mixture

Abstract

The present invention relates to a composition for manufacturing an optical layer containing a metal oxide. The composition may exhibit at least one of the characteristics of an advanced material or a high-performance material. The composition may be used in a nanotechnology process for manufacturing a liquid crystal, quantum dot, or OLED display manufactured on a substrate controlled by a semiconductor chip, for example, a semiconductor chip or a semiconductor device / display device application example.

Description

Technology Field

[0001] The present invention relates to a composition comprising a metal halide, a use of the composition, a method for manufacturing the composition, a method for manufacturing a composite, a composite, an optical device, and a display device. Background Technology

[0002] State-of-the-art optical devices typically include optical gratings made of composite materials that have a substrate as a support and a complex, interlaced pattern thereon, the pattern consisting of different layers or stacks of layers. Typically, the creation of such complex, interlaced patterns requires a structuring process, which becomes increasingly difficult as the size of the structural dimensions to be manufactured decreases.

[0003] In addition to a wide range of possible applications in various fields such as spectrometers or optical storage systems (CDs, DVDs, etc.), diffraction gratings are typically a core component of so-called XR devices, which are usually in the form of glasses. In this context, R stands for the term reality, and X represents various attributes such as virtual, augmented, or mixed. Thus, diffraction gratings form part of the core of the so-called optical engine in XR devices, specifically in augmented reality and mixed reality glasses. When virtual reality glasses are manufactured as head-mounted displays, they often consist of conventional liquid crystal displays (LCDs) or organic light-emitting diode displays (OLEDs) embedded in the device directly in front of the user's eyes, so diffraction gratings are not strictly necessary. In contrast, augmented reality and mixed reality glasses are designed to allow consumers to obtain a visual impression of their environment, which, in the best case, is possible as if they were not wearing glasses at all. However, this also enables the provision, transmission, and projection of digital information into the individual's field of vision. Additional digital information is collected by perceiving and analyzing the environment that the individual is examining or looking at. To deliver and project supporting digital information into an individual's eyes, augmented reality or mixed reality glasses are equipped with an information supply unit, which is coupled to an optical waveguide system that delivers optically coded supporting information directly to the eye of the glasses. Here, the information passes through a diffraction grating, which couples the incident light into the eye and splits it according to angular information and spectral bands by diffraction. After the optical incoupling, the eye acts as a waveguide that enables the light to be delivered to and into the individual's pupil. The location of the optical incoupling is independent of any preferred location and is therefore independent of the constraints of technical requirements.The direction of light passage within the eyepiece is determined by diffraction gratings that diffract or split the light. At specific locations within the eyepiece, the second and third diffraction gratings serve to change the direction of light passage, thereby forcing the light into the user's pupil. Since light passage within the glasses is carried out by total internal reflection (TIR), the light bounces off glass interfaces multiple times until it reaches other diffraction gratings, thereby changing the direction of the TIR (see FIG. 2). Because the second and third gratings are geometrically aligned in different directions relative to the first grating and the coupling grating—for example, by a specific angular distortion of the longitudinal axis—the direction of propagation of the total internal reflection light can be changed. Needless to say, the eyepiece itself or the material constituting the eyepiece must not be absorptive. Otherwise, the supporting information will never reach the user's pupil or will only reach it with a very weakened light intensity. This process operates regardless of the use of reflective or transmissive gratings. Typically, the eyepiece is equipped with both types of gratings to properly guide the light. It should also be noted that while there are differences in the optical performance of reflection gratings and transmission gratings, this is no longer significant in the context of the present invention. The basic structure of the gratings is very similar, which is more important at this point.

[0004] Nevertheless, various designs and structures exist to achieve waveguides, such as surface relief (SR) or volume phase holographic (VPH) gratings. The two types are very similar in appearance. In the simplest case, the grating is mounted on the surface of the waveguide material, in this case, the edge. The grating itself consists of an array of microstructures, usually but not limited to trenches of Material 01 having a refractive index RI 01 of the first material type. The geometric shape of the trenches can vary from square to V-shaped, U-shaped, etc. The width, geometric shape, and pitch of the trenches, as well as the depth, including structures of different widths, are specifically designed to influence the diffraction pattern of the incident light to be diffracted.

[0005] In the case of a VPH grating, a trench or structure of a first material type (Material 01) having a refractive index (RI 01) is filled by a second material type (Material 02) having a refractive index (RI 02), wherein RI 02 is incrementally different from RI 01 (see FIG. 1 and FIG. 3). For completeness, it should be noted that Material 01 or Material 02 may consist of a stack of structured layers containing different material compositions having different refractive indices, stacked on top of each other, thereby forming Material 01 or Material 02 having an effective or graded refractive index RI 01 or RI 02, respectively. Incidentally, the (effective or graded) refractive indices RI 01 and RI 02 depend on the refractive index of the waveguide or lens constituting the glasses. When glass lenses with a high refractive index (nO3 > 1.46) are used, the (effective or oblique) refractive index of Material O1 and Material O2 is considered to be higher than the refractive index of the lens itself, and accordingly, the RI value can reach and exceed 2.0. Surface relief (SR) gratings may look similar and may contain the second type of material as a trench filler, but the trenches may be just air. High-performance gratings, particularly VPH type gratings, can be manufactured using standard lithography and film deposition techniques known from microfabrication, such as the manufacture of integrated circuits, for example.

[0006] These standard techniques typically involve physical vapor deposition (PVD) or chemical vapor deposition (CVD) processes and often suffer from incomplete gap filling due to adverse film and / or layer growth characteristics, including increased film and / or growth rates at corners and edges. This incomplete gap filling results in the formation of voids within the structure that must be filled by the PVD and CVD materials. In addition to void formation, the surface of the substrate is covered with a PVD and / or CVD layer nearly as thick as the maximum depth of the deepest structure that must be filled by the deposited gap-filling material (see Figs. 4 and 5). However, in some applications, it may be necessary to expose the surface of the substrate so that it can be used for further processing. Consequently, the unwanted overburden layer resulting from the PVD or CVD must be removed, for example, by chemical mechanical planarization (CMP) without damaging the original substrate surface underneath. Although CMP is a very well-established process in integrated circuit manufacturing, it is a time-consuming and costly process and can be considered a potential economic disadvantage in the mass production of state-of-the-art optical devices, particularly in the mass production of diffraction gratings. Therefore, it would be desirable to have a solution for the advanced and cost-effective fabrication of optical gratings where gap filling does not require CMP (see Fig. 6).

[0007] For this reason, more cost-effective production technologies are needed to reduce holding costs.

