 3, the contact material is initially prepared to be conductive (eg, pure Ag, then lower oxidation buffer, then upper oxide layer). As mentioned above, selective conductivity reversal is IR radiation (eg, IR radiation from a radiant heat source) by shortwave or other IR heaters or other forms of oven depending on the presence or absence of forced cooling under vacuum or atmospheric pressure. May be achieved by applying. In certain embodiments, heat irradiation may be performed via an optionally adiabatic proximity mask.

As shown in FIG. 3, the resulting conductive layer 13 initially becomes an Ag layer (13') patterned by oxygen ions or atoms flowing from at least the initial upper dielectric oxide layer 17. In certain embodiments, such activity may cause the upper oxide dielectric layer 17 to be totally oxidized or slightly converted to a lower oxide dielectric layer (17'). However, in certain other embodiments, the dielectric layer may be top-oxidized according to the amount of oxygen moving from the dielectric layer 17 to the conductive layer 17.

FIG. 4A is a detailed cross-sectional view of the embodiment of FIG. As shown in FIG. 4A, the heat or irradiation source 23 is used to remove oxygen ions or atoms from the upper dielectric oxide layer (17') containing TiOx at least initially to the lower oxide barrier layer 15 containing TiOx and / or ZrOx. It is transferred to the Ag-based layer via the above to produce a patterned layer (13').

FIG. 4B is similar to FIG. 4A, except that it includes a laser source (23') that emits a laser beam. As shown in FIG. 4A, oxygen ions or atoms are moved from the upper dielectric oxide layer (17') containing TiOx to the Ag-based layer at least initially via the lower oxidation barrier layer 15 containing TiOx and / or ZrOx to form a pattern. A modified layer (13') is produced.

In certain embodiments, the surface temperature of the glass is 200-650 ° C. and the ambient air temperature is 20-300 ° C. during exposure. Preferably, the surface temperature is kept below 800 ° C and the ambient air temperature is kept below 500 ° C. In other embodiments, the exposure time may be retained for 5 seconds to 10 minutes. Therefore, in certain embodiments, it can be seen that such a method can be carried out under room temperature or elevated external temperature conditions, preferably keeping the glass temperature below the melting point or softening point.

The mask 25 helps adjust the exposed area, for example, so that the selected area is patterned. As mentioned above, in certain embodiments, the mask may help control the temperature of the glass by blocking heat. However, it can be seen that a laser of appropriate resolution does not require such a mask 25. If the laser is operated at the appropriate wavelength, the heat treatment may be accomplished with layers with or without a mask. In certain embodiments, for example, a YAG laser with an working wavelength of 1064 nm may be used to apply the required energy to the selected region.

The sheet resistance of the conductive portion of the contact material may vary from 0.2 to 500 ohms / square, while the sheet resistance of the non-conductive portion is at least about 50 ohms / square, more preferably at least about 100. Ohms / squares, more preferably at least about 1,000 ohms / square, and in some cases may exceed 1 megaohm / square in certain embodiments. In other embodiments, such a wide subrange is also possible. For example, in connection with the application of a particular solar cell, a sheet resistance of less than 10 ohms / square is preferred for conductive portions, while a sheet resistance of less than 30-50 ohms / square. This may be sufficient for use in certain active matrix LCD devices. In a specific embodiment, a sheet resistance ratio of more than 30,000: 1 may be provided, and in other embodiments, a sheet resistance ratio of more than 100,000: 1 may be provided.

FIG. 5 is a plan view showing an example of a grid-type matrix containing the plane-patterned contact material of the embodiment of FIG. 4A or FIG. 4B. In FIG. 5, the X mark indicates a conductive portion of the substrate. Good material blocking (abruptness) is achieved with a proximity mask (and / or laser beam) due to the low thermal conductivity of the laterally very thin Ag (or other conductive material) layer. .. In the selected region, the change in conductivity is achieved not because of the removal of the substance, but because of the change in the physical properties of the substance.

