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Tuesday, October 24, 2023

Silver nanoparticle

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Silver_nanoparticle

Silver nanoparticles are nanoparticles of silver of between 1 nm and 100 nm in size. While frequently described as being 'silver' some are composed of a large percentage of silver oxide due to their large ratio of surface to bulk silver atoms. Numerous shapes of nanoparticles can be constructed depending on the application at hand. Commonly used silver nanoparticles are spherical, but diamond, octagonal, and thin sheets are also common.

Their extremely large surface area permits the coordination of a vast number of ligands. The properties of silver nanoparticles applicable to human treatments are under investigation in laboratory and animal studies, assessing potential efficacy, biosafety, and biodistribution.

Synthesis methods

Wet chemistry

The most common methods for nanoparticle synthesis fall under the category of wet chemistry, or the nucleation of particles within a solution. This nucleation occurs when a silver ion complex, usually AgNO₃ or AgClO₄, is reduced to colloidal Ag in the presence of a reducing agent. When the concentration increases enough, dissolved metallic silver ions bind together to form a stable surface. The surface is energetically unfavorable when the cluster is small, because the energy gained by decreasing the concentration of dissolved particles is not as high as the energy lost from creating a new surface. When the cluster reaches a certain size, known as the critical radius, it becomes energetically favorable, and thus stable enough to continue to grow. This nucleus then remains in the system and grows as more silver atoms diffuse through the solution and attach to the surface When the dissolved concentration of atomic silver decreases enough, it is no longer possible for enough atoms to bind together to form a stable nucleus. At this nucleation threshold, new nanoparticles stop being formed, and the remaining dissolved silver is absorbed by diffusion into the growing nanoparticles in the solution.

As the particles grow, other molecules in the solution diffuse and attach to the surface. This process stabilizes the surface energy of the particle and blocks new silver ions from reaching the surface. The attachment of these capping/stabilizing agents slows and eventually stops the growth of the particle. The most common capping ligands are trisodium citrate and polyvinylpyrrolidone (PVP), but many others are also used in varying conditions to synthesize particles with particular sizes, shapes, and surface properties.

There are many different wet synthesis methods, including the use of reducing sugars, citrate reduction, reduction via sodium borohydride, the silver mirror reaction, the polyol process, seed-mediated growth, and light-mediated growth. Each of these methods, or a combination of methods, will offer differing degrees of control over the size distribution as well as distributions of geometric arrangements of the nanoparticle.

A new, very promising wet-chemical technique was found by Elsupikhe et al. (2015). They have developed a green ultrasonically-assisted synthesis. Under ultrasound treatment, silver nanoparticles (AgNP) are synthesized with κ-carrageenan as a natural stabilizer. The reaction is performed at ambient temperature and produces silver nanoparticles with fcc crystal structure without impurities. The concentration of κ-carrageenan is used to influence particle size distribution of the AgNPs.

Monosaccharide reduction

There are many ways silver nanoparticles can be synthesized; one method is through monosaccharides. This includes glucose, fructose, maltose, maltodextrin, etc., but not sucrose. It is also a simple method to reduce silver ions back to silver nanoparticles as it usually involves a one-step process. There have been methods that indicated that these reducing sugars are essential to the formation of silver nanoparticles. Many studies indicated that this method of green synthesis, specifically using Cacumen platycladi extract, enabled the reduction of silver. Additionally, the size of the nanoparticle could be controlled depending on the concentration of the extract. The studies indicate that the higher concentrations correlated to an increased number of nanoparticles. Smaller nanoparticles were formed at high pH levels due to the concentration of the monosaccharides.

Another method of silver nanoparticle synthesis includes the use of reducing sugars with alkali starch and silver nitrate. The reducing sugars have free aldehyde and ketone groups, which enable them to be oxidized into gluconate. The monosaccharide must have a free ketone group because in order to act as a reducing agent it first undergoes tautomerization. In addition, if the aldehydes are bound, it will be stuck in cyclic form and cannot act as a reducing agent. For example, glucose has an aldehyde functional group that is able to reduce silver cations to silver atoms and is then oxidized to gluconic acid. The reaction for the sugars to be oxidized occurs in aqueous solutions. The capping agent is also not present when heated.

Citrate reduction

An early, and very common, method for synthesizing silver nanoparticles is citrate reduction. This method was first recorded by M. C. Lea, who successfully produced a citrate-stabilized silver colloid in 1889. Citrate reduction involves the reduction of a silver source particle, usually AgNO₃ or AgClO₄, to colloidal silver using trisodium citrate, Na₃C₆H₅O₇. The synthesis is usually performed at an elevated temperature (~100 °C) to maximize the monodispersity (uniformity in both size and shape) of the particle. In this method, the citrate ion traditionally acts as both the reducing agent and the capping ligand, making it a useful process for AgNP production due to its relative ease and short reaction time. However, the silver particles formed may exhibit broad size distributions and form several different particle geometries simultaneously. The addition of stronger reducing agents to the reaction is often used to synthesize particles of a more uniform size and shape.

Reduction via sodium borohydride

The synthesis of silver nanoparticles by sodium borohydride (NaBH₄) reduction occurs by the following reaction:

Ag⁺ + BH₄⁻ + 3 H₂O → Ag⁰ +B(OH)₃ +3.5 H₂

The reduced metal atoms will form nanoparticle nuclei. Overall, this process is similar to the above reduction method using citrate. The benefit of using sodium borohydride is increased monodispersity of the final particle population. The reason for the increased monodispersity when using NaBH₄ is that it is a stronger reducing agent than citrate. The impact of reducing agent strength can be seen by inspecting a LaMer diagram which describes the nucleation and growth of nanoparticles.

When silver nitrate (AgNO₃) is reduced by a weak reducing agent like citrate, the reduction rate is lower which means that new nuclei are forming and old nuclei are growing concurrently. This is the reason that the citrate reaction has low monodispersity. Because NaBH₄ is a much