[0008] Summary of the Invention

[0009] The inventors have newly discovered that one or more important problems requiring improvement still exist, as listed below:

[0010] Expanding the parameter space to enable tuning of optical parameters / optical properties of an optical layer / composite obtained through a combination of at least two metal precursors; optimizing the solid content in the formulation by improving the solubility of the metal precursor; changing / optimizing the solvent of the formulation; providing a printable formulation for manufacturing an optical layer / composite containing a material that provides a sufficiently high refractive index after curing, i.e., after low-temperature curing; providing a formulation for manufacturing an optical layer / composite capable of manufacturing a high-density, crack-free or crack-free optical layer and capable of filling cavities, trenches, or gaps after curing; providing a formulation for manufacturing an optical layer / composite containing a metal oxide precursor material of a high refractive index material that is well dispersed within the formulation; a simpler and / or more cost-effective method for manufacturing an optical layer / composite using the formulation; realizing a more stable formulation; Providing a formulation suitable for wet printing, i.e., spin-coating or inkjetting, and realizing continuous inkjet printing.

[0011] The inventors aimed to solve one or more of the aforementioned problems.

[0012] Subsequently, the inventors surprisingly discovered that one or more of the above technical problems could be solved by the features defined in the claims.

[0013] That is, a novel formulation has been discovered comprising at least the following, or essentially consisting of or consisting of the following, which is preferably used to manufacture an optical layer comprising a metal oxide or to fill one or more trenches on a patterned or non-uniform surface of a substrate:

[0014] A first metal halide represented by any one of the following chemical formulas (I) to (V);

[0015] A second metal halide represented by any one of the following chemical formulas (I') to (V'); and

[0016] menstruum.

[0017]

[0018] In the above formula,

[0019] M 1 Silver is a divalent metal, and preferably M 1 It is selected from Zn or Sn;

[0020] M 2 is a trivalent metal, and preferably M 2 is Bi and;

[0021] M 3 It is a tetravalent metal selected from Zr, Ti, or Hf;

[0022] M 4 is a pentavalent metal selected from V, Nb, or Ta;

[0023] M 5 is Mo or W;

[0024] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 It is Cl.

[0025]

[0026] In the above formula,

[0027] M 1'Silver is a divalent metal, and preferably M 1' It is selected from Zn or Sn;

[0028] M 2' Silver is a trivalent metal, and preferably M 2' is Bi;

[0029] M 3' It is a tetravalent metal selected from Zr, Ti, or Hf;

[0030] M 4' It is a pentavalent metal selected from V, Nb, or Ta;

[0031] M 5' is Mo or W;

[0032] X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' is Cl;

[0033] The first metal halide and the second metal halide are different from each other;

[0034] The weight ratio of the second metal halide to the first metal halide is less than 1, preferably in the range of 0.01 to 1. Preferably, the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%.

[0035] In another aspect, the present invention also relates to the use of the formulation of the present invention for manufacturing a composite, preferably for manufacturing a layered composite, more preferably for manufacturing an optical layer, or for filling one or more trenches of a patterned surface or a non-uniform surface of a substrate.

[0036] In another aspect, the present invention also relates to a method for preparing a mixture of the present invention, comprising at least the following step (A) or essentially consisting of the following step (A):

[0037] (A) A step of mixing a first metal halide represented by any one of the following chemical formulas (I) to (V), a second metal halide represented by any one of the following chemical formulas (I') to (V'), and a solvent.

[0038]

[0039] In the above formula,

[0040] M 1 Silver is a divalent metal, and preferably M 1 is Zn or Sn;

[0041] M 2 is a trivalent metal, and preferably M 2 is Bi and;

[0042] M 3 It is a tetravalent metal selected from Ti, Zr, or Hf;

[0043] M 4 is a pentavalent metal selected from V, Nb, or Ta;

[0044] M 5 is Mo or W;

[0045] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 It is Cl.

[0046]

[0047]

[0048] In the above formula,

[0049] M 1' Silver is a divalent metal, and preferably M 1' is Zn or Sn;

[0050] M 2' Silver is a trivalent metal, and preferably M 2' is Bi;

[0051] M 3' It is a tetravalent metal selected from Ti, Zr, or Hf;

[0052] M 4' It is a pentavalent metal selected from V, Nb, or Ta;

[0053] M 5' is Mo or W;

[0054] X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X3' , X 4' , X 5' , X 6' is Cl;

[0055] The first metal halide and the second metal halide are different from each other;

[0056] The weight ratio of the second metal halide to the first metal halide is 1 or less, preferably in the range of 0.01 to 1. Preferably, the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%.

[0057] In another aspect, the present invention also relates to a method for preparing a composite containing a metal oxide, wherein, preferably, the metal oxide is selected from a metal monooxide, a metal dioxide and a metal pentoxide, or a combination thereof, and the method comprises the following steps (a) and (b):

[0058] (a) providing the composition of the present invention to the surface of a substrate, preferably by a wet film deposition method, more preferably by spin-coating or area-selective printing (preferably the area-selective printing is ink-jetting), more preferably by ink-jetting; and

[0059] (b) a step of applying heat treatment to a mixture provided on the surface of a substrate to convert at least a portion of the metal oxide precursors of the mixture into metal oxides.

[0060] Preferably, the composite is a layered composite, and more preferably, the layered composite is an optical layer.

[0061] In another aspect, the present invention also relates to a composite, preferably a layered composite, obtained or obtainable by the method of the present invention, preferably said layered composite is an optical layer.

[0062] In another aspect, the present invention also relates to a composite derived from a composition of the present invention, preferably a layered composite, wherein the layered composite is preferably an optical layer.

[0063] In another aspect, the present invention also relates to an optical device comprising a composite of the present invention and a substrate comprising a patterned surface or a non-uniform surface. Preferably, gaps or trenches in the patterned surface or non-uniform surface of the substrate are at least partially filled with the composite.

[0064] Preferably, the substrate is a patterned substrate having topographic features on its surface. Preferably, the composite fills at least a portion of the gaps of the topographic features, and more preferably, the composite fills the trenches of the patterned substrate.

[0065] In another aspect, the present invention also relates to a display device comprising at least one functional medium configured to induce and control light or to emit light; and a composite of the present invention.

[0066] Technical effects of the invention

[0067] The present invention may provide one or more of the following effects:

[0068] Expanding the parameter space to enable tuning of optical parameters / optical properties of an optical layer / composite obtained through a combination of at least two metal precursors; optimizing the solid content in the formulation by improving the solubility of the metal precursor; changing / optimizing the solvent of the formulation; providing a printable formulation for manufacturing an optical layer / composite containing a material that provides a sufficiently high refractive index after curing, i.e., after low-temperature curing; providing a formulation for manufacturing an optical layer / composite capable of manufacturing a high-density, crack-free or crack-free optical layer and capable of filling cavities, trenches, or gaps after curing; providing a formulation for manufacturing an optical layer / composite containing a metal oxide precursor material of a high refractive index material that is well dispersed within the formulation; a simpler and / or more cost-effective method for manufacturing an optical layer / composite using the formulation; realizing a more stable formulation; Providing a formulation suitable for wet printing, i.e., spin-coating or ink jetting, and realizing continuous inkjet printing.

