Exemplary embodiments generally relate to materials fabrication, and more specifically, relate to fabrication of nanostructure materials.
Nanostructure materials, which include structures on the nanometer scale, for example, a scale of 1 to 1000 nanometers (nm), have been found to exhibit interesting or unexpected properties relative to bulk material counterparts. For example, nanostructure materials have been found to act upon electromagnetic radiation similar to a lens to focus the radiation and otherwise affect propagation of photons. As a result, new uses for nanostructure materials are currently being researched in a variety of applications. Some of the properties that are exhibited by nanostructure materials are a function of the height and the width of the structures that made up the material. The ratio of the height of these structures to their width may be referred to as the aspect ratio of the structure, which may take the form of a pillar.
Many fabrication processes are used to the form nanostructures and associated nanostructure materials. However, conventional fabrication processes have limitations with respect to the aspect ratios of structures that can be constructed. In some instances, attempts to increase the height of a structure with a given width using conventional fabrication methods results in poor structural integrity and frequent breakage and collapsing of the structures. As such, low or no yield results can be the outcome using conventional fabrication methods. Additionally, conventional fabrication techniques can be limited in the architectures and geometries that can be used when constructing a nanostructure, thereby limiting the properties that can be realized by the materials.
Accordingly, there is a need for improved fabrication processes that can reliably yield high aspect ratio structures for use in forming nanostructure materials. Such high aspect ratio structures would facilitate new applications based on the properties that can be realized by such nanostructure materials having the high aspect ratio structures.
According to some non-limiting, example embodiments, an example fabrication method is provided. The example method may include depositing a semiconductor material onto a substrate, applying hard mask layer, applying a photoresist layer, and performing lithography to form voids in the photoresist layer that form a pattern. The example method may further include applying the pattern to the hard mask layer based on the pattern in the photoresist layer, etching the semiconductor material based on the pattern in the hard mask layer to form a cavity in the semiconductor material, and performing atomic layer deposition to deposit pillar material into the cavity. The atomic layer deposition may apply the pillar material to sidewalls of the cavity such that the pillar material accumulates inwardly from the sidewalls until the cavity is filled. The example method may further include planarizing to remove the hard mask layer and pillar material disposed above a pillar height from a surface of the substrate, and removing the semiconductor material to release a pillar of the pillar material supported by the substrate.
According to some example embodiments, an example fabrication method for a nanostructure material array is provided. The example method may include depositing a semiconductor material onto a substrate, applying hard mask layer, applying a photoresist layer, and performing lithography to form voids in the photoresist layer that form a pattern. The example method may further include applying the pattern to the hard mask layer based on the pattern in the photoresist layer, and etching the semiconductor material based on the pattern in the hard mask layer to form a plurality of cavities including a first cavity in the semiconductor material and a second cavity in the semiconductor material. The first cavity may have a first cross-sectional dimension that is larger than a largest cross-sectional dimension of the second cavity. The example method may further include performing atomic layer deposition to deposit pillar material into the first cavity and the second cavity. The atomic layer deposition may apply the pillar material to sidewalls of the first cavity and the second cavity such that the pillar material accumulates inwardly from the sidewalls until the first cavity and the second cavity are filled. The example method may further include planarizing to remove the hard mask layer and pillar material disposed above a pillar height from a surface of the substrate, and removing the semiconductor material to release a first pillar of the pillar material supported by the substrate and a second pillar of the pillar material supported by the substrate.
According to some example embodiments, a nanostructure material is provided. The nanostructure material may include a substrate and a nanostructure pillar disposed on the substrate. The nanostructure pillar may have a pillar width of about 20 nanometers to about 1000 nanometers and an aspect ratio of a pillar height to the pillar width may be within a range from about 10 to 1 to about 4 to 1.
Having thus described some example embodiments in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
Some example embodiments now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all example embodiments are shown. Indeed, the examples described and pictured herein should not be construed as being limiting as to the scope, applicability or configuration of the present disclosure. Rather, these example embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like reference numerals refer to like elements throughout.
In light of the considerations raised above, example methods, and resultant materials, are described herein directed to nanostructure materials including nanostructures with high aspect ratios that are planar and free-standing. In this regard, according to some example embodiments, the aspect ratio of a nanostructure may be defined as the height of the structure relative to the width of the structure. According to some example embodiments, nanostructures as described herein may have different widths depending on where the width measurement is taken, and in these instances, the width used for determining the aspect ratio may be largest width of the nanostructure.
