WO2022232047A2 - Multilayer organic solid thin films having a biaxial refractive index - Google Patents
Multilayer organic solid thin films having a biaxial refractive index Download PDFInfo
- Publication number
- WO2022232047A2 WO2022232047A2 PCT/US2022/026180 US2022026180W WO2022232047A2 WO 2022232047 A2 WO2022232047 A2 WO 2022232047A2 US 2022026180 W US2022026180 W US 2022026180W WO 2022232047 A2 WO2022232047 A2 WO 2022232047A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biaxially
- thin film
- layer
- crystal
- organic solid
- Prior art date
Links
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
Definitions
- the present disclosure is directed to, for example, thin film optical elements and methods of manufacturing thin film optical elements.
- Polymer and other organic materials may be incorporated into a variety of different optic and electro-optic device architectures, including active and passive optics and electroactive devices.
- Lightweight and conformable, one or more polymer/organic solid layers may be incorporated into wearable devices such as smart glasses and are attractive candidates for emerging technologies including virtual reality/augmented reality devices where a comfortable, adjustable form factor is desired.
- Virtual reality (VR) and augmented reality (AR) eyewear devices or headsets may enable users to experience events, such as interactions with people in a computer-generated simulation of a three-dimensional world or viewing data superimposed on a real-world view.
- superimposing information onto a field of view may be achieved through an optical head-mounted display (OHMD) or by using embedded wireless glasses with a transparent heads-up display (HUD) or augmented reality (AR) overlay.
- OHMD optical head-mounted display
- HUD transparent heads-up display
- AR augmented reality
- VR/AR eyewear devices and headsets may be used for a variety of purposes. For example, governments may use such devices for military training, medical professionals may use such devices to simulate surgery, and engineers may use such devices as design visualization aids.
- a circular reflective polarizer may be configured to reflect light of one circular polarization and transmit light having the orthogonal polarization.
- broadband circular reflective polarizers are typically core components where the reflective polarizer quality may impact the display viewing experience of a user or the recycling efficiency of the device.
- a circular reflective polarizer may include a linear reflective polarizer and quarter waveplate, where the linear reflective polarizer is often made using one or more polymer materials, such as PEN.
- a circular reflective polarizer can also be made using cholesteric materials, such as a cholesteric liquid crystal (CLC).
- CLC cholesteric liquid crystal
- a multilayer organic thin film comprising a plurality of biaxially-oriented layers, wherein each biaxially-oriented layer is characterized by mutually orthogonal refractive indices, ni1n21n3.
- each biaxially-oriented layer may comprise an optically anisotropic organic material.
- each biaxially-oriented layer may comprise a single crystal or polycrystalline material.
- each biaxially-oriented layer may comprise an optically anisotropic glassy material, the glassy material comprising molecules aligned along predetermined directions.
- the plurality of biaxially-oriented layers may be compositionally equivalent.
- each biaxially-oriented layer may directly overlie an adjacent biaxially-oriented layer.
- in-plane refractive indices (n2, P3) of a chosen biaxially-oriented layer may be rotated by an angle (Q) with respect to corresponding in-plane refractive indices (n2, P3) of a biaxially-oriented layer located adjacent to the chosen biaxially- oriented layer.
- in-plane refractive indices (n2, n3) of each biaxially- oriented layer may be characterized by (n 2 +n 3 )/2 > 1.5.
- in-plane refractive indices (n2, P3) of each biaxially- oriented layer may be characterized by
- an out-of-plane refractive index ( ) for a chosen biaxially-oriented layer may be related to in-plane refractive indices (n2, P3) for the chosen biaxially-oriented layer according to n2 ⁇ ni ⁇ n3.
- a circular reflective polarizer comprising a multilayer organic thin film of the first aspect.
- a method comprising: forming a layer of a molecular feedstock over a surface of a mold, the molecular feedstock comprising an organic solid crystal precursor; forming a selected number of crystal nuclei from the organic solid crystal precursor within a nucleation region of the layer of the molecular feedstock; and growing the selected number of crystal nuclei to form an organic solid crystal thin film.
- forming the selected number of crystal nuclei may comprise heating the layer of the molecular feedstock to a temperature greater than a melting onset temperature of the organic solid crystal precursor within the nucleation region.
- forming the selected number of crystal nuclei may comprise melting crystal nuclei outside of the nucleation region.
- the selected number of crystal nuclei may be one.
- the method may further comprise forming a release layer over the mold surface prior to forming the layer of molecular feedstock.
- he method may further comprise separating the organic solid crystal thin film from the surface of the mold.
- the molecular feedstock may comprise a process enhancer selected from the group consisting of polymers, oligomers, and small molecules, the process enhancer having a melting onset temperature of at least 20°C less than a melting onset temperature of the organic solid crystal precursor.
- forming the layer of molecular feedstock may comprise injecting the molecular feedstock into the mold.
- a multilayer organic thin film comprising a stack of biaxially-oriented organic solid crystal layers, wherein each biaxially-oriented layer is characterized by mutually orthogonal refractive indices, ni1n 1n , and respective in-plane refractive indices (n , ns) of adjacent biaxially-oriented layers within the stack are rotationally offset by an angle (Q).
- FIG. 1 illustrates example methods for manufacturing (A) a free-standing organic solid crystal material and (B) a supported organic solid crystal material according to various embodiments.
- FIG. 2 shows cross-polarized microscope images of an organic solid crystal thin film manufactured (A) without a non-volatile medium material and (B) with a non-volatile medium material according to some embodiments.
- FIG. 3 is a schematic representation of a vapor deposition-based epitaxial growth process for forming organic solid crystals according to some embodiments.
- FIG. 4 is a schematic representation of a melt-based epitaxial growth process for forming organic solid crystals according to some embodiments.
- FIG. 5 is a schematic representation of a melt-based epitaxial growth process for forming organic solid crystals according to further embodiments.
- FIG. 6 shows (A) double-sided mold and (B) single-side mold epitaxial growth processes for forming organic solid crystals according to further embodiments.
- FIG. 7 shows a seeded single-side mold epitaxial growth process for forming organic solid crystals according to some embodiments.
- FIG. 8 is a schematic illustration of a solvent-based epitaxial/non-epitaxial growth process for forming organic solid crystals according to some embodiments.
- FIG. 9 is a schematic illustration of a non-epitaxial growth process for forming organic solid crystals according to certain embodiments.
- FIG. 10 illustrates an example organic solid crystal-containing architecture according to some embodiments.
- FIG. 11 illustrates an example organic solid crystal-containing architecture according to further embodiments.
- FIG. 12 illustrates example organic solid crystal geometries according to some embodiments.
- FIG. 13 is a schematic illustration of an example crystal growth apparatus for manufacturing an organic solid crystal according to various embodiments.
- FIG. 14 is an illustration of example nucleation surface and scaffold geometries according to certain embodiments.
- FIG. 15 is an illustration showing (A) a top down view and (B) a side view of an example crystal growth configuration having a single nucleation site for manufacturing an organic solid crystal (OSC) thin film according to some embodiments.
- OSC organic solid crystal
- FIG. 16 is an illustration showing (A) a top down view and (B) a side view of an example crystal growth configuration having plural nucleation sites for manufacturing an organic solid crystal (OSC) thin film according to some embodiments.
- OSC organic solid crystal
- FIG. 17 is an illustration showing an OSC thin film manufacturing configuration for facilitating mass transport to a crystallization front according to some embodiments.
- FIG. 18 shows example crystallizable organic molecules for manufacturing an organic solid crystal according to certain embodiments.
- FIG. 19 is a cross-sectional schematic illustration of an optical element including a reflective organic solid crystal-containing polarizer according to some embodiments.
- FIG. 20 is a graphic representation of the orientation of the major in-plane index (ns) in a biaxial multilayer organic solid thin film according to various embodiments.
- FIG. 21 is a plot of signal efficiency and ghost image suppression as a function of reflective polarizer thickness for a reflective polarizer including a biaxial ly oriented organic solid material according to some embodiments.
- FIG. 22 is an illustration of exemplary augmented-reality glasses that may be used in connection with embodiments of this disclosure.
- FIG. 23 is an illustration of an exemplary virtual-reality headset that may be used in connection with embodiments of this disclosure.
- Polymer and other organic materials may be incorporated into a variety of different optic and electro-optic device architectures, including active and passive optics and electroactive devices.
- Lightweight and conformable, one or more polymer/organic solid layers may be incorporated into wearable devices such as smart glasses and are attractive candidates for emerging technologies including virtual reality/augmented reality devices where a comfortable, adjustable form factor is desired.