Although it is described that the specific embodiment contains Ag or contains a conductive layer of Ag, other substances may be used in other embodiments of the present invention. For example, the conductive layer may include gold, platinum, palladium, silver, and / or a combination thereof or the like. Other substances that are sufficiently transparent in the visible spectrum and capable of high conductive patterning in the selected region are zirconium, indium, tin, and / or titanium, and compounds containing them (eg, AgZr, AgIn, AgSn, AgTi). , Etc.), but are not limited to these.

The thickness of the conductive layer 13 may be about 1 to 50 nm, more preferably about 3 to 25 nm, and most preferably 5 to 15 nm. The conductive layer 13 may be sputter-deposited from a metal target or a ceramic target by sputter deposition and / or reactive sputtering. If the conductive layer 13 contains more than one material, it may be deposited by co-sputtering with the alloy target and / or (from more than one target).

As described above, in the specific embodiment, the contact material may be manufactured so as to have an initial conductivity. However, in certain other embodiments, the contact material may be manufactured to be initially non-conductive. In such cases, oxidized Ag (eg, AgO, Ag)_２O, AgO_x,Here, after a layer containing 0.1 &lt;x &lt;1, more preferably 0.2 &lt;x &lt;0.8, most preferably x &lt;= 0.5, etc. is arranged on the substrate, the lower oxide layer ( A layer containing a sub-oxidized layer), such as TiOx, ZrOx, or other suitable material, may be arranged. In this regard, FIG. 6 is a cross-sectional view of another intermediate product used to produce a planar patterned contact material according to a particular embodiment, and FIG. 7 is a cross-sectional view of the particular embodiment. FIG. 5 is a cross-sectional view illustrating that the intermediate product of FIG. 6 can be used to produce the planar patterned contact material according to the example. The non-conductive layer 21 initially arranged is AgO, Ag._２It may contain O, or any other suitable substance, or may be another suitable substance. The non-conductive layer 21 may support a lower oxidation buffer layer 15 that helps reduce its potential for oxidation during deposition. However, the non-conductive layer 21 may serve as a storage region for oxygen ions or atoms that are about to move. For example, as shown in FIG. 7, the heat or irradiation source 23 may move oxygen atoms to the lower oxide layer (15') to form a patterned Ag-based layer (21').

FIG. 8 is a plan view showing an example of a grid-type matrix containing the plane-patterned contact material of the embodiment of FIG. 7. FIG. 8 is similar to FIG. 5 except that Y shows the high resistance portion of the contact material plane-patterned on substrate 1.

It can be seen that the contact material produced by moving oxygen ions or atoms to the conductive layer or from the dielectric layer or non-conductive metal oxide layer may be substantially flat. In certain embodiments, it is not necessary to deliberately remove the material to form a patterned region. As mentioned above, changes in the physical properties of a substance may occur due to selective exposure to an energy source. In certain embodiments, the thickness of the planar patterned contact material is preferably less than 25%, more preferably less than 20%, and in some cases more than 10-15%, a substantially uniform thickness. It may be. In certain embodiments, the overall flatness is equal to or better than that achieved by photolithography techniques.

Although specific embodiments have been described for patterned rows and / or heat (eg, matrix-type arrays), other patterns are possible in other embodiments of the invention. For example, FIG. 9 is a plan view showing an example of a diamond-shaped array containing a plane-patterned contact material according to a specific embodiment. One or more rows and / or patterns patterned with an array-type array, the illustrated diamond-type array of FIG. 9, or any other suitable sequence using the techniques described herein. More than one heat may be formed.

As mentioned above, the selectively applied heat, radiation, and / or energy may allow oxygen atoms to flow from a particular layer to a particular other layer. Therefore, as described above, the contact material may initially be conductive or non-conductive. This is because if heat, radiation, and / or energy is selectively applied, oxygen can flow from the region of high enthalpy of formation to the region of low enthalpy of formation at a particular location of the contact material. That is, in certain embodiments, oxygen atoms or ions may be transferred from a layer of high enthalpy of formation to a layer of low enthalpy of formation if the oxygen atoms or ions are properly excited.