[0069] Preferred embodiments of the present invention are described below and in independent claims. Brief explanation of the drawing

[0070] Fig. 1 : A schematic cross-sectional view of a VPH grating having Material 01 and Material 02, wherein the refractive index RI 01 of Material 01 differs incrementally from the refractive index RI 02 of Material 02. Fig. 2 : Schematic cross-sectional view of a VPH grating that enables optical diffraction (in the case of a transmission type) including the propagation of diffracted light within a waveguide (e.g., a lens) by total internal reflection. Fig. 3: A schematic cross-sectional view of a VPH grid providing a gap (trench) to be filled with a high refractive index material (Material O2), wherein the refractive index of Material O2 is incrementally different from the refractive index of Material O1 located on the side of the gap (trench). Fig. 4 Schematic diagram of PVD or CVD-mediated gap filling process and removal of unwanted overburden. Fig. 5 Schematic diagram of a PVD or CVD-mediated gap filling process that creates and leaves voids within the gap and the deposited layer. Fig. 6 Schematic diagram of a gap filling process using a compound containing a metal complex of the present invention that is converted into a metal oxide, or a compound thereof. List of reference symbols 1. Material O2 having RI O2 2. Material 01 having RI 01 3. Substrate (e.g., glass) 4. Diffraction of incident light indicated by the broad arrow 5. Total Internal Reflection (TIR) 6. Waveguide 7. Structured layer stack with gaps (trench) 8. Substrate (e.g., glass or silicon) 9. Overburden of the material (e.g., high refractive index materials or high etching-resistant materials) 10. A material that provides gap filling (e.g., a high refractive index material or a high etching-resistant material) 11. Void 12. Compounds of high-refractive-index materials (e.g., metal oxide precursors) (e.g., ink) 13. High-refractive-index materials (e.g., metal oxides) providing gap filling with optional concave geometric shapes 14. Overburdened Floor (Optional) 15. Energy Specific details for implementing the invention

[0071] Definition of Terms

[0072] In the context of the present invention, the term “combination medium” or the plural term “combination media” as used herein refers to one or more compounds that act as a solvent, suspending agent, carrier, and / or matrix for the metal oxide precursor compound and any other component included in the combination. The combination medium is generally an inert compound that does not react with the metal oxide precursor compound and the other component. The combination medium may be a liquid compound, a solid compound, or a mixture thereof. Typically, the combination medium is an organic compound.

[0073] The term "surfactant" as used herein refers to an additive that reduces the surface tension of a specified formulation.

[0074] As used herein, the terms "wetting agent and dispersant" refer to additives that increase the diffusion and filling characteristics of a given formulation. In this way, the tendency of molecules to adhere to each other is reduced.

[0075] The term "adhesion promoter" as used herein refers to an additive that increases the adhesive strength of a specified formulation.

[0076] The term "polymer matrix" as used herein refers to an additive that acts as a macromolecular matrix for one or more components of a given formulation.

[0077] As used herein, the term “optical device” relates to a device comprising one or more optical components for forming a light beam, including but not limited to gratings, lenses, prisms, mirrors, optical windows, filters, polarizing optical elements, UV and IR optical elements, waveguides, and optical coatings. In the context of the present invention, a preferred optical device is a waveguide for an augmented reality (AR) device, a virtual reality (VR) device, and / or a mixed reality (MR) device, or a preferred optical device is an augmented reality (AR) glasses, a virtual reality (VR) glasses, and / or a mixed reality (MR) glasses.

[0078] As used herein, the term "display device" refers to a type of optical device configured to output / represent information in a visual or tactile form. Examples include liquid crystal displays (LCDs), light-emitting diode displays (LED displays), organic light-emitting diode displays (OLEDs), micro-LED displays, quantum dot displays (QLEDs), AR displays, VR displays, MR displays, plasma display (PDP) displays, and electroluminescent (ELD) displays. In the context of the present invention, a preferred optical device is an AR display, a VR display, or an MR display.

[0079] Detailed description of the invention

[0080] The present invention relates to a formulation comprising or essentially consisting of, or consisting of, for the manufacture of an optical layer containing a metal oxide, preferably for the manufacture of a composite, more preferably for the manufacture of a layered composite:

[0081] - A first metal halide represented by any one of chemical formulas (I) to (V),

[0082] - A second metal halide represented by any one of the chemical formulas (I') to (V'), and

[0083] - Solvent.

[0084]

[0085] In the above formula,

[0086] M 1 Silver is a divalent metal, and preferably M 1 is Zn or Sn;

[0087] M 2 is a trivalent metal, and preferably M 2 is Bi and;

[0088] M 3 It is a tetravalent metal selected from Zr, Ti, or Hf;

[0089] M 4 is a pentavalent metal selected from V, Nb, or Ta;

[0090] M 5 is Mo or W;

[0091] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 It is Cl.

[0092]

[0093] In the above formula,

[0094] M 1' Silver is a divalent metal, and preferably M 1' It is selected from Zn or Sn;

[0095] M2' Silver is a trivalent metal, and preferably M 2' is Bi;

[0096] M 3' It is a tetravalent metal selected from Zr, Ti, or Hf;

[0097] M 4' It is a pentavalent metal selected from V, Nb, or Ta;

[0098] M 5' is Mo or W;

[0099] X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' is Cl;

[0100] The first metal halide and the second metal halide are different from each other;

[0101] The weight ratio of the second metal halide to the first metal halide is less than 1, preferably in the range of 0.01 to 1. Preferably, the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%.

[0102] - First metal halide

[0103] According to the present invention, the first metal halide is represented by one of the following chemical formulas (I) to (V):

[0104]

[0105] In the above formula,

[0106] M 1 Silver is a divalent metal, and preferably M 1 is Zn or Sn;

[0107] M 2 is a trivalent metal, and preferably M 2 is Bi and;

[0108] M 3 It is a tetravalent metal selected from Zr, Ti, or Hf;

[0109] M 4 is a pentavalent metal selected from V, Nb, or Ta;

[0110] M 5 is Mo or W;

[0111] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 It is Cl.

[0112] As the first metal halide mentioned above, a publicly known metal halide belonging to one of the aforementioned chemical formulas may be used.

[0113] Examples of first metal halides are W halide, Ta halide, Sn halide, Zr halide, Zn halide, Bi halide, Mo halide, Ti halide, V halide, Hf halide, or any combination of these.

[0114] More preferably, the first metal halide is selected from ZnCl2, BiCl3, ZrCl4, TiCl4, HfCl4, TaCl5, NbCl5, VCl5, WCl6, MoCl6, or any combination of these.

[0115] - Second metal halide

[0116] According to the present invention, the second metal halide is represented by one of the following chemical formulas (I') to (V');

[0117]

[0118] In the above formula,

[0119] M 1' Silver is a divalent metal, and preferably M 1' It is selected from Zn or Sn;

[0120] M 2' Silver is a trivalent metal, and preferably M 2' is Bi;

[0121] M 3' It is a tetravalent metal selected from Zr, Ti, or Hf;

[0122] M 4' It is a pentavalent metal selected from V, Nb, or Ta;

[0123] M 5' is Mo or W;

[0124] X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' It is Cl.

[0125] According to the present invention, the first metal halide and the second metal halide are different from each other;

[0126] The weight ratio of the second metal halide to the first metal halide is 1 or less, preferably in the range of 0.01 to 1. Preferably, the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%.