- Virtual reality (VR) and augmented reality (AR) eyewear devices or headsets may enable users to experience events, such as interactions with people in a computer-generated simulation of a three-dimensional world or viewing data superimposed on a real-world view.
- superimposing information onto a field of view may be achieved through an optical head-mounted display (OHMD) or by using embedded wireless glasses with a transparent heads-up display (HUD) or augmented reality (AR) overlay.
- OHMD optical head-mounted display
- HUD transparent heads-up display
- AR augmented reality
- VR/AR eyewear devices and headsets may be used for a variety of purposes. For example, governments may use such devices for military training, medical professionals may use such devices to simulate surgery, and engineers may use such devices as design visualization aids.
- a circular reflective polarizer may be configured to reflect light of one circular polarization and transmit light having the orthogonal polarization.
- broadband circular reflective polarizers are typically core components where the reflective polarizer quality may impact the display viewing experience of a user or the recycling efficiency of the device.
- a circular reflective polarizer may include a linear reflective polarizer and quarter waveplate, where the linear reflective polarizer is often made using one or more polymer materials, such as PEN.
- a circular reflective polarizer can also be made using cholesteric materials, such as a cholesteric liquid crystal (CLC).
- CLC cholesteric liquid crystal
- Such comparative approaches may not provide a desired combination of broadband efficiency (e.g., as a function of gaze angle) and ghost image suppression.
- broadband efficiency e.g., as a function of gaze angle
- a multilayer thin film that includes plural layers of an organic solid crystal material may be incorporated into a variety of optical systems and devices.
- an optical assembly such as a lens system including a circular reflective polarizer, may include a multilayer organic solid thin film.
- the multilayerthin film may include a plurality of biaxially oriented organic solid material layers. Each biaxial layer may be characterized by three mutually orthogonal refractive indices ( , n , ns) where ni1n 1n .
- a multilayer organic solid thin film may be incorporated into a circular reflective polarizer for use in display systems to provide high broadband efficiency and high off-axis contrast.
- a quarter waveplate may be omitted.
- Such biaxially oriented multilayer thin films may enable optical elements such as circular reflective polarizers having higher signal efficiency, improved off- angle selectivity, and greater ghost image suppression than architectures using comparative materials.
- Organic solid thin films can also be used in various projectors as a brightness enhancement layer.
- One or more source materials may be used to form an organic solid thin film, including a multilayer thin film.
- Example organic materials may include various classes of crystallizable organic semiconductors.
- organic semiconductors may include small molecules, macromolecules, liquid crystals, organometallic compounds, oligomers, and polymers.
- Organic semiconductors may include p-type, n-type, or ambipolar polycyclic aromatic hydrocarbons, such as anthracene, phenanthrene, carbon 60, pyrene, corannulene, fluorene, biphenyl, ter-phenyl, etc.
- Example compounds may include cyclic, linear and/or branched structures, which may be saturated or unsaturated, and may additionally include heteroatoms and/or saturated or unsaturated heterocycles, such as furan, pyrrole, thiophene, pyridine, pyrimidine, piperidine, and the like. Heteroatoms may include fluorine, chlorine, nitrogen, oxygen, sulfur, phosphorus, as well as various metals.
- Suitable feedstock for molding solid organic semiconductor materials may include neat organic compositions, melts, solutions, or suspensions containing one or more of the organic materials disclosed herein.
- the disclosed organic materials may be single crystal, polycrystalline, or glassy.
- Organic solid crystals may include closely packed structures (e.g., organic molecules) that exhibit desirable optical properties such as a high and tunable refractive index, and high birefringence.
- Anisotropic organic solid materials may include a preferred packing of molecules or a preferred orientation or alignment of molecules.
- organic solid crystal (OSC) materials may provide functionalities, including phase modulation, beam steering, wave-front shaping and correction, optical communication, optical computation, holography, and the like. Due to their optical and mechanical properties, organic solid crystals may enable high-performance devices, and may be incorporated into passive or active optics, including AR/VR headsets, and may replace comparative material systems such as polymers, inorganic materials, and liquid crystals. In certain aspects, organic solid crystals may have optical properties that rival those of inorganic crystals while exhibiting the processability and electrical response of liquid crystals.
- organic solid crystal materials may be molded to form a desired structure. Molding processes may enable complex architectures and may be more economical than the cutting, grinding, and polishing of bulk crystals.
- a single crystal or polycrystalline shape such as a sheet or cube may be partially or fully melted into a desired form and then controllably cooled to form a single crystal having a new shape.
- a process of molding an optically anisotropic crystalline or partially crystalline thin film may include operational control of the thermodynamics and kinetics of nucleation and crystal growth.
- a temperature during molding proximate to a nucleation region of a mold may be less than a melting onset temperature (T m ) of a molding composition, while the temperature remote from the nucleation region may be greater than the melting onset temperature.
- a temperature during molding proximate to a nucleation region of a mold may be a nucleation temperature equal to or greater than a melting onset temperature (T m ) of a molding composition, while the temperature remote from the nucleation region may be greater than the nucleation temperature.
- Such a temperature gradient paradigm may be obtained through a spatially applied thermal gradient, optionally in conjunction with a selective melting process (e.g., laser, soldering iron, etc.) to remove excess nuclei, leaving few nuclei (e.g., a single nucleus) for crystal growth.
- a selective melting process e.g., laser, soldering iron, etc.
- a selected temperature and temperature gradient may be applied to a crystallization front of a nascent thin film.
- the temperature and temperature gradient proximate to the crystallization front may be determined based on the selected feedstock (i.e., molding composition), including its melting temperature, thermal stability, and rheological attributes.
- a suitable mold for molding an organic solid thin film may be formed from a material having a softening temperature or a glass transition temperature (T g ) greater than the melting onset temperature (T m ) of the molding composition.
- the mold may include any suitable material, e.g., silicon, silicon dioxide, fused silica, quartz, glass, nickel, silicone, siloxanes, perfluoropolyethers, polytetrafluoroethylenes, perfluoroalkoxy alkanes, polyimide, polyethylene naphthalate, polyvinylidene fluoride, polyphenylene sulfide, and the like.
- An epitaxial or non-epitaxial growth process may be used to form an organic solid crystal (OSC) layer over a suitable substrate or mold.
- a seed crystal for encouraging crystal nucleation and an anti-nucleation layer configured to locally inhibit nucleation may collectively promote the formation of a limited number of crystal nuclei within one or more specified location(s), which may in turn encourage the formation of larger organic solid crystals.
- a nucleation-promoting layer or seed crystal may itself be configured as a thin film.
- Example nucleation-promoting or seed materials may include one or more metallic or inorganic elements orcompounds, such as Pt, Ag, Au, Al, Pb, indium tin oxide, S1O2, and the like.
- Further example nucleation-promoting or seed crystal materials may include organic compounds, such as a polyimide, polyamide, polyurethane, polyurea, polythiolurethane, polyethylene, polysulfonate, polyolefin, as well as mixtures and combinations thereof.
- a nucleation-promoting material may be configured as a textured or aligned layer, such as a rubbed polyimide or photoalignment layer, which may be configured to induce directionality or a preferred orientation to an over-formed organic solid crystal thin film.
- An example method for manufacturing an organic solid crystal thin film includes providing a mold, forming a layer of a nucleation-promoting material over at least a portion of a surface of the mold, and depositing a layer of molten feedstock over the surface of the mold and in contact with the layer of the nucleation-promoting material, while maintaining a temperature gradient across the layer of the molten feedstock.
- An anti-nucleation layer may include a dielectric material.
- an anti-nucleation layer may include an amorphous material.
- crystal nucleation may occur independent of the substrate or mold.
- a surface treatment or release layer disposed over the substrate or mold may be used to control nucleation and growth of the organic solid crystal (OSC) and later promote separation and harvesting of a bulk crystal or thin film.
- OSC organic solid crystal
- a coating having a solubility parameter mismatch with the deposition chemistry may be applied to the substrate (e.g., globally or locally) to suppress interaction between the substrate and the crystallizing layer during the deposition process.
- Example surface treatment coatings may include oleophobic coatings or hydrophobic coatings.
- a thin layer, e.g., monolayer or bilayer, of an oleophobic material or a hydrophobic material may be used to condition the substrate or mold prior to an epitaxial process.
- the coating material may be selected based on the substrate and/or the organic crystalline material.
- Further example surface treatment coating materials include siloxanes, fluorosiloxanes, phenyl siloxanes, fluorinated coatings, polyvinyl alcohol, and other OFI bearing coatings, acrylics, polyurethanes, polyesters, polyimides, and the like.
- a release agent may be applied to an internal surface of the mold and/or combined with the molding composition.
