Nanowire grid polarizer on a curved surface and methods of making and using
11371134 · 2022-06-28
Assignee
Inventors
Cpc classification
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
G02B5/3058
PHYSICS
C23C14/35
CHEMISTRY; METALLURGY
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
C23C14/35
CHEMISTRY; METALLURGY
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
An array of nanowires with a period smaller than 150 nm on the surface of curved transparent substrate can be used for applications such as optical polarizers. A curved hard nanomask can be used to manufacture such structures. This nanomask includes a substantially periodic array of substantially parallel elongated elements having a wavelike cross-section. The fabrication method of the nanomask uses ion beams.
Claims
1. A method of forming a curved hard nanomask for transferring a substantially periodic pattern into a curved substrate, the method comprising: depositing a first material to form a curved surface layer on top of a surface of the curved substrate; and irradiating a surface of the curved surface layer with a flow of ions until a curved hard nanomask is formed, the curved hard nanomask comprising a substantially periodic array of substantially parallel elongated elements having a wave-shaped cross-section, at least some of the elongated elements having the following structure in cross-section: an inner region of first material, a first outer region of a second material covering a first portion of the inner region, and a second outer region of the second material covering a second portion of the inner region and connecting with the first outer region at a wave crest, wherein the first outer region is substantially thicker than the second outer region, and wherein the second material is formed by modifying the first material by the flow of ions, wherein the elongated elements are oriented along lines of intersections of the curved surface layer with a set of parallel planes, and wherein the flow of ions is arranged so as a local plane of ion incidence is substantially perpendicular to the set of parallel planes and oriented along a local surface normal of the curved surface layer.
2. The method of claim 1, wherein a wavelength of the substantially periodic array is in a range from 20 to 150 nm.
3. The method of claim 1, wherein the first material is silicon, amorphous silicon, silicon containing 5-15 at % of gold, silicon oxide, gallium arsenide, epitaxial gallium arsenide, gallium aluminum arsenide, epitaxial gallium aluminum arsenide, germanium, or silicon-germanium.
4. The method of claim 1, wherein the flow of ions comprises a flow of N.sub.2.sup.+, N.sup.+, NO.sup.+, NH.sub.m.sup.+, O.sub.2.sup.+, Ar.sup.+, Kr+, Xe.sup.+, or a mixture of Ar.sup.+ and N.sub.2.sup.+ ions.
5. The method of claim 1, wherein a thickness of the first outer region is at least 4 nm.
6. The method of claim 1, wherein a thickness of the second outer region is no more than 2 nm.
7. The method of claim 1, wherein the second material is silicon nitride, silicon nitride containing 5-15 at % of gold, silicon-germanium nitride, silicon oxide, gallium nitride, gallium oxide, aluminum nitride, aluminum oxide, gallium aluminum nitride, or gallium aluminum oxide.
8. The method of claim 1, further comprising, during the irradiating of the surface of the curved surface layer with the flow of ions until the curved hard nanomask is formed, moving the curved substrate with respect to the flow of ions which is shaped to have an ion beam with a size (D1) in the local plane of ion incidence which is determined by a radius (R) of substrate surface curvature as D1≤R/6.
9. A method of forming a curved hard nanomask for transferring a substantially periodic pattern into a curved substrate, the method comprising: depositing a first material to form a curved surface layer on top of a surface of the curved substrate; irradiating a surface of the curved surface layer with a flow of ions until a curved hard nanomask is formed, the curved hard nanomask comprising a substantially periodic array of substantially parallel elongated elements having a wave-shaped cross-section, at least some of the elongated elements having the following structure in cross-section: an inner region of first material, a first outer region of a second material covering a first portion of the inner region, and a second outer region of the second material covering a second portion of the inner region and connecting with the first outer region at a wave crest, wherein the first outer region is substantially thicker than the second outer region, and wherein the second material is formed by modifying the first material by the flow of ions, wherein the elongated elements are oriented along lines of intersections of the curved surface layer with a set of parallel planes, and wherein the flow of ions is arranged so as a local plane of ion incidence is substantially perpendicular to the set of parallel planes and oriented along a local surface normal of the curved surface layer, and during the irradiating of the surface of the curved surface layer with the flow of ions until the curved hard nanomask is formed, moving the curved substrate with respect to the flow of ions which is shaped to have an ion beam with a size (D1) in the local plane of ion incidence which is determined by a radius (R) of substrate surface curvature as D1≤R/3.
