A high-refractive-index polymer (HRIP) is a

polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...

that has a

refractive index In optics, the refractive index (or refraction index) of an optical medium is the ratio of the apparent speed of light in the air or vacuum to the speed in the medium. The refractive index determines how much the path of light is bent, or refrac ...

greater than 1.50. Such materials are required for

anti-reflective coating An antireflective, antiglare or anti-reflection (AR) coating is a type of optical coating applied to the surface of lens (optics), lenses, other optical elements, and photovoltaic cells to reduce reflection (physics), reflection. In typical ima ...

and photonic devices such as light emitting diodes (LEDs) and

image sensor An image sensor or imager is a sensor that detects and conveys information used to form an image. It does so by converting the variable attenuation of light waves (as they refraction, pass through or reflection (physics), reflect off objects) into s ...

s. The refractive index of a polymer is based on several factors which include

polarizability Polarizability usually refers to the tendency of matter, when subjected to an electric field, to acquire an electric dipole moment in proportion to that applied field. It is a property of particles with an electric charge. When subject to an elect ...

, chain flexibility,

molecular geometry Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It includes the general shape of the molecule as well as bond lengths, bond angles, torsional angles and any other geometrical parameters that det ...

and the polymer backbone orientation. As of 2004, the highest refractive index for a polymer was 1.76. Substituents with high molar fractions or high-n

nanoparticle A nanoparticle or ultrafine particle is a particle of matter 1 to 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 100 nm in only two directions. At ...

s in a polymer matrix have been introduced to increase the refractive index in polymers.

Properties

Refractive index

A typical polymer has a refractive index of 1.30–1.70, but a higher refractive index is often required for specific applications. The refractive index is related to the molar refractivity, structure and weight of the monomer. In general, high molar refractivity and low molar volumes increase the refractive index of the polymer.

Optical properties

Optical dispersion Dispersion is the phenomenon in which the phase velocity of a wave depends on its frequency. Sometimes the term chromatic dispersion is used to refer to optics specifically, as opposed to wave propagation in general. A medium having this common ...

is an important property of an HRIP. It is characterized by the

Abbe number In optics and lens design, the Abbe number, also known as the Vd-number or constringence of a Transparency (optics), transparent material, is an approximate measure of the material's dispersion (optics), dispersion (change of refractive index versu ...

. A high refractive index material will generally have a small Abbe number, or a high optical dispersion. A low birefringence has been required along with a high refractive index for many applications. It can be achieved by using different

functional groups In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...

in the initial

monomer A monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called polymerization. Classification Chemis ...

to make the HRIP.

Aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...

monomers both increase refractive index and decrease the optical anisotropy and thus the birefringence. Calcite

A high clarity (optical transparency) is also desired in a high refractive index polymer. The clarity is dependent on the refractive indexes of the polymer and of the initial monomer.

Thermal stability

When looking at thermal stability, the typical variables measured include

glass transition The glass–liquid transition, or glass transition, is the gradual and Reversible reaction, reversible transition in amorphous solid, amorphous materials (or in amorphous regions within Crystallinity, semicrystalline materials) from a hard and rel ...

, initial decomposition temperature, degradation temperature and the

melting Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid. This occurs when the internal energy of the solid increases, typically by the application of heat or pressure, which inc ...

temperature range. The thermal stability can be measured by thermogravimetric analysis and

differential scanning calorimetry Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and re ...

Polyesters Polyester is a category of polymers that contain one or two ester linkages in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include some natura ...

are considered thermally stable with a degradation temperature of 410 °C. The decomposition temperature changes depending on the substituent that is attached to the monomer used in the

polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...

of the high refractive index polymer. Thus, longer

alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl group is derived from a cy ...

substituents results in lower thermal stability.

Solubility

Most applications favor polymers which are soluble in as many

solvents A solvent (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for p ...

as possible. Highly refractive

polyesters Polyester is a category of polymers that contain one or two ester linkages in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include some natura ...

and polyimides are soluble in common organic solvents such as

dichloromethane Dichloromethane (DCM, methylene chloride, or methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odor is widely used as a solvent. Although it is not miscible with ...

methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...

, hexanes,

acetone Acetone (2-propanone or dimethyl ketone) is an organic compound with the chemical formula, formula . It is the simplest and smallest ketone (). It is a colorless, highly Volatile organic compound, volatile, and flammable liquid with a charact ...

and

toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...