- a surface treatment of an inner surface ofthe mold may include the chemical bonding or physical adsorption ofsmall molecules, or polymers/oligomers having linear, branched, dendritic, or ringed structures, that may be functionalized or terminated, for example, with fluorinated groups, silicones, or hydrocarbon groups.
- a buffer layer may be formed over the deposition surface of a substrate or mold.
- a buffer layer may include a small molecule that may be similar to or even equivalent to the small molecule forming the organic solid crystal, e.g., an anthracene single crystal.
- a buffer layer may be used to tune one or more properties of the deposition/growth surface of the substrate or mold, including surface energy, wettability, crystalline or molecular orientation, etc.
- a further example method for manufacturing an organic solid crystal thin film includes forming a layer of a molecular feedstock over a surface of a mold, the molecular feedstock including crystallizable organic molecules, forming a selected number of crystal nuclei from the organic molecules within a nucleation region of the molecular feedstock layer, and growing the selected number of crystal nuclei to form an organic solid crystal thin film.
- the selected number of crystal nuclei may be one. Crystal growth may be controlled using an isothermal process, slow cooling, and zone annealing.
- an additive may be used to encourage the growth of a single crystal and/or its release from the mold.
- a molecular feedstock may include an additive selected from polymers, oligomers, and small molecules, where the additive may have a melting onset temperature of at least 20°C less than a melting onset temperature of the organic solid crystal precursor, e.g., 20°C, 30°C, or even 40°C less than the melting onset temperature of the molding composition.
- An additive may promote crystal growth and the formation of a large crystal size.
- an additive may be integrated with a molding process to improve the characteristics of a molded organic solid thin film, including its surface roughness.
- a cover plate may be applied to a free surface of the organic solid crystal thin film.
- the cover plate may be oriented at an angle with respect to a major surface of the thin film.
- a force may be applied to the cover plate to generate capillary forces that facilitate mass transport of the molten feedstock, i.e., between the cover plate and the substrate and in the direction of a crystallization front of a growing crystalline thin film.
- the force of gravity may contribute to mass transport and the delivery of the molten feedstock to the crystallization front.
- Suitable materials for the cover plate and the substrate may independently include silicon dioxide, fused silica, high index glasses, high index inorganic crystals, and high melting temperature polymers (e.g., siloxanes, polyimides, PTFE, PFA, etc.), although further material compositions are contemplated.
- silicon dioxide fused silica
- high index glasses high index inorganic crystals
- high melting temperature polymers e.g., siloxanes, polyimides, PTFE, PFA, etc.
- a method of forming an organic solid crystal may include contacting an organic precursor (i.e., crystallizable organic molecules) with a non-volatile medium material, forming a layer including the organic precursor over a surface of a substrate or mold, and processing the organic precursor to form an organic crystalline phase, where the organic crystalline phase may include a preferred orientation of molecules.
- organic precursor i.e., crystallizable organic molecules
- the act of contacting the organic precursor with the non-volatile medium material may include forming a homogeneous mixture of the organic precursor and the non volatile medium material.
- the act of contacting the organic precursor with the non-volatile medium material may include forming a layer of the non-volatile medium material over a surface of a substrate or mold and forming a layer of the organic precursor over the layer of the non-volatile medium material.
- a non-volatile medium material may be disposed between the mold surface and the organic precursor and may be adapted to decrease the surface roughness of the molded organic thin film and promote its release from the mold while locally inhibiting nucleation of a crystalline phase.
- Example non-volatile medium materials include liquids such as silicone oil, a fluorinated polymer, a polyolefin and/or polyethylene glycol. Further example non-volatile medium materials may include crystalline materials having a melting temperature that is less than the melting temperature of the organic precursor material.
- the mold surface may be pre-treated in order to improve wetting and/or adhesion of the non-volatile medium material.
- the substrate or mold may include a surface that may be configured to provide a desired shape to the molded organic solid thin film.
- the substrate or mold surface may be planar, concave, or convex, and may include a three-dimensional architecture, such as surface relief gratings, or a curvature (e.g., compound curvature) configured to form microlenses, microprisms, or prismatic lenses.
- a substrate or mold geometry may be transferred and incorporated into a surface of an over-formed organic solid crystal thin film.
- the terms "substrate” and “mold” may be used interchangeably herein unless the context indicates otherwise.
- the deposition surface of a substrate or mold may include a functional layer that is configured to be transferred to the organic solid crystal after formation of the organic solid crystal and its separation from the substrate or mold.
- Functional layers may include an interference coating, an AR coating, a reflectivity enhancing coating, a bandpass coating, a band-block coating, blanket or patterned electrodes, etc.
- an electrode may include any suitably electrically conductive material such as a metal, a transparent conductive oxide (TCO) (e.g., indium tin oxide or indium gallium zinc oxide), or a metal mesh or nanowire matrix (e.g., including metal nanowires or carbon nanotubes).
- TCO transparent conductive oxide
- nanowire matrix e.g., including metal nanowires or carbon nanotubes.
- deposition methods for forming organic solid crystals include vapor phase growth, solid state growth, melt-based growth, solution growth, etc., optionally in conjunction with a suitable substrate and/or seed crystal.
- a substrate may be organic or inorganic.
- thin film solid organic materials may be manufactured using one or more processes selected from chemical vapor deposition and physical vapor deposition. Further coating processes, e.g., from solution or a melt, may include 3D printing, ink jet printing, gravure printing, doctor blading, spin coating, and the like.
- Such processes may induce shear during the act of coating and accordingly may contribute to crystallite or molecular alignment and a preferred orientation of crystallites and/or molecules within an organic solid crystal thin film.
- a still further example method may include pulling a free-standing crystal from a melt.
- solid-, liquid-, or gas-phase deposition processes may include epitaxial processes.
- epitaxial As used herein, the terms “epitaxy,” “epitaxial” and/or “epitaxial growth and/or deposition” refer to the nucleation and growth of an organic solid crystal on a deposition surface where the organic solid crystal layer being grown assumes the same crystalline habit as the material of the deposition surface.
- chemical reactants may be controlled, and the system parameters may be set so that depositing atoms or molecules alight on the deposition surface and remain sufficiently mobile via surface diffusion to orient themselves according to the crystalline orientation of the atoms or molecules of the deposition surface.
- An epitaxial process may be homogeneous or heterogeneous.
- the optical and electrooptical properties of an organic solid crystal thin film may be tuned using doping and related techniques.
- Doping may influence the polarizability of an organic solid crystal, for example.
- the introduction of dopants, i.e., impurities, into an organic solid crystal may influence, for example, the highest occupied molecular orbital (FIOMO) and lowest unoccupied molecular orbital (LUMO) bands and hence the band gap thereof, induced dipole moment, and/or molecular/crystal polarizability.
- FIOMO highest occupied molecular orbital
- LUMO lowest unoccupied molecular orbital
- Doping may be performed in situ, i.e., during epitaxial growth, or following epitaxial growth, for example, using ion implantation or plasma doping.
- doping may be used to modify the electronic structure of an organic solid crystal without damaging molecular packing or the crystal structure itself.
- a post implantation annealing step may be used to heal crystal defects introduced during ion implantation or plasma doping. Annealing may include rapid thermal annealing or pulsed annealing, for example.
- a doped organic solid crystal may be p-type or n-type.
- p-type refers to the addition of impurities to an organic solid crystal that create a deficiency of valence electrons
- n-type refers to the addition of impurities that contribute free electrons to an organic solid crystal.
- doping may influence "p-stacking" and "p-p interactions" within an organic solid crystal.
- Example dopants include Lewis acids (electron acceptors) and Lewis bases (electron donors). Particularexamples include charge-neutral and ionic species, e.g., Brpnsted acids and Brpnsted bases, which in conjunction with the aforementioned processes may be incorporated into an organic solid crystal by solution growth or co-deposition from the vapor phase.
- a dopant may include an organic molecule, an organic ion, an inorganic molecule, or an inorganic ion.
- a doping profile may be homogeneous or localized to a particular region (e.g., depth or area) of an organic solid crystal.
- the orientation of the in-plane axes of an OSC thin film may be controlled using one or more of substrate temperature, deposition pressure, solvent vapor pressure, or non-solvent vapor pressure.
- High refractive index and highly birefringent organic solid thin films may be supported by a substrate or mold or removed therefrom to form a free-standing thin film.
- a substrate, if used, may be rigid or deformable.
- Example processes may be integrated with a real-time feedback loop that is configured to assess one or more attributes of the organic solid crystal and accordingly adjust one or more process variables, including melt temperature, mold temperature, feedstock injection rate into a mold, etc.
- an OSC thin film may be diced and polished to achieve a desired form factor and surface quality.
- Dicing may include diamond turning, for example, although other cutting methods may be used.
- Polishing may include chemical mechanical polishing.