[0127] As the second metal halide mentioned above, a publicly known metal halide belonging to one of the aforementioned chemical formulas may be used.

[0128] Examples of second metal halides are Sn halide, W halide, Ta halide, Sn halide, Zr halide, Zn halide, Bi halide, Mo halide, Ti halide, V halide, Hf halide, or any combination of these.

[0129] More preferably, the second metal halide precursor is selected from ZnCl2, SnCl2, BiCl3, ZrCl4, TiCl4, HfCl4, TaCl5, NbCl5, VCl5, WCl6, MoCl6, or any combination of these.

[0130] According to the present invention, the total content of all metal halide(s) in the mixture is in the range of 0.1% to 50% by weight, preferably 1% to 30% by weight, more preferably 5% to 20% by weight, based on the total mass of the mixture.

[0131] The total amount of the aforementioned metal halide precursor, based on the total amount of the formulation, is considered suitable for realizing improved gap filling or for manufacturing a thin layer placed on a patterned surface of a substrate / underlayer or directly on a non-uniform surface.

[0132] - Solvent

[0133] According to the present invention, the composition of the present invention contains a solvent.

[0134] In a preferred embodiment of the present invention, the solvent is an organic solvent. More preferably, the organic solvent is an ethylene glycol monoalkyl ether, preferably an ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and / or ethylene glycol monobutyl ether; a diethylene glycol dialkyl ether, preferably an diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and / or diethylene glycol dibutyl ether; a propylene glycol monoalkyl ether, preferably an propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether and / or propylene glycol monopropyl ether; 1,3-dimethoxy-2-propanol, an ethylene glycol alkyl ether acetate, preferably a methyl cellosolve acetate and / or ethyl cellosolve acetate; Selected from one or more members of the group consisting of propylene glycol alkyl ether acetate, preferably propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and / or propylene glycol monopropyl ether acetate; ketone, preferably methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and / or cyclohexanone; alcohol, preferably ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, triethylene glycol and / or glycerin; ester, preferably ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and / or ethyl lactate; and cyclic ester, preferably gamma-butyro-lactone;Preferably, the solvent is ethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol, ethylene glycol, propylene glycol monoalkyl ether, ethylene glycol alkyl ether acetate, propylene glycol alkyl ether acetate, and more preferably, the solvent is propylene glycol alkyl ether acetate, ethylene glycol monoalkyl ether, propylene glycol and propylene glycol monoalkyl ether, 1,3-dimethoxy-2-propanol.

[0135] Printing of structures, particularly inkjet printing, is considered a highly cost-effective production step. Spin-coating is a convenient method and is desirable for forming a uniform thin layer. Accordingly, suitable solvents for spin-coating / inkjet printing structures or for filling cavities and structures are described herein.

[0136] After printing, forming, and filling the structure, at least a portion of the material as a metal halide precursor needs to be converted into each metal oxide by any known means (thermal, photochemical, etc.) known to those skilled in the art.

[0137] - water

[0138] According to the present invention, the mixture contains water, and the stoichiometric amount of water is in the range of 100 to 400 mol% based on the total amount of metal oxide precursor, preferably the stoichiometric amount of water based on the total amount of metal oxide precursor is in the range of 150 to 300 mol%, more preferably 180 to 270 mol%.

[0139] - Additives

[0140] In some embodiments of the present invention, the formulation may optionally include a surfactant, a wetting agent and a dispersant, an adhesion promoter, and one or more additives selected from a polymer matrix.

[0141] Or, in some embodiments, the formulation of the present invention does not contain any additives.

[0142] In a preferred embodiment of the present invention, the formulation is an ink formulation suitable for inkjet printing. Typical requirements for the ink formulation are a surface tension in the range of 20 mN / m to 30 mN / m and a viscosity in the range of 5 mPa·s to 30 mPa·s.

[0143] - Uses

[0144] In another aspect, the present invention also relates to the use of the formulation of the present invention for manufacturing an optical layer containing a metal oxide, preferably for manufacturing a composite, more preferably for manufacturing a layered composite. The present invention may also relate to the use of the formulation of the present invention for manufacturing an encapsulation layer of an electronic device.

[0145] - Method for preparing the mixture

[0146] In another aspect, the present invention also relates to a method for preparing a mixture of the present invention, comprising at least the following step (A) or essentially consisting of the following step (A):

[0147] (A) A step of mixing a first metal halide represented by any one of the following chemical formulas (I) to (V), a second metal halide represented by any one of the following chemical formulas (I') to (V'), and a solvent.

[0148]

[0149] In the above formula,

[0150] M 1 Silver is a divalent metal, and preferably M 1 It is selected from Zn or Sn;

[0151] M 2 is a trivalent metal, and preferably M 2 is Bi and;

[0152] M 3 It is a tetravalent metal selected from Ti, Zr, or Hf;

[0153] M 4 is a pentavalent metal selected from V, Nb, or Ta;

[0154] M 5 is Mo or W;

[0155] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 It is Cl.

[0156]

[0157] In the above formula,

[0158] M 1' Silver is a divalent metal, and preferably M 1' is Zn and;

[0159] M 2' Silver is a trivalent metal, and preferably M 2' is Bi;

[0160] M 3' It is a tetravalent metal selected from Ti, Zr, or Hf;

[0161] M 4' It is a pentavalent metal selected from V, Nb, or Ta;

[0162] M 5' is Mo or W;

[0163] X1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' is Cl;

[0164] The first metal halide and the second metal halide are different from each other;

[0165] The weight ratio of the second metal halide to the first metal halide is 1 or less, preferably in the range of 0.01 to 1. Preferably, the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%.

[0166] - Method for manufacturing a composite containing a metal oxide

[0167] In another aspect, the present invention also relates to a method for preparing a composite containing a metal oxide, preferably said metal oxide is selected from a metal monooxide, a metal dioxide or a metal pentoxide, or a combination thereof, and said method comprises at least the following steps (a) and (b):

[0168] (a) a step of providing the formulation of the present invention to the surface of a substrate or to the surface of a sublayer disposed on the substrate, preferably by a wet film deposition process, more preferably by spin-coating or ink-jetting, and even more preferably by ink-jetting; and

[0169] (b) a step of applying heat treatment to a composition provided on the surface of a substrate or on the surface of a lower layer disposed on the substrate to convert at least a portion of the metal oxide precursors of the composition into metal oxides.

[0170] Preferably, the composite is a layered composite, and more preferably, the layered composite is an optical layer.

[0171] - Step (a)

[0172] According to the present invention, the composition may preferably be provided on the surface of a substrate or the surface of an underlying layer by a wet film deposition process. The wet film deposition process is drop casting, coating, or printing. A more preferred coating method is spin-coating, spray coating, slit coating, or slot-die coating. A more preferred printing method is flexographic printing, gravure printing, inkjet printing, EHD printing, offset printing, or screen printing. Additionally, preferred printing methods are spray coating and inkjet printing, and the most preferred is inkjet printing.