Enthalpy, as is well known, is the thermodynamic world that includes the amount of internal energy (the energy required to form a system) and the amount of energy required to form a space by setting volumes and pressures that oppose the environment of the system. It is an index of the total energy of. Enthalpy is usually considered in some cases in terms of changes in the enthalpy of the system (Delta H), which is the same as changes in the internal energy of the system, and the work done by the system in the surrounding environment. Under these conditions, the change in enthalpy is the heat absorbed or released by a chemical reaction. The enthalpy of formation of a substance is a change in the enthalpy that accompanies the formation of a substance from its constituent elements in the standard state in the standard state. Zirconium oxide (eg ZrO_２), The theoretical standard enthalpy of formation is -1080 kJ / mol, but on the other hand, when the silver layer is vapor-deposited, the theoretical enthalpy of formation may be 0 if the layer mainly contains silver. (Because no new compound is produced substantially). However, the enthalpy of formation can be different if the lower oxide of the zirconium oxide is formed. The theoretical standard enthalpy of formation of silver oxide is -31.1 kJ / mol. Therefore, it can be seen that oxygen moves from the upper oxidized ZrOx layer to the Ag-based layer, and oxygen moves from the silver oxide-containing layer to the lower oxide buffer layer.

In certain embodiments, two substantially planar patterned contacts may be provided on the common side of the substrate. This can be achieved if the laser and / or energy depth is properly limited or vertically adjusted. However, certain embodiments can provide a planar patterned contact material on the opposite side of the substrate to obtain a suitable matrix address.

Further, in another embodiment, the conventional photolithography technique and the technique of the plane-patterned contact material described in the present specification can be mixed and matched. 10 and 11 are cross-sectional views of an example illustrating that a planar patterned contact material can be used, for example, in connection with the contact material formed by the photolithography method according to a particular embodiment. As shown in FIG. 10, the planar patterned contact material 3'may be arranged on the substrate 1. The contact material 3 formed by the photolithography method may be located on the plane-patterned contact material 3'. In certain embodiments, this may provide a suitable matrix address. Of course, the plane-patterned contact substance 3'and the contact substance 3 formed by the photolithography method include the contact substance 3'in which the contact substance 3 formed by the photolithography method is patterned adjacent to the substrate 1. The arrangement order may be changed so as to be located above it. Unlike FIG. 10, FIG. 11 shows a contact material 3'plane-patterned on the first main surface of the substrate 1 and a contact material 3 formed by photolithography on the opposite main surface of the substrate 1.

In certain embodiments, for example, when the vapor-deposited silver layer is conductive, silver agglomeration may be used as part of a mechanism for promoting a change in conductivity with an oxidative change. After oxidation promotes agglomeration, it can cause discontinuity of the silver layer in the thermal region, followed by interruption of conductivity.

In certain embodiments, dopants such as Zr, Al, Ni, etc. may be added to the silver to help adjust (eg decrease) the threshold for aggregation and / or oxidation. In a particular example, the dopant value may be 0.0001% by weight (wt%) to 5% by weight, preferably 0.5% by weight. Suitable dopants to Ag to reduce oxidation can include Ti, Mg, Zr, Ni, Pd, PdCu, and Hf, which help reduce oxygen diffusion in Ag and crystal growth. It can also act as an inhibitor.