- a chemical or mechanical surface treatment may be used to create structures on a surface of an OSC thin film.
- Example surface treatment methods include diamond turning and photolithography and etch processes.
- a cover plate or substrate with reciprocal structures may be used to fabricate surface structures in an OSC thin film.
- An organic thin film may include a surface that is planar, convex, or concave.
- the surface may include a three-dimensional architecture, such as a periodic surface relief grating.
- a thin film may be configured as a microlens or a prismatic lens.
- polarization optics may include a microlens that selectively focuses one polarization of light over another.
- a structured surface may be formed in situ, i.e., during crystal growth of the organic solid crystal thin film over a suitably shaped mold.
- a structured surface may be formed after crystal growth, e.g., using additive or subtractive processing, such as 3D printing or photolithography and etching.
- additive or subtractive processing such as 3D printing or photolithography and etching.
- the nucleation and growth kinetics and choice of chemistry may be selected to produce a solid organic crystal thin film having areal (lateral) dimensions of at least approximately 1 cm.
- the organic crystalline phase may be single crystal or polycrystalline. In some embodiments, the organic crystalline phase may include amorphous regions. In some embodiments, the organic crystalline phase may be substantially crystalline. The organic crystalline phase may be characterized by a refractive index along at least one principal axis of at least approximately 1.5 at 589 nm.
- the refractive index of the organic crystalline phase at 589 nm and along at least one principal axis may be at least approximately 1.5, at least approximately 1.6, at least approximately 1.7, at least approximately 1.8, at least approximately 1.9, at least approximately 2.0, at least approximately 2.1, at least approximately 2.2, at least approximately 2.3, at least approximately 2.4, at least approximately 2.5, or at least approximately 2.6, including ranges between any of the foregoing values.
- the organic crystalline phase may be characterized by a birefringence (Dh), where ni1n 1n , of at least approximately 0.05, e.g., at least approximately 0.05, at least approximately 0.1, at least approximately 0.2, at least approximately 0.3, at least approximately 0.4, or at least approximately 0.5, including ranges between any of the foregoing values.
- Dh birefringence
- a birefringent organic crystalline phase may be characterized by a birefringence of less than approximately 0.05, e.g., less than approximately 0.05, less than approximately 0.1, less than approximately 0.05, less than approximately 0.02, less than approximately 0.01, less than approximately 0.005, less than approximately 0.002, or less than approximately 0.001, including ranges between any of the foregoing values.
- Table 1 Three axis ellipsometry data for example isotropic or anisotropic organic molecules are shown in Table 1.
- the data include predicted and measured refractive index values and birefringence values for 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2-diphenylethyne (1,2-DPE), and phenazine. Shown are larger than anticipated refractive index values and birefringence compared to calculated values based on the HOMO-LUMO gap for each organic material composition.
- Organic solid thin films may be optically transparent and exhibit low bulk haze.
- a material or element that is "transparent” or “optically transparent” may, for a given thickness, have a transmissivity within the visible light spectrum of at least approximately 80%, e.g., approximately 80, 90, 95, 97, 98, 99, or 99.5%, including ranges between any of the foregoing values, and less than approximately 5% bulk haze, e.g., approximately 0.1, 0.2, 0.4, 1, 2, or 4% bulk haze, including ranges between any of the foregoing values.
- Transparent materials will typically exhibit very low optical absorption and minimal optical scattering.
- haze and “clarity” may refer to an optical phenomenon associated with the transmission of light through a material, and may be attributed, for example, to the refraction of light within the material, e.g., due to secondary phases or porosity and/or the reflection of light from one or more surfaces of the material.
- haze may be associated with an amount of light that is subject to wide angle scattering (i.e., at an angle greater than 2.5° from normal) and a corresponding loss of transmissive contrast
- clarity may relate to an amount of light that is subject to narrow angle scattering (i.e., at an angle less than 2.5° from normal) and an attendant loss of optical sharpness or "see through quality.”
- one or more organic solid thin film layers may be diced and stacked to form a multilayer.
- a multilayer thin film may be formed by clocking and stacking individual layers. That is, in an example "clocked" multilayer stack, an angle of refractive index misorientation between successive layers may range from approximately 1° to approximately 90°, e.g., 1, 2, 5, 10, 20, 30, 40, 45, 50, 60, 70, 80, or 90°, including ranges between any of the foregoing values.
- the thickness of each layer may be determined from an average value of in-plane refractive indices (n2 and ns), where (n2+ns)/2 may be greater than approximately 1.5, e.g., greater than 1.5, greater than 1.55, or greater than 1.6.
- the thickness of a given layer may be inversely proportional to the arithmetic average of its in-plane indices.
- the total number of layers in a multilayer stack may be determined from the in-plane birefringence (
- the variation in ni may be less than ⁇ 0.7, less than ⁇ 0.6, less than ⁇ 0.5, less than ⁇ 0.4, less than ⁇ 0.3, or less than ⁇ 0.2.
- a value for ni may be between values for n2 and n3, i.e., n2 ⁇ hi ⁇ P3 ⁇
- organic solid crystals having an actively tunable refractive index and birefringence.
- Methods of manufacturing such organic solid crystals may enable control of their surface roughness independent of surface features (e.g., gratings, etc.) and may include the formation of an optical element therefrom, such as a circular reflective polarizer.
- an optical element including an organic solid crystal (OSC) may be integrated into an optical component or device, such as an OFET, OPV, OLED, etc., and may be incorporated into a structure or a device such as a waveguide, Fresnel lens (e.g., a cylindrical Fresnel lens or a spherical Fresnel lens), grating, photonic integrated circuit, birefringent compensation layer, reflective polarizer, index matching layer (LED/OLED), and the like.
- grating architectures may be tunable along one, two, or three dimensions.
- Optical elements may include a single layer or a multilayer OSC architecture.
- one or more characteristics of organic solid crystals may be specifically tailored for a particular application. For many optical applications, for instance, it may be advantageous to control crystallite size, surface roughness, mechanical strength and toughness, and the orientation of crystallites and/or molecules within an organic solid crystal thin film.
- the composition, structure, and properties of each organic layer may be independently selected.
- Organic solid crystals may be incorporated into passive and active optical waveguides, resonators, lasers, optical modulators, etc.
- active optics include projectors and projection optics, ophthalmic high index lenses, eye tracking, gradient-index optics, Pancharatnam-Berry phase (PBP) lenses, microlenses, pupil steering elements, optical computing, fiber optics, rewritable optical data storage, all-optical logic gates, multi-wavelength optical data processing, optical transistors, etc.
- PBP Pancharatnam-Berry phase
- organic solid crystals may be incorporated into passive optics, such as waveguides, reflective polarizers, refractive/diffractive lenses, and the like.
- passive optics such as waveguides, reflective polarizers, refractive/diffractive lenses, and the like.
- Related optical elements for passive optics may include waveguides, polarization selective gratings, Fresnel lenses, microlenses, geometric lenses, PBP lenses, and multilayer thin films.
- FIG. 1 relates to example mold-based processes for forming an organic solid crystal thin film.
- the discussion associated with FIG. 2 relates to the structure and properties of example organic solid crystals.
- the discussion associated with FIGS. 3-9 includes a description of example epitaxial and non-epitaxial growth processes for forming organic solid crystals.
- the discussion associated with FIGS. 10-12 includes a description of ID and 2D structured organic solid crystals.
- the discussion associated with FIGS. 13-17 includes a description of example manufacturing methods and apparatus for forming organic solid crystal thin films.
- FIG. 1 relates to example mold-based processes for forming an organic solid crystal thin film.
- FIG. 2 relates to the structure and properties of example organic solid crystals.
- the discussion associated with FIGS. 3-9 includes a description of example epitaxial and non-epitaxial growth processes for forming organic solid crystals.
- the discussion associated with FIGS. 10-12 includes a description of ID and 2D structured organic solid crystals.
- the discussion associated with FIGS. 13-17 includes
- FIGS. 18 and 23 includes a description of example crysta I lizable organic molecules suitable for the manufacture of organic solid crystal (OSC) thin films.
- the discussion associated with FIG. 19 includes a description of a circular reflective polarizer that may include a multilayer organic solid thin film having a biaxial refractive index.
- the discussion associated with FIG. 20 includes a description of the orientation of an in-plane refractive index (ns) in an example multilayer organic solid thin film.
- the discussion associated with FIG. 21 includes a description of the performance of an example circular reflective polarizer that includes a multilayer organic solid thin film having a biaxial refractive index.
- the discussion associated with FIGS. 22 and 23 relates to exemplary virtual reality and augmented reality devices that may include one or more organic solid crystal thin films as disclosed herein.