[0173] Accordingly, in a preferred embodiment, the formulation is applied to the surface of the substrate or the surface of the underlying layer by spin-coating or ink-jetting in step (a). From the perspective of cost-efficiency, ink-jetting may preferably be used.

[0174] In a preferred embodiment of the present invention, the formulation provided in step (a) of the method is an ink formulation suitable for inkjet printing. Typical requirements for the ink formulation are a surface tension in the range of 20 mN / m to 30 mN / m and a viscosity in the range of 5 mPa·s to 30 mPa·s.

[0175] Depending on the specific problem to be solved, the composition may need to be deposited as a homogeneous, dense, and thin layer covering the entire surface of the substrate or the entire surface of the underlying layer by a coating method, or a printing method may be required because the composition needs to be deposited locally in a structured manner. Both coating and printing methods require that the composition be formulated in an appropriate manner to comply with the physicochemical requirements of each coating and printing method and to comply with specific requirements regarding the surface of the substrate to be coated or printed.

[0176] In a preferred embodiment of the method of the present invention, the surface of the substrate is pretreated by a surface cleaning process. A preferred surface cleaning process is a silicon wafer cleaning process as described in the literature [W. Kern, The Evolution of Silicon Wafer Cleaning Technology, J. Electrochem. Soc., Vol. 137, 6, 1990, 1887-1892] and [New Process Technologies for Microelectronics, RCA Review 1970, 31, 2, 185-454]. Such a silicon wafer cleaning process comprises: a wet cleaning process comprising a cleaning solvent (e.g., isopropanol (IPA)); a wet etching process comprising a hydrogen peroxide solution (e.g., piranha solution, SC1 and SC2), a choline solution, or an HF solution; and a dry etching process comprising chemical vapor etching, UV / ozone treatment, or a glow discharge technique (e.g., O2 plasma etching). and includes mechanical processes including brush scrubbing, fluid jet, or ultrasonic techniques (ultrasonic treatment). The surface of the substrate may also be pretreated by silanization or atomic layer deposition (ALD) processes. Pretreatment of the substrate surface serves to modify the hydrophobicity / hydrophilicity of the surface. This can improve the adhesion and filling characteristics of the optical metal oxide layer on the substrate surface.

[0177] In a more preferred embodiment, a wet cleaning process comprising a cleaning solvent (e.g., isopropanol (IPA)) is combined with one or more of a wet etching process comprising a hydrogen peroxide solution (e.g., piranha solution, SC1 and SC2), a choline solution, or an HF solution; a dry etching process comprising chemical vapor etching, UV / ozone treatment, or a glow discharge technique (e.g., O2 plasma etching); and a mechanical process comprising brush scrubbing, a fluid jet, or an ultrasonic technique (ultrasonic treatment).

[0178] In the most preferred embodiment, a wet cleaning process comprising a cleaning solvent (e.g., isopropanol (IPA)) is combined with a mechanical process comprising brush scrubbing, fluid jet, or ultrasonic techniques (ultrasonic treatment), and a wet etching process comprising a hydrogen peroxide solution (e.g., piranha solution, SC1 and SC2), a choline solution, or an HF solution.

[0179] Accordingly, in a preferred embodiment, in step (a), the composition is applied to the surface of the substrate or the surface of the underlying layer by spin-coating or ink-jetting.

[0180] In a preferred embodiment, the composition is converted at least partially into a composite on the surface of a substrate or on the surface of an underlying layer, said composite containing a metal oxide, preferably a metal oxide selected from metal monoxide, metal dioxide and / or metal pentoxide; and a metal oxide precursor.

[0181] In a preferred embodiment, the substrate is a patterned substrate having topographic features on its surface. The patterned structure of the substrate may be a sublayer disposed on the substrate (e.g., a sublayer of a semiconductor device).

[0182] - Step (b)

[0183] The composition is believed to be at least partially converted into a metal oxide on the surface of the substrate or on the surface of the underlying layer by exposure to heat treatment in step (b) to form a complex. The complex is preferably a layered complex. And the solvent is typically removed in step (b).

[0184] A preferred heat treatment includes exposure to a high temperature of 50°C to 600°C, preferably 80°C to 500°C, more preferably 100°C to 300°C. It is believed that applying higher temperatures, such as in the range of 100°C to 600°C, preferably 125°C to 450°C, more preferably 150°C to 250°C, can achieve improved gap filling.

[0185] In step (a), it is preferable to achieve improved gap filling by using a formulation containing a metal oxide precursor in a smaller amount based on the total amount of the formulation, for example, in the range of 0.1 to 30 weight% based on the total amount of the formulation, more preferably in the range of 1 to 20 weight% based on the total amount of the formulation, and more preferably in the range of 5 to 15 weight% based on the total amount of the formulation, and in step (b), it is preferable to achieve improved gap filling by applying a higher temperature such as 100 to 600°C, preferably 125 to 450°C, more preferably 150 to 250°C.

[0186] The heat treatment method in step (b) is not limited to any specific heat treatment method or time. Depending on the type of substrate and composition, a person skilled in the art can determine a suitable heat treatment method.

[0187] In some embodiments of the method for manufacturing an optical metal oxide layer according to the present invention, a pre-baking step may be applied after step (a) and before step (b) to remove the solvent from the mixture. The mixture may also be partially converted into an optical metal oxide layer on the surface of a substrate by pre-baking (soft baking) at a temperature of 40 to 150°C, preferably 50 to 120°C, more preferably 60 to 100°C; and then baking (hard baking, sintering, or annealing) of step (b) is applied at a temperature of 100 to 600°C, preferably 125 to 450°C, more preferably 150 to 255°C.

[0188] Pre-baking (soft baking) achieves the purpose of removing volatile and low-boiling point components, such as volatile and low-boiling point formulation media or additives, from a drop-cast, coated, or printed film. Pre-baking is preferably performed for a period of 1 to 60 minutes. After pre-baking, a layer of a substrate adhesion film of a metal oxide precursor or a metal oxide precursor mixture is obtained. The film may still contain residual formulation media or additives.

[0189] In an alternative preferred embodiment of the method for manufacturing an optical metal oxide layer according to the present invention, pre-baking is omitted, and the mixture is directly converted into an optical metal oxide layer on the surface of the substrate or on the surface of the lower layer in step (b).

[0190] Baking (hard baking, sintering, or annealing) achieves the purpose of converting a layer of a metal oxide precursor or a mixture of metal oxide precursors on a substrate into a metal oxide layer. Additionally, the final properties of the metal oxide layer can be adjusted by the baking treatment. Baking is preferably performed for a time ranging from 1 to 60 minutes, preferably from 2 to 20 minutes, and more preferably from 3 to 10 minutes.

[0191] The above pre-baking and baking (step (b)) can be performed under an ambient atmosphere or an atmosphere with increased oxygen content to decompose unwanted organic components, which is believed to lead to lower activation energy when the composite is formed and improve the physicochemical properties of the resulting layered composite material.

[0192] In a preferred embodiment of the method of the present invention, a substrate or a sublayer is patterned to include topographic features on its surface, and a layered composite is preferably an optical layer and forms a coating layer that covers the surface of the substrate and fills the topographic features. As a result, the topographic features are filled and planarized by the composition.

