Method for producing doped organic solid crystals

Abstract

A method of forming an organic solid crystal (OSC) thin film includes forming a molecular feedstock of an organic solid crystal precursor and a molecular dopant, forming a layer of the molecular feedstock on a surface of a substrate, forming a crystal nucleus from the organic solid crystal precursor within a nucleation region of the layer of the molecular feedstock, and forming the organic solid crystal (OSC) thin film. And growing the crystal nucleus to form a doped organic solid crystal thin film.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 579,410, filed on August 29, 2023, and to U.S. Provisional Application No. 18 / 543,040, filed on December 18, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present application relates to a method for producing a doped organic solid crystal. Background Art

[0004] Polymers and other organic materials can be incorporated into a variety of different optical and electro-optical device architectures, including passive and active optical devices and electrically active devices. Lightweight and compliant one or more polymer / organic solid layers can 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.

[0005] For example, virtual reality (VR) and augmented reality (AR) eyewear devices or headsets can enable users to experience events such as interactions with people in a computer-generated three-dimensional world simulation, or view data superimposed on a real-world view. For example, superimposing information on the field of view can 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. VR / AR eyewear devices and headsets can be used for various purposes. For example, governments can use such devices for military training, medical professionals can use such devices to simulate surgery, and engineers can use such devices as design visualization aids.

[0006] Despite recent developments, it would be advantageous to provide polymers and other organic solid materials having improved optical properties, including one or more of controlled refractive index and birefringence, optical clarity, and optical transparency. Such materials can be formed into thin films, and multiple films can be stacked to form multilayers. Summary of the invention

[0007] One aspect of the present invention relates to a method, which includes forming a molecular raw material, the molecular raw material including an organic solid crystal precursor and a molecular dopant; forming a layer of the molecular raw material above a surface of a substrate; forming crystal nuclei from the organic solid crystal precursor within a nucleation region of the layer of the molecular raw material; and growing the crystal nuclei to form a doped organic solid crystal film.

[0008] Another aspect of the present invention relates to a method comprising forming a layer of molecular raw materials above a surface of a substrate, the molecular raw materials comprising an organic solid crystal precursor and a molecular dopant; forming an organic solid crystal film from the layer of molecular raw materials; forming a main electrode above a first portion of the organic solid crystal film; forming a sub-electrode above a second portion of the organic solid crystal film; and changing a bias state between the main electrode and the sub-electrode by an amount effective to change the optical properties of the organic solid crystal film.

[0009] Yet another aspect of the present invention relates to a method comprising forming a layer comprising a doped organic solid crystal; forming a primary electrode over a first portion of the layer; and forming a secondary electrode over a second portion of the layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The accompanying drawings illustrate several exemplary embodiments and are a part of the specification. Together with the following description, these drawings illustrate and explain various principles of the present disclosure.

[0011] Figure 1 Exemplary methods for making (A) free-standing organic solid crystalline materials and (B) supported organic solid crystalline materials are shown according to various embodiments.

[0012] Figure 2 Cross-polarized microscope images of organic solid crystals (A) without a non-volatile dielectric material and (B) with a non-volatile dielectric material, fabricated according to some embodiments are shown.

[0013] Figure 3 is a schematic diagram of a vapor deposition-based epitaxial growth process for forming organic solid crystals according to some embodiments.

[0014] Figure 4 is a schematic diagram of a melt-based epitaxial growth process for forming organic solid crystals, according to some embodiments.

[0015] Figure 5 is a schematic diagram of a melt-based epitaxial growth process for forming organic solid crystals according to further embodiments.

[0016] Figure 6(A) Double-sided mold and (B) Single-sided mold epitaxial growth processes for forming organic solid crystals according to further embodiments are shown.

[0017] Figure 7 A seeded single-sided mold epitaxial growth process for forming an organic solid crystal is shown according to some embodiments.

[0018] Figure 8 is a schematic diagram of a solvent-based epitaxial / non-epitaxial growth process for forming organic solid crystals according to some embodiments.

[0019] Fig. 9 is a schematic diagram of a non-epitaxial growth process for forming an organic solid crystal, according to certain embodiments.

[0020] Fig.10 An exemplary organic solid crystal containing grating architecture is shown according to some embodiments.

[0021] Fig.11 An exemplary tripolar concentric ring electrode (CRE) is shown in accordance with certain embodiments.

[0022] Fig.12 An example organic solid crystal containing grating architecture according to further embodiments is shown.

[0023] Fig.13 Example non-planar organic solid crystal geometries are shown according to some embodiments.

[0024] Fig.14 An example mechanism for actively tuning the refractive index in a biased organic solid crystal is shown according to some embodiments.

[0025] Fig.15 The integration of optically isotropic or optically anisotropic organic solid crystal layers into example optical elements is shown according to various embodiments.

[0026] Fig.16 The integration of optically isotropic or anisotropic organic solid crystal thin films into exemplary optical elements is shown according to further embodiments.

[0027] Fig.17 An optical modulator having a pair of electrodes disposed on the same side of an organic solid crystal (OSC) layer is shown according to some embodiments.

[0028] Fig.18 An optical modulator having a pair of electrodes disposed on the same side of an organic solid crystal (OSC) layer according to a further embodiment is shown.

[0029] Fig.19 An optical modulator having an organic solid crystal (OSC) layer disposed between conductive electrodes is shown according to some embodiments.

[0030] Fig. 20 An optical modulator having an organic solid crystal (OSC) layer and a dielectric layer disposed between conductive electrodes according to further embodiments is shown.

[0031] Fig.21 An optical modulator having an organic solid crystal (OSC) layer and a semiconductor layer disposed between conductive electrodes according to a further embodiment is shown.

[0032] Fig. 22 is a graph of elliptical polarization peak shift over time for an example OSC-containing optical modulator, showing the effect of applied voltage, according to some embodiments.

[0033] Fig.23 is a graph of elliptical polarization peak shift over time for an example OSC-containing optical modulator, showing the effect of applied voltage, according to some embodiments.

[0034] Fig.24 is a schematic diagram of a crystal growth apparatus for producing an example organic solid crystal according to various embodiments.

[0035] Fig.25 is an illustration of example nucleation surfaces and scaffold geometries according to certain embodiments.

[0036] Fig.26 are diagrams showing (A) a top view and (B) a side view of an example crystal growth configuration with a single nucleation site for fabricating an organic solid crystal (OSC) thin film according to some embodiments.

[0037] Fig. 27 are diagrams showing (A) a top view and (B) a side view of an example crystal growth configuration with multiple nucleation sites for making an organic solid crystal (OSC) thin film according to some embodiments.

[0038] Fig.28 is a diagram showing an OSC thin film fabrication configuration for facilitating mass transport to the crystallization front during crystal growth, according to some embodiments.

[0039] Fig.29 Exemplary crystallizable organic molecules for making organic solid crystals according to certain embodiments are shown.

[0040] Fig.30 Example dopant molecules for making organic solid crystals according to certain embodiments are shown.

[0041] Fig.31 is a schematic cross-sectional view of an optical element including a polarizer comprising reflective organic solid crystals according to some embodiments.

[0042] Fig.32 is a graphical representation of the orientation of the refractive index (n3) within the principal planes of a biaxial multilayer organic solid crystal thin film according to various embodiments.

[0043] Fig.33 is a graph of signal efficiency and ghost image suppression as a function of reflective polarizer thickness for a reflective polarizer including a biaxially oriented organic solid crystal material, according to some embodiments.

[0044] Fig.34 is an illustration of exemplary augmented reality glasses that may be used in conjunction with embodiments of the present disclosure.

[0045] Fig.35 is an illustration of an exemplary virtual reality headset that may be used in conjunction with embodiments of the present disclosure.

[0046] Throughout the drawings, the same reference numerals and descriptions indicate similar but not necessarily identical elements. Although the exemplary embodiments described herein are susceptible to various modifications and alternative forms, specific embodiments have been shown in the drawings by way of example and will be described in detail herein. However, the exemplary embodiments described herein are not intended to be limited to the specific forms disclosed. On the contrary, the present disclosure encompasses all modifications, equivalents, and alternatives that fall within the scope of the appended claims. DETAILED DESCRIPTION

[0047] As disclosed herein, a variety of methods can be used to fabricate layers of organic solid crystal (OSC) materials, including vapor and liquid phase epitaxy and non-epitaxial methods. The resulting single layer OSC film or multilayer film including multiple layers of organic solid crystal material can be incorporated into various optical systems and devices. According to specific embodiments, a reflective polarizer based on a multilayer organic solid crystal film can be incorporated into a display system to provide high broadband efficiency and high off-axis contrast.

[0048] For example, an optical component (such as a lens system including a circular reflective polarizer) may include a multilayer organic solid crystal film. Each biaxial OSC layer may be characterized by three mutually orthogonal refractive indices (n1, n2, n3), where n1≠n2≠n3. The multilayer film may include multiple rotationally offset biaxially oriented organic solid material layers. By misaligning (i.e., rotating) each layer relative to adjacent layers, such a biaxially oriented multilayer film may achieve higher signal efficiency and greater ghost image suppression compared to architectures using comparative materials. Organic solid crystal films may also be used as brightness enhancement layers in various projectors.

[0049] As will be explained in greater detail herein, embodiments of the present disclosure also relate to a switchable optical element comprising an organic solid crystal (OSC) material layer. The OSC layer can exhibit a first refractive index in a first bias state and a second refractive index in a second bias state, and can be actively tuned within a range of refractive index values ​​between the first refractive index and the second refractive index.

[0050] One or more source materials can be used to form organic solid crystal films, including multilayer films. Example organic materials include various types of crystallizable organic semiconductors. Organic semiconductors can include small molecules, macromolecules, liquid crystals, organometallic compounds, oligomers and polymers. Organic semiconductors can include p-type, n-type or bipolar polycyclic aromatic hydrocarbons, such as anthracene, phenanthrene, tolane, thiophene, pyrene, corannulene, fluorene, biphenyl, terphenyl, phthalocyanine, etc. Further example small molecules include fullerenes, such as carbon 60.

[0051] Example compounds can include cyclic, linear and / or branched structures, which can be saturated or unsaturated, and can additionally include heteroatoms and / or saturated or unsaturated heterocycles, such as furan, pyrrole, thiophene, pyridine, pyrimidine, piperidine, etc. Heteroatoms (e.g., dopants) can include fluorine, chlorine, nitrogen, oxygen, sulfur, phosphorus, and various metals. Functional groups can include saturated or unsaturated polycyclic hydrocarbons, nitrogen-containing heterocycles, sulfur-containing heterocycles or oxygen-containing heterocycles, quinoline, benzothiophene, benzopyran, bent and asymmetric benzophenone, 2,6-naphthalene oxalic acid and 2,6-dimethylcarboxylate. Additional functional groups can include amines, alcohols, and carboxylic acids, etc. Suitable raw materials for molding solid organic semiconductor materials can include pure organic compositions, melts, solutions, or suspensions containing one or more organic materials of the present disclosure.