- FIG. 1 shown schematically are example manufacturing architectures that may be implemented in accordance with certain methods of forming an organic solid crystal thin film.
- a layer of a crystallizable organic precursor 110 may be deposited over a surface of a mold 120 or between mold surfaces and processed to form an organic solid crystal thin film 112.
- the organic precursor layer 110 may be disposed between upper and lower mold bodies 120, which may be respectively coated with upper and lower layers of a non-volatile medium material 130.
- the non-volatile medium material layer 130 may include an anti-nucleation layer.
- the resulting organic solid thin film 112 may be removed from the mold 120.
- the organic solid thin film 112 may be birefringent (e.g., ni1n 1n ) and may be characterized by a high refractive index (e.g., n > 1.5 and/or n > 1.5).
- FIG. IB shown is a further manufacturing architecture for forming a supported organic solid crystal thin film.
- a crystallizable organic precursor layer 110 may be disposed over a substrate 140.
- An upper mold body 120 may overlie the organic precursor layer 110 7 and a non-volatile medium material layer 130 may be located between the mold 120 and the organic precursor layer 110.
- the layer of non-volatile medium material 130 may directly overlie the organic precursor layer 110 and may be configured to control the surface roughness of an upper surface of the organic solid crystal thin film 112 during crystal growth.
- the direction of movement of a crystallization front 111 during crystal growth is denoted with an arrow A.
- FIG. 2 shown are polarized optical microscope images of organic solid crystal thin films formed according to a mold-based method.
- the thin films 211, 212 were manufactured (A) without using a non-volatile medium material, and (B) with a layer of non-volatile medium material pre-disposed over a surface of the mold (for example, using a method illustrated in FIG. 1A or FIG. IB).
- the improved surface morphology associated with use of the non-volatile medium material layer is evident in the appearance of organic solid thin film 212 in FIG. 2B.
- Vaporized molecules 310 of an organic solid crystal material may be directed, e.g., within a vacuum chamber (not shown), to a deposition surface 341 of a substrate 340 to form a layer of an organic solid crystal over the substrate.
- the choice of solvent, concentration of the vaporized molecules, substrate temperature, temperature gradient(s), gas pressure, etc. may be used to control the gas phase mobility of the molecules 310, the adsorption and desorption rates of the molecules 310, and the crystallization rate and crystal structure of the organic solid thin film.
- FIG. 4 A further example epitaxial growth process for forming an organic solid crystal is illustrated schematically in FIG. 4.
- an organic crystal melt 410 may be contained and heated within a mold 420.
- the mold 420 may be formed from a glass or glass ceramic material, for example.
- the organic crystal melt 410 may be directly in contact with a non-volatile medium material 430 contained by the mold 420.
- the non-volatile medium material 430 may include silicone oil, a fluorinated polymer or fluorinated oligomer, polyethylene glycol, polyolefin, and the like.
- a seed crystal 450 may be contacted with the organic crystal melt 410 and drawn from the melt phase at a desired rate, e.g., under continuous operation, to form an organic solid crystal.
- the seed crystal 450 may include an organic solid crystal material.
- the composition of the organic crystal melt 410 and the composition of the seed crystal 450 may be equivalent or substantially equivalent.
- the seed crystal 450 may have a planar or non-planar contact surface 452 that contacts the melt phase, which may be chosen to control the curvature of an over-formed organic solid crystal.
- FIG. 5 A still further example epitaxial growth process and process architecture for forming an organic solid crystal is illustrated schematically in FIG. 5.
- an organic crystal melt 510 may be contained and heated within a mold 520.
- the mold 520 may be configured to provide mechanical support and may include, for example, a glass or glass ceramic material.
- the organic crystal melt 510 may be directly in contact with a layer of a non-volatile medium material 530 overlying an inner surface of the mold 520.
- the non volatile medium material 530 may include silicone oil, a fluorinated polymer or fluorinated oligomer, polyethylene glycol, polyolefin, and the like.
- the non-volatile medium material layer 530 may include a conformal layer of free-standing molecules (e.g., an oil or a brushed layer of a polymer, oligomer, or small molecules (e.g., silane or a fluorinated polymer).
- a conformal layer of free-standing molecules e.g., an oil or a brushed layer of a polymer, oligomer, or small molecules (e.g., silane or a fluorinated polymer).
- Seed crystal 550 may be contacted with the organic crystal melt 510 and drawn from the melt phase at a desired rate, e.g., under continuous operation, to form an organic solid crystal.
- the seed crystal 550 may include an organic solid crystal material.
- the organic crystal melt 510 and the seed crystal 550 may be compositionally equivalent or substantially equivalent.
- the seed crystal 550 may have a planar or non-planar contact surface 552, which may be chosen to control the curvature of an over-formed organic solid crystal.
- the atmosphere overlyingthe melt phase may be controlled.
- the atmosphere overlying the melt may contain an inert gas such as argon that is maintained under a controlled pressure and/or flow rate.
- FIG. 6 An example molding process architecture for forming an organic solid crystal is shown in FIG. 6, where both (A) a double-sided mold, and (B) a single-side mold architecture are illustrated.
- a layer of a non-volatile medium material (i.e., anti-nucleation layer) 630 may be disposed between the mold 620 and the melt phase 610.
- a localized seed layer (not shown) may be used to initiate crystal nucleation and growth.
- FIG. 7A shown is a seed crystal 750 located within mold 720 and in contact with an anti-nucleation layer 730.
- a dispensing element 760 may be configured to deliver organic crystal molecules to a nucleation site proximate to the seed crystal 750, and subsequently to a crystallization front during crystal growth.
- FIG. 8 shown is a schematic set-up for an epitaxial or non- epitaxial growth process where an organic crystal seed 850 may be brought into contact with, and drawn from, a super saturated organic solution 810.
- the organic solution may include one or more crysta I liza ble organic molecules dissolved in a suitable solvent.
- the organic solution 810 may be contained within mold 820 and separated from the mold 820 by an anti- nucleation layer 830.
- a further nucleation and growth process may include providing an anti-nucleation layer 930 over a substrate 920 and introducing an organic crystal solution 910 overthe anti-nucleation layer 930.
- the organic crystal solution 910 may solidify to form an organic solid crystal.
- a photomicrograph of a free-standing organic solid crystal 912 is shown in FIG. 9B.
- the organic solid crystal 912 may be characterized by a length dimension of at least approximately 1 cm.
- FIGS. 10 and 11 dynamic and static methods for forming an organic solid crystal having structured surface features are shown schematically in FIGS. 10 and 11.
- a layer of an organic crystal solution or melt 1010 and an adjacent layer of an electrically conductive liquid 1070 may be disposed between opposing substrates 1040. Patterned and paired electrodes 1080 may overlie the respective substrates 1040.
- FIG. 10B under an applied electric field (E), a pattern may be induced in the electrically conductive liquid layer 1070, which may create a reciprocal pattern in the organic crystal material layer 1010.
- crystallization of the organic crystal material layer 1010 may be carried out by thermally-induced nucleation and growth, for example, optionally in conjunction with a seed crystal (not shown) to form an organic solid crystal thin film having periodic surface features.
- FIG. 11 shown is a static approach to forming an organic solid crystal having structured surface features.
- a layer of an organic crystal solution or melt 1110 and an adjacent pre-patterned mold 1120 may be disposed between opposing substrates 1140. With the organic crystal solution or melt 1110 conforming to the shape of the patterned mold, crystallization of the organic crystal material layer 1110 may be carried out by thermally-induced nucleation and growth to form an organic solid crystal thin film having periodic surface features.
- Such structured organic solid crystal thin films may form or be incorporated into a variety of optical elements, including gratings, micro lenses, prismatic lenses, Fresnel lenses, and the like.
- FIG. 12 a schematic view of example organic solid crystal structures formed by drawing from a melt phase are shown in FIG. 12.
- the organic solid crystal 1214 depicted in FIG. 12A and the organic solid crystal 1216 depicted in FIG. 12B may include respective surface features, such as nodules 1215 or facets 1217, for example.
- One or more process variables, including draw rate from the melt, pressure, and temperature may be controlled to create a desired surface pattern.
- FIG. 13 shown is a perspective view of an example melt-based deposition method and apparatus for forming an organic solid crystal from molten feedstock.
- Molten feedstock 1310 may be contained by reservoir 1390.
- Reservoir 1390 may be formed from a glass or glass ceramic composition, for example, and may include an internal passivation layer (not shown) to suppress nucleation.
- a seed crystal 1350 may be mounted at a distal end of a rotatable and translatable rod 1355, such that the seed crystal 1350 may be lowered into the molten feedstock 1310 and withdrawn therefrom.