[0193] Desirable topographic features include, for example, gaps, grooves, trenches, and vias. Topographic features may be distributed uniformly or non-uniformly on the surface of the substrate. Preferably, they are arranged in an array or grid on the surface of the substrate. It is desirable for the topographic features to have different lengths, widths, and diameters, as well as different aspect ratios. It is desirable for the topographic features to have an aspect ratio of 1:20 to 20:1, more preferably 1:10 to 10:1. The aspect ratio is defined as the width to the height (or depth) of the structure. In terms of dimensions, the depth of the topographic features is preferably in the range of 10 nm to 10 μm, more preferably 50 nm to 5 μm, and most preferably 100 nm to 1 μm.

[0194] In addition, it is desirable that the topographic feature be inclined at a specific angle, such as 10 to 80°, preferably 20 to 60°, more preferably 30 to 50°, and most preferably about 40°. Such inclined topographic feature is also referred to as a slanted or blazed topographic feature.

[0195] In addition, it may be necessary to locally fill the topographic features with an optical metal oxide layer, either completely or to a certain level, but not to cover adjacent surfaces of the substrate where the topographic features to be filled do not exist.

[0196] The substrate is preferably a substrate for an optical device. The preferred substrate is made of an inorganic or organic base material, preferably an inorganic base material. The preferred inorganic base material contains a material selected from a list consisting of ceramics, glass, fused silica, sapphire, silicon, silicon nitride, quartz, and transparent polymers or resins. The geometric shape of the substrate is not specifically limited, but a sheet or wafer is preferred.

[0197] In step (a) of the method, the composition is applied to the surface of a substrate or the surface of a sublayer, wherein the surface may be the surface of the base material of the substrate or the surface of a layer of material different from the base material of the substrate, and such a layer is formed before applying the composition.

[0198] In this way, sequences of different layers (layer stacks) can be formed on top of each other. These layer stacks can also be structured, and such structures typically have nanometer-scale dimensions with respect to at least diameter, width, and / or aspect ratio.

[0199] Accordingly, in a preferred embodiment, in step (b), the mixture is at least partially converted into a composite, preferably a layered composite, on the surface of a substrate by baking at a temperature of 50 to 400°C, preferably 80 to 350°C, more preferably 100 to 300°C.

[0200] In a preferred embodiment of the present invention, the heat treatment of step (b) is applied for a time ranging from 1 to 60 minutes, preferably from 2 to 20 minutes, more preferably from 3 to 10 minutes.

[0201] In some embodiments, the composition is converted at least partially into a composite on the surface of the substrate during the heat treatment process of step (b), said composite contains a metal oxide, preferably a metal oxide selected from metal monooxide, metal dioxide and / or metal pentoxide; and a metal alkoxide.

[0202] - complex

[0203] In another aspect, the present invention relates to a composite, preferably a layered composite, obtained or obtainable by the method of the present invention, preferably said layered composite is an optical layer.

[0204] In another aspect, the present invention relates to a composite derived from a composition of the present invention, preferably a layered composite, wherein the layered composite is preferably an optical layer.

[0205] In a preferred embodiment of the present invention, the complex comprises at least a metal oxide derived from a metal oxide precursor of the mixture, and a metal halide as a non-converted portion of the mixture used in step (a) of the method.

[0206] Accordingly, in some embodiments, the complex comprises at least one metal halide and a metal oxide derived from said metal halide. Preferably, said metal halide is a first metal halide. More preferably, the complex further comprises a second metal halide and a metal oxide derived from the second metal halide.

[0207] Details of the metal halides are shown in the first and second metal halide sections above.

[0208] - Optical device

[0209] The present invention relates to an optical device comprising a composite of the present invention that is preferably obtained or obtainable by the method of the present invention described above.

[0210] Preferably, the optical device is a device comprising one or more optical components for forming a light beam, including but not limited to gratings, lenses, prisms, mirrors, optical windows, filters, polarizing optical elements, UV and IR optical elements, waveguides, and optical coatings. In the context of the present invention, a preferred optical device is a waveguide for an augmented reality (AR) device, a virtual reality (VR) device, and / or a mixed reality (MR) device, or a preferred optical device is an augmented reality (AR) glasses, a virtual reality (VR) glasses, and / or a mixed reality (MR) glasses.

[0211] - Display device

[0212] Finally, the present invention relates to a display device comprising at least one functional medium configured to control light or to emit light, and a composite, or to an optical device of the present invention.

[0213] Examples of the display devices are selected from liquid crystal displays (LCD), light-emitting diode displays (LED displays), organic light-emitting diode displays (OLED), micro-LED displays, quantum dot displays (QLED), augmented reality (AR) hardware, virtual reality (VR) hardware, mixed reality (MR) hardware, plasma display (PDP) displays, and electroluminescent display (ELD) displays. The AR, VR, and MR hardware are also referred to as AR, VR, and MR displays. Preferably, the display device is AR hardware, VR hardware, or MR hardware.

[0214] The present invention is further described by the following examples, but should not be construed as limiting in any way. Those skilled in the art will recognize that various modifications, additions, and alternatives to the present invention may be made without departing from the spirit and scope of the invention as defined in the appended claims.

[0215] Examples

[0216] - Analysis and Measurement Methods

[0217] The layer thickness (nm), refractive index (n) (RI), and absorption index (k) of the metal oxide layer were determined using ellipsometry. Measurements were performed using a JA Woolam M2000 ellipsometer at three different angles of incidence (65°, 70°, and 75°). The measurement data were analyzed using JA Woolam's CompleteEase software, assuming complete or nearly complete transparent behavior at wavelengths greater than 600 nm (at 560 nm), and B-spline fitting was applied to obtain the absorption index (k) as well as the refractive index (n). Optical constants were averaged from three to four measured samples, each of which provides a different layer thickness after soft baking, after hard baking, or after a combination of soft baking and subsequent hard baking.

[0218] Typically, 2-inch diameter quartz and / or silicon wafers were used throughout all coating experiments, where flat and unstructured carriers were required for the metal oxide (e.g., spectroscopy and ellipsometry measurements).

[0219] SEM images were recorded using Tescan's Mira 3 LMU, Carl Zeiss's Sigma 300VP, or Carl Zeiss's Supra 35.

[0220] Coating of a substrate, typically a wafer, was performed using a Suess spin coater (LabSpin 150i). The spin coating process using a planar substrate is as follows: 0.5 ml of coating was deposited on a stationary quartz wafer, followed by rotation at a predetermined rotational speed for 30 seconds, with an acceleration of 500 rpm / s to reach the final rotational speed. 2The conditions were set as follows. Different layers and coating thicknesses were achieved using different coating formulations having different rotation speeds, different concentrations of metal oxide precursors, or mixtures of different metal oxide precursors. After spin coating, the coated substrates were heat-cured on a conventional laboratory hot plate. Typically, but not exclusively, the coated layers were baked at 100°C to 200°C for 1 to 10 minutes. Layer baking was performed using a Harry Gestigkeit high-temperature hot plate capable of reaching temperatures up to 600°C. The aforementioned conditions and parameters were applied to all subsequent experimental examples unless other conditions were explicitly mentioned elsewhere.