In this regard, example embodiments may facilitate the construction of nanostructures, also referred to as nanostructure pillars or pillars herein, with aspect ratios that are greater than 4 to 1, greater than 6 to 1, and even greater than 10 to 1. In this regard, the nanostructures that make up a nanostructure material may formed as pillars or posts. A nanostructure material may include a substrate with a plurality of nanostructure pillars disposed thereon. The physical attributes of the nanostructure pillars may define the characteristic properties that the nanostructure material exhibits. For example, the height of the nanostructure pillars may have a relationship to the frequencies of electromagnetic radiation or light that the nanostructure material is tuned to act upon. As such, the ability to construct nanostructures with higher aspect ratios enables the ability to tune the nanostructure material to a greater range of frequencies making additional applications accessible.
As mentioned above, the nanostructure materials that may be formed via the example methods described herein may be used in various applications including, for example, meta-lenses and meta-optics. The nanostructure pillars constructed via the example methods provided herein may be sized to have a subwavelength height (e.g., a multiple of the target wavelength), which facilitates use in meta-lens and metasurface applications. For example, the heights of pillars may contribute to defining a focal length of a meta-lens constructed using the pillars. In this regard, an array of nanostructure pillars may be formed, according to some example embodiments, that can operate as a meta-lens or other type of meta-material. As such, example embodiments may have applications in the augmented reality/virtual reality space, solar cell space, electro-optical sensors, infrared sensors, medical imaging, optical communications, light detection and ranging (LiDAR), vision therapeutics, taggants, power generation, and energy harvesting applications, to name a few.
Referring to
In this regard, the pillar 10 may be disposed on a substrate 20. The pillar 10 may be formed of, for example, a dielectric material, such as titanium dioxide (TiO2), zinc dioxide (ZnO2), hafnium dioxide (HfO2), or the like. The substrate 20 may be a formed of a dielectric material or a semiconductor material. As a dielectric material, the substrate 20 may be, for example, quartz. However, as a semiconductor material, the substrate 20 may be a silicon-based material or other material that exhibits semiconductor properties.
As further described below, example embodiments of nanostructure pillars may be constructed having a variety of different cross-sectional geometries. In the example embodiment shown in
As mentioned above, a nanostructure pillar, such as the pillar 10, may have an aspect ratio that is defined by the height 12 of the pillar 10 relative to the width 14 of the pillar 10. The height 12 of the pillar 10 may be the distance from the interface between the pillar 10 and the substrate 20 at the pillar 10's base and the top surface of the pillar 10, opposite the interface with the substrate 20. The width 14 of the pillar 10 may be a distance across the top surface of the pillar 10 or across a cross-section of the pillar 10 that is measured parallel to the surface of the substrate 20, which in the example embodiment of
As mentioned above, the dimensions of the pillar 10 may be on the nanometer scale. In this regard, for example, the width 14, according to some example embodiments, may be from about 20 nanometers (nm) to about 1000 nm. The height of the pillar 10, according to some example embodiments, may be between about 100 nm and about 4000 nm. Further, with respect to aspect ratio, the pillar 10 may, according to some example embodiments, have an aspect ratio of greater than 4 to 1. Alternatively, according to some example embodiments, the pillar 10 may have an aspect ratio of greater than 6 to 1. Alternatively, according to some example embodiments, the pillar 10 may have an aspect ratio of about 10 to 1. Accordingly, example dimensions for the pillar 10 may be a height 12 of 1000 nm and a width 14 of 100 nm (i.e., a 10 to 1 aspect ratio).
As further described below, the pillar 10 may be formed within a cavity that is filled via an atomic layer deposition (ALD) process. However, in example embodiments where the cavity is formed via an etching process, the base of the cavity may be rounded. As such, the base of the pillar 10 at the interface with the substrate may be rounded or tapered toward a center axis of the pillar 10, where the center axis is perpendicular to the surface of the substrate.