[0052] These materials, which can be incorporated into doped organic solid crystal films, can provide various functions, including phase modulation, beam steering, wavefront shaping and correction, optical communications, optical computing, and holography. In some instances, the dopant can be configured to modulate the HOMO-LUMO energy gap (HOMO-LUMO gap) in the doped organic solid crystal. Due to its optical and mechanical properties, organic solid crystals can enable high-performance devices, and can be incorporated into passive or active optical devices (including AR / VR headsets) and can replace comparative material systems (such as polymers, inorganic materials, and liquid crystals). In some aspects, organic solid crystals can have optical properties comparable to inorganic crystals while exhibiting the processability and electrical response of liquid crystals.

[0053] Structurally, the disclosed organic materials can be glassy, ​​polycrystalline or single crystal. For example, the organic solid crystal can include a tightly packed structure (e.g., organic molecules) that exhibits desired optical properties, such as a high and tunable refractive index and a high birefringence. Anisotropic organic solid materials can include a preferred molecular packing, i.e., a preferred molecular orientation or arrangement. Example devices can include one or more organic solid crystal films with a high refractive index, which can be further characterized by a smooth outer surface.

[0054] According to some embodiments, one or more organic material layers can be used to form various devices, including transistors, diodes, capacitors, etc. Exemplary transistor architectures include MOSFET, JFET, ESFET, HEMT, BJT, etc. In certain embodiments, the transistor architecture may include an organic field effect transistor (OFET), which may have a geometry selected from TGTC, BGTC, TGBC, and BGBC. Exemplary diodes may include pn junction, Schottky, electron avalanche, and PIN geometries. Exemplary capacitors may include parallel plate geometries. In a multilayer architecture, the composition, structure, and properties of each organic layer may be independently selected.

[0055] Thus, the present disclosure relates generally to organic thin films and devices containing such thin films, and more particularly to organic solid crystal thin films and methods of making the same.

[0056] Due to its relatively low melting point, organic solid crystals can be molded to form desired structures. The molding process can achieve complex architectures, and may be more economical than the cutting, grinding and polishing of bulk crystals. In one embodiment, a single crystal or a polycrystalline basic shape (such as a sheet or a cube) can be partially or completely melted into a desired form, and then controllably cooled to form a single crystal with an equivalent shape or a different shape. Suitable raw materials for molding solid organic semiconductor materials can include pure organic compositions, solutions, dispersions or suspensions. In addition, as further disclosed herein, chemical additives can be combined with the molding process to improve the surface roughness of the molded organic solid crystals in situ.

[0057] The process of molding optically anisotropic crystalline or partially crystalline films may include the manipulation of thermodynamic and kinetic control of nucleation and crystal growth. In certain embodiments, the temperature of the nucleation region closest to the mold during molding may be less than the melting start temperature (T m ), while the temperature away from the nucleation region can be greater than the melting onset temperature. Such a temperature gradient paradigm can be obtained by a spatially applied thermal gradient, optionally combined with a selective melting process (e.g., laser, soldering iron, etc.) to remove excess nuclei, leaving a small number of nuclei (e.g., a single nucleus) for crystal growth.

[0058] High refractive index and high birefringence organic semiconductor materials can be manufactured as self-supporting articles or as thin films deposited on substrates. For example, epitaxial or non-epitaxial growth processes can be used to form organic solid crystal (OSC) layers on suitable substrates or in molds. A seed layer for promoting crystal nucleation and an anti-nucleation layer configured to locally inhibit nucleation can jointly promote the formation of a limited number of crystal nuclei within a specified location, which in turn can promote the formation of larger organic solid crystals.

[0059] A suitable substrate or mold can be made of a material having a melting start temperature (T m )Higher softening temperature or glass transition temperature (T g ) material. The substrate or mold may include any suitable material, such as silicon, silicon dioxide, fused silica, quartz, glass, nickel, silicone, siloxane, perfluoropolyether, polytetrafluoroethylene, perfluoroalkoxyalkane, polyimide, polyethylene naphthalate, polyvinylidene fluoride, polyphenylene sulfide, etc. For convenience, unless the context indicates otherwise, the terms "substrate" and "mold" may be used interchangeably herein.

[0060] To promote nucleation and crystal growth, selected temperatures and temperature gradients may be applied to the crystallization front of the initial thin film. The temperature and temperature gradient near the crystallization front may be determined based on the selected raw materials, including their melting temperature, thermal stability, and rheological properties. In some embodiments, a seed layer configured to promote crystal nucleation may be formed on at least a portion of the surface of the substrate or mold.

[0061] Exemplary nucleation promoting materials or seed layer materials may include one or more metals or inorganic elements or compounds, such as Pt, Ag, Au, Al, Pb, indium tin oxide and SiO2, etc. Further example nucleation promoting materials or seed layer materials may include organic compounds, such as polyimide, polyamide, polyurethane, polyurea, polythiourea, polyethylene, polysulfonate, polyolefin, and mixtures and combinations thereof. In some examples, the nucleation promoting material may be configured as a textured layer or alignment layer, such as a rubbed polyimide layer or a photoalignment layer, which may be configured to cause the directionality or preferred orientation of over-formed organic crystals. On the other hand, the anti-nucleation layer may include a dielectric material. In a further embodiment, the anti-nucleation layer may include an amorphous material. In the example process, crystal nucleation may occur independently of the substrate or mold.

[0062] In some embodiments, the surface treatment or release layer provided on the substrate or mold can be used to control the nucleation and growth of organic solid crystals (OSC), and then promote separation and harvesting bulk crystals or thin films. For example, a coating with a solubility parameter that does not match the deposition chemistry can be applied to the substrate (for example, locally) to suppress the interaction between the substrate and the crystalline layer during the deposition process. The example of such a coating includes an oleophobic coating or a hydrophobic coating. A thin layer (for example, a monolayer or a bilayer) of an oleophobic material or a hydrophobic material can be used to control a substrate or a mold before the epitaxial process. Coating materials can be selected based on substrates and / or crystalline materials. Further example coating materials include siloxanes, fluorosilicone, phenylsiloxane, fluorinated coatings, polyvinyl alcohol and other OH-resistant coatings, acrylic acid, polyurethane, polyester and polyimide, etc.

[0063] The buffer layer can be formed on the deposition surface of the substrate or mold. The buffer layer can include small molecules similar to or even equal to the small molecules that make up the organic solid crystal, such as anthracene single crystals. The buffer layer can be used to tune one or more properties of the growth surface of the substrate or mold, including surface energy, wettability, crystal shape or molecular orientation, etc.

[0064] The substrate or mold may include a surface configured to provide the desired shape and size specifications to the molded organic article. For example, the substrate or mold surface may be planar, concave, or convex, and may include a three-dimensional structure, such as a surface relief grating, or a curvature configured to form a microlens, microprism, or prismatic lens. That is, according to some embodiments, the substrate or mold geometry may be transferred and incorporated into the surface of the over-formed organic solid crystal film.

[0065] An example method for making an organic solid crystal thin film includes providing a mold, forming a nucleation promoting material layer on at least a portion of a surface of the mold, and depositing a molten feedstock layer on the surface of the mold and contacting the nucleation promoting material layer while maintaining a temperature gradient on the molten feedstock layer.

[0066] In the molding process, and according to a specific embodiment, the cover plate can be applied to the free surface of the raw material layer. The cover plate can be tilted at a certain angle relative to the main surface of the film. Force can be applied to the cover plate to produce a capillary force, which promotes the mass transfer of molten raw materials, i.e., between the cover plate and the substrate and in the direction of the crystallization front of the growing crystalline film. In some embodiments, such as by the vertical orientation of the deposition system, gravity can contribute to the mass transfer and transportation of molten raw materials to the crystallization front. Suitable materials for cover plate and substrate can independently include silicon dioxide, fused silica, high refractive index glass, high refractive index inorganic crystals and high melting temperature polymers (such as siloxanes, polyimides, PTFE, PFA, etc.), although further material components are considered.

[0067] According to certain embodiments, a method of forming an organic solid crystal (OSC) may include combining an organic precursor (i.e., a crystallizable organic molecule) with a non-volatile dielectric material, forming a layer including the organic precursor and the non-volatile dielectric material on a surface of a substrate or a mold, and treating the organic precursor layer to form an organic crystalline phase, wherein the organic crystalline phase may include a preferred orientation of the molecules.

[0068] The action of contacting the organic precursor with the non-volatile dielectric material may include forming a homogenous mixture of the organic precursor and the non-volatile dielectric material. In further embodiments, the action of contacting the organic precursor with the non-volatile dielectric material may include forming a non-volatile dielectric material layer on a surface of the substrate or mold, and forming an organic precursor layer on the non-volatile dielectric material layer.

[0069] According to further embodiments, the method may include forming a layer of non-volatile dielectric material on a surface of a mold, forming a layer of molecular raw material on the surface of the non-volatile dielectric material, the molecular raw material including an organic solid crystal precursor, forming crystal nuclei from the organic solid crystal precursor, and growing the crystal nuclei to form an organic solid crystal film.

[0070] In some embodiments, a non-volatile dielectric material may be disposed between the mold surface and the organic precursor and may be adapted to reduce the surface roughness of the molded organic solid crystal film and facilitate its release from the mold while locally inhibiting nucleation of a crystalline phase.

[0071] Example non-volatile dielectric materials include liquids such as silicone oil, paraffin oil, fluorinated polymers, polyolefins, and / or polyethylene glycol. Thus, in some embodiments, the non-volatile dielectric material layer can provide a liquid surface for the growth of organic solid crystals (such as organic solid crystal films). Further example non-volatile dielectric materials can include crystalline materials having a melting temperature lower than the melting temperature of the organic precursor material. In some embodiments, the mold surface can be pre-treated to improve the wettability and / or adhesion of the non-volatile dielectric material.

[0072] The deposition surface of the substrate or mold may include a functional layer configured to be transferred to the organic solid crystal after the organic solid crystal is formed and separated from the substrate or mold. The functional layer may include an interference coating, an AR coating, an enhanced reflectivity coating, a bandpass coating, a bandstop coating, a blanket or patterned electrode, etc. For example, the electrode may include any suitable 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).

[0073] In some embodiments, the surface (i.e., crystal growth surface) roughness of the substrate itself can be controlled to enable the formation of large (area) organic solid crystals. By reducing the substrate surface roughness, the number of nucleation sites can be reduced, which can enable the formation of a film of higher quality (i.e., optical quality). In addition, by reducing the substrate surface roughness, the contact area between the substrate and the initial solid crystal can be reduced, which can improve releasability.

[0074] The thin film or bulk crystal of the organic semiconductor can be self-supporting or disposed on a substrate. If used, the substrate can be optically transparent. Nucleation and growth kinetics and chemical selection can be selected to produce a solid organic crystal film having an area (lateral) dimension of at least about 1 cm. In another example, the organic solid crystal fiber can have a length (axial) dimension of at least about 1 cm.

[0075] The organic solid crystal film can have a thickness of about 10 nm to about 500 microns, such as a thickness of about 50 microns to about 250 microns. In certain embodiments, the OSC film can have an optical transmittance of at least about 50%, for example, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 97%, about 98%, or about 99%, including ranges between any of the foregoing values.