10. The method of claim 1, wherein A method of forming a curved hard nanomask for transferring a substantially periodic pattern into a curved substrate, the method comprising: depositing a first material to form a curved surface layer on top of a surface of the curved substrate, irradiating a surface of the curved surface layer with a flow of ions until a curved hard nanomask is formed, the curved hard nanomask comprising a substantially periodic array of substantially parallel elongated elements having a wave-shaped cross-section, at least some of the elongated elements having the following structure in cross-section: an inner region of first material, a first outer region of a second material covering a first portion of the inner region, and a second outer region of the second material covering a second portion of the inner region and connecting with the first outer region at a wave crest, wherein the first outer region is substantially thicker than the second outer region, and wherein the second material is formed by modifying the first material by the flow of ions, wherein the elongated elements are oriented along lines of intersections of the curved surface layer with a set of parallel planes, and wherein the flow of ions is arranged so as a local plane of ion incidence is substantially perpendicular to the set of parallel planes and oriented along a local surface normal of the curved surface layer; and during the irradiating of the surface of the curved surface layer with the flow of ions until the curved hard nanomask is formed, moving the curved substrate with respect to the flow of ions which is shaped to have an ion beam with a size (D2) in a direction perpendicular to the local plane of ion incidence which is determined by radius (R) of curvature of curved lens surface as D2≤R/15.
11. The method of claim 1, wherein, during the irradiating, the curved substrate is positioned stationary with respect to the flow of ions, wherein the flow of ions is shaped by grids.
12. The method of claim 1, wherein the first material is amorphous silicon and wherein the method further comprises, prior to irradiating the surface of the curved surface layer with the flow of ions, depositing a layer of amorphous silicon containing 5-15 at % of gold onto the curved surface layer.
13. The method of claim 12, further comprising, during the irradiating of the surface of the curved surface layer with the flow of ions until the curved hard nanomask is formed, moving the curved substrate with respect to the flow of ions which is shaped to have an ion beam with a size (D1) in the local plane of ion incidence which is determined by a radius (R) of substrate surface curvature as D1≤R/2.
14. The method of claim 9, wherein a wavelength of the substantially periodic array is in a range from 20 to 150 nm.
15. The method of claim 9, wherein the first material is silicon, amorphous silicon, silicon containing 5-15 at % of gold, silicon oxide, gallium arsenide, epitaxial gallium arsenide, gallium aluminum arsenide, epitaxial gallium aluminum arsenide, germanium, or silicon-germanium.
16. The method of claim 9, wherein the flow of ions comprises a flow of N.sub.2.sup.+, N.sup.+, NO.sup.+, NH.sub.m.sup.+, O.sub.2.sup.+, Ar.sup.+, Kr+, Xe.sup.+, or a mixture of Ar.sup.+ and N.sub.2.sup.+ ions.
17. The method of claim 9, wherein a thickness of the first outer region is at least 4 nm.
18. The method of claim 9, wherein a thickness of the second outer region is no more than 2 nm.
19. The method of claim 9, wherein the second material is silicon nitride, silicon nitride containing 5-15 at % of gold, silicon-germanium nitride, silicon oxide, gallium nitride, gallium oxide, aluminum nitride, aluminum oxide, gallium aluminum nitride, or gallium aluminum oxide.
20. The method of claim 9, wherein the first material is amorphous silicon and wherein the method further comprises, prior to irradiating the surface of the curved surface layer with the flow of ions, depositing a layer of amorphous silicon containing 5-15 at % of gold onto the curved surface layer.
21. The method of claim 10, wherein a wavelength of the substantially periodic array is in a range from 20 to 150 nm.
22. The method of claim 10, wherein the first material is silicon, amorphous silicon, silicon containing 5-15 at % of gold, silicon oxide, gallium arsenide, epitaxial gallium arsenide, gallium aluminum arsenide, epitaxial gallium aluminum arsenide, germanium, or silicon-germanium.
23. The method of claim 10, wherein the flow of ions comprises a flow of N.sub.2.sup.+, N.sup.+, NO.sup.+, NH.sub.m.sup.+, O.sub.2.sup.+, Ar.sup.+, Kr+, Xe.sup.+, or a mixture of Ar.sup.+ and N.sub.2.sup.+ ions.
24. The method of claim 10, wherein a thickness of the first outer region is at least 4 nm.
25. The method of claim 10, wherein a thickness of the second outer region is no more than 2 nm.
26. The method of claim 10, wherein the second material is silicon nitride, silicon nitride containing 5-15 at % of gold, silicon-germanium nitride, silicon oxide, gallium nitride, gallium oxide, aluminum nitride, aluminum oxide, gallium aluminum nitride, or gallium aluminum oxide.