As such, using the example methods described herein, a nanostructure material may be constructed that includes a substrate and a nanostructure pillar disposed on the substrate, where the nanostructure pillar has a pillar width of about 20 nanometers to about 1000 nanometers. Further, the nanostructure pillar may have an aspect ratio of a pillar height to the pillar width that is within a range from about 10 to 1 to about 4 to 1. According to some example embodiments, nanostructure pillars may be constructed that have an aspect ratio of up about 20 to 1. The nanostructure pillar may be one of a plurality of nanostructure pillars making up a nanostructure array. The nanostructure pillars within the example array may have different geometries (e.g., cross-sectional shapes), but may be planar with respect to height. According to some example embodiments, the nanostructure pillars may be formed of dielectric materials including, for example, titanium, zinc, hafnium, or the like, such as titanium oxide, zinc oxide, hafnium oxide or the like.
Referring now to
According to some example embodiments, the semiconductor material 110 may be silicon-based or other semiconductor material that exhibits semiconductor properties. According to some example embodiments, the semiconductor material 110 may be amorphous silicon. Further, the process for depositing the semiconductor material 110 on the substrate 100 may include plasma enhanced vapor deposition (PECVD). Alternatively, the semiconductor material 110 may be applied via evaporation using an electron beam, or another deposition process may be used. Further, the height of the semiconductor material 110 (e.g., height above the substrate 100 to a top surface of the semiconductor material 110) may be selected to be larger than the desired pillar height that is being constructed to allow for subsequent planarizing to the desired height as described below.
Referring now to
On the hard mask layer 120, according to some example embodiments, a photoresist layer 130 may be applied. Similar to the hard mask layer 120, the photoresist layer 130 may be applied across an entire top surface of the hard mask layer 120. In this regard, the material of the photoresist may be applied as a layer 130 via, for example, a spin and bake process. According to some example embodiments, the photoresist material may be an electron beam (e-beam) photoresist material. According to some example embodiments, the photoresist layer 130 may be applied with patterning using, for example, techniques including nano-imprinting and double patterning lithography (DLP) resulting in a patterned photoresist layer 130 as shown in
Alternatively, to pattern the photoresist layer 130, a metal layer 140 may be applied to the photoresist layer 130, as shown in
As shown in
According to some example embodiments, other lithography approaches may be used that, for example, do not require a hard mask layer. For example, laser or stepper lithography may be used to form the voids photoresist layer 130 for patterning. In some example embodiments, since the hard mask layer is not included, the photoresist layer 130 may operate as the mask to form the cavities in the semiconductor material 110.
The lithography that is performed may be conducted in a manner that facilitates the patterning of various cross-sectional shapes for the nanostructure pillars, as further described with respect to
Now referring to
In some example embodiments, the hard mask layer 120 may be alternately formed via a lift off process. In this regard, a negatively polarized photoresist layer 130 may be used and the patterning of the photoresist layer 130 may be inverted (relative to the description above) such that the photoresist layer 130 remains in locations where the hard mask layer 130 is to be removed (rather than preserved). As such, the hard mask layer 120 is applied over top of the patterned photoresist layer 130. In such example embodiments, the photoresist layer 130, after patterning, may be disposed in areas where the hard mask layer 120 that will be lifted off (e.g., at the location on the semiconductor material 110 where the cavity 160 is to be formed. After patterning the photoresist layer 130, the hard mask layer 120 may be applied such that the portion of the hard mask layer 120 to be lifted off will be disposed on the patterned photoresist layer 130 and the portion of the hard mask layer 120 to remain will be disposed directly on the semiconductor material 110. The lift off process may be performed using laser or stepper lithography to remove the patterned photoresist layer 130 and the portion of the hard mask layer 120 that is disposed on the patterned photoresist layer 130 to arrive at a hard mask layer 120 as shown in
With the hard mask layer 120 patterned, etching of the semiconductor material 110 may be performed as shown in
Since the cavities 160 will be used to form the nanostructure pillars, the cavities 160 may be formed as molds for the nanostructure pillars. In this regard, the width of the cavity 160 may be same as the desired width of the nanostructure pillar and the depth of the cavity 160 may be larger than the desired height of the nanostructure pillar to achieve the desired aspect ratio for the nanostructure pillar. In this regard, the width of the cavity 160 may be 20 nm to 1000 nm, according to some example embodiments. Further, since the top portion of the structure will be later cut or planarized, the depth of the cavity 160 may be greater than the desired height of the nanostructure pillars, according to some example embodiments. Additionally, because the etching process may not be capable of creating right-angle interfaces at the base of the cavity 160 (i.e., at the interface between the cavity 160 and the substrate 100), the cavity 160 may be slightly tapered or curved at the base, which may cause the nanostructure pillars to have slightly tapered or curved edges.
