1. Field of the Invention
This invention generally relates to nanostructure devices and, more particularly, nanostructure membranes suitable for fabrication in display pixel applications.
2. Description of the Related Art
Reflective display or color-tunable device technology is attractive primarily because it consumes substantially less power than liquid crystal displays (LCDs) and organic light emitting diode (OLED) displays. A typical LCD used in a laptop or cellular phone requires internal (backlight) illumination to render a color image. In most operating conditions the internal illumination that is required by these displays is in constant competition with the ambient light of the surrounding environment (e.g., sunlight or indoor overhead lighting). Thus, the available light energy provided by these surroundings is wasted, and in fact, the operation of these displays requires additional power to overcome this ambient light. In contrast, reflective display technology makes good use of the ambient light and consumes substantially less power.
The full range of colors produced by plasmon resonances resulting from metal nanostructures has been known since ancient times as a means of producing stained colored glass. For instance, the addition of gold nanoparticles to otherwise transparent glass produces a deep red color. The creation of a particular color is possible because the plasmon resonant frequency is generally dependent upon the size, shape, material composition of the metal nanostructure, as well as the dielectric properties of the surrounding environment. Thus, the optical absorption and scattering spectra (and therefore the color) of a metal nanostructure can be varied by altering any one or more of these characteristics. The parent applications listed above describe means of electronically controlling these color-producing characteristics.
The properties of metallic nanoparticles have drawn significant attention due to their application in photonics and electro-optics, as well as their potential application in biological/chemical sensors and renewable energy. Moreover, the fabrication of periodic metallic nanoparticle arrays for applications in photonics utilizing their localized surface plasmon resonance (LSPR) properties has been extensively studied in recent years. Among various processing techniques, depositing a film of metal on a nano-size patterned mask and using a lift-off process to remove the sacrificial layer is becoming a widely used technique, because it allows for fabricating nanoparticles with precisely controlled shape, size, and particle spacing. Moreover, advanced research has revealed that ordered array nanostructures have improved quantum characteristics utilized in LSPR properties, or photoluminescence and electroluminescence properties of semiconductor nanophosphors. Therefore, a method to achieve ordered nanoparticles and nanostructures is of significant importance.
One method of forming nanoparticles in an ordered array which has been proposed is a nano-imprinting process using a mold to generate ordered dot patterns on poly methyl methacrylate (PMMA) mask layers. After forming an array of nanostructures to a predefined depth, the residual PMMA layers at the bottom of the pattern are removed to reveal the surface underneath the mask. The metallic nanoparticles are formed by depositing the desired metals and removing the PMMA mask layers in a solution to lift off the residual metals deposited on the mask. According to this technique, the size and spacing of the nanostructures are limited by the photolithography patterning capability of the mold. Also, the manufacturing cost is high due to expensive capital costs associated with the nanoimprint lithography process. Alternatively, nano-scale structures can be patterned using e-beam lithography. However, this process is extremely slow and costly.
Among other processing techniques, forming an array of ordered nanostructures using self-assembly solution process is desired due to low capital cost without sacrificing manufacturing scalability. It is possible to anodize an aluminum layer in an electrolyte solution to form aluminum oxide pores with diameters of several nanometers to several hundred of nanometers arranged in hexagonal order. This anodized aluminum oxide (AAO) template can then be used as a mask to generate an array of nanoparticles on a substrate by depositing desired materials and lifting off the mask to form the nanostructures.
However, conventionally known techniques using an AAO template to form nanostructures are limited to the formation of a single pattern of pores, and therefore, only one set of ordered array of particles. Some research has been done to initiate the patterning of the aluminum layer with a hard mask using silicon dioxide [Zhao et al, J. of Electrochemical Society, 152 (10) B411-B414 (2005)] or metallic tantalum [Zhao et al, Nanotechnology 17 (2006) 35-39] to generate AAO template selectively on a substrate. However, this process is isotropic in nature, anodizing the aluminum underneath the hard mask, either creating unwanted pores or severe undercut underneath the mask. This is especially evident in very thick Al films (e.g. >100 microns). Further, Zhou does not disclose a means for obtaining different pore diameters and/or different pitches between pores on a single substrate.
It would be advantageous if a method existed for forming more than one set of ordered particle arrays with different diameter sizes or pitches on the same substrate, for applications like displays where different colored pixels require different nanostructure sizes.