It was found that the change in conductivity between the activated and inactivated regions of the planar patterned contact material mainly changes the light transmission in the infrared range. This preferably reduces the difference in appearance between the conductive and non-conductive regions of the contact material. This is a graph which is clearly shown in FIG. 12 and shows the transmittance of the vapor-deposited electrode and the heat-activated electrode manufactured according to a specific embodiment. As can be seen from the graph of FIG. 12, there is little change in the UV spectrum between the coated electrode and the heat treated electrode or other activated electrode. It is clear that such a shift actually increases the transmittance in the visible range and has a considerable benefit in the infrared part of the spectrum. In exemplary applications where infrared transmission is an issue (eg, applications for some flat panel displays or other electronic devices), suitable IR filters may be provided to help reduce the effects of EMI. ..

FIG. 13 is a graph showing the reflected color difference between the vapor-deposited electrode and the heat-activated electrode manufactured according to a specific embodiment of the present invention, together with the ITO shift and glass shown for comparison. Is a graph showing the transmission color difference between the vapor-deposited electrode and the heat-activated electrode manufactured according to a specific embodiment of the present invention, together with the ITO shift and glass shown for comparison. As can be seen from such a graph, the reflection color and the transmission color delta a^＊And b^＊The value is very small, which is preferable as compared with the shift by ITO deposition on glass. In certain embodiments, the reflective and transmissive color delta a^＊Is less than 10, more preferably less than 5, and in some cases 2 or 3 or less. Similarly, in certain embodiments, the reflective and transmissive color delta b^＊Is less than 10, more preferably less than 5, more preferably 2 or 3 or less.

In a particular embodiment, there may be no significant difference in color difference between the conductive and non-conductive regions. Preferably, in certain embodiments, the haze may be improved, i.e. a value very close to zero.

As mentioned above, the planar patterned contact material described herein may be used in connection with a variety of electronic devices. An OLED is a form of electronic device that can provide the benefits of the planar patterned contact material described herein. OLEDs are used in television screens, computer monitors, small and lightweight system screens such as mobile phones and PDAs, watches, advertisements, information, indications and the like. OLEDs may also be used in spatial lighting light sources and large area light emitting elements. OLED devices are described, for example, in US Pat. Nos. 7,663,311; 7,663,312; 7,662,663; 7,659,661; 7,629,741 and 7,601,436. The entire contents of each are included herein by reference. The organic light emitting diode (OLED) is a light emitting diode (LED) which is a film of an organic compound whose electroluminescent layer emits light with respect to an electric current. Optionally, such a layer of organic semiconductor material is located between the two electrodes. In general, for example, at least one electrode is transparent. Such one electrode or two electrodes may be the planar patterned transparent contact material described herein.

As mentioned above, the oxygen exchange system (eg, two layers) may be used in connection with the OLED display. A typical OLED contains two organic layers sandwiched between two electrodes, namely an electron and hole transport layer. The top layer electrode is generally a metal mirror with high reflectance. The bottom electrode is a transparent conductive layer that is generally supported by a glass substrate. The top layer electrode is generally the cathode and the bottom layer electrode is generally the anode. ITO is often used as an anode. When a voltage is applied to the electrodes, the charge begins to move in the device under the influence of an electric field. Electrons depart from the cathode and holes move in the opposite direction from the anode. Such charge recombination forms photons with the frequency provided by the energy gap (E = hν) between the LUMO and HOMO levels of the luminescent molecule, and the power applied to the electrodes is deformed by light. Other materials and / or dopants may be used to produce other colors, and such colors can be combined to obtain additional colors.

FIG. 15 is a cross-sectional view showing an example of an OLED including one or more plane-patterned contact material layers according to an embodiment. The glass substrate 1502 may support the transparent anode layer 1504. The hole transport layer may be a carbon nanotube (CNT) -based layer as long as the hole transport layer 1506 is doped with a suitable dopant. Conventional electron transport and emission layers 1508 and cathode layers 1510 may also be provided. As mentioned above, one or two of the anode layer 1504 and the cathode layer 1510 may benefit from the planar patterned contact material techniques described herein.

Such techniques may also be used in inorganic light emitting diodes (ILEDs), polymer light emitting diodes (PLEDs), and / or other applications. See, for example, U.S. Patent Applications 12 / 923,842 and 12/926,713, which document includes examples of such devices as references herein.