Synthesis

The synthesis route depends on the HRIP type. The Michael polyaddition is used for a polyimide because it can be carried out at room temperature and can be used for step-growth polymerization. This synthesis was first succeeded with polyimidothiethers, resulting in optically transparent polymers with high refractive index. Polycondensation reactions are also common to make high refractive index polymers, such as polyesters and polyphosphonates.

Types

High refractive indices have been achieved either by introducing substituents with high molar refractions (intrinsic HRIPs) or by combining high-n nanoparticles with polymer matrixes (HRIP nanocomposites).

Intrinsic HRIP

Sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...

-containing substituents including linear

thioether In organic chemistry, a sulfide (British English sulphide) or thioether is an organosulfur functional group with the connectivity as shown on right. Like many other sulfur-containing compounds, Volatile organic compound, volatile sulfides have ...

and sulfone, cyclic

thiophene Thiophene is a heterocyclic compound with the formula C4H4S. Consisting of a planar five-membered ring, it is aromatic as indicated by its extensive substitution reactions. It is a colorless liquid with a benzene-like odor. In most of its reacti ...

, thiadiazole and thianthrene are the most commonly used groups for increasing refractive index of a polymer. Polymers with sulfur-rich thianthrene and tetrathiaanthracene moieties exhibit n values above 1.72, depending on the degree of molecular packing. Wiki-halogen

Halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...

elements, especially

bromine Bromine is a chemical element; it has chemical symbol, symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between th ...

and

iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...

, were the earliest components used for developing HRIPs. In 1992, Gaudiana ''et al.'' reported a series of polymethylacrylate compounds containing lateral brominated and iodinated carbazole rings. They had refractive indices of 1.67–1.77 depending on the components and numbers of the halogen substituents. However, recent applications of halogen elements in

microelectronic Microelectronics is a subfield of electronics. As the name suggests, microelectronics relates to the study and manufacture (or microfabrication) of very small electronic designs and components. Usually, but not always, this means micrometre- ...

s have been severely limited by the WEEE directive and

RoHS The Restriction of Hazardous Substances Directive 2002/95/EC (RoHS 1), short for Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment, was adopted in February 2003 by the European Uni ...

legislation adopted by the

European Union The European Union (EU) is a supranational union, supranational political union, political and economic union of Member state of the European Union, member states that are Geography of the European Union, located primarily in Europe. The u ...

to reduce potential pollution of the environment.

Phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...

-containing groups, such as

phosphonate In organic chemistry, phosphonates or phosphonic acids are organophosphorus compounds containing Functional group, groups, where R is an organic group (alkyl, aryl). If R is hydrogen then the compound is a Phosphite_ester#Chemistry_of_HP(O)(OR ...

s and

phosphazene Phosphazenes refer to various classes of organophosphorus compounds featuring phosphorus(V) with a double bond between P and N. One class of phosphazenes have the formula . These phosphazenes are also known as iminophosphoranes and phosphine imides ...

s, often exhibit high molar refractivity and optical

transmittance Electromagnetic radiation can be affected in several ways by the medium in which it propagates. It can be Scattering, scattered, Absorption (electromagnetic radiation), absorbed, and Fresnel equations, reflected and refracted at discontinui ...

in the visible light region. Polyphosphonates have high refractive indices due to the

phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...

moiety even if they have chemical structures analogous to

polycarbonates Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups in their chemical structures. Polycarbonates used in engineering are strong, tough materials, and some grades are optically transparent. They are easily wor ...

. Shaver ''et al.'' reported a series of polyphosphonates with varying backbones, reaching the highest refractive index reported for polyphosphonates at 1.66. In addition, polyphosphonates exhibit good thermal stability and optical transparency; they are also suitable for

casting Casting is a manufacturing process in which a liquid material is usually poured into a mold, which contains a hollow cavity of the desired shape, and then allowed to solidify. The solidified part is also known as a casting, which is ejected or ...

into plastic lenses. Wiki-organometallic2

Organometallic Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...

components result in HRIPs with good

film A film, also known as a movie or motion picture, is a work of visual art that simulates experiences and otherwise communicates ideas, stories, perceptions, emotions, or atmosphere through the use of moving images that are generally, sinc ...

forming ability and relatively low optical dispersion. Polyferrocenylsilanes and polyferrocenes containing phosphorus spacers and

phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula , and is often represented by the symbol Ph (archaically φ) or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ...

side chains show unusually high n values (n=1.74 and n=1.72). They might be good candidates for all-polymer photonic devices because of their intermediate optical dispersion between organic polymers and

inorganic An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemistry''. Inor ...

glass Glass is an amorphous (non-crystalline solid, non-crystalline) solid. Because it is often transparency and translucency, transparent and chemically inert, glass has found widespread practical, technological, and decorative use in window pane ...

es.