[0221] As an alternative film fabrication technique, inkjet printing can be used. The formulation can be loaded into a disposable cartridge (a Dimatix Materials Cartridge with a nominal droplet weight of 10 pL) and printed using laboratory-scale inkjet printing equipment (Dimatix Materials Printer DMP-2850 or Pixdro LP50). The temperature of the printhead and substrate holder can be set to 30°C. Squares of approximately 2 cm x 2 cm were printed at various resolutions to obtain different film thicknesses. After printing, the substrates were heat-dried and hard-baked.

[0222] Unless otherwise noted, all substrates were immersed in 2-propanol and sonicated for 10 minutes; subsequently, they were immersed in deionized water and sonicated for 10 minutes, and cleaned by drying on a hot plate at 100°C for 10 minutes. Afterward, the substrates were treated in an oxygen plasma oven (450 watts, 5 minutes).

[0223] A structured substrate, typically a silicon wafer, was used as a square die having an edge length of 1.5 cm to 2 cm. Wafer dies were cut and split from a mother wafer typically having a diameter of 12 inches. The structure consisted of SiO2 / SiN deposited on the wafer surface. x It is created and arranged in a layer stack composed of. The dimensions of the structure (e.g., cross-sectional width and length of the trench) represent the architecture of the Sematech mask 854. Typically, but not exclusively, to investigate the filling behavior by a wet chemically coated metal oxide precursor and / or a metal oxide obtained upon thermal conversion of said metal oxide precursor, cross-sectional sections perpendicular to a trench array providing a width of 40 nm to 50 nm were used as the trench structure of primary interest. In addition to the foregoing, trench filling by metal oxide was also investigated using cross-sections of a trench array having widths of 100 nm and 150 nm.

[0224] Structured wafer dies were coated by spin coating unless otherwise noted. To this end, the coating formulation was pipetted into a volume typically of 0.15 ml to 0.5 ml per die and cast onto the surface of the wafer. The formulation was allowed to spread and settle on the surface for 1 minute, followed by a step of dispensing and spreading the formulation over the entire surface of the wafer die at 500 rpm for 30 seconds, and then a final spin-off step was performed at 2,000 rpm for an additional 60 seconds. The acceleration of the rotational speed was 500 rpm / s 2 It was set to. The soft baking and hard conditions of the structured wafer die were selected to be similar or identical to those already mentioned for a flat substrate.

[0225] All chemicals for the described synthesis were purchased from Sigma Aldrich and used without further purification unless otherwise noted elsewhere. 98% anhydrous SnCl2 was used in the experiments described sequentially.

[0226] Work Example 1 : Preparation of Mixture 1

[0227] Formulation 1: A nominal solid content of NbCl5 (5 wt%) and SnCl22H2O (5 wt%) was prepared by dissolving it in 90 wt% PGME. A clear, transparent, and colorless solution was obtained, and it was filtered using a 0.2 μm syringe filter to remove any type of particles and other suspended substances.

[0228] Working Examples 2 and 3 : Preparation of Mixtures 2 and 3

[0229] Blend 2: was prepared by dissolving NbCl5 (5.6 wt%) and SnCl22H2O (4.4 wt%) in 90 wt% PGME with nominal solid content. Blend 3 was also prepared by changing the amounts of NbCl5 and SnCl22H2O, by dissolving NbCl5 (6.3 wt%) and SnCl22H2O (3.7 wt%) with nominal solid content in 90 wt% PGME.

[0230] Work Example 4 : Layer formation

[0231] Sample 1 (layer prepared from formulation 1, baking temperature 150℃ / 5 min) was prepared by the following process.

[0232] Formulation 1 of Work Example 1 (WE1) was spin-coated at 2,000 rpm onto an O2 plasma-pretreated Si3N4 / Si substrate having trenches 150 nm wide on the surface. Then, the coated layer was baked at 150°C for 5 minutes. Finally, Sample 1 was obtained.

[0233] Work Example 5 : Layer formation

[0234] Sample 2 (layer prepared from formulation 1, baking temperature 200℃ / 5 min), Sample 3 (layer prepared from formulation 1, baking temperature 250℃ / 5 min), and Sample 4 (layer prepared from formulation 1, baking temperature 300℃ / 5 min) were prepared in the same manner as described in the above work example 4, except that different baking temperature conditions were applied (200℃ / 5 min for Sample 2, 250℃ / 5 min for Sample 3, and 300℃ / 5 min for Sample 4).

[0235] Work Example 6 : Layer formation

[0236] Samples 5 (layer prepared from mixture 2, baking temperature 150°C / 5 min), 6 (layer prepared from mixture 2, baking temperature 200°C / 5 min), 7 (layer prepared from mixture 2, baking temperature 250°C / 5 min), 8 (layer prepared from mixture 2, baking temperature 300°C / 5 min), 9 (layer prepared from mixture 3, baking temperature 150°C / 5 min), 10 (layer prepared from mixture 3, baking temperature 200°C / 5 min), 11 (layer prepared from mixture 3, baking temperature 250°C / 5 min), and 12 (layer prepared from mixture 3, baking temperature 300°C / 5 min) were prepared in the same manner as described in the above work example 4, except that different baking temperature conditions and mixtures were used as mentioned in Table 1. These exhibit good gap filling characteristics.

[0237]

[0238] Operation Example 6: Measurement of Layer Thickness and Refractive Index (n) (RI) Values

[0239] The layer thickness and refractive index values ​​of each of samples 1 to 12 were evaluated using ellipsometry. Table 2 shows the results.

[0240]

[0241] Working Example 7: Preparation of Formulation 4

[0242] Mixture 4: Prepared by dissolving the nominal solid content of NbCl5 (5.7 wt%) and SnCl22H2O (4.3 wt%) in 90 wt% PGME.

[0243] Operation Example 8: Layer Formation

[0244] Sample 15 (layer prepared from Formulation 4, baking temperature 150°C / 5 min), Sample 16 (layer prepared from Formulation 4, baking temperature 200°C / 5 min), and Sample 17 (layer prepared from Formulation 4, baking temperature 250°C / 5 min) were prepared in the same manner as described in Example 4 above, except that Formulation 4 was used for the formation of Samples 15, 16, and 17, and baking temperatures of 150°C / 5 min were used for Sample 15, 200°C / 5 min for the formation of Sample 16, and 250°C / 5 min for the formation of Sample 17 were used. The RI values ​​of the obtained samples were measured in the same manner as described in Working Example 6.

[0245] Table 3 below shows the RI measurement results.

[0246] As mentioned in Table 3, higher RI values ​​(approx. 2.0 or higher) could be obtained by applying lower baking temperatures (150℃ / 5 min, 200℃ / 5 min, 250℃ / 5 min). These indicate good gap filling characteristics.