As mentioned above, the techniques described herein may be used in connection with LCDs and / or other flat panel displays. LCD devices are known in the art. See, for example, U.S. Pat. Nos. 7,602,360; 7,408,606; 6,356,335; 6,016,178; and 5,598,285, and U.S. Patent Application No. 13 / 020,987. , Each is included throughout this specification. FIG. 16 is a cross-sectional view of an LCD display device including one or more planar patterned contact material layers according to an embodiment. Generally, the display device 1601 usually includes a layer of liquid crystal material 1602 interposed between the first substrate 1604 and the second substrate 1606, and the first substrate 1604 and the second substrate 1606 are usually borosilicate glass substrates. Is. The first substrate 1604 is often referred to as a color filter substrate and the second substrate 1606 is often referred to as an active or TFT substrate.

The first substrate or color filter substrate 1604 usually includes a black matrix 1608 formed on it in order to improve the color quality of the display. A polymer, acrylic, polyimide, metal, or other suitable base may be placed as a blanket layer and then patterned using photolithography or the like to form a black matrix. Individual color filters 1610 are placed in the holes formed by the black matrix. In general, individual color filters often include a red filter (1610a), a green filter (1610b), and a blue filter (1610c), but other colors may be used in place of or in combination with such elements. May be good. The individual color filters may be formed by photolithography, inkjet, or other suitable technique. A common electrode 1612 formed from indium tin oxide (ITO) or other suitable conductive material is substantially on the entire substrate or on the black matrix 1612 and individual color filters (1610a, 1610b, and 1610c). It is formed.

The second substrate or TFT substrate 1606 has an array of TFTs 1614 formed on the second substrate or TFT substrate 1606. Such a TFT is selectively operated by a drive electronic device (not shown) to adjust the function of the liquid crystal optical bulb with the layer of the liquid crystal substance 2. The TFT substrate and the TFT array formed on it are described, for example, in US Pat. No. 7,589,799; 7,071,036; 6,884,569; 6,580,093; 6,362,028; 5,926. , 702; and 5,838,037, each of which is included throughout the specification. A light source (not shown in FIG. 16), one or more polarizing plates, an alignment layer, and the like may be included in a general LCD display device. Cover glass may be provided, for example, to help protect the color filter substrate and / or other internal components. The TFT substrate 1606 and / or the color filter substrate 1604 may support, for example, a planar patterned contact material as a patterned electrode.

As described above, the techniques described herein may be used in connection with touch panel devices. The touch panel display may be an electrostatic or resistance touch panel display that includes a planar patterned contact material or other conductive layer as described herein. For example, U.S. Pat. Nos. 7,436,393; 7,372,510; 7,215,331; 6,204,897; 6,177,918; and 5,650,597, and U.S. Application No. 12/292. , 406, the contents of which are incorporated herein by reference. For example, FIG. 17 is a schematic cross-sectional view of a touch screen that includes one or more planar patterned contact material layers according to an embodiment. FIG. 17 includes a lower layer display 1702, which may be an LCD, plasma or other flat panel display in certain embodiments. The optically transparent adhesive 1704 binds the display 1702 to a thin glass sheet 1706. In the example embodiment of FIG. 17, modified PET foil 1708 is provided as the top layer. The PET foil 1708 has multiple pillar spacers 1710 and an edge seal. It is separated from the upper surface of the thin glass substrate 1706 by seal) 1712. First and / or second planar patterned contact material layers (1714 and 1716) may be provided on a thin glass substrate 1706 on the surface of the PET foil 1708 adjacent to the display 1702 and on the opposite surface of the PET foil 1708. .. One or two contact material layers may be patterned according to the techniques described herein.

Although examples of specific electronic devices have been identified, the techniques disclosed herein may also be used in the application of solar cells in connection with other electronic devices included as gates or data lines in a variety of devices and the like. Good.

