1. Field of the Invention
The present invention generally relates to optoelectronic devices and their forming methods.
2. Description of Related Art
Recently, organic optoelectronic devices, such as organic solar cells (OSC), organic light emitting diodes (OLED), organic light sensors, and so on, become increasingly advantageous according to the degree produced in light-weight, small-thickness, large-area, flexible, low-cost, and environmental protection forms.
In another aspect, because moisture may damage materials of the organic optoelectronic devices and thus decrease the lifetime, manufacturers promote the packaging level of the devices and thus inevitability increase the cost. There hence remains a need to provide organic optoelectronic devices with better efficiency, longer lifetime, higher reliability, and lower cost.
For solar cells, bulk heterojunction is usually employed to promote the power conversion efficiency (PCE) by means of increased interface area between the donor and acceptor, resulting in more excitons reaching the interface and then separating into electron-hole pairs.
In order to augment the power conversion efficiency of organic optoelectronic devices, a buffer layer may be interposed between the organic layer and the transparent electrode. For example, a thin layer composed of calcium or lithium fluoride may be disposed between the aluminum electrode and the organic layer. A buffer layer including, for instance, poly(3,4-ethylenedioxythiophene), or PEDOT, may be disposed between the transparent electrode and the organic layer to increase the power conversion efficiency.
However, an aluminum electrode, or a buffer layer of calcium or lithium fluoride, is susceptible to being oxidized in the presence of air, causing the resistance of the device to increase. On the other hand, a buffer layer of PEDOT may over time result in corrosion of the transparent electrode, causing the device to be damaged.
In order to overcome the problems described above, efforts have been made to replace the aluminum electrode with a high work-function metal to be used as an anode, and with transition metal oxides, such as vanadium oxide or tungsten oxide, being formed between the anode and the organic layer for transporting or injecting holes effectively so as to increase the power conversion efficiency. In addition, another transition metal oxide, zinc oxide, which is not corrosive to the transparent electrode, can be formed between the transparent electrode and the organic layer to be used as an electron-transporting or electron-injecting layer in place of PEDOT.
The transition metal oxide layers described above are usually formed by using a vacuum evaporation process, which is costly and difficult for producing a large-area device. Some transition metal oxide layers can be formed by the sol-gel method. While it is possible to produce a large-area device using the sol-gel method, the sol-gel method includes a high temperature annealing treatment. Consequently, the processing temperature is usually higher than the glass transition temperature (Tg) of the organic material, which may damage the organic layer.
An object of the present invention is to provide optoelectronic devices and their forming methods, in which the devices have excellent efficiency and the methods are simple, speedy, cost-saved, and capable of producing the devices in low temperatures.
Accordingly, one embodiment of this invention provides an optoelectronic device, comprising; a first electrode; one or more first transition metal oxide layers, arranged on the first electrode; an active layer arranged on the one or more first transition metal oxide layers; one or more second transition metal oxide layers, arranged on the active layer, wherein the one or more second transition metal oxide layers comprise a nickel oxide (NiO) layer and/or a copper oxide (CuO) layer; and a second electrode, arranged on the one or more second transition metal oxide layers.
Accordingly, another embodiment of this invention provides an optoelectronic device, comprising: a first electrode; a transition metal oxide layer, arranged on the first electrode; an active layer, arranged on the transition metal oxide layer; a transition metal oxide mixing layer, arranged on the active layer, wherein the transition metal oxide mixing layer comprises two or more metal oxides comprising CuO and/or NiO mixed with at least an n-type transition metal oxide; and a second electrode arranged on the transition metal oxide mixing layer.
Accordingly, another embodiment of this invention provides a method for producing an optoelectronic device, comprising the steps of forming a first electrode; coating then drying one or more first solutions on the first electrode in sequence, thus forming one or more first transition metal oxide layers on the first electrode; coating then drying a second solution on the one or more first transition metal oxide layers, thus forming an active layer on the one or more first transition metal oxide layers; coating then drying one or more third solutions on the active layers in sequence, thus forming one or more second transition metal oxide layers on the active layer; and forming a second electrode on the one or more second transition metal oxide layers.
Reference will now be made in detail to specific embodiments of the invention. Examples of these embodiments are illustrated in accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to these embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well-known components and process operations have not been described in detail in order not to unnecessarily obscure the present invention. While drawings are illustrated in detail, it is appreciated that the quantity of the disclosed components may be greater or less than that disclosed, except where expressly restricting the amount of the components.
In embodiments shown in
The 1st, 2nd, 3rd, and 4th embodiments are at least characterized in that the two electrodes, the active layer, and all the transition metal oxide layers can be formed by a solution process under a low temperature or room temperature, and the transition metal oxide layers comprising nickel oxide and/or copper oxide, as a buffer layer, can promote the efficiency of the devices. The detail to fabricate the two electrodes by using solution process is described in U.S. patent application Ser. No. 13/110,862, filed on May 18, 2011 and entitled “Method of Producing Conductive Thin Film,” the entire contents of which are incorporated herein by reference. Alternatively, conventional thermal evaporation or sputtering method may be employed to fabricate the two electrodes; however, the processing temperature should be controlled below 200° C.