[0247]

Claims

Claim 1 A composition preferably used to form an optical layer comprising a metal oxide, comprising at least a first metal halide represented by any one of the following formulas (I) to (V), a second metal halide represented by any one of the following formulas (I') to (V'), and a solvent, and In the above equation, M 1 Silver is a divalent metal, and preferably M 1 It is selected from Zn or Sn; M 2 is a trivalent metal, and preferably M 2 is Bi and;M 3 It is a tetravalent metal selected from Zr, Ti, or Hf; M 4 is a pentavalent metal selected from V, Nb, or Ta; M 5 is Mo or W and;X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 is Cl; In the above equation, M 1' Silver is a divalent metal, and preferably M 1' It is selected from Zn or Sn; M 2' Silver is a trivalent metal, and preferably M 2' is Bi and;M 3' It is a tetravalent metal selected from Zr, Ti, or Hf; M 4' It is a pentavalent metal selected from V, Nb, or Ta; M 5' is Mo or W and;X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' A formulation in which the silver is Cl; the first metal halide and the second metal halide are different from each other; the weight ratio of the second metal halide to the first metal halide is less than 1, preferably in the range of 0.01 to 1; and preferably the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%. Claim 2 A mixture according to claim 1, wherein the total content of all metal halide(s) in the mixture is in the range of 0.1% to 50% by weight based on the total mass of the mixture, preferably 1% to 30% by weight, and more preferably 5% to 20% by weight. Claim 3 In claim 1 or 2, the solvent is an organic solvent, preferably said organic solvent is ethylene glycol monoalkyl ether, preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and / or ethylene glycol monobutyl ether; diethylene glycol dialkyl ether, preferably diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and / or diethylene glycol dibutyl ether; propylene glycol monoalkyl ether, preferably propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether and / or propylene glycol monopropyl ether; 1,3-dimethoxy-2-propanol, ethylene glycol alkyl ether acetate, preferably methyl cellosolve acetate and / or ethyl cellosolve acetate; Selected from one or more members of the group consisting of propylene glycol alkyl ether acetate, preferably propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and / or propylene glycol monopropyl ether acetate; ketone, preferably methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and / or cyclohexanone; alcohol, preferably ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, triethylene glycol and / or glycerin; ester, preferably ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and / or ethyl lactate; and cyclic ester, preferably gamma-butyro-lactone;Preferably, the solvent is ethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol, ethylene glycol, propylene glycol monoalkyl ether, ethylene glycol alkyl ether acetate, propylene glycol alkyl ether acetate, and more preferably, the solvent is selected from propylene glycol alkyl ether acetate, ethylene glycol monoalkyl ether, propylene glycol and propylene glycol monoalkyl ether, and 1,3-dimethoxy-2-propanol, in a formulation.; Claim 4 Use of the formulation of any one of claims 1 to 3 for the manufacture of a composite, preferably for the manufacture of a layered composite, more preferably for the manufacture of an optical layer, or for filling one or more trenches on a patterned surface or a non-uniform surface of a substrate. Claim 5 A method for preparing a formulation of any one of claims 1 to 3, comprising at least the following step (A): (A) mixing a first metal halide represented by any one of the following chemical formulas (I) to (V), a second metal halide represented by any one of the following chemical formulas (I') to (V'), and a solvent; In the above equation, M 1 Silver is a divalent metal, and preferably M 1 It is selected from Zn or Sn; M 2 is a trivalent metal, and preferably M 2 is Bi and;M 3 It is a tetravalent metal selected from Ti, Zr, or Hf; M 4 is a pentavalent metal selected from V, Nb, or Ta; M 5 is Mo or W and;X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently a halogen, preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 Each is independently selected from F, Cl, Br, and I, and more preferably X 1 , X 2 , X 3 , X 4 , X 5 , X 6 is Cl; In the above equation, M 1' Silver is a divalent metal, and preferably M 1' is Zn and;M 2' Silver is a trivalent metal, and preferably M 2' is Bi and;M 3' It is a tetravalent metal selected from Ti, Zr, or Hf; M 4' It is a pentavalent metal selected from V, Nb, or Ta; M 5' is Mo or W and;X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently a halogen, preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' Each is independently selected from F, Cl, Br, and I, and more preferably X 1' , X 2' , X 3' , X 4' , X 5' , X 6' A method for manufacturing, wherein the silver is Cl; the first metal halide and the second metal halide are different from each other; the weight ratio of the second metal halide to the first metal halide is 1 or less, preferably in the range of 0.01 to 1; and preferably the total content of the second metal halide based on the total mass of the first metal halide is in the range of 0.1 to 100 weight%. Claim 6 A method for manufacturing a composite containing a metal oxide, wherein preferably the metal oxide is selected from a metal monooxide, a metal dioxide, or a metal pentoxide, or a combination thereof, and the method comprises the following steps (a) and (b): (a) providing a composition of any one of claims 1 to 3 to a substrate surface, preferably by a wet film deposition method, more preferably by spin-coating or ink-jetting, and more preferably by ink-jetting; and (b) applying a heat treatment to the composition provided to the substrate surface to convert at least a portion of the metal alkoxide of the composition into a metal oxide, wherein preferably the composite is a layered composite, and more preferably the layered composite is an optical layer. Claim 7 In claim 6, the method wherein, in step (a), the composition is applied to the surface of a substrate by spin-coating or ink-jetting. Claim 8 A method according to claim 6 or 7, wherein in step (b), the mixture is at least partially converted into a composite, preferably a layered composite, on the surface of a substrate by baking at a temperature of 50 to 400°C, preferably 80 to 350°C, more preferably 100 to 300°C. Claim 9 A method according to any one of claims 6 to 8, wherein the composition is at least partially converted into a composite on the surface of a substrate, and the composite comprises a metal oxide, preferably a metal oxide selected from a metal monooxide, a metal dioxide and / or a metal pentoxide; and a metal alkoxide. Claim 10 A method according to any one of claims 6 to 9, wherein the substrate is a patterned substrate having topographic features on its surface. Claim 11 A composite derived from a composition of any one of claims 1 to 3, preferably a layered composite, and preferably the layered composite is an optical layer. Claim 12 A composite manufactured from the method of any one of claims 6 to 8, preferably a layered composite, and preferably the layered composite is an optical layer. Claim 13 A composite according to claim 11 or 12, comprising at least one metal halide and a metal oxide derived from said metal halide, wherein preferably the metal halide is a first metal halide, and more preferably the composite further comprises a second metal halide and a metal oxide derived from the second metal halide. Claim 14 An optical device comprising a composite of any one of claims 11 to 13 and a substrate having a patterned surface or a non-uniform surface, wherein, preferably, a gap or trench of the patterned surface or non-uniform surface of the substrate is at least partially filled with said composite, preferably, said substrate is a patterned substrate having a topographic feature on its surface, preferably, said composite fills at least a portion of the gap of said topographic feature, and more preferably, said composite fills a trench of the patterned substrate. Claim 15 A display device comprising at least one functional medium configured to induce and control light or to emit light; and a composite of claim 11 or 13, or an optical device of claim 14.

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