The advantage obtained by using the techniques described herein is that the contact material can be produced at a lower cost than conventional ITO-based contact materials. The key to cost savings is related to replacing ITO with a relatively inexpensive thin layer of silver. Another key to cost savings is related to the numerous steps and material removal used in photolithography. The planar patterned contact material preferably has increased durability because it is patterned against conductivity and / or resistance without interfering with the actual structure of the layer.

Although it has been described that IR irradiation is used for patterning in a specific embodiment, other techniques may be used in other embodiments. For example, UV laser wavelengths and visible laser wavelengths may be used in place of IR or in combination with IR. In such techniques, IR may be reflected at least partially by the coating, while UV and / or partially visible wavelengths are effectively absorbed by layers other than Ag to heat the stack. Since it is used, it is preferable in some cases. For example, with UV, energy can be absorbed by the seed layer (which may be a semiconductor with a bandgap suitable for UV absorption with an energy of about 3.0-3.6 eV). Therefore, in certain embodiments, the seed layer may absorb possible heat from the UV energy and then transfer it to the upper oxide layer.

Thus, in certain embodiments, the selective conductivity change of the thin film material in the desired region of the contact material may be achieved by applying radiant energy in the form of light of selective wavelength. Depending on the irradiation wavelength, the light energy is selectively absorbed by a specific layer of the multilayer stack, for example, a seed layer containing tin oxide or zinc oxide, and then supplied by photons to the silver layer and the adjacent upper oxide layer. You may. The supplied energy causes ion exchange and / or agglutination of the conductive silver layer between the specific layers of the contact material to change the conductivity in a desired region. Proper tuning of the irradiation method can change the conductivity without supplying sufficient heat to the multi-layer stack to remove material. Contact materials add many advantages to virtually flat and integrated electronics.

Specific embodiments relate to heat source embodiments and stack thermal interaction mechanisms. Light energy from a heat source may be supplied by an appropriate mechanism.

In the first option, the light energy from the heat source is essentially supplied by selective absorption in at least one layer of the stack in addition to the silver conductive layer. In this option, energy is transferred to the silver layer and the adjacent upper oxide layer, causing silver aggregation and / or ion and / or atom (eg, oxygen) exchange to alter conductivity (in this case highly conductive). Suspend or suppress). Any one or more layers can be used in the stack to absorb light energy, but to help ensure high levels of energy transfer, which is advantageous in certain implementations targeting the layer closest to silver. .. In this case, the light energy may be greater than the bandgap of the material in at least one layer of the stack. Therefore, a seed layer containing tin oxide or zinc oxide located directly below the silver layer may be a preferred target layer. The photon energy may be at least 3.2 eV for the layer containing zinc oxide (ZnO) and at least 3.8 eV for the layer containing tin oxide. Such values correspond to ultraviolet (UV) light having wavelengths less than 390 nm and 326 nm.

In the second option, the light energy from the heat source is supplied by the absorption of the silver layer. As shown in FIG. 18, silver is mostly reflected by near-infrared and infrared rays and is substantially transparent in the visible range. Therefore, absorption tends to be small in such regions and IR light is substantially "consumed". Also, other layers (including dielectrics in the stack of exemplary layers disclosed herein) and wide bandgap semiconductors (eg, seed layers) may be inherently transparent to IR. Therefore, it is preferable to use UV light because UV light is easily absorbed by the silver layer. In certain embodiments, one or more UV wavelengths may be selected such that absorption exceeds 10%, more preferably greater than 15%, more preferably greater than 25%. As shown in FIG. 18, this corresponds to a UV wavelength, particularly less than 400 nm, more preferably less than 375 nm, more preferably 300-350 nm.