[0076] The organic film may include a planar, convex or concave surface. In some embodiments, the surface may include a three-dimensional structure, such as a periodic surface relief grating. In further embodiments, the film may be configured as a microlens or a prismatic lens. For example, a polarizing optical device may include a microlens that selectively passes one polarization of light and focuses on another polarization. In some embodiments, the structured surface may be formed in situ, i.e., during crystal growth of an organic solid crystal. In further embodiments, the structured surface may be formed after crystal growth, for example, using additive or subtractive processing, such as photolithography and etching.

[0077] According to some embodiments, organic solid crystal films can be characterized by a preferred orientation of molecules defined within a range of at least about 1 cm 2 In some embodiments, the surface roughness (Ra) of at least one surface of the OSC film may be less than about 10000 nm, less than about 5000 nm, less than about 2000 nm, less than about 1000 nm, less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, or less than about 2 nm, including ranges between any of the foregoing values.

[0078] Organic crystal phase can be single crystal or polycrystalline.In some embodiments, organic crystal phase can include amorphous region.In some embodiments, organic crystal phase can be crystallization basically.The feature of organic crystal phase can be at least about 1.9 along the refractive index of at least one major axis at 589nm, and can be isotropic or anisotropic.For example, organic crystal phase can be at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.8, at least about 1.9, at least about 2.0, at least about 2.1, at least about 2.2, at least about 2.3, at least about 2.4, at least about 2.5 or at least about 2.6 at 589nm and along the refractive index of at least one major axis, including the scope between any aforementioned values.

[0079] The organic solid crystal film may include a crystalline phase having at least one refractive index of at least about 1.9 along its major axis. In some embodiments, the major axis (n1, n2, n3) of the crystalline phase may be consistent with the spatial dimensions (e.g., length, width, and thickness) of the film. In some embodiments, the major axis (n1, n2, n3) of the crystalline phase may be independent of the spatial dimensions of the film.

[0080] In some embodiments, the organic crystalline phase can be isotropic (n1=n2=n3) or birefringent, wherein n1≠n2≠n3 or n1≠n2=n3 or n1=n2≠n3, and can be characterized by a birefringence (Δn) of at least about 0.1, such as at least about 0.1, at least about 0.2, at least about 0.3, at least about 0.4, or at least about 0.5, including ranges between any of the foregoing values. In some embodiments, the birefringent organic crystalline phase can be characterized by a birefringence of less than about 0.1, such as less than about 0.1, less than about 0.05, less than about 0.02, less than about 0.01, less than about 0.005, less than about 0.002, or less than about 0.001, including ranges between any of the foregoing values.

[0081] Table 1 shows, for example, triaxial ellipsometry data for isotropic or anisotropic organic molecules. The data include predicted and measured refractive index and birefringence values ​​for 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2-diphenylacetylene (1,2-DPE), and phenazine. For each organic material composition, the refractive index and birefringence values ​​shown are greater than the predicted refractive index and birefringence values ​​compared to the values ​​calculated based on the HOMO-LUMO energy gap.

[0082] Table 1. Refractive index and birefringence data for example organic semiconductors

[0083]

[0084] Organic solid crystal films (including multilayer organic solid crystal films) can be optically transparent and exhibit low bulk haze. As used herein, for a given thickness, a "transparent" or "optically transparent" material or element can have a transmittance of at least about 80%, such as about 80, 90, 95, 97, 98, 99, or 99.5%, including ranges between any of the foregoing values, and a bulk haze of less than about 5%, such as about 0.1, 0.2, 0.4, 1, 2, or 4%, including ranges between any of the foregoing values. Transparent materials generally exhibit very low optical absorption and minimal optical scattering.

[0085] As used herein, the terms "haze" and "clarity" may refer to optical phenomena associated with the transmission of light through a material and may be due, for example, to refraction of light within the material, for example, due to secondary phases or porosity and / or reflection of light from one or more surfaces of the material. It will be appreciated that haze may be associated with the amount of light subject to wide-angle scattering (i.e., angles greater than 2.5° from the normal) and the corresponding loss of transmission contrast, while clarity may be associated with the amount of light subject to narrow-angle scattering (i.e., angles less than 2.5° from the normal) and the resulting loss of optical clarity or "see-through quality."

[0086] In some embodiments, one or more organic solid crystal thin film layers can be stacked to form multilayer.Multilayer film can be formed by clockwise arrangement (clock) and stacking each layer.That is to say, in exemplary "clockwise arrangement" multilayer stacking, the refractive index orientation error of the in-plane angle between adjacent layers can be in the range of about 1 ° to about 90 °, such as 1,2,5,10,20,30,40,45,50,60,70,80 or 90 °, including the range between any value in the aforementioned values.

[0087] In an example multilayer architecture, the thickness of each layer can be determined by the average of the in-plane refractive indices (n2 and n3), where (n2+n3) / 2 can be greater than about 1.4, e.g., greater than 1.4, greater than 1.45, greater than 1.5, greater than 1.55, or greater than 1.6. In general, the thickness of a given layer can be inversely proportional to the arithmetic mean of its in-plane indices. Similarly, the total number of layers in a multilayer stack can be determined by the in-plane birefringence (|n3-n2|), which can be greater than about 0.05, e.g., greater than 0.05, greater than 0.1, or greater than 0.2.

[0088] According to some embodiments, for a given biaxially oriented organic solid material layer within a multilayer stack, the out-of-plane refractive index (n1) can be determined by the relationship is related to the in-plane refractive index (n2 and n3), where represents the rotation angle of the refractive index vector between adjacent layers. The variation of n1 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.

[0089] Instead of molding or in addition to molding, further exemplary deposition methods for forming organic solid crystals include vapor growth, solid growth, growth based on melt, solution growth, etc., optionally in combination with suitable substrates and / or seed crystals. The substrate can be organic or inorganic. For example, thin film solid organic materials can be manufactured using one or more processes selected from chemical vapor deposition (CVD) and physical vapor deposition (PVD). Further coating processes (for example, from solution or melt) can include 3D printing, inkjet printing, gravure printing, scraper, spin coating, etc. Such processes can cause shearing during coating, and can accordingly contribute to the preferred orientation of crystallites or molecular orientation and crystallites and / or molecules in organic solid crystal films. Further exemplary methods can include pulling self-supporting crystals from a melt. According to some embodiments, solid phase, liquid phase or vapor deposition processes can include epitaxial processes.

[0090] As used herein, the terms "epitaxial", "epitaxial" and / or "epitaxial growth and / or deposition" refer to the nucleation and growth of organic solid crystals on a deposition surface, where it is assumed that the growing layer of organic solid crystals exhibits the same crystallographic habit as the material of the deposition surface. For example, in an epitaxial deposition process, the chemical reactants can be controlled and the system parameters can be set so that the deposited atoms or molecules fall on the deposition surface and remain sufficiently mobile via surface diffusion to orient themselves according to the crystallographic orientation of the atoms or molecules of the deposition surface. The epitaxial process can be homogeneous or heterogeneous.

[0091] According to various embodiments, doping and related techniques can be used to tune the optical and electro-optical properties of organic solid crystals. Doping can affect, for example, the polarizability of organic solid crystals. Introducing dopants (i.e., impurities) into organic solid crystals can affect, for example, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) band, and therefore affect its band gap, induced dipole moment and / or molecule / crystal polarizability. Doping can be carried out in situ, i.e., during epitaxial growth or after epitaxial growth, such as using ion implantation or plasma doping. In an exemplary embodiment, doping can be used to modify the electronic structure of organic solid crystals without damaging molecular stacking or the crystal structure itself. An annealing step after implantation can be used to repair crystal defects introduced during ion implantation. Annealing can include, for example, rapid thermal annealing or pulse annealing.

[0092] Doping changes the electron and hole carrier concentrations of the host material at thermal equilibrium. Doped organic solid crystals can be p-type or n-type. As used herein, "p-type" refers to the addition of impurities to an organic solid crystal, resulting in a lack of valence electrons, while "n-type" refers to the addition of impurities to an organic solid crystal, which contributes free electrons. Without wishing to be bound by theory, doping can affect "π-stacks" and "π-π interactions" in organic solid crystals.

[0093] Exemplary dopants include Lewis acids (electron acceptors) and Lewis bases (electron donors). Specific examples include charge neutral and ionic species such as Bronsted Acid and Bronster base, in addition to the above process, Lewis acid and Lewis base can be incorporated into organic solid crystals by solution growth or vapor co-deposition. In a specific embodiment, dopant can include organic molecules, organic ions, inorganic molecules or inorganic ions. Example dopant includes luminescent phosphor, which can be configured to emit light with selected polarization. In a specific embodiment, phosphor can be oriented in a way that effectively produces selective polarization (e.g., P or S) at the operating wavelength by organic crystal. Doping distribution can be homogeneous or confined to a specific area (e.g., depth) of organic solid crystal. Suitable phosphor emits from triplet excited state. Example phosphors and fluorescent groups include metal complexes such as platinum-complexed porphyrin PtOEP (platinum-octaethyl-porphyrin), bi[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III), di(2-phenylpyridinyl)iridium acetylacetonate (Ir(ppy2)(acac)) and tris[2-(2-pyridinyl-kN)-5-(trifluoromethyl)phenyl-kC]iridium, tris(2-(4-trifluoromethylphenyl)pyridinium)iridium (Ir(p-CF3-ppy)3), although further components are contemplated. The choice of phosphor / fluorescent group can be determined by the host organic solid crystal and / or the desired absorption / emission fraction. The melting point and / or sublimation temperature of the molecular dopant and the organic precursor can be substantially equal. In some embodiments, the molecular dopant can be configured to effectively fill into the crystal matrix of the organic solid crystal.

[0094] During nucleation and growth, one or more of substrate temperature, deposition pressure, solvent vapor pressure, or non-solvent vapor pressure can be used to control the orientation of the in-plane axes of the OSC film. The high refractive index and high birefringence organic solid crystal thin films can be supported by a substrate or mold, or removed therefrom to form a self-supporting film. The substrate, if used, can be rigid or deformable.

[0095] The doped organic crystals may be planar or non-planar and may be formed using one or a combination of processes including, but not limited to, chemical vapor deposition, physical vapor transport, melt growth, solution growth, thermal annealing, zone annealing, spin coating, doctor blading, ink jetting, and roll-to-roll processing.

[0096] The organic solid crystal (OSC) layer may be disposed on an electrode or between a pair of electrodes, wherein, for example, a voltage applied between the electrodes may be used to tune one or more optical properties of the OSC layer. According to certain embodiments, the optical modulator may include an active layer of an organic solid crystalline phase, a primary electrode disposed on a first portion of the active layer, and a secondary electrode disposed on a second portion of the active layer, wherein the optical property of the active layer has a first value along a selected direction in a first bias state, and a second value along the selected direction in a second bias state. The optical property may include a refractive index, a birefringence, and / or an absorptivity of visible light.

[0097] Disclosed are organic solid crystals with actively tunable refractive index and birefringence. Methods of making such organic solid crystals may be able to control their surface roughness independently of surface features (e.g., gratings), and may include forming organic articles therefrom. Variable and controllable refractive index architectures may be incorporated into or implemented in a variety of optical and photonic devices and systems.