27. The method of claim 10, wherein the first material is amorphous silicon and wherein the method further comprises, prior to irradiating the surface of the curved surface layer with the flow of ions, depositing a layer of amorphous silicon containing 5-15 at % of gold onto the curved surface layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(16) Detailed descriptions of the preferred embodiments are provided herein. It is to be understood, however, that the present inventions may be embodied in various forms. Therefore, specific implementations disclosed herein are not to be interpreted as limiting.
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(18) In at least some other embodiments, the transparent polarizer substrate 21a has a concave spherical surface, as shown in
(19) In at least some embodiments, uniform and parallel alignment of the nanomask elements on a spherical surface is achieved through the movement of the substrate under a fixed ion beam as shown in
(20) In some embodiments with divergent ion beams, another sequence of substrate motion in a meander scanning pattern is implemented. This meander scanning pattern 26a is labeled 302b in
(21) In at least some embodiments, in the scanning system of
(22) In some embodiments, substrate motion under a fixed ion beam is carried out in a repetitive manner with the ion fluence subdivided between multiple repetitive meander scans 26 or 26a. In this case, the uniformity of ion fluence over the substrate surface may be less dependent on the ion current stability and the greater the number of scans the more uniform is the ion fluence.
(23) In some embodiments, substrate scanning is implemented with a variable, position-dependent speed along lines 22 and 24 of
(24) The formation of a curved WOS nanomask was implemented in an ion beam system, which is schematically illustrated in
(25) On the spherical surface, the larger the beam size (D2) in the plane perpendicular to the ion incidence plane, the greater is the deviation of the WOS nanomask elements from the lines 22 of
(26) In some embodiments, the spherical segment is a lens having a radius R of the curvature of the external surface. The collimated ion beam, depending on its diameter, has different angles of ion incidence θ across the beam on the curved surface. In some embodiments, the variation of θ in the ion incidence plane may be within the range θ=44°-60° and the ion beam size D1 in the ion incidence plane is limited to D1≤R/6. Taking into account the ion dose dependence of the WOS formation process, this ion beam size restriction may be relaxed. In at least some embodiments, the ion beam size D1 is limited by the surface curvature radius R to D1≤R/3.
(27) In some embodiments, to accelerate the WOS formation process, a gold-containing film is deposited onto the amorphous silicon layer prior to ion irradiation. In some embodiments, the gold-containing film has a thickness in the range of 10 to 25 nm. It has been found that a gold-containing film deposited onto a silicon surface may greatly reduce the time of WOS formation process under nitrogen ion bombardment. Au.sup.+ ions implanted into monocrystalline silicon at the energy of 12 keV and fluence 10.sup.16 cm.sup.−2 accelerated the WOS formation process by about a factor of two for N.sub.2.sup.+ ions with E=8 keV and an angle of ion incidence of θ=45°. It is noteworthy that Au implantation did not result in any topographical roughness. Thus, the presence of gold in a surface silicon layer can result in the acceleration of WOS formation. It was also found that the acceleration effect is often angular dependent and may be greater for N.sub.2.sup.+ ion incidence angles of θ=41°-43° whereas almost no acceleration is observed for θ=55°-60°. The nature of angular dependence of WOS formation acceleration may make WOS formation depth almost independent for θ in the range of θ=41°-60°, which means that the ion beam size restriction in scanning system may be further relaxed. In at least some embodiments, on the basis of these observations the ion beam size D1 in the ion incidence plane is related to the substrate surface curvature radius R by D1≤R/2.
(28) In some embodiments, a composite Si—Au layer, 10-40 nm thick, with Au content ranging from 5-15 at % is deposited on the surface of an amorphous (a-Si) layer prior to N.sub.2.sup.+ ion irradiation. The Si—Au layer may be deposited, for example, by magnetron sputtering using a two-component Si/Au target, in which the silicon wafer is used as a mask with through holes leading to a closely attached Au wafer. For this two-component target with masked Au surface the Au content in the deposited Si—Au film is related to the amount of exposed gold area and by sputtering rates of Au and Si in the particular magnetron sputtering system.
(29) In some embodiments, depending on beam focusing, the substrate (lens) diameter 25 shown in
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(32) The amorphous silicon layer 602 may be deposited onto the curved substrate surface, for example, by magnetron sputtering of a silicon target, by silicon target evaporation with an electron beam in high vacuum, or by any other method known in art. The thickness of the layer 602 is selected to enable the formation of a nanostructure with desired period, λ, (for example, a period of approximately 70-90 nm).