Described herein are a multi-structure pore membrane and a manufacturing method for creating different pore sizes of anodized aluminum oxide on a single substrate. Moreover, the pore membrane can be used to form multiple ordered arrays of nanostructures with different sizes on the same substrate. In one aspect, a multi-structure pore membrane includes at least one portion with an ordered array of pores having larger diameters than the ordered array of pores on other portions of the same membrane. Moreover, the pitch of pores may be made the same for all the pores on the membrane, or varied between membrane portions. Another aspect includes manufacturing methods to form a multi-ordered array of nanoparticles on the same substrate. The methods include the step of generating an anodized aluminum oxide (AAO) template from an aluminum metal layer deposited on a substrate. The AAO template is patterned using conventional lithography with portions of the template covered with photoresist. Steps to widen the pores or pitch are pursued using etching and anodizing chemistries, respectively. A target material is deposited on the exposed pore regions, and nanostructures are formed at the bottom of the pores. The photoresist and the excess materials deposited on the photoresist layer are removed in a solvent solution. The patterning of the AAO template, and photoresist lift-off steps are repeated as necessary to generate a multiple-ordered array of nanoparticles on a substrate.
Accordingly, a method is provided for fabricating a multi-structure pore membrane. An AAO template is formed with an array of pores exposing underlying regions of a conductive layer top surface. A plurality of photoresist layers is patterned to sequentially expose a plurality of AAO template sections. Each exposed AAO template section is sequentially etched to widen pore diameters, so that each AAO template section may be associated with a corresponding unique pore diameter. A target material is deposited in the pores of the AAO template and, as a result, an array of target material structures is formed on the top surface, where the target material structures associated with each AAO template section have a corresponding diameter.
In one variation, the method forms an aluminum film over a conductive layer top surface, which is patterned using a plurality of photoresist layers to sequentially expose a plurality of aluminum film sections. Each aluminum film section is sequentially anodized with a chemistry to form a plurality of AAO template sections with corresponding pore features associated with pore diameter, pitch between pores, and both pore diameter and pitch between pores. After depositing a target material in the pores of the AAO template sections, an array of target material structures is formed on the top surface, with the target material structures associated with each AAO template section having a corresponding structure feature related to material structure diameter, pitch between material structures, and both material structure diameter and pitch between material structures.
Additional details of the above-described methods and a multi-structure pixel device are presented below.
Further, as shown in
In another aspect, as shown in
In another aspect, as shown in
In one aspect, as shown in
Typically, the structures 110 in each subpixel 108 are formed in an approximately hexagonal array. Depending on the process, the anodizing aluminum films results in arrays with varying degrees of irregularity. These can generally be described as having a local or short-range hexagonal order, but not long-range hexagonal order. An array not having a long range hexagonal order is referred to herein as having an approximately hexagonal order.
Fabrication of the devices of
The anodization can take place either with a one-step anodization, or with a two-step anodization treatment using a thicker initial aluminum layer, which gives better control of the pore uniformity. In general, the two-step anodization requires the first anodization treatment to take place under low reaction speed conditions for an aluminum thickness in the range of 1 to 100 μm. A film removal treatment is generally carried out after the first anodization using mixed aqueous solution of phosphoric acid and nitric acid, or phosphoric and chromic acid, for an appropriate length of time, from minutes to hours, as is known in the art.
The second anodization treatment is done after removal of the anodized Al from the first step, and after an ordered array of pits has been formed on the aluminum surface by the first anodization treatment. The second anodization is carried out under a method known in the art or under the same conditions used as above for the first anodization. This step is used to selectively form the pitch between pores, and in a separate process, selectively widen the pores. For example, the pore widening may be carried out by immersing the anodized aluminum oxide layer in an aqueous solution of an acid or alkali as to dissolve portions of the template to enlarge the diameter of the pores. Using a different acid and/or voltages for anodization generates different pore sizes and hexagonal pitches. Typical solutions used are acids such as diluted sulfuric acid, oxalic acid, phosphoric acid, nitric acid, or hydrochloric acid. Only the areas of pores that are exposed to the solution are widened by the step, and not the areas of pores under the sacrificial layer. Typical anodization voltages are in the range of 20 to 200 volts.
After anodizing the Al film, Step 606 deposits the target material in the open pores. Some material of interest include metals such as Ag, Au, Al, Pt, or semiconductor materials such as Si, Ge, GaN, CdSe, or any other compound materials. The method of deposition can be physical sputtering, chemical vapor deposition (CVD), electrodeposition (electroplating), or electron beam evaporation. An electron beam evaporation method is likely to deposit materials at the bottom of the pores and not the sidewalls.