An exemplary method for forming the active layer is described as follows. An organic solution is firstly coated on a surface prepared to form the active layer, for example, coated on the transition metal oxide layer 33 as shown in
As mentioned above, embodiments of this invention will employ a solution process to fabricate the transition metal oxide layers, including the one or more first transition metal oxide layers 13/25, the one or more second transition metal oxide layers 15/23, the transition metal oxide layer 33/45, and the transition metal oxide mixing layer 35/43. The solution process may comprises a “micro/nano particle stacking method or a sol-gel method; the former is preferred. The following example describes how to fabricate a nickel oxide layer, i.e., a transition metal oxide layer, by using the micro/nano particle stacking method. Several milligrams of nickel oxide powders are firstly weighted then placed into several milliliters of a solvent in a container, thus forming a nickel oxide solution, i.e., a transition metal oxide solution, whose concentration is between about 0.01 mg/ml and about 100 mg/ml. Moreover, the morphology of the nickel oxide powders or other micro/nano transition metal oxide powders may comprise micro/nano particle, micro/nano island, micro/nano rod, micro/nano wire, micro/nano tube, micro/nano porous structure, and combinations thereof. Ultrasonic waves then vibrate the nickel oxide solution for about tens of minutes to several hours, such that the nickel oxide powders are well dissolved or suspended in the solution. After vibration, one of the foregoing coating methods is employed to coat the nickel oxide solution on a surface prepared to form the nickel oxide layer. The nickel oxide solution is then spontaneously or artificially dried, thus forming the nickel oxide layer. Similarly, the steps described in this example can form other transition metal oxide layers.
Typically, the solvent of the transition metal oxide solution may be water or general organic solvents; however, if the transition metal oxide layer will be formed on the active layer, the dielectric constant of the solvent should be considered. Taking the embodiment shown in
The micro/nano particle stacking method has advantages including low cost, capability of fabricating large area formation, and speedy process. By this method, a single transition metal oxide layer can be formed within a minute. In contrast, the thermal evaporation is costly and time-consumed. Moreover, the crystal structure of the transition metal oxide layer formed by this method is amorphous, and an annealing step is needed to make it crystalline. However, the annealing step may damage the active layer, and the selectivity of the substrate is therefore limited. For example, it cannot select a plastic substrate due to the annealing temperature. The micro/nano particle stacking method coats a solution comprising micro/nano transition metal oxide structures on a surface, and then the structures are stacked to form a transition metal oxide layer. Depending on the morphology of the structures, the formed transition metal oxide layer can be single crystalline, polycrystalline, or amorphous. Therefore, the micro/nano particle stacking method needs not an annealing step and will not damage the active layer. The selectivity of the substrate is hence broadened.
In addition, the micro/nano particle stacking method is used to fabricate the transition metal oxide mixing layer 35/43, which comprises nickel oxide and/or copper oxide, and at least an n-type transition metal oxide, and the weight ratio of the elements can be easily adjusted to optimize the efficiency of the devices. In contrast, because metal oxides have different boiling points, conventional co-evaporation method is difficult to fabricate a transition metal oxide mixing layer, particularly with a specific weight ratio of the elements. In addition, it may generate unwanted metal oxide alloys during fabrication.
Additional description regarding the micro/nano particle stacking method may refer to U.S. application Ser. No. 12/574,697, filed on Oct. 6, 2009 and entitled “Suspension or Solution for Organic Optoelectronic Device, Making Method thereof, and Applications,” the entire contents of which are incorporated herein by reference.
As mentioned above, the sol-gel method may be used as well to produce the transition metal oxide layers. The first is to prepare a transition metal oxide sol-gel solution, which comprises reactants or precursors (as solute) of the transition metal oxide and a solvent, and the concentration of the solute is between about 0.01 M and about 10 M. One of the foregoing coating methods is used to coat the sol-gel solution on a surface that prepared to form the transition metal oxide layer. After that, a temperature below 140° C. is used to heat the sol-gel solution, thus forming a transition metal oxide layer. Experiments show that the concentration of the solute should be determined according to the material of other layers, such as the active layer.
The following example describes using the sol-gel method to produce a copper oxide layer. The first is to prepare a copper oxide sol-gel solution comprising Cu(CH3COO)2H2O, monoethanolamine (MBA), deionized water, and isopropanol (IPA). The concentration of Cu(CH3COO)2H2O may be 0.025 M, 2.5 M, or 8 M according various situations. The copper oxide sol-gel solution is coated then heated by a temperature between about 100° C. and about 130° C., thus forming the copper oxide layer.
Experiment show that when using the micro/nano particle stacking method to form the transition metal oxide layers, the concentration of the transition metal oxide solution will affect the thickness of the transition metal oxide layer and the performance of the device.
The results show that the transition metal oxide layers of this invention can effectively prevent moisture and oxygen from entering the device, and thus can promote the reliability of the device. Additional experiments show that the long-term performances are better if the devices are roughly encapsulated. This indicates that a well, costly encapsulation may be unnecessary for the optoelectronic devices of this invention, thereby saving the cost.
Notice that in this context the term “micro/nano” refers to “micro or nano” or “micro and nano,” and the term “and/or” refers to “and” or “or.”
Although specific embodiments have been illustrated and described, it will be appreciated by those skilled in the art that various modifications may be made without departing from the scope of the present invention, which is intended to be limited solely by the appended claims.
Number | Date | Country | Kind |
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100110260 | Mar 2011 | TW | national |
This application is a continuation-in-part of co-pending U.S. application Ser. No. 12/726,202 (Att. Docket NU8368P), filed on Mar. 17, 2010 and entitled “Optoelectronic Device Having a Sandwich Structure and Method for Forming the Same” and claims priority to Taiwan Patent Application No. 100110260, filed on Mar. 25, 2011, the entire contents both of which are incorporated herein by reference, U.S. application Ser. No. 12/726,202 claims priority to Taiwan Patent Application No. 098140465, filed on Nov. 27, 2009, the entire contents of which are incorporated herein by reference.
Number | Date | Country | |
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Parent | 12726202 | Mar 2010 | US |
Child | 13160450 | US |