- a control system (not shown) may be configured to control one or more of the melt temperature, seed temperature, gas pressure and gas composition overlying the melt, rotation rate of the molten feedstock, rotation rate and draw rate of the seed crystal, etc.
- a crystal growth scaffold located proximate to a seed crystal and a corresponding nucleation region, may be configured to template the growth of a desirably-shaped organic solid crystal.
- a planar scaffold 1442 may support the crystal growth of an organic solid crystal having a planar surface.
- a concave scaffold 1444 may support the crystal growth of an organic solid crystal having a convex outer surface.
- plural seed crystals and plural associated scaffolds may be arrayed to form multiple nucleation sites from which several nuclei may grow and merge into larger crystals.
- FIGS. 15A and 15B relate to a thin film forming architecture having a substrate 1540 and a single seed crystal 1550 disposed over the substrate 1540
- FIGS. 16A and 16B relate to a thin film forming architecture having a substrate 1640 and plural seed layers 1650 disposed over the substrate 1640.
- a layer of a crystallizable organic precursor 1510, 1610 may be deposited over a respective substrate 1540, 1640 and over respective seed crystal(s) 1550, 1650.
- An organic solid thin film 1512, 1612 may be formed by zone annealing using a suitable temperature profile (Ti, T2, T3).
- a suitable temperature profile Ti, T2, T3
- An example thermal profile is shown in FIG. 16B, where an organic solid crystal layer 1612 may nucleate proximate to seed crystal 1650.
- the direction of movement of a crystallization front 1511, 1611 during crystal growth is denoted in FIGS. 15B and 16B with an arrow A.
- a thin film forming architecture includes a substrate 1740 and a seed crystal 1750 disposed over the substrate 1740.
- a layer of a crystallizable organic precursor 1710 may be deposited over the substrate 1740 and over the seed crystal 1750.
- Application of a suitable thermal gradient (Ti, T2, T3) may induce nucleation and growth of an organic solid crystal thin film 1712.
- the thin film forming architecture may be translated relative to the thermal profile to advance a crystallization front 1711 and increase the area of the organic solid crystal thin film 1712 through crystal growth.
- a cover plate 1740a may overlie the crystallizable organic precursor layer 1710.
- the cover plate 1740a may be oriented at an angle (Q) relative to the substrate 1740 and may be configured to generate capillary forces that improve mass transport of the molten feedstock to a region containing the crystallization front 1711.
- the apparatus of FIG. 17A may be oriented vertically.
- gravitational forces (F g ) may advantageously promote mass transfer of the molten feedstock 1710 to the crystallization front 1711.
- Example OSC materials suitable for forming a feedstock composition include small molecules, macromolecules, liquid crystals, organometallic compounds, oligomers, and polymers, and may include organic semiconductors such as polycyclic aromatic compounds, e.g., anthracene, phenanthrene, and the like.
- Methods of manufacturing organic solid crystals may include crystal growth from a melt or solution, chemical or physical vapor deposition, and solvent coating onto a substrate. A deposition surface of the substrate may be treated globally or locally to impact, for example, nucleation density, crystalline orientation, adhesion, etc.
- the foregoing methods may be applied in conjunction with one or more optional post-deposition steps, such as annealing, polishing, dicing, etc., which may be carried out to improve one or more OSC attributes, including crystallinity, thickness, curvature, and the like.
- OSC attributes including crystallinity, thickness, curvature, and the like.
- Example organic molecules that may be used to form an organic solid crystal are shown in FIG. 18.
- optical element 1900 may include a display 1902, a polarizer 1904, a 50/50 mirror 1906, and a circular reflective polarizer 1908.
- the circular reflective polarizer 1908 may include a multilayer organic solid thin film 1912 optically encapsulated by a protective layer 1914.
- the multilayer organic solid thin film 1912 may include a clocked and stacked configuration of multiple organic solid thin films (not separately shown).
- the multilayer organic solid thin film 1912 may be configured to reflect a first polarization of incident light (PI) and transmit a second polarization of incident light (P2)
- the circular reflective polarizer may include a multilayer organic solid thin film where each OSC layer in the multilayer stack includes a biaxially- oriented organic solid crystal material (i.e., ni1n 1n ), as shown schematically in FIG. 20A.
- the multilayer may be characterized by a pitch length (P), which may correspond to two periods (2L) of index change.
- the plurality of arrows represent the orientation of a refractive index vector (e.g., ns) in each OSC layer of the multilayer.
- the right-handed (RH) circular reflective polarizer transmits light having left-hand circular polarization (LCP) and reflects light having right-hand circular polarization (RCP).
- FIG. 21 A plot of signal efficiency and ghost-to-signal ratio versus reflective polarizerthickness is shown in FIG. 21, and shows that a reflective polarizer including multiple clocked and stacked OSC thin films each having a biaxial refractive index may have higher signal efficiency and improved ghost suppression relative to comparative reflective polarizers.
- a multilayer thin film includes stacked layers of biaxially-oriented organic solid materials.
- Each biaxially-oriented layer has three principal indices, where ni1n 1n .
- the biaxial multilayer presents greater signal efficiency and ghost image suppression than comparative architectures.
- Example organic solid materials include crystalline (e.g., single crystal), partially crystalline, or amorphous materials such as anisotropic glasses.
- the layers within a multilayer thin film may be formed using a physical vapor transport (PVT) or molding process, although other deposition methods are contemplated.
- PVT physical vapor transport
- Example 1 A multilayer organic thin film includes a plurality of biaxially- oriented layers, where each biaxially-oriented layer is characterized by mutually orthogonal refractive indices, ni1n21n3.
- Example 2 The multilayer organic thin film of Example 1, where each biaxially-oriented layer includes an optically anisotropic organic material.
- Example 3 The multilayer organic thin film of any of Examples 1 and 2, where each biaxially-oriented layer includes a single crystal or polycrystalline material.
- Example 4 The multilayer organic thin film of any of Examples 1-3, where each biaxially-oriented layer includes an optically anisotropic glassy material, the glassy material including molecules aligned along predetermined directions.
- Example 5 The multilayer organic thin film of any of Examples 1-4, where the plurality of biaxially-oriented layers are compositionally equivalent.
- Example 6 The multilayer organic thin film of any of Examples 1-5, where each biaxially-oriented layer directly overlies an adjacent biaxially-oriented layer.
- Example 7 The multilayer organic thin film of any of Examples 1-6, where in-plane refractive indices (n2, ns) of a chosen biaxially-oriented layer are rotated by an angle (Q) with respect to corresponding in-plane refractive indices (n2, ns) of a biaxially-oriented layer located adjacent to the chosen biaxially-oriented layer.
- Example 8 The multilayer organic thin film of any of Examples 1-7, where in-plane refractive indices (n2, ns) of each biaxially-oriented layer are characterized by (n 2 +n 3 )/2 > 1.5.
- Example 9 The multilayer organic thin film of any of Examples 1-8, where in-plane refractive indices (n2, n3) of each biaxially-oriented layer are characterized by
- Example 10 The multilayer organic thin film of any of Examples 1-9, where an out-of-plane refractive index (ni) for a chosen biaxially-oriented layer is related to in-plane refractive indices (n2, n3) for the chosen biaxially-oriented layer according to n2 ⁇ ni ⁇ n3.
- Example 11 A circular reflective polarizer including the multilayer organic thin film of any of Examples 1-10.
- Example 12 A method includes forming a layer of a molecular feedstock over a surface of a mold, the molecular feedstock including an organic solid crystal precursor, forming a selected number of crystal nuclei from the organic solid crystal precursor within a nucleation region of the layer of the molecular feedstock, and growing the selected number of crystal nuclei to form an organic solid crystal thin film.
- Example 13 The method of Example 12, where forming the selected number of crystal nuclei includes heating the layer of the molecular feedstock to a temperature greater than a melting onset temperature of the organic solid crystal precursor within the nucleation region.
- Example 14 The method of any of Example 12 and 13, where forming the selected number of crystal nuclei includes melting crystal nuclei outside of the nucleation region.
- Example 15 The method of any of Example 12-14, where the selected number of crystal nuclei is one.
- Example 16 The method of any of Example 12-15, further including forming a release layer over the mold surface prior to forming the layer of molecular feedstock.
- Example 17 The method of any of Example 12-16, further including separating the organic solid crystal thin film from the surface of the mold.
- Example 18 The method of any of Example 12-17, where the molecular feedstock includes a process enhancer selected from polymers, oligomers, and small molecules, the process enhancer having a melting onset temperature of at least 20°C less than a melting onset temperature of the organic solid crystal precursor.
- a process enhancer selected from polymers, oligomers, and small molecules, the process enhancer having a melting onset temperature of at least 20°C less than a melting onset temperature of the organic solid crystal precursor.