As can be seen from the above, UV light may be an effective light source for energizing the stack to change its conductivity. Thus, certain embodiments are substantially flat, thin film transparent using light supplied to at least one layer of the multilayer stack, preferably UV light of less than 400 nm, without removing or damaging the material in the stack. It can be seen that the conductive contact material may include selectively patterning (eg, changing conductivity). The selected wavelength may be tuned with respect to the target layer, for example, so that the corresponding light energy is greater than the bandgap of material in the target layer in the stack. For example, for the target layer containing ZnO, the photon energy is preferably 2.7 to 3.7 eV, more preferably 2.9 to 3.5 eV, and in some cases about 3.2 eV. The corresponding wavelength may be 330-450 nm, more preferably 350-430 nm, and in some cases about 390 nm. For the seed target layer containing the tin oxide, the photon energy may be preferably 3.2 to 4.4 eV, more preferably 3.4 to 4.2 eV, and in some cases about 3.8 eV. The corresponding wavelength may be 275-375 nm, more preferably 290-360 nm, and in some cases about 326 nm. In certain embodiments, the output of the supplied light may be 1-50 mW. In certain embodiments, the output of the supplied light may be 1-5 mW, while the output of the supplied light in other embodiments may be 20 mW.

Appropriate patterning may be achieved using the exemplary setups described in relation to FIGS. 4A-4B. Using the laser shown in FIG. 4B may be advantageous when a high resolution region is required or preferred (eg, for high resolution displays and the like). UV irradiation through a mask using one or more two-dimensional light sources such as a UV lamp (exemplified in FIG. 4A) may be allowed for applications such as, for example, a particular form of touch panel display. The solid-state laser may be used for UV irradiation. In other embodiments, deuterium, xenon, or other lamps may be used.

Excimer lasers (eg, based on XeF, XeCl, etc.) may be used for or instead of laser UV exposure. Such lasers are usually available at very high powers of about 1200 W or less. The excimer laser may be used for exposing the film through a mask or for increasing the amount of processing. It has been noted that excimer lasers are used fairly regularly to crystallize amorphous silicon (a-Si) into polycrystalline silicon (poly-Si) for displays and can be easily incorporated into commercial production.

Short pulse yttrium aluminum garnet (YAG, Nd-YAG, Ho-YAG, Er-YAG) laser or CO_２A laser may be used.

Certain techniques have been found to include providing sufficient power to the absorption layer without significantly damaging or removing material from the multi-layer stack. This may be achieved in certain cases where the average output per unit area is used below the ablation threshold. This may be achieved by properly balancing the utilization, frequency, and peak output and / or by having the beam defocused using optical means.

FIG. 19 schematically illustrates laser patterning of a particular embodiment in which the laser leaves an undamaged conductive modified imprint. The imprint is shown in dark areas, but the imprint has significant properties that are substantially the same as the non-conductive change areas adjacent to the conductive change areas (eg, recognizable transmission changes and / or colors). There is no shift). The conductive modification imprint may be in a series of partially overlapping or adjacent visible or invisible circles, rectangles or other forms depending on the laser or light source used. In certain embodiments, the conductivity of such regions may be about 30,000 less than that of the untreated regions. In certain embodiments, the conductivity cost may be 100,000: 1 or more, depending on the desired application.

Specific embodiments described herein are described to include a thin film layer stack placed on a glass substrate. For example, it can be seen that the glass substrate may be a soda lime silica-based substrate or a borosilicate glass substrate. However, in other embodiments, the substrate may be a silicon wafer or chip. In other embodiments, the substrate may be a flexible and / or plastic-based polymeric material. That is, the substrate described herein may be any suitable material.

As used herein, terms such as "above" and "supported by" do not mean that the two elements are directly adjacent to each other, unless otherwise specified. Should be interpreted as not. In other words, even if there is one or more layers between the first and second layers, the first layer is "above" or "supported" by the second layer. Can be done.

Although the present invention has described what is currently considered to be the most practical and preferred embodiment, the present invention is not limited to the disclosed embodiments, and on the contrary, the gist and scope of the claims. It should be understood to cover the various changes and equivalent arrangements contained in.