[0098] According to various embodiments, organic articles including organic solid crystals (OSCs) can be integrated into optical components or devices, such as OFETs, OPVs, OLEDs, etc., and can be incorporated into waveguides, Fresnel lenses (e.g., cylindrical Fresnel lenses or spherical Fresnel lenses), gratings, photonic integrated circuits, birefringent index compensation layers, reflective polarizers, refractive index matching layers (LED / OLED), holographic data storage elements, etc.

[0099] As used herein, a grating is an optical element having a periodic structure that is configured to scatter or diffract light into a plurality of partial beams. The direction or diffraction angle of the diffracted light may depend on the wavelength of the light incident on the grating, the orientation of the incident light relative to the grating surface, and the spacing between adjacent diffraction elements. In certain embodiments, the grating architecture may be tuned along one, two, or three dimensions. The optical element may include a single or multilayer OSC architecture.

[0100] As will be appreciated, one or more properties of an organic solid crystal can be specifically tailored for a particular application. For example, for many optical applications, it can be advantageous to control the crystallite size, surface roughness, mechanical strength and toughness, and orientation of crystallites and / or molecules within an organic solid crystal film or fiber.

[0101] Active modulation of the refractive index can improve the performance of photonic systems and devices, including passive and active optical waveguides, resonators, lasers, optical modulators, etc. Further exemplary active optical devices include projectors and projection optics, ophthalmic high-index lenses, eye tracking, gradient-index optics, Pancharatnam-Berry phase (PBP) lenses, pupil manipulation elements, microlenses, optical computers, optical fibers, rewritable optical data storage, all-optical logic gates, multi-wavelength optical data processing, optical transistors, etc.

[0102] Features from any of the embodiments described herein may be used in combination with each other according to the general principles described herein. These and other embodiments, features and advantages will be more fully understood by reading the following detailed description in conjunction with the accompanying drawings and claims.

[0103] The following will refer to Figure 1-35 Provides a detailed description of organic solid crystals, their preparation methods and potential applications. Figure 1 Related discussion relates to example mold-based processes for forming thin films of organic solid crystals. Figure 2 Related discussions concern the structures and properties of example organic solid crystals fabricated with and without nonvolatile dielectric materials. Figure 3-9 The related discussion includes descriptions of exemplary epitaxial growth processes and non-epitaxial growth processes for forming organic solid crystals. Figure 10-23 The associated discussion includes a description of the architecture and performance of example organic solid crystals and optical modulators containing the organic solid crystals.

[0104] and Figure 24-28 The related discussion includes a description of exemplary fabrication methods and apparatus for forming organic solid crystal thin films. Fig.29 The related discussion includes a description of exemplary organic molecules suitable for making organic solid crystals. Fig.30 The related discussion includes a description of exemplary dopant molecules suitable for making organic solid crystals. Fig.31 The related discussion includes a description of a circular reflective polarizer that may include a multilayer organic solid crystal film having a biaxial refractive index. Fig.32 The related discussion includes a description of the orientation of the in-plane refractive index (n3) in an exemplary multilayer organic solid crystal film. Fig.33The related discussion includes a description of the performance of an example circular reflective polarizer comprising a multilayer organic solid crystal thin film having a biaxial refractive index. Fig.34 and Fig.35 A related discussion relates to example virtual reality and augmented reality devices that may include one or more organic solid crystal films as disclosed herein.

[0105] Steering Figure 1 , schematically illustrates an example fabrication architecture that can be implemented according to certain methods of forming an organic solid crystalline film. In some embodiments, a layer of a crystallizable organic precursor can be deposited between mold surfaces or on a surface of a substrate and processed to form an organic solid crystalline film. The crystallizable organic precursor can include one or more crystallizable organic molecules.

[0106] refer to Figure 1 A, shown at an intermediate stage of fabrication, an organic precursor layer 110 may be disposed between an upper mold body 120 and a lower mold body 120, and the organic precursor layer may be coated with an upper layer and a lower layer of a non-volatile dielectric material 130, respectively. The non-volatile dielectric material layer 130 may include an anti-nucleation layer. Subsequent treatment to induce nucleation and growth of organic solid crystals, the resulting organic solid crystal film 112 may be removed from the mold 120. Exemplary process steps may include zone annealing. The organic solid film 112 may be birefringent (e.g., n1≠n2≠n3) and may be characterized by a high refractive index (e.g., n2>1.4 and / or n3>1.4).

[0107] Reference Figure 1 B, shows another fabrication structure for forming a supported organic solid crystal thin film. Figure 1 In the architecture of FIG. 1B , at an intermediate stage of manufacturing, a crystallizable organic precursor layer 110 may be disposed on a substrate 140 . An upper mold body 120 may cover the organic precursor layer 110 , and a non-volatile dielectric material layer 130 may be located between the mold body 120 and the organic precursor layer 110 . The non-volatile dielectric material layer 130 may directly cover the organic precursor layer 110 , and may be configured to control the surface roughness of the upper surface of the organic solid crystal thin film 112 during crystal growth. According to certain embodiments, in Figure 1 A and Figure 1 In B, the direction of movement of the crystallization front 111 during crystal growth is indicated by arrow A.

[0108] Reference Figure 2, showing polarized optical microscope images of organic solid crystal thin films formed using a mold-based method. The thin films 211 and 212 are produced (A) without using a non-volatile dielectric material layer, and (B) with a non-volatile dielectric material layer pre-set on the mold surface (e.g., using Figure 1 A or Figure 1 The improved surface morphology associated with the use of a non-volatile dielectric material layer is Figure 2 The appearance of the organic solid film 212 in B is obvious.

[0109] An example vapor phase epitaxial growth process for forming organic solid crystal thin films is shown in Figure 3 Schematically shown in FIG. Evaporated molecules 310 of organic solid crystalline material and dopant molecules 320 can be directed together to a deposition surface 341 of a substrate 340, for example, in a vacuum chamber (not shown) to form a doped organic solid crystalline layer on the substrate. The choice of solvent, the concentration of evaporated molecules, substrate temperature, one or more temperature gradients, gas pressure, etc. can be used to control the gas phase mobility of molecules 310, 320, the adsorption and desorption rates of molecules 310, 320, and the crystallization rate and crystal structure of the organic solid crystalline film.

[0110] A further exemplary epitaxial growth process for forming organic solid crystals is described in Figure 4 It is schematically shown in Figure 4 In the method, the organic crystal melt 410 can be contained in a crucible 420 and heated. The crucible 420 can be formed of, for example, glass or glass ceramic material. The organic crystal melt 410 can be in direct contact with the non-volatile dielectric material 430 contained in the crucible 420. The non-volatile dielectric material 430 can include silicone oil, paraffin oil, fluorinated polymers or fluorinated oligomers, polyethylene glycol, polyolefins, etc.

[0111] Seed crystal 450 can be in contact with organic crystal melt 410, and optionally, for example, drawn from the molten phase at a desired rate under continuous operation to form an organic solid crystal. Seed crystal 450 can include organic solid crystal material. In some embodiments, the composition of organic crystal melt 410 and the composition of seed crystal 450 can be equal or substantially equal. Seed crystal 450 can have a flat or non-flat contact surface 452 that contacts the molten phase, which surface can be selected to control the shape (e.g., curvature) of the over-formed organic solid crystal. In some embodiments, crucible 420 can be configured as a mold, and organic crystal melt 410 can be crystallized in crucible 420 to form an organic solid crystal.

[0112] Further example epitaxial growth processes and process architectures for forming organic solid crystals are described in Figure 5 It is schematically shown in Figure 5 In the method, an organic crystal melt 510 can be contained in a crucible 520 and heated. The crucible 520 can be configured to provide mechanical support and can include, for example, a glass or glass ceramic material. The organic crystal melt 510 can be in direct contact with a non-volatile dielectric material layer 530 covering the inner surface of the crucible 520. The non-volatile dielectric material 530 can include silicone oil, paraffin oil, fluorinated polymers or fluorinated oligomers, polyethylene glycol, polyolefins, etc. In the illustrated embodiment, the non-volatile dielectric material layer 530 can include a conformal layer of self-supporting molecules (e.g., an oil layer or a brushed layer of a polymer, oligomer or small molecule (such as a silane or a fluorinated polymer)).

[0113] Seed crystal 550 can be in contact with organic crystal melt 510, and optionally, for example, stretched from the molten phase at a desired rate under continuous operation to form organic solid crystal. Seed crystal 550 can include organic solid crystal material. In some embodiments, organic crystal melt 510 and seed crystal 550 can be equal or substantially equal in composition. In some embodiments, seed crystal 550 can have a flat or non-flat contact surface 552, which can be selected to control the shape (e.g., curvature) of the over-formed organic solid crystal. In some embodiments, crucible 520 can be configured as a mold, and organic crystal melt 510 can be crystallized in crucible 520 to form organic solid crystal.

[0114] exist Figure 4 and Figure 5 In embodiments of the present invention, the atmosphere covering the molten phase can be controlled. For example, the atmosphere covering the melt can include an inert gas such as argon maintained at a controlled pressure and / or flow rate.

[0115] According to further embodiments, an exemplary molding process architecture for forming organic solid crystals is shown in Figure 6 , where both (A) double-sided mold and (B) single-sided mold architectures are shown. In each approach, a non-volatile dielectric material layer (i.e., anti-nucleation layer) 630 can be disposed between mold 620 and molten phase 610. A local seed layer (not shown) can be used to initiate crystal nucleation and growth. Figure 7 It is shown in Figure 6 Cross-sectional view of the single-sided die method of B. Figure 7 In FIG. 7A , a seed crystal 750 is shown located within the mold 720 and in contact with the anti-nucleation layer 730 . Figure 7 B, the distribution element 760 can be configured to deliver the organic crystal molecules to the nucleation site near the seed crystal 750, and subsequently to the crystallization front during crystal growth.

[0116] refer to Figure 8 , shows a schematic setup for an epitaxial or non-epitaxial growth process, wherein an organic seed 850 can be contacted with a supersaturated organic solution 810 and optionally drawn from the supersaturated organic solvent 810. The organic solution can include one or more crystallizable organic molecules dissolved in a suitable solvent. The organic solution 810 can be contained within a crucible 820 and separated from the crucible 820 by an anti-nucleation layer 830. By contacting the seed 850 with the solution 810, an organic solid crystal layer can nucleate and grow within the crucible 820.

[0117] Reference Fig. 9 The further nucleation process and growth process may include providing an anti-nucleation layer 930 on the substrate 920 and introducing the organic crystal solution 910 on the anti-nucleation layer 930. Fig. 9 As shown in A, optionally, in the absence of a seed layer, the organic crystal solution 910 can be solidified to form an organic solid crystal. A micrograph of a self-supporting organic solid crystal 912 is shown in Fig. 9 B. According to some embodiments, the organic solid crystals 912 can be characterized by a length dimension of at least about 1 cm.