- Example 19 The method of any of Example 12-18, where forming the layer of molecular feedstock includes injecting the molecular feedstock into the mold.
- Example 20 A multilayer organic thin film includes a stack of biaxially- oriented organic solid crystal layers, where each biaxially-oriented layer is characterized by mutually orthogonal refractive indices, ni1n 1n , and respective in-plane refractive indices (n , ns) of adjacent biaxially-oriented layers within the stack are rotationally offset by an angle (Q).
- Embodiments of the present disclosure may include or be implemented in conjunction with various types of artificial-reality systems.
- Artificial reality is a form of reality that has been adjusted in some manner before presentation to a user, which may include, for example, a virtual reality, an augmented reality, a mixed reality, a hybrid reality, or some combination and/or derivative thereof.
- Artificial-reality content may include completely computer-generated content or computer-generated content combined with captured (e.g., real-world) content.
- the artificial-reality content may include video, audio, haptic feedback, or some combination thereof, any of which may be presented in a single channel or in multiple channels (such as stereo video that produces a three-dimensional (3D) effect to the viewer).
- artificial reality may also be associated with applications, products, accessories, services, or some combination thereof, that are used to, for example, create content in an artificial reality and/or are otherwise used in (e.g., to perform activities in) an artificial reality.
- Artificial-reality systems may be implemented in a variety of different form factors and configurations. Some artificial-reality systems may be designed to work without near-eye displays (NEDs). Other artificial-reality systems may include an NED that also provides visibility into the real world (e.g., augmented-reality system 2200 in FIG. 22) or that visually immerses a user in an artificial reality (e.g., virtual-reality system 2300 in FIG. 23). While some artificial-reality devices may be self-contained systems, other artificial-reality devices may communicate and/or coordinate with external devices to provide an artificial- reality experience to a user. Examples of such external devices include handheld controllers, mobile devices, desktop computers, devices worn by a user, devices worn by one or more other users, and/or any other suitable external system.
- augmented-reality system 2200 may include an eyewear device 2202 with a frame 2210 configured to hold a left display device 2215(A) and a right display device 2215(B) in front of a user's eyes.
- Display devices 2215(A) and 2215(B) may act together or independently to present an image or series of images to a user.
- augmented-reality system 2200 includes two displays, embodiments of this disclosure may be implemented in augmented-reality systems with a single NED or more than two NEDs.
- augmented-reality system 2200 may include one or more sensors, such as sensor 2240.
- Sensor 2240 may generate measurement signals in response to motion of augmented-reality system 2200 and may be located on substantially any portion of frame 2210.
- Sensor 2240 may represent a position sensor, an inertial measurement unit (IMU), a depth camera assembly, a structured light emitter and/or detector, or any combination thereof.
- IMU inertial measurement unit
- augmented-reality system 2200 may or may not include sensor 2240 or may include more than one sensor.
- the IMU may generate calibration data based on measurement signals from sensor 2240. Examples of sensor 2240 may include, without limitation, accelerometers, gyroscopes, magnetometers, other suitable types of sensors that detect motion, sensors used for error correction of the IMU, or some combination thereof.
- Augmented-reality system 2200 may also include a microphone array with a plurality of acoustic transducers 2220(A)-2220(J), referred to collectively as acoustic transducers 2220.
- Acoustic transducers 2220 may be transducers that detect air pressure variations induced by sound waves.
- Each acoustic transducer 2220 may be configured to detect sound and convert the detected sound into an electronic format (e.g., an analog or digital format).
- 22 may include, for example, ten acoustic transducers: 2220(A) and 2220(B), which may be designed to be placed inside a corresponding ear of the user, acoustic transducers 2220(C), 2220(D), 2220(E), 2220(F), 2220(G), and 2220(H), which may be positioned at various locations on frame 2210, and/or acoustic transducers 2220(1) and 2220(J), which may be positioned on a corresponding neckband 2205.
- ten acoustic transducers 2220(A) and 2220(B), which may be designed to be placed inside a corresponding ear of the user
- acoustic transducers 2220(C), 2220(D), 2220(E), 2220(F), 2220(G), and 2220(H) which may be positioned at various locations on frame 2210
- acoustic transducers 2220(1) and 2220(J) which may be positioned on a
- acoustic transducers 2220(A)-(F) may be used as output transducers (e.g., speakers).
- acoustic transducers 2220(A) and/or 2220(B) may be earbuds or any other suitable type of headphone or speaker.
- the configuration of acoustic transducers 2220 of the microphone array may vary. While augmented-reality system 2200 is shown in FIG. 22 as having ten acoustic transducers 2220, the number of acoustic transducers 2220 may be greater or less than ten. In some embodiments, using higher numbers of acoustic transducers 2220 may increase the amount of audio information collected and/or the sensitivity and accuracy of the audio information. In contrast, using a lower number of acoustic transducers 2220 may decrease the computing power required by an associated controller 2250 to process the collected audio information. In addition, the position of each acoustic transducer 2220 of the microphone array may vary.
- the position of an acoustic transducer 2220 may include a defined position on the user, a defined coordinate on frame 2210, an orientation associated with each acoustic transducer 2220, or some combination thereof.
- Acoustic transducers 2220(A) and 2220(B) may be positioned on different parts of the user's ear, such as behind the pinna, behind the tragus, and/or within the auricle or fossa. Or, there may be additional acoustic transducers 2220 on or surrounding the ear in addition to acoustic transducers 2220 inside the ear canal.
- augmented- reality device 2200 may simulate binaural hearing and capture a 3D stereo sound field around about a user's head.
- acoustic transducers 2220(A) and 2220(B) may be connected to augmented-reality system 2200 via a wired connection 2230, and in other embodiments acoustic transducers 2220(A) and 2220(B) may be connected to augmented- reality system 2200 via a wireless connection (e.g., a Bluetooth connection). In still other embodiments, acoustic transducers 2220(A) and 2220(B) may not be used at all in conjunction with augmented-reality system 2200.
- Acoustic transducers 2220 on frame 2210 may be positioned along the length of the temples, across the bridge, above or below display devices 2215(A) and 2215(B), or some combination thereof. Acoustic transducers 2220 may be oriented such that the microphone array is able to detect sounds in a wide range of directions surrounding the user wearing the augmented-reality system 2200. In some embodiments, an optimization process may be performed during manufacturing of augmented-reality system 2200 to determine relative positioning of each acoustic transducer 2220 in the microphone array.
- augmented-reality system 2200 may include or be connected to an external device (e.g., a paired device), such as neckband 2205.
- an external device e.g., a paired device
- Neckband 2205 generally represents any type or form of paired device.
- the following discussion of neckband 2205 may also apply to various other paired devices, such as charging cases, smart watches, smart phones, wrist bands, other wearable devices, hand-held controllers, tablet computers, laptop computers, other external compute devices, etc.
- neckband 2205 may be coupled to eyewear device 2202 via one or more connectors.
- the connectors may be wired or wireless and may include electrical and/or non-electrical (e.g., structural) components.
- eyewear device 2202 and neckband 2205 may operate independently without any wired or wireless connection between them. While FIG. 22 illustrates the components of eyewear device 2202 and neckband 2205 in example locations on eyewear device 2202 and neckband 2205, the components may be located elsewhere and/or distributed differently on eyewear device 2202 and/or neckband 2205. In some embodiments, the components of eyewear device 2202 and neckband 2205 may be located on one or more additional peripheral devices paired with eyewear device 2202, neckband 2205, or some combination thereof.
- Pairing external devices such as neckband 2205
- augmented-reality eyewear devices may enable the eyewear devices to achieve the form factor of a pair of glasses while still providing sufficient battery and computation power for expanded capabilities.
- Some or all of the battery power, computational resources, and/or additional features of augmented-reality system 2200 may be provided by a paired device or shared between a paired device and an eyewear device, thus reducing the weight, heat profile, and form factor of the eyewear device overall while still retaining desired functionality.
- neckband 2205 may allow components that would otherwise be included on an eyewear device to be included in neckband 2205 since users may tolerate a heavier weight load on their shoulders than they would tolerate on their heads.
- Neckband 2205 may also have a larger surface area over which to diffuse and disperse heat to the ambient environment. Thus, neckband 2205 may allow for greater battery and computation capacity than might otherwise have been possible on a stand-alone eyewear device. Since weight carried in neckband 2205 may be less invasive to a user than weight carried in eyewear device 2202, a user may tolerate wearing a lighter eyewear device and carrying or wearing the paired device for greater lengths of time than a user would tolerate wearing a heavy standalone eyewear device, thereby enabling users to more fully incorporate artificial-reality environments into their day-to-day activities.