(33) A curved WOS is formed on the surface of substrate 604, which results in the structure 611. In this example, the curved WOS is formed using an oblique ion beam 31 of nitrogen N.sub.2.sup.+ ions positioned at the local ion incidence plane XZ (the plane which is defined by a local normal to the surface of the material and a vector oriented in the direction of the ion flow) at angle θ to the surface normal (Z-axis). In this particular example, to reduce the number of intersections of WOS nanomask elements (waves), the nitrogen ion bombardment is implemented in two steps with different bombardment angles θ. At the first step θ=44° and at the second step θ=60°. The ion energy for both steps is approximately equal to 3.7 keV. The ion fluence for the first step is approximately ten times greater than that for the second step. The resultant WOS nanomask having a period of 80 nm is shown in
(34) Depending on the chosen thickness of the modified layer 20 on the back side of waves of the wavelike nanostructure, a preliminary breakthrough etching step might be performed using argon ion sputtering or sputtering by ions of etching plasma for a relatively short period of time to remove the modified layer 20 from the back side. To remove regions 20 one can also perform wet etching in HNO.sub.3—HF solution for a short period of time.
(35) In at least some embodiments, the structure 611 may be optionally wet-etched to form the structure 611a having nanotrenches 12a in place of regions 20. This optional wet etching may improve further etching steps in plasma.
(36) The curved WOS and nanostructures formed from the curved WOS by etching with the use of regions 10 and 20 as a nanomask can be characterized as a quasi-periodic, anisotropic array of elongated ridge elements having a WOS pattern, each ridge element having a wavelike cross-section and oriented substantially in one direction (Y-axis). An example of the pattern of a WOS is shown in
(37) Referring again to
(38) In the next step, anisotropic etching is applied to the substrate 604. Depending on the type of the substrate material, different types of plasma can be used (for example, for a quartz substrate, CF.sub.4—H.sub.2, CHF.sub.3, C.sub.4F.sub.6—Ar or C.sub.4F.sub.8—Ar based plasma can be used). The resulting structures 613-615 may include trenches 607, 607a, and 607b. During etching the amorphous silicon stripes 602 may be modified by plasma to the structures 602a and 602b or may be fully etched, which may result in tilted sidewalls 608 of quartz nanoridges 609. In some embodiments, the structure 612 is modified by ion sputtering using a N.sub.2.sup.+ ion beam directed along the ridge elements 602 in the YZ ion incidence plane at an angle of, for example, about 53° to the Z axis. The resultant quartz nanoridges have a sawtooth triangular profile with sharp bottoms and tops as shown in
(39) Oblique deposition of aluminum can be performed on the array of quartz nanoridges as shown in the structure 616 to produce a curved wire-grid polarizer. For uniform deposition, the curved substrate may be moved under the flow of metal atoms 610. In some embodiments, special masks may be applied across the flow of metal atoms to obtain uniform metal nanowires 611. In some embodiments, the mask may include a slit. During the aluminum deposition, the slit mask is positioned along the quartz nanoridges, and the quartz substrate is rotated under the mask in a direction perpendicular to the mask extension for uniform aluminum deposition to the nanoridges.
(40) In at least some embodiments, a curved hard WOS nanomask may be manufactured on fixed spherical substrates by a gridded ion source having a special grid surface, which is shown in
(41) In at least some embodiments, the spherical surface of a quartz substrate with quartz nanoridges may be used as a master mold to transfer a nanoridge pattern to the surface of a curved polymeric substrate. It will be recognized that materials other than quartz can also be used for the substrate and nanoridges. In at least some embodiments, the spherical surface of a silicon substrate with silicon nanoridges may be used as a master mold to transfer a nanoridge pattern to the surface of a curved polymeric substrate. In some embodiments, the master mold has a convex surface. In some other embodiments, the master mold has a concave surface. In some embodiments, the nanoridge pattern of the silicon master mold is transferred into the surface of a nickel thin layer using, for example, nickel electroless plating onto the silicon mold surface and then a thick nickel layer is electrodeposited to make a nickel mold.
(42) In structure 810 of
(43) In at least some embodiments, the formation of a WOS nanomask on a concave substrate is carried out by linear ion flow to irradiate a linear stripe area on the substrate surface.
(44) In comparison with the arrangement shown in
(45) The arrangement shown in
(46) In the arrangement shown in
(47) In the arrangement shown in
(48) In at least some embodiments, in the arrangements shown in
(49) The invention can be used, for example, for forming curved nanowire arrays for nanoelectronics and optoelectronics devices.