HRIP nanocomposite

Hybrid techniques which combine an organic polymer matrix with highly refractive inorganic nanoparticles could result in high n values. The factors affecting the refractive index of a high-n nanocomposite include the characteristics of the polymer matrix, nanoparticles and the hybrid technology between inorganic and organic components. The refractive index of a nanocomposite can be estimated as

=  +

, where

and

stand for the refractive indices of the nanocomposite, nanoparticle and organic matrix, respectively.

and

represent the volume fractions of the nanoparticles and organic matrix, respectively. The nanoparticle load is also important in designing HRIP nanocomposites for optical applications, because excessive concentrations increase the optical loss and decrease the processability of the nanocomposites. The choice of nanoparticles is often influenced by their size and surface characteristics. In order to increase optical transparency and reduce

Rayleigh scattering Rayleigh scattering ( ) is the scattering or deflection of light, or other electromagnetic radiation, by particles with a size much smaller than the wavelength of the radiation. For light frequencies well below the resonance frequency of the scat ...

of the nanocomposite, the diameter of the nanoparticle should be below 25 nm. Direct mixing of nanoparticles with the polymer matrix often results in the undesirable aggregation of nanoparticles – this is avoided by modifying their surface. The most commonly used nanoparticles for HRIPs include TiO₂ (

anatase Anatase is a metastable mineral form of titanium dioxide (TiO2) with a Tetragonal crystal system, tetragonal crystal structure. Although colorless or white when pure, anatase in nature is usually a black solid due to impurities. Three other Pol ...

, n=2.45;

rutile Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase, akaogiite, and brookite. Rutile has one of the highest refractive indices at vis ...

, n=2.70), ZrO₂ (n=2.10),

amorphous silicon Amorphous silicon (a-Si) is the non-crystalline form of silicon used for solar cells and thin-film transistors in LCDs. Used as semiconductor material for a-Si solar cells, or thin-film silicon solar cells, it is deposited in thin films onto ...

(n=4.23),

PbS The Public Broadcasting Service (PBS) is an American public broadcaster and non-commercial, free-to-air television network based in Arlington, Virginia. PBS is a publicly funded nonprofit organization and the most prominent provider of educat ...

(n=4.20) and ZnS (n=2.36). Polyimides have high refractive indexes and thus are often used as the matrix for high-n nanoparticles. The resulting nanocomposites exhibit a tunable refractive index ranging from 1.57 to 1.99. Wiki-nano

Applications

Image sensors

A microlens array is a key component of optoelectronics, optical communications,

CMOS Complementary metal–oxide–semiconductor (CMOS, pronounced "sea-moss ", , ) is a type of MOSFET, metal–oxide–semiconductor field-effect transistor (MOSFET) semiconductor device fabrication, fabrication process that uses complementary an ...

image sensors An image sensor or imager is a sensor that detects and conveys information used to form an image. It does so by converting the variable attenuation of light waves (as they pass through or reflect off objects) into signals, small bursts of curren ...

and displays. Polymer-based microlenses are easier to make and are more flexible than conventional glass-based lenses. The resulting devices use less power, are smaller in size and are cheaper to produce.

Lithography

Another application of HRIPs is in

immersion lithography Immersion lithography is a technique used in semiconductor manufacturing to enhance the resolution and accuracy of the lithographic process. It involves using a liquid medium, typically water, between the lens and the wafer during exposure. By ...

. In 2009 it was a new technique for circuit manufacturing using both photoresists and high refractive index fluids. The photoresist needs to have an n value of greater than 1.90. It has been shown that non-aromatic, sulfur-containing HRIPs are the best materials for an optical photoresist system.

LEDs

Light-emitting diodes (LEDs) are a common solid-state light source. High-brightness LEDs (HBLEDs) are often limited by the relatively low light extraction efficiency due to the mismatch of the refractive indices between the LED material ( GaN, n=2.5) and the organic encapsulant (

epoxy Epoxy is the family of basic components or Curing (chemistry), cured end products of epoxy Resin, resins. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. The epoxide fun ...

or silicone, n=1.5). Higher light outputs can be achieved by using an HRIP as the encapsulant.