- Neckband 2205 may be communicatively coupled with eyewear device 2202 and/or to other devices. These other devices may provide certain functions (e.g., tracking, localizing, depth mapping, processing, storage, etc.) to augmented-reality system 2200.
- neckband 2205 may include two acoustic transducers (e.g., 2220(1) and 2220(J)) that are part of the microphone array (or potentially form their own microphone subarray).
- Neckband 2205 may also include a controller 2225 and a power source 2235.
- Acoustic transducers 2220(1) and 2220(J) of neckband 2205 may be configured to detect sound and convert the detected sound into an electronic format (analog or digital).
- acoustic transducers 2220(1) and 2220(J) may be positioned on neckband 2205, thereby increasing the distance between the neckband acoustic transducers 2220(1) and 2220(J) and other acoustic transducers 2220 positioned on eyewear device 2202.
- increasing the distance between acoustic transducers 2220 of the microphone array may improve the accuracy of beamforming performed via the microphone array.
- the determined source location of the detected sound may be more accurate than if the sound had been detected by acoustic transducers 2220(D) and 2220(E).
- Controller 2225 of neckband 2205 may process information generated by the sensors on neckband 2205 and/or augmented-reality system 2200.
- controller 2225 may process information from the microphone array that describes sounds detected by the microphone array.
- controller 2225 may perform a direction-of-arrival (DOA) estimation to estimate a direction from which the detected sound arrived at the microphone array.
- DOA direction-of-arrival
- controller 2225 may populate an audio data set with the information.
- controller 2225 may compute all inertial and spatial calculations from the IMU located on eyewear device 2202.
- a connector may convey information between augmented-reality system 2200 and neckband 2205 and between augmented-reality system 2200 and controller 2225.
- the information may be in the form of optical data, electrical data, wireless data, or any other transmittable data form. Moving the processing of information generated by augmented-reality system 2200 to neckband 2205 may reduce weight and heat in eyewear device 2202, making it more comfortable to the user.
- Power source 2235 in neckband 2205 may provide power to eyewear device 2202 and/or to neckband 2205.
- Power source 2235 may include, without limitation, lithium ion batteries, lithium-polymer batteries, primary lithium batteries, alkaline batteries, or any other form of power storage.
- power source 2235 may be a wired power source. Including power source 2235 on neckband 2205 instead of on eyewear device 2202 may help better distribute the weight and heat generated by power source 2235.
- some artificial-reality systems may, instead of blending an artificial reality with actual reality, substantially replace one or more of a user's sensory perceptions of the real world with a virtual experience.
- a head-worn display system such as virtual-reality system 2300 in FIG. 23, that mostly or completely covers a user's field of view.
- Virtual-reality system 2300 may include a front rigid body 2302 and a band 2304 shaped to fit around a user's head.
- Virtual-reality system 2300 may also include output audio transducers 2306(A) and 2306(B).
- front rigid body 2302 may include one or more electronic elements, including one or more electronic displays, one or more inertial measurement units (IMUs), one or more tracking emitters or detectors, and/or any other suitable device or system for creating an artificial reality experience.
- IMUs inertial measurement units
- Artificial-reality systems may include a variety of types of visual feedback mechanisms.
- display devices in augmented-reality system 2200 and/or virtual- reality system 2300 may include one or more liquid crystal displays (LCDs), light emitting diode (LED) displays, organic LED (OLED) displays, digital light project (DLP) micro-displays, liquid crystal on silicon (LCoS) micro-displays, and/or any other suitable type of display screen.
- LCDs liquid crystal displays
- LED light emitting diode
- OLED organic LED
- DLP digital light project
- micro-displays liquid crystal on silicon micro-displays
- any other suitable type of display screen may include a single display screen for both eyes or may provide a display screen for each eye, which may allow for additional flexibility for varifocal adjustments or for correcting a user's refractive error.
- Some artificial-reality systems may also include optical subsystems having one or more lenses (e.g., conventional concave or convex lenses, Fresnel lenses, adjustable liquid lenses, etc.) through which a user may view a display screen.
- These optical subsystems may serve a variety of purposes, including to collimate (e.g., make an object appear at a greater distance than its physical distance), to magnify (e.g., make an object appear larger than its actual size), and/or to relay (to, e.g., the viewer's eyes) light.
- optical subsystems may be used in a non-pupil-forming architecture (such as a single lens configuration that directly collimates light but results in so-called pincushion distortion) and/or a pupil-forming architecture (such as a multi-lens configuration that produces so- called barrel distortion to nullify pincushion distortion).
- a non-pupil-forming architecture such as a single lens configuration that directly collimates light but results in so-called pincushion distortion
- a pupil-forming architecture such as a multi-lens configuration that produces so- called barrel distortion to nullify pincushion distortion
- some artificial-reality systems may include one or more projection systems.
- display devices in augmented-reality system 2200 and/or virtual-reality system 2300 may include micro-LED projectors that project light (using, e.g., a waveguide) into display devices, such as clear combiner lenses that allow ambient light to pass through.
- the display devices may refract the projected light toward a user's pupil and may enable a user to simultaneously view both artificial-reality content and the real world.
- the display devices may accomplish this using any of a variety of different optical components, including waveguide components (e.g., holographic, planar, diffractive, polarized, and/or reflective waveguide elements), light- manipulation surfaces and elements (such as diffractive, reflective, and refractive elements and gratings), coupling elements, etc.
- waveguide components e.g., holographic, planar, diffractive, polarized, and/or reflective waveguide elements
- light- manipulation surfaces and elements such as diffractive, reflective, and refractive elements and gratings
- coupling elements etc.
- Artificial-reality systems may also be configured with any other suitable type or form of image projection system, such as retinal projectors used in virtual retina displays.
- Artificial-reality systems may also include various types of computer vision components and subsystems.
- augmented-reality system 2200 and/or virtual- reality system 2300 may include one or more optical sensors, such as two-dimensional (2D) or 3D cameras, structured light transmitters and detectors, time-of-flight depth sensors, single-beam or sweeping laser rangefinders, 3D LiDAR sensors, and/or any other suitable type or form of optical sensor.
- An artificial-reality system may process data from one or more of these sensors to identify a location of a user, to map the real world, to provide a user with context about real-world surroundings, and/or to perform a variety of other functions.
- Artificial-reality systems may also include one or more input and/or output audio transducers.
- output audio transducers 2306(A) and 2306(B) may include voice coil speakers, ribbon speakers, electrostatic speakers, piezoelectric speakers, bone conduction transducers, cartilage conduction transducers, tragus-vibration transducers, and/or any other suitable type or form of audio transducer.
- input audio transducers may include condenser microphones, dynamic microphones, ribbon microphones, and/or any other type or form of input transducer. In some embodiments, a single transducer may be used for both audio input and audio output.
- artificial-reality systems may include tactile (i.e., haptic) feedback systems, which may be incorporated into headwear, gloves, body suits, handheld controllers, environmental devices (e.g., chairs, floormats, etc.), and/or any other type of device or system.
- Ha ptic feedback systems may provide various types of cutaneous feedback, including vibration, force, traction, texture, and/or temperature.
- Haptic feedback systems may also provide various types of kinesthetic feedback, such as motion and compliance.
- Haptic feedback may be implemented using motors, piezoelectric actuators, fluidic systems, and/or a variety of other types of feedback mechanisms.
- Haptic feedback systems may be implemented independent of other artificial-reality devices, within other artificial-reality devices, and/or in conjunction with other artificial-reality devices.
- artificial-reality systems may create an entire virtual experience or enhance a user's real- world experience in a variety of contexts and environments. For instance, artificial-reality systems may assist or extend a user's perception, memory, or cognition within a particular environment. Some systems may enhance a user's interactions with other people in the real world or may enable more immersive interactions with other people in a virtual world.
- Artificial-reality systems may also be used for educational purposes (e.g., for teaching or training in schools, hospitals, government organizations, military organizations, business enterprises, etc.), entertainment purposes (e.g., for playing video games, listening to music, watching video content, etc.), and/or for accessibility purposes (e.g., as hearing aids, visual aids, etc.).
- the embodiments disclosed herein may enable or enhance a user's artificial-reality experience in one or more of these contexts and environments and/or in other contexts and environments.
- numeric value "50" as “approximately 50” may, in certain embodiments, include values equal to 50 ⁇ 5, i.e., values within the range 45 to 55.
- the term "substantially" in reference to a given parameter, property, or condition may mean and include to a degree that one of ordinary skill in the art would understand that the given parameter, property, or condition is met with a small degree of variance, such as within acceptable manufacturing tolerances.
- the parameter, property, or condition may be at least approximately 90% met, at least approximately 95% met, or even at least approximately 99% met.
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