Now referring to
According to some example embodiments, the pillar material 150 may be any type of material that may be deposited using ALD. According to some example embodiments, the pillar material 150 may be a dielectric material having a desired dielectric value for the nanostructure material application. For example, according to some example embodiments, the pillar material 150 may include a metal such as titanium, zinc, hafnium, or the like. In this regard, the pillar material 150 may be titanium dioxide (TiO2), zinc dioxide (ZnO2), hafnium dioxide (HfO2), or the like.
With the cavity 160 filled with the pillar material 150, planarization may be performed as shown in
Now referring to
As mentioned above, it is understood that the pillar 170 is described as being a singular pillar on the substrate 100, but any number of pillars may be formed with the pillar 170 in a similar manner.
As can be seen in
As such, referring to
Having described various methods for constructing a nanostructure pillar,
Referring to
Now referring to
According to some example embodiments, the ordering of operations 610, 620, and 630 may be different to perform a lift off variation of the example method. In this regard, at 620, the photoresist layer may be first applied to the semiconductor material. Then, at 630, patterning of the photoresist layer may be performed, followed by application of the hard mask layer onto the patterned photoresist layer in preparation for lifting off the hard mask layer.
The example method may also include, at 640, applying the pattern to the hard mask layer based on the pattern in the photoresist layer to form the pattern in the hard mask layer. Subsequently, at 650, the pattern in the hard mask layer may be used for etching the semiconductor material to form a cavity in the semiconductor material.
According to some example embodiments, the example method may further include, at 660, performing atomic layer deposition to deposit pillar material into the cavity. In this regard, the atomic layer deposition may apply the pillar material to sidewalls of the cavity such that the pillar material accumulates inwardly from the sidewalls until the cavity is filled. Additionally, at 670, the example method may include planarizing to remove the hard mask layer and pillar material disposed above a pillar height from a surface of the substrate. The example method may also include removing the semiconductor material to release a pillar of the pillar material supported by the substrate.
According to some example embodiments, the example method may additionally, include applying a conductive layer to the photoresist layer prior to performing the lithography. In this regard, the performing the lithography may include performing electron beam lithography to form the pattern in the photoresist layer and remove the conductive layer. Additionally or alternatively, the semiconductor material may include silicon, according to some example embodiments. Additionally or alternatively, according to some example embodiments, the hard mask layer may include Aluminum, such as, for example aluminum oxide.
Additionally or alternatively, accordingly to some example embodiments, applying the pattern to the hard mask layer includes ion milling the hard mask layer. Additionally or alternatively, according to some example embodiments, planarizing includes ion milling or plasma etching. Additionally or alternatively, according to some example embodiments, the pillar material may include titanium, zinc, hafnium, or the like. Additionally or alternatively, an aspect ratio of the pillar may be between 10 to 1 and 4 to 1. Additionally or alternatively, the cross-sectional shape of the pillar may be a polygon.
Additionally or alternatively, the cavity may be a first cavity, and a second cavity may be formed in association with the first cavity in the same manner as the first cavity. Additionally, the first cavity may have a first cross-sectional dimension that is larger than a largest cross-sectional dimension of the second cavity.
Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Moreover, although the foregoing descriptions and the associated drawings describe exemplary embodiments in the context of certain exemplary combinations of elements and/or functions, it should be appreciated that different combinations of elements and/or functions may be provided by alternative embodiments without departing from the scope of the appended claims. In this regard, for example, different combinations of elements and/or functions than those explicitly described above are also contemplated as may be set forth in some of the appended claims. In cases where advantages, benefits or solutions to problems are described herein, it should be appreciated that such advantages, benefits and/or solutions may be applicable to some example embodiments, but not necessarily all example embodiments. Thus, any advantages, benefits or solutions described herein should not be thought of as being critical, required or essential to all embodiments or to that which is claimed herein. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
This application claims priority to and the benefit of prior-filed, co-pending U.S. Provisional Application No. 63/274,166 filed on Nov. 1, 2021, the entire content of which is hereby incorporated herein by reference.
Number | Date | Country | |
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63274166 | Nov 2021 | US |