It is possible to electrodeposit a variety of metals inside the pores such as Au, Ag, Fe, Ni, Co, Bi, etc. Electrodeposition of Al can be done with a modified procedure involving ionic liquids. The advantages of electrodeposition is that it is a wet chemical process, not a vacuum process (with a controlled environment), and the metal grows from the bottom (conductive layer) up. Unlike sputtering or evaporation, there is no “pinch-off” at the top of the pores, so there is better control over the aspect ratio, even producing vertically oriented nanorods or nanowires if desired. Furthermore, a sequence of different metals can be deposited in the same pore.
Alternatively but not shown, the target material may be performed after the final iteration of Step 610, or after the final iteration of Step 612.
After material deposition in Step 606, the photoresist is removed in Steps 608 or 612 in a solution that dissolves the photoresist, such as acetone or other remover. This step also removes any excess materials deposited on the photoresist, leaving the target materials inside the pores and the AAO template. Steps 602 through 612 are iteratively repeated as necessary to achieve multiple ordered arrays of pores with different diameters, pitches, or both pores and pitches on the same substrate. The deposition materials and the thickness can be altered for every iteration cycle, thereby forming different nanostructures of different sizes. Finally, the AAO template is removed in Step 614 by etching in diluted potassium hydroxide (KOH) or tetramethylammonium hydroxide (TMAH) to form ordered arrays of nanostructures with different structure features on the same substrate.
As an alternative, after removing the photoresist and AAO template in Step 608, Step 610 masks a different region of the conductive layer-covered substrate, and Steps 600 through 610 are iteratively repeated, so that a different AAO template is formed and then removed for each grouping of like subpixels.
Step 702 provides a substrate, and Step 704 forms a conductive layer, with a top surface, overlying the substrate. Step 706 forms an AAO template with an array of pores exposing underlying regions of the top surface. Typically, the pores are formed in an approximately hexagonal array. Step 708 patterns a plurality of photoresist (PR) layers to sequentially expose a plurality of AAO template sections. Step 710 sequentially etches each exposed AAO template section to widen pore diameters, where each AAO template section is associated with a corresponding pore diameter. Typically, the pitch between pores is in the range from 50 to 1000 nm. Step 712 deposits a target material in the pores of the AAO template. As a result, Step 714 forms an array of target material structures on the top surface, where the target material structures associated with each AAO template section have a corresponding diameter. Typically, the target material structures have a diameter in the range of 5 to 500 nm.
In one aspect, Steps 708 and 710 are iteratively performed, so that in a first iteration the patterning of the plurality of photoresist layers in Step 708 includes forming a first patterned photoresist layer covering a first section of the AAO template and exposing a second section of the AAO template, and sequentially etching each exposed AAO template section in Step 710 includes etching the second section of the AAO template to widen the second section AAO template pores to a first diameter. In the next iteration, Step 708, subsequent to etching the second section of the AAO template in Step 710, forms a second patterned photoresist layer covering the second section of the AAO template and exposing the first section of the AAO template. Then, Step 710 etches the first section of the AAO template to widen the first section AAO template pores to a second diameter. Thus, forming the array of target material structures in Step 714 includes forming target material structures with the first diameter on the top surface region that underlay the second section of the AAO template second section, and target material structures with the second diameter on a top surface region that underlay the first section of the AAO template first section. In one aspect, depositing the target material in the pores of the AAO template in Step 712 includes simultaneously depositing the target material into the pores of the plurality of AAO template sections, subsequent to removing a final photoresist pattern.
Alternatively, as shown with the dotted arrow path, Step 712 sequentially deposits the target material in the pores of each AAO template section, prior to removing each corresponding photoresist pattern. In this aspect each AAO template section may be associated with a corresponding amount of deposition material in the pores, and in Step 714 the target material structures associated with each AAO template section have a corresponding height. In other words, the structures associated with different AAO template sections may have different heights. Further, Step 712 may deposit a selected type of target material in the pores of each corresponding AAO template section. In other words, the structures associated with different AAO template sections may be different materials. In addition, Step 712 may sequentially deposit a plurality of target material types selectively in the pores of at least one AAO template section, if the dotted arrow approach is used, or in all the AAO template sections, if the solid arrow approach is used.
Some examples of the target material that may be deposited in Step 712 include Ag, Au, Al, Pt, Si, Ge, GaN, CdSe, Fe, Ni, Co, Bi, CdS, Type III-IV compounds, Type II-VI compounds, and combinations of the above-mentioned materials. The target material may be deposited using one of the following processes: physical sputtering, chemical vapor deposition (CVD), electrodeposition, or electron beam evaporation.