[0118] According to a further embodiment, in Fig.10 and Fig.11 The dynamic and static methods for forming organic solid crystals with structured surface features are schematically shown in FIG. Fig.10 A, a layer of organic crystal solution or melt 1010 and an adjacent layer of conductive liquid 1070 may be disposed between opposing substrates 1040. Patterned and paired electrodes 1080 may be overlaid on the respective substrates 1040. Fig.10 B, under an applied electric field E, a pattern can be induced in the conductive liquid layer 1070, which can produce a reciprocal pattern in the organic crystalline material layer 1010. Furthermore, the crystallization of the organic crystalline material layer 1010 can be performed by thermally induced nucleation and growth, for example, optionally combined with a seed crystal (not shown) to form an organic solid crystalline film having a periodic surface feature or structure, such as an array of raised elements.

[0119] Fig.11An exemplary structure of a tripolar concentric ring electrode (CRE) 1100 such as electrode 1080 is shown. CRE 1100 may include multiple electrode segments, such as a center disk 1102, an inner ring 1104, and an outer ring 1106. The electrodes may include metals such as aluminum, gold, silver, tin, copper, indium, gallium, zinc, etc. Other conductive materials may be used, including carbon nanotubes, graphene, and transparent conductive oxides (TCOs, e.g., indium tin oxide (ITO), indium gallium zinc oxide (IGZO), zinc oxide (ZnO), etc.).

[0120] The electrodes may be fabricated using any suitable process. For example, the electrodes may be fabricated using physical vapor deposition (PVD), chemical vapor deposition (CVD), evaporation, spraying, spin coating, atomic layer deposition (ALD), etc. In other aspects, the electrodes may be fabricated using a thermal evaporator, a sputtering system, a spray coater, a spin coater, printing, stamping, etc.

[0121] The electrode can have a thickness of about 1 nm to about 1000 nm, with an exemplary thickness of about 10 nm to about 50 nm. In certain embodiments, the electrode can have an optical transmittance of at least about 50%, for example, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 97%, about 98%, or about 99%, including ranges between any of the foregoing values.

[0122] Reference Fig.12 , showing a static method for forming an organic solid crystal with structured surface features. A layer of an organic crystal solution or melt 1210 and an adjacent pre-patterned mold 1220 can be disposed between opposing substrates 1240. In the case where the organic crystal solution or melt 1210 conforms to the shape of the patterned mold 1220, crystallization of the organic crystal material layer 1210 can be performed by thermally induced nucleation and growth to form an organic solid crystal film with periodic surface features. Such a structured organic solid crystal film can be formed or incorporated into various optical elements, including gratings, microlenses, prisms, Fresnel lenses, etc.

[0123] According to a further embodiment, Fig.13 A schematic diagram of an example organic solid crystal structure formed by drawing from a melt phase is shown in FIG. Fig.13 The organic solid crystals 1314 and Fig.13 The organic solid crystal 1316 depicted in B may include corresponding surface features such as nodules 1315 or facets 1317. One or more process variables, including pull rate from the melt, pressure, and temperature, may be controlled to produce a desired surface pattern.

[0124] Without being bound by theory, the source of active refractive index modulation in organic solid crystals may be due to the change in polarizability of charged molecules caused by hole or electron injection. In organic molecules, the time required for the molecule to repolarize upon charge injection may be an order of magnitude faster than the residence time of the charge. Therefore, Fig.14 As schematically depicted in FIG, within an organic solid crystalline material 1400, a charge 1401 can be on a molecule 1402 long enough to cause the molecule to modulate its electron cloud and the electron clouds of neighboring molecules 1405. This change in the local electronics of the crystal can result in changes in polarizability and refractive index.

[0125] Reference Fig.15 , the example optical element 1500 has a top gate-top contact (TGTC) architecture and includes a patterned gate 1502 disposed above an insulating layer 1504 and between source 1506 and drain 1508 contacts. The insulating layer 1504 may include any suitable dielectric material, including organic compounds (e.g., polymers) and inorganic compounds (e.g., silicon dioxide). The gate 1502 is disposed on an optically isotropic or anisotropic organic solid crystal (OSC) layer 1510. The gate 1502, source 1506, and drain 1508 are supported by a substrate 1520.

[0126] During operation, charge can be injected into the optically isotropic or anisotropic organic solid crystal (OSC) layer 1510 through the source (S) and drain (D) contacts. The optical element shown can form an active grating, where voltages applied to the gate and / or the source and drain can be used to locally control the geometry (e.g., depth and orientation) of a portion of the (OSC) layer below the gate and thus affect its interaction with light. According to further embodiments, Fig.15 The optical components can be suitable for photonic data storage.

[0127] According to some embodiments, Fig.15 The optical element may optionally include a charge transport layer (not shown) located between the source electrode and the OSC layer and / or between the drain electrode and the OSC layer. The charge transport layer may include an organic compound (e.g., carbon nanotubes) or an inorganic compound. In a further exemplary embodiment, the optical element may include a waveguide.

[0128] Reference Fig.16, the exemplary optical element 1600 has a bottom gate-top contact (BGTC) architecture and includes a gate 1602 disposed below an optically isotropic or anisotropic organic solid crystal (OSC) layer 1610. An insulating layer 1604 is disposed between the gate 1602 and the OSC layer 1610. The insulating layer 1604 can include any suitable dielectric material, including organic compounds (e.g., polymers) and inorganic compounds (e.g., silicon dioxide). The source 1606 and drain 1608 contacts directly cover the corresponding portions of the OSC layer 160 opposite the gate 1602.

[0129] During operation, charge can be injected through the source and drain contacts into the optically isotropic or anisotropic organic solid crystal (OSC) layer 1610. The optical element shown can form an active grating, where voltages applied to the gate and / or source and drain can be used to locally control the geometry (e.g., depth and orientation) of a portion of the OSC layer above the gate and thus affect its interaction with light.

[0130] Fig.17 A schematic cross-sectional view of an optical modulator according to some embodiments is shown in FIG. The modulator structure may include a substrate 1720 defining a well and an OSC layer 1710 disposed within the well. A pair of electrodes 1706, 1708 may directly cover respective portions of the OSC layer 1710. The electrodes 1706, 1708 may be spaced apart from each other, and a dielectric layer 1704 may cover the OSC layer 1710 between the electrodes 1706, 1708.

[0131] Now refer to Fig.18 , a schematic cross-sectional view of an optical modulator according to a further embodiment is shown. The modulator structure may include an OSC layer 1810 sandwiched between top and bottom semiconductor layers 1830 and 1840, respectively. The bottom semiconductor layer 1840 may define a groove having both the OSC layer 1810 and the top semiconductor layer 1830 located within the groove. A pair of electrodes 1806, 1808 may directly cover respective portions of the OSC layer 1810. The electrodes 1806, 1808 may be spaced apart from each other, and a dielectric layer 1804 may cover the top semiconductor layer 1830 between the electrodes 1806, 1808.

[0132] Reference Fig.19 , a further example optical modulator may include an organic solid crystal layer 1910 sandwiched between a pair of electrodes 1906, 1908. Referring to Fig. 20In some embodiments, the dielectric layer 2004 can be disposed between the OSC layer 2010 and the one or more electrodes 2006, 2008. During operation, the dielectric layer 2004 can be configured to regulate the current or voltage applied to the OSC layer 2010. Fig.21 A further optical modulator is shown in FIG. Fig.21 In an embodiment, a bilayer comprising a semiconductor layer 2110b directly overlying an OSC layer 2110a is sandwiched between a pair of electrodes 2106, 2108.

[0133] Fig. 22 The structure and performance of an example optical modulator containing an OSC are shown in FIG. Fig. 22 A, the optical modulator includes an anthracene layer disposed between a pair of indium tin oxide (ITO) electrodes. For example, the anthracene layer may include a single crystal or may be polycrystalline. Fig. 22 B, shows the shift of an arbitrary peak measured by ellipsometry versus time (applied voltage). The shift in peak position correlates well with the applied voltage, including a well-defined decay corresponding to removal of the voltage.

[0134] Reference Fig.23 A further example optical modulator includes a bilayer of anthracene and silicon dioxide disposed between a pair of indium tin oxide (ITO) electrodes. Fig.23 A is schematically shown. Fig.23 As shown in B, the position of any peak measured by ellipsometry shows good correlation with the applied voltage, including a clear decay corresponding to the removal of the voltage. Fig. 22 and Fig.23 In both, the peak shift can be related to a change in the refractive index and / or birefringence of the OSC layer.

[0135] Reference Fig.24 , a perspective view of a further example melt-based deposition method and apparatus for forming organic solid crystals from molten raw materials is shown. The molten raw material 2410 can be contained in a reservoir 2490. The reservoir 2490 can be formed, for example, of a glass or glass-ceramic composition, and can include an internal passivation layer (not shown) to inhibit nucleation. The seed crystal 2450 can be mounted at the distal end of a rotatable and transferable rod 2455 so that the seed crystal 2450 can be dropped into the molten raw material 2410 and removed therefrom. The control system (not shown) can be configured to control one or more of the melt temperature, the seed crystal temperature, the gas pressure and the gas composition covering the melt, the rotation speed of the molten raw material, the rotation speed of the seed crystal, and the stretching speed, etc.

[0136] Steering Fig.25According to various embodiments, a crystal growth scaffold located near a seed crystal and a corresponding nucleation region can be configured to template the growth of an organic solid crystal of a desired shape. Fig.25 As shown in A, adjacent to the nucleation region 2541, a planar support 2542 can support the crystal growth of an organic solid crystal having a flat surface. Fig.25 As shown in Figure B, adjacent to the nucleation region 2541, the non-planar support 2544 can support the crystal growth of an organic solid crystal having a concave or convex growth surface. In some embodiments, multiple seed crystals and multiple associated supports can be arranged to form multiple nucleation sites, and several nuclei can grow from multiple nucleation points and merge into larger crystals.

[0137] Fig.26 and 27 2 shows top-down plan and cross-sectional views of an example fabrication architecture and method for forming an organic solid crystal thin film according to further embodiments. Fig.26 A and Fig.26 B relates to a thin film forming architecture having a substrate 2640 and a single seed crystal 2650 disposed on the substrate 2640, while Fig. 27 A and Fig. 27 B relates to a thin film formation architecture having a substrate 2740 and a plurality of seed layers 2750 disposed on the substrate 2740. A layer of a crystallizable organic precursor 2610, 2710 may be deposited on the respective substrate 2640, 2740 and the respective one or more seed crystals 2650, 2750.

[0138] The organic solid crystal thin films 2612, 2712 can be formed by zone annealing using a suitable temperature profile (T1, T2, T3). Fig. 27 An example thermal profile is shown in B, where an organic solid crystalline layer 2712 may nucleate near a seed crystal 2750. The direction of movement of the crystallization front 2611, 2711 during crystal growth is Fig.26 B and Fig. 27 Indicated by arrow A in B.

[0139] Further thin film formation architecture in Fig.28 See Fig.28 A, the thin film forming framework includes a substrate 2840 and a seed crystal 2850 disposed on a portion of the substrate 2840. A layer of a crystallizable organic precursor 2810 can be deposited on the substrate 2840 and the seed crystal 2850. Application of a suitable temperature gradient (T1, T2, T3) can induce nucleation and growth of an organic solid crystal thin film 2812. The thin film forming framework can be translated relative to the thermal profile to advance the crystallization front 2811 through crystal growth and increase the area of ​​the organic solid crystal thin film 2812.