Step 812 deposits a target material in the pores of the AAO template sections. As a result, Step 814 forms an array of target material structures on the top surface, where the target material structures associated with each AAO template section have a corresponding structure feature. The corresponding structure features may be target material structure diameter, pitch between target material structures, or both target material structure diameter and pitch between target material structures. That is, the target material structures may differ by diameter, pitch, or pitch and diameter, depending AAO template section. Typically, the target material structures have a diameter in the range of 5 to 500 nm.
In one aspect, Steps 808 and 810 are iteratively performed, so that patterning the plurality of photoresist layers in a first iteration of Step 808 includes forming a first patterned photoresist layer covering a first section of the aluminum film and exposing a second section of the aluminum film, and sequentially anodizing each exposed aluminum film section in Step 810 includes anodizing the second section of the aluminum film to form a first pore feature. In the next iteration, Step 808, subsequent to anodizing the second section of the aluminum film, forms a second patterned photoresist layer covering the second section of the aluminum film and exposing the first section of the aluminum film. Then, Step 810 anodizes the first section of the aluminum film to form a second pore feature, and forming the array of target material structures in Step 812 includes forming target material structures with a first structure feature on a top surface region that underlay an AAO template second section, and target material structures with a second structure feature on a top surface region that underlay an AAO template first section.
In one aspect, depositing the target material in the pores of the AAO template in Step 812 includes simultaneously depositing the target material into the pores of the plurality of AAO template sections, subsequent to removing a final photoresist pattern.
Alternatively, Step 812 sequentially deposits the target material into the pores of each AAO template section, prior to removing each corresponding photoresist pattern, see the dotted arrow path. In this aspect, each AAO template section may be associated with a corresponding amount of deposition material in the pores, and in Step 814 the target material structures associated with each AAO template section have a corresponding height. That is, the structure heights associated with different AAO template sections may differ. Further, Step 812 may deposit a selected type of target material in the pores of each corresponding AAO template section. That is, the structure materials associated with different AAO template sections may differ. This deposition approach can be used to selectively deposit (layer) a plurality of different target material types in the pores of at least one AAO template section. Alternatively, if the simultaneous deposition approach is used (solid arrow path), a plurality of different target materials can be formed in the pores of a plurality of AAO template sections.
As noted above, the target material deposited in Step 812 may be Ag, Au, Al, Pt, Si, Ge, GaN, CdSe, Fe, Ni, Co, Bi, CdS, Type III-IV compounds, Type II-VI compounds, or combinations of the above-mentioned materials. The target material may be deposited using a process selected from a group consisting of physical sputtering, CVD, electrodeposition, or electron beam evaporation.
Many of the method aspects discussed above in the explanation of
A multi-structure pixel device and associated fabrication methods have been provided. Examples of particular materials and process steps have been presented to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.
The application is a Continuation-in-Part of a pending application entitled, PLASMONIC REFLECTIVE DISPLAY FABRICATED USING ANODIZED ALUMINUM OXIDE, invented by Aki Hashimura et al., Ser. No. 13/449,370, filed on Apr. 19, 2012, Attorney Docket No. SLA3106; which is a Continuation-in-Part of a pending application entitled, METHOD FOR IMPROVING METALLIC NANOSTRUCTURE STABILITY, invented by Aki Hashimura et al., Ser. No. 13/434,548, filed on Mar. 29, 2012, Attorney Docket No. SLA3026; which is a Continuation-in-Part of a pending application entitled, PLASMONIC ELECTRONIC SKIN, invented by Tang et al., Ser. No. 12/836,121, filed on Jul. 14, 2012, Attorney Docket No. SLA2752; which is a Continuation-in-Part of a pending application entitled, PLASMONIC DEVICE TUNED USING PHYSICAL MODULATION, invented by Tang et al., Ser. No. 12/646,585, filed on Dec. 23, 2009, Attorney Docket No. SLA2686; which is a Continuation-in-Part of a pending application entitled, PLASMONIC DEVICE TUNED USING LIQUID CRYSTAL MOLECULE DIPOLE CONTROL, invented by Tang et al., Ser. No. 12/635,349, filed on Dec. 10, 2009, Attorney Docket No. SLA2711; which is a Continuation-in-Part of a pending application entitled, PLASMONIC DEVICE TUNED USING ELASTIC AND REFRACTIVE MODULATION MECHANISMS, invented by Tang et al., Ser. No. 12/621,567, filed on Nov. 19, 2009, Attorney Docket No. SLA2685; which is a Continuation-in-Part of a pending application entitled, COLOR-TUNABLE PLASMONIC DEVICE WITH A PARTIALLY MODULATED REFRACTIVE INDEX, invented by Tang et al., Ser. No. 12/614,368, filed on Nov. 6, 2009, Attorney Docket No. SLA2684. All the above-referenced applications are incorporated herein by reference.