[0140] The cover plate 2840a may cover the crystallizable organic precursor layer 2810. The cover plate 2840a may be tilted at an angle (θ) relative to the substrate 2840 and may be configured to generate capillary forces that improve mass transport of the molten feedstock to the region containing the crystallization front 2811. Fig.28 B, Fig.28 The device of A can be oriented vertically. Fig.28 In the vertical orientation of B, in addition to or instead of the capillary force, the gravity F g The mass transfer of the molten feedstock 2810 to the crystallization front 2811 can be advantageously promoted.

[0141] Example OSC materials suitable for forming the feedstock composition include small molecules, macromolecules, liquid crystals, organometallic compounds, oligomers and polymers, and may include organic semiconductors, such as polycyclic aromatic compounds, for example, anthracene and phenanthrene, etc. Methods for making organic solid crystals may include growing crystals from a melt or solution, chemical or physical vapor deposition, and coating a solvent on a substrate. The deposition surface of the substrate may be treated in its entirety or locally to affect, for example, nucleation density, crystallization orientation, adhesion, etc. The foregoing methods may be applied in conjunction with one or more optional post-deposition steps, such as annealing, polishing, cutting, etc., which post-deposition steps may be implemented to improve one or more OSC properties, including crystallinity, thickness, curvature, etc. Example organic molecules that can be used to form organic solid crystals are Fig.29 Shown in.

[0142] Fig.30 Example phosphors are depicted. In these materials, phosphorescence can arise from light emission from a triplet excited state, where the electrons in the excited orbital have the same spin orientation as the n ground state electrons.

[0143] Reference Fig.31 , a cross-sectional view of an example optical element is shown. An optical element 3100 arranged in optical alignment may include a display 3102, a polarizer 3104, a 50 / 50 mirror 3106, and a circular reflective polarizer 3108. The circular reflective polarizer 3108 may include a multilayer organic solid crystal film 3112 optically encapsulated by a protective layer 3114. The multilayer organic solid crystal film 3112 may include a clockwise arrangement and stacking configuration of multiple organic solid crystal films (not shown separately). The multilayer organic solid crystal film 3112 may be configured to reflect a first polarization (P1) of incident light and transmit a second polarization (P2) of incident light.

[0144] Steering Fig.32, showing the architecture and operation of an example circular reflective polarizer. The circular reflective polarizer may include a multilayer organic solid crystal thin film, wherein each OSC layer in the multilayer stack includes a bi-directionally oriented organic solid crystal material (i.e., n1≠n2≠n3), such as Fig.32 This is schematically shown in A. The multilayer film can be characterized by a pitch (P), which can correspond to two periods (2Λ) of refractive index variation.

[0145] exist Fig.32 In B, the arrows indicate the orientation of the refractive index vector (e.g., n3) in each OSC layer of the multilayer. Fig.32 In the embodiment shown in B, the right-hand RH circular reflecting polarizer transmits light having left-hand circular polarization (LCP) and reflects light having right-hand circular polarization (RCP).

[0146] The relationship between signal efficiency and ghost signal ratio and the thickness of the reflective polarizer is shown in the figure Fig.33 As shown, and illustrated, a reflective polarizer including a plurality of clockwise arranged and stacked OSC films each having a biaxial refractive index can have higher signal efficiency and improved ghost suppression relative to a comparative reflective polarizer.

[0147] A method for forming a doped organic solid crystal film is disclosed. In a specific embodiment, the method can be used to control the surface roughness of the film without the need for post-forming slicing, grinding and polishing steps. Using a seed crystal to nucleate an organic solid crystal from a liquid or molten phase containing an organic precursor, in an exemplary method, a non-volatile dielectric material (e.g., oil) can be used to cast or mold an organic solid crystal film to template crystal growth. Gas phase and solid phase nucleation and growth paradigms are also disclosed. In some embodiments, an anti-nucleation layer or surface can be used to locally prevent crystallization and achieve large-area crystallization. In some embodiments, the substrate surface can include a photoalignment layer. In a specific example, the substrate surface can be chemically treated to promote the desired molecular alignment of the over-formed organic solid crystal.

[0148] In some embodiments, the organic precursor may be deposited directly on the layer of non-volatile dielectric material, which may provide a smooth interface for the formation of an organic solid crystalline film. Thermal treatment may be used to induce nucleation and growth of the organic solid phase.

[0149] In a further embodiment, a mixture containing an organic precursor and a non-volatile dielectric material can be deposited on a substrate. If provided, the substrate can be patterned to include a 3D structure incorporating an over-formed thin film. In a similar vein, a functional layer can be formed on the deposition surface of a substrate or a mold, and the functional layer can be transferred to the over-formed organic solid crystal when the organic solid crystal is separated from the substrate or the mold. Thermal treatment can be used to induce uniform mixing and subsequent phase separation of organic precursors and non-volatile dielectric materials, as well as nucleation and growth of organic solid crystal phases. During nucleation and growth, according to various embodiments, at least one surface of the film can directly contact the non-volatile dielectric material, which may effectively adjust the molecular-level surface roughness of the newly formed one or more organic crystals.

[0150] Also disclosed are materials and methods for actively modulating refractive index and birefringence in optical devices and systems. Various embodiments relate to solid organic materials including organic semiconductors, wherein by applying a voltage or current, a direction-specific change in refractive index (Δn) can be achieved without significantly increasing light absorption at an operating wavelength. An optical modulator can include an organic crystal layer located near or sandwiched between one or more electrodes.

[0151] Example organic crystalline materials include small molecules, macromolecules, liquid crystals, organometallic compounds, oligomers and polymers, and may include organic semiconductors, such as polycyclic aromatic compounds, for example anthracene and phenanthrene, etc. Methods for making organic crystals may include growing crystals from a melt or solution, and chemical or physical vapor deposition using suitable precursors. Doped organic crystals can be formed in situ, wherein the type and amount of dopant can be selected to affect the crystal structure and optical properties of the organic crystalline material. Doped organic crystals may include up to about 50wt.% of a suitable dopant, and may be characterized by a high refractive index, i.e., a refractive index of at least about 1.9 along a selected crystallization direction. Dopants may include organic molecules, including molecules similar to the host crystal. For example, anthracene crystals may be doped with fluorinated anthracene.

[0152] Also disclosed are active and passive optical devices and systems including optical modulators configured to modulate a beam of light. The optical modulators can be characterized as absorptive and / or refractive and can be adapted to manipulate various parameters of the beam, including its frequency, amplitude, phase, absorption, polarization, etc. According to various embodiments, the optical modulator can include a doped organic solid crystal (OSC) layer located near or sandwiched between one or more electrodes.

[0153] In some embodiments, the refractive index and / or birefringence of the doped OSC layer can be tuned by an amount of at least about 0.0005 in response to an applied current or an applied voltage. In further embodiments, the absorption of the OSC layer over a specified wavelength band can be modulated by 10% or more. Example OSC-containing optical modulators can include resistive or capacitive architectures that can be used independently or co-integrated with other modulators and implemented as or incorporated into surface relief gratings, photonic integrated circuits, Mach-Zehnder interferometers, reflective and refractive polarizers, volume Bragg gratings, and active geometric and diffractive lenses.

[0154] The example process can be integrated with a real-time feedback loop configured to evaluate one or more properties of the organic solid crystal film or fiber and adjust one or more process variables accordingly. The resulting organic solid crystal structure can be incorporated into optical elements such as AR / VR headsets and other devices, such as waveguides, prisms, and Fresnel lenses.

[0155] Example Embodiments

[0156] Embodiment 1: A method, comprising: forming a molecular raw material from an organic solid crystal precursor and a molecular dopant, forming a layer of the molecular raw material on the surface of a substrate, forming crystal nuclei from the organic solid crystal precursor in a nucleation region of the layer of the molecular raw material, and growing the crystal nuclei to form a doped organic solid crystal film.

[0157] Embodiment 2: The method according to embodiment 1, wherein the organic solid crystal precursor comprises a crystallizable organic molecule.

[0158] Embodiment 3: The method according to any one of embodiments 1 and 2, wherein the organic solid crystal comprises a hydrocarbon compound selected from the group consisting of anthracene, phenanthrene, diphenylacetylene, thiophene, pyrene, cyclopentene, fluorene, biphenyl, terphenyl and phthalocyanine.

[0159] Embodiment 4: The method according to any one of embodiments 1-3, wherein the molecular dopant is configured to modulate the HOMO-LUMO energy gap in the doped organic solid crystal thin film.

[0160] Embodiment 5: The method according to any one of embodiments 1-4, wherein the concentration of the molecular dopant in the organic solid crystal thin film ranges from about 0.01 wt.% to about 50 wt.%.

[0161] Embodiment 6: The method according to any one of embodiments 1-5, wherein the molecular raw material comprises a heterocycle selected from furan, pyrrole, thiophene, pyridine, pyrimidine and piperidine.

[0162] Embodiment 7: The method according to any one of embodiments 1-6, wherein the layer of molecular raw material is molten before forming the crystal nucleus.

[0163] Embodiment 8: The method of any one of embodiments 1-7, wherein forming crystal nuclei in the nucleation zone comprises heating the layer of molecular raw materials to a temperature below a melting onset temperature of the organic solid crystalline precursor.

[0164] Embodiment 9: The method according to any one of embodiments 1-8, further comprising forming a layer of non-volatile dielectric material on the surface of the substrate, and forming a layer of molecular raw material directly on the layer of non-volatile dielectric material.

[0165] Embodiment 10: The method according to any one of embodiments 1-9, further comprising forming a seed layer on the surface of the substrate, and forming a layer of molecular raw materials directly on the seed layer.

[0166] Embodiment 11: The method according to any one of embodiments 1-10, further comprising placing a cover plate on the layer of molecular raw material while growing the nuclei.

[0167] Embodiment 12: The method according to embodiment 11, wherein the cover plate is inclined at a certain angle relative to the surface of the substrate.

[0168] Embodiment 13: The method according to any one of embodiments 1-12, wherein the organic solid crystal thin film comprises a single crystal layer.

[0169] Embodiment 14: The method according to any one of embodiments 1-12, wherein the organic solid crystal thin film comprises a polycrystalline layer.

[0170] Example 15: According to a method, the method includes: forming a layer of molecular raw materials on the surface of a substrate, the molecular raw materials including an organic solid crystal precursor and a molecular dopant; forming an organic solid crystal film from the layer of molecular raw materials; forming a main electrode on a first portion of the organic solid crystal film; forming a sub-electrode on a second portion of the organic solid crystal film; and changing the bias state between the main electrode and the sub-electrode by an amount effective to change the optical properties of the organic solid crystal film.

[0171] Embodiment 16: The method of Embodiment 15, wherein the optical property is selected from the group consisting of: refractive index, birefringence, and absorptivity of visible light.

[0172] Embodiment 17: The method of any one of Embodiments 15 and 16, wherein changing the bias state changes the refractive index of the organic solid crystal film by at least about 0.01.

[0173] Embodiment 18: The method according to any one of embodiments 15-17, wherein changing the bias state changes the birefringence of the organic solid crystal film by at least about 0.01.

[0174] Embodiment 19: The method of any one of Embodiments 15-18, wherein the organic solid crystal film comprises a refractive index of at least about 1.9.

[0175] Embodiment 20: According to a method, the method includes: forming a layer containing doped organic solid crystals, forming a main electrode on a first portion of the layer, and forming a sub-electrode on a second portion of the layer.

[0176] Embodiments of the present disclosure may include various types of artificial-reality systems or be implemented in combination with various types of artificial-reality systems. Artificial reality is a form of reality that has been adjusted in some way before being presented to a user, which may include, for example, virtual reality, augmented reality, mixed reality, hybrid reality, or some combination and / or derivative thereof. Artificial reality content may include computer-generated content entirely or computer-generated content combined with captured (e.g., real-world) content. Artificial reality content may include video, audio, tactile feedback, or some combination thereof, any of which may be presented in a single channel or in multiple channels (such as, stereoscopic video that produces a three-dimensional 3D effect to the audience). In addition, in some embodiments, artificial reality may also be associated with applications, products, accessories, services, or some combination thereof that are used, for example, to create content in artificial reality and / or otherwise used in artificial reality (e.g., to perform activities therein).

[0177] Artificial reality systems can be implemented in a variety of different form factors and configurations. Some artificial reality systems can be designed to work without a near-eye display (NED). Other artificial reality systems can include the NED, which also provides a view of the real world (such as, for example, Fig.34 visibility of an augmented reality system 3400 in an image, or visually immersing a user in an artificial reality (such as, for example, Fig.35 3500). 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.

[0178] Steering Fig.34, the augmented reality system 3400 may include an eyewear device 3402 having a frame 3410, the frame 3410 being configured to hold a left display device 3415(A) and a right display device 3415(B) in front of the user's eyes. The display devices 3415(A) and 3415(B) may function together or independently to present an image or group of images to the user. Although the augmented reality system 3400 includes two displays, embodiments of the present disclosure may be implemented in an augmented reality system having a single NED or more than two NEDs.

[0179] In some embodiments, the augmented reality system 3400 may include one or more sensors, such as sensor 3440. Sensor 3440 may generate a measurement signal in response to the movement of the augmented reality system 3400, and the sensor may be located on substantially any portion of the frame 3410. Sensor 3440 may represent a positioning sensor, an inertial measurement unit (IMU), a depth camera assembly, a structured light emitter and / or detector, or any combination thereof. In some embodiments, the augmented reality system 3400 may or may not include sensor 3440 or may include more than one sensor. In embodiments where sensor 3440 includes an IMU, the IMU may generate calibration data based on the measurement signal from sensor 3440. Examples of sensor 3440 may include, but are not limited to, accelerometers, gyroscopes, magnetometers, other suitable types of sensors that detect movement, sensors for error correction of the IMU, or some combination thereof.

[0180] The augmented reality system 3400 may also include a microphone array having a plurality of acoustic transducers 3420(A)-3420(J), collectively referred to as acoustic transducers 3420. The acoustic transducers 3420 may be transducers that detect changes in air pressure caused by sound waves. Each acoustic transducer 3420 may be configured to detect sound and convert the detected sound into an electronic format (e.g., an analog or digital format). Fig.34 The microphone array in can include, for example, 10 acoustic transducers: 3420(A) and 3420(B), which can be designed to be placed in the user's respective ears; acoustic transducers 3420(C), 3420(D), 3420(E), 3420(F), 3420(G) and 3420(H), which can be positioned at different locations on the frame 3410, and / or acoustic transducers 3420(I) and 3420(J), which can be positioned on the respective neckbands 3405.

[0181] In some embodiments, one or more of the acoustic transducers 3420(A)-(F) can be used as an output transducer (e.g., a speaker). For example, the acoustic transducers 3420(A) and / or 3420(B) can be earbuds or any other suitable type of earbuds or speakers.

[0182] The configuration of the acoustic transducer 3420 of the microphone array can vary. Fig.34 3410, but the number of acoustic transducers 3420 may be greater than or less than ten. In some embodiments, the use of a greater number of acoustic transducers 3420 may increase the amount of audio information collected and / or the sensitivity and accuracy of the audio information. In contrast, the use of a smaller number of acoustic transducers 3420 may reduce the computing power required for the associated controller 3450 to process the collected audio information. In addition, the position of each acoustic transducer 3420 of the microphone array may vary. For example, the position of the acoustic transducer 3420 may include a position defined on the user, a coordinate defined on the frame 3410, an orientation associated with each acoustic transducer 3420, or some combination thereof.

[0183] The acoustic transducers 3420(A) and 3420(B) can be positioned on different parts of the user's ear, such as behind the pinna, behind the tragus, and / or in the auricle or fossa. Alternatively, in addition to the acoustic transducer 3420 in the ear canal, there can be additional acoustic transducers 3420 on or around the ear. Positioning the acoustic transducer 3420 near the user's ear canal can enable the microphone array to collect information about how sound reaches the ear canal. By positioning at least two of the acoustic transducers 3420 on either side of the user's head (e.g., as binaural microphones), the augmented reality device 3400 can simulate binaural hearing and capture a 3D stereo sound field around the user's head. In some embodiments, acoustic transducers 3420(A) and 3420(B) may be connected to augmented reality system 3400 via wired connection 3430, and in other embodiments, acoustic transducers 3420(A) and 3420(B) may be connected to augmented reality system 3400 via a wireless connection (e.g., a Bluetooth connection). In other embodiments, acoustic transducers 3420(A) and 3420(B) may not be used in conjunction with augmented reality system 3400 at all.

[0184] The acoustic transducers 3420 on the frame 3410 can be positioned along the length of the temples, across the bridge, above or below the display devices 3415(A) and 3415(B), or some combination thereof. The acoustic transducers 3420 can be oriented so that the microphone array can detect sound in a wide range of directions around the user wearing the augmented reality system 3400. In some embodiments, an optimization process can be performed during the manufacture of the augmented reality system 3400 to determine the relative positioning of each acoustic transducer 3420 in the microphone array.

[0185] In some examples, the augmented reality system 3400 can include or be connected to an external device (e.g., a paired device), such as a neckband 3405. Neckband 3405 generally represents any type or form of paired device. Therefore, the following discussion about neckband 3405 also applies to various other paired devices, such as charging boxes, smart watches, smartphones, wristbands, other wearable devices, handheld controllers, tablet computers, laptop computers, other external computing devices, etc.

[0186] As shown, the neckband 3405 can be coupled to the eyeglass device 3402 via one or more connectors. The connectors can be wired or wireless and can include electrical and / or non-electrical (e.g., structural) components. In some cases, the eyeglass device 3402 and the neckband 3405 can operate independently without any wired or wireless connection between them. Although Fig.34 Components of the eyeglass device 3402 and neckband 3405 are shown in example locations on the eyeglass device 3402 and neckband 3405, but the components may be positioned in other locations and / or distributed differently on the eyeglass device 3402 and / or neckband 3405. In some embodiments, components of the eyeglass device 3402 and neckband 3405 may be located on one or more additional peripheral devices that are paired with the eyeglass device 3402, the neckband 3405, or some combination thereof.

[0187] Pairing an external device (such as a neckband 3405) with an augmented reality eyewear device can enable the eyewear device to achieve the form factor of a pair of glasses while still providing sufficient battery and computing power for expanded capabilities. Some or all of the battery power, computing resources, and / or additional features of the augmented reality system 3400 can be provided by a paired device or shared between a paired device and the eyewear device, thereby reducing the weight, heat distribution, and form factor of the overall eyewear device while still maintaining the desired functionality. For example, the neckband 3405 can allow components originally included on the eyewear device to be included in the neckband 3405 because the user can bear more weight on their shoulders than they can on their heads. The neckband 3405 can also have a larger surface area through which heat is diffused and dispersed to the surrounding environment. Therefore, the neckband 3405 can allow for a larger battery and computing capacity than what might be available on a standalone eyewear device. Because the weight carried in the neckband 3405 may be less intrusive to the user than the weight carried in the eyeglass device 3402, the user may be able to tolerate wearing the lighter eyeglass device and carrying or wearing the paired device for longer periods of time than the user could tolerate wearing a heavy standalone eyeglass device, thereby enabling the user to more fully integrate the artificial-reality environment into their daily activities.

[0188] The neckband 3405 can be communicatively coupled to the eyewear device 3402 and / or other devices. These other devices can provide certain functions (e.g., tracking, positioning, depth mapping, processing, storage, etc.) to the augmented reality system 3400. Fig.34 In an embodiment, the neckband 3405 may include two acoustic transducers (e.g., 3420(I) and 3420(J)) that are part of a microphone array (or may form their own microphone subarray). The neckband 3405 may also include a controller 3425 and a power supply 3435.

[0189] The acoustic transducers 3420(I) and 3420(J) of the neckband 3405 may be configured to detect sound and convert the detected sound into an electronic format (analog or digital). Fig.34In an embodiment of the present invention, the acoustic transducers 3420(I) and 3420(J) can be positioned on the neckband 3405, thereby increasing the distance between the neckband acoustic transducers 3420(I) and 3420(J) and other acoustic transducers 3420 positioned on the eyeglass device 3402. In some cases, increasing the distance between the acoustic transducers 3420 of the microphone array can improve the accuracy of the beamforming performed via the microphone array. For example, if the acoustic transducers 3420(C) and 3420(D) detect a sound, and the distance between the acoustic transducers 3420(C) and 3420(D) is greater than, for example, the distance between the acoustic transducers 3420(D) and 3420(E), the determined source location of the detected sound may be more accurate than the sound detected by the acoustic transducers 3420(D) and 3420(E).

[0190] The controller 3425 of the neckband 3405 can process information generated by sensors on the neckband 3405 and / or the augmented reality system 3400. For example, the controller 3425 can process information from the microphone array describing the sound detected by the microphone array. For each detected sound, the controller 3425 can perform a direction of arrival (direction-of-arrival, DOA) estimation to estimate the direction of the detected sound arriving at the microphone array. When the microphone array detects a sound, the controller 3425 can fill the audio data set with this information. In an embodiment in which the augmented reality system 3400 includes an inertial measurement unit, the controller 3425 can calculate all inertial and spatial calculations based on the IMU located on the glasses device 3402. The connector can transmit information between the augmented reality system 3400 and the neckband 3405 and between the augmented reality system 3400 and the controller 3425. The information can be in the form of optical data, electrical data, wireless data, or any other transmittable data form. Moving the processing of information generated by the augmented reality system 3400 to the neck strap 3405 can reduce the weight and heat of the eyewear device 3402, making it more comfortable for the user.

[0191] The power supply 3435 in the neckband 3405 can provide power to the eyeglass device 3402 and / or the neckband 3405. The power supply 3435 can include, but is not limited to, lithium-ion batteries, lithium polymer batteries, lithium primary batteries, alkaline batteries, or any other form of power storage. In some cases, the power supply 3435 can be a wired power supply. Including the power supply 3435 on the neckband 3405 instead of on the eyeglass device 3402 can help better distribute the weight and heat generated by the power supply 3435.

[0192] As described, some artificial-reality systems can essentially replace one or more of a user's sensory perceptions of the real world with a virtual experience, rather than mixing the artificial reality with the actual reality. An example of this type of system is a head-mounted display system, such as Fig.35 Virtual reality system 3500 in which most or all of the user's field of view is covered. Virtual reality system 3500 may include a front rigid body 3502 and a band 3504 shaped to fit around the user's head. Virtual reality system 3500 may also include output audio transducers 3506 (A) and 3506 (B). In addition, although in Fig.35 Not shown, but front rigid body 3502 may include one or more electronic components, including one or more electronic displays, one or more inertial measurement units (IMUs), one or more tracking transmitters or detectors, and / or any other suitable device or system for creating an artificial-reality experience.

[0193] Artificial-reality systems may include various types of visual feedback mechanisms. For example, the display devices in the augmented reality system 3400 and / or the virtual reality system 3500 may include one or more liquid crystal displays (LCD), light emitting diode (LED) displays, organic LED (OLED) displays, digital light project (DLP) microdisplays, liquid crystal on silicon (LCoS) microdisplays, and / or any other suitable type of display screen. The artificial-reality system may include a single display screen for both eyes or a display screen may be provided for each eye, which may allow additional flexibility for zoom adjustment or for correcting the user's refractive error. Some of these artificial reality systems may also include an optical subsystem having one or more lenses (e.g., conventional concave or convex lenses, Fresnel lenses, adjustable liquid lenses, etc.) through which a user can view the display screen. These optical subsystems may be used for various purposes, including collimation (e.g., making an object appear to be at a greater distance than its physical distance), magnification (e.g., making an object appear larger than its actual size), and / or transmission (e.g., to the viewer's eyes) of light. These optical subsystems can be used in non-pupil forming architectures (such as a single lens configuration, which directly collimates light but results in so-called pincushion distortion) and / or pupil forming architectures (such as a multi-lens configuration, which produces so-called barrel distortion to offset pincushion distortion).

[0194] In addition to or in lieu of using a display screen, some of the artificial reality systems may include one or more projection systems. For example, a display device in the augmented reality system 3400 and / or virtual reality system 3500 may include a micro-LED projector that projects light into the display device (using, for example, a waveguide), such as a transparent combiner lens that allows ambient light to pass through. The display device may refract the projected light into the user's pupil, and may enable the user to view both the artificial-reality content and the real world simultaneously. The display device may use any of a variety of different optical components to achieve this, including waveguide components (e.g., holographic, planar, diffractive, polarizing and / or reflective waveguide elements), light manipulation surfaces and elements (such as diffractive, reflective and refractive elements and grids), coupling elements, etc. The artificial-reality system may also be configured with any other suitable type or form of image projection system, such as a retinal projector for a virtual retinal display.

[0195] The artificial reality system may also include various types of computer vision components and subsystems. For example, the augmented reality system 3400 and / or the virtual reality system 3500 may include one or more optical sensors, such as two-dimensional 2D or 3D cameras, structured light emitters and detectors, time-of-flight depth sensors, single-beam or scanning laser rangefinders, 3D LiDAR sensors, and / or any other suitable type or form of optical sensor. The artificial-reality system may process data from one or more of these sensors to identify the user's location, to map the real world, to provide context to the user about the real-world environment, and / or to perform various other functions.

[0196] The artificial reality system may also include one or more input and / or output audio transducers. Fig.35 In the example shown, the output audio transducers 3506(A) and 3506(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 transducers. Similarly, the input audio transducers may include condenser microphones, dynamic microphones, ribbon microphones, and / or any other type or form of input transducers. In some embodiments, a single transducer may be used for both audio input and audio output.

[0197] Although not in Fig.34. However, the artificial-reality system may include a tactile (i.e., haptic) feedback system that may be incorporated into headgear, gloves, tights, handheld controllers, environmental equipment (e.g., chairs, floor mats, etc.), and / or any other type of device or system. The tactile feedback system may provide various types of skin feedback, including vibration, force, traction, texture, and / or temperature. The tactile feedback system may also provide various types of kinesthetic feedback, such as motion and compliance. Tactile feedback may be implemented using motors, piezoelectric actuators, fluid systems, and / or various other types of feedback mechanisms. The tactile feedback system may be implemented independently of, within, and / or in combination with other artificial-reality devices.

[0198] By providing tactile, auditory content and / or visual content, artificial-reality systems can create a complete virtual experience or enhance the user's real-world experience in various backgrounds and environments. For example, artificial-reality systems can help or expand the user's perception, memory or cognition in a specific environment. Some systems can enhance the user's interaction with other people in the real world, or can achieve a more immersive interaction with other people in the virtual world. Artificial-reality systems can also be used for educational purposes (e.g., for teaching or training in schools, hospitals, government organizations, military organizations, commercial 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 can realize or enhance the user's artificial-reality experience in one or more backgrounds and environments and / or other backgrounds and environments in these backgrounds and environments.

[0199] The process parameters and order of steps described and / or illustrated herein are provided as examples only and may be changed as desired. For example, although the steps illustrated and / or described herein may be illustrated or discussed in a particular order, the steps do not necessarily need to be performed in the order illustrated or discussed. The various exemplary methods described and / or illustrated herein may also omit one or more of the steps described or illustrated herein, or include additional steps in addition to the disclosed steps.

[0200] The foregoing description has been provided to enable others skilled in the art to best utilize the various aspects of the exemplary embodiments disclosed herein. This exemplary description is not intended to be exhaustive or limited to any precise form disclosed. Many modifications and variations are possible without departing from the spirit and scope of the present disclosure. The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The attached claims and their equivalents should be referenced when determining the scope of the present disclosure.

[0201] Unless otherwise indicated, the terms "connected to" and "coupled to" (and their derivatives) as used in the specification and claims should be interpreted as allowing both direct and indirect (i.e., via other elements or components) connections. In addition, the terms "a" or "an" as used in the specification and claims should be interpreted as meaning "at least one". Finally, for ease of use, the terms "including" and "having" (and their derivatives) as used in the specification and claims may be interchangeable with the word "comprising" and have the same meaning.

[0202] As used herein, in certain embodiments, the term "about" with respect to a particular numerical value or numerical range can mean and include the numerical value and all values ​​within 10% of the numerical value. Thus, as an example, in certain embodiments, a reference to a numerical value of "50" as "about 50" can include values ​​equal to 50±5, i.e., values ​​in the range of 45 to 55.

[0203] As used herein, the term "substantially" with reference to a given parameter, property, or condition may mean and encompass that a person skilled in the art will understand to a certain extent that the given parameter, property, or condition complies with a small degree of variance, such as within acceptable manufacturing tolerances. As an example, depending on the particular parameter, property, or condition that is substantially complied with, the parameter, property, or condition may be at least about 90% complied with, at least about 95% complied with, or even at least about 99% complied with.

[0204] It should be understood that when an element such as a layer or region is referred to as being formed, deposited, or disposed “on” or “over” another element, it can be directly on at least a portion of the other element, or one or more intervening elements may also be present. Conversely, when an element is referred to as being “directly on” or “directly over” another element, it can be on at least a portion of the other element, with no intervening elements present.

[0205] Although the transition phrase "comprising" may be used to disclose various features, elements, or steps of a particular embodiment, it should be understood that alternative embodiments, including those embodiments that may be described using the transition phrases "consisting of" or "consisting essentially of," are implied. Thus, for example, implicit alternative embodiments of a non-volatile dielectric material that comprises or includes paraffin oil include embodiments in which the non-volatile dielectric material consists essentially of paraffin oil and embodiments in which the non-volatile dielectric material consists of paraffin oil.

Claims

1. A method, wherein: The method comprises: forming a molecular raw material comprising an organic solid crystal precursor and a molecular dopant; forming a layer of the molecular material over a surface of a substrate; forming crystal nuclei from the organic solid crystalline precursor within the nucleation region of the layer of the molecular feedstock; and The crystal nuclei are grown to form a doped organic solid crystal thin film.

2. The method according to claim 1, wherein: The organic solid crystal precursor includes a crystallizable organic molecule.

3. The method according to claim 1, wherein: The organic solid crystal precursor includes a hydrocarbon compound selected from the group consisting of anthracene, phenanthrene, tolanthyl, thiophene, pyrene, cyclopentene, fluorene, biphenyl, terphenyl and phthalocyanine.

4. The method according to claim 1, wherein: The molecular dopant is configured to modulate the HOMO-LUMO energy gap in the doped organic solid crystal film.

5. The method according to claim 1, wherein: The concentration of the molecular dopant within the organic solid crystal thin film ranges from about 0.01 wt. % to about 50 wt. %.

6. The method according to claim 1, wherein: The molecular starting material includes a heterocycle selected from the group consisting of furan, pyrrole, thiophene, pyridine, pyrimidine and piperidine.

7. The method according to claim 1, wherein: The layer of the molecular raw material is molten prior to forming the crystal nucleus.

8. The method according to claim 1, wherein: Forming the crystal nuclei within the nucleation zone includes heating the layer of the molecular feedstock to a temperature below a melting onset temperature of the organic solid crystalline precursor.

9. The method according to claim 1, wherein: The method further comprises: forming a layer of non-volatile dielectric material over the surface of the substrate; and The layer of the molecular raw material is formed directly over the layer of the non-volatile dielectric material.

10. The method according to claim 1, wherein: The method further comprises: forming a seed layer over the surface of the substrate; and The layer of the molecular feedstock is formed directly over the seed layer.

11. The method according to claim 1, wherein: The method also includes positioning a cover plate over the layer of molecular feedstock while growing the nuclei.

12. The method according to claim 11, wherein: The cover plate is inclined at a certain angle relative to the surface of the substrate.

13. The method according to claim 1, wherein: The organic solid crystal thin film includes a single crystal layer.

14. The method according to claim 1, wherein: The organic solid crystal thin film includes a polycrystalline layer.

15. A method, wherein: The method comprises: forming a layer of molecular raw material over a surface of a substrate, the molecular raw material comprising an organic solid crystal precursor and a molecular dopant; forming an organic solid crystalline film from said layer of said molecular raw material; forming a main electrode over the first portion of the organic solid crystal thin film; forming a sub-electrode over the second portion of the organic solid crystal thin film; and The bias state between the primary electrode and the secondary electrode is changed by an amount effective to change an optical property of the organic solid crystal thin film.

16. The method according to claim 15, wherein: The optical property is selected from the group consisting of: refractive index, birefringence, and absorptivity of visible light.

17. The method according to claim 15, wherein: Changing the bias state changes the refractive index of the organic solid crystal film by at least about 0.

01.

18. The method according to claim 15, wherein: Changing the bias state changes the birefringence of the organic solid crystal film by at least about 0.

01.

19. The method according to claim 15, wherein: The organic solid crystal film comprises a refractive index of at least about 1.

9.

20. A method wherein: The method comprises: forming a layer comprising doped organic solid crystals; forming a main electrode over the first portion of the layer; and A secondary electrode is formed over the second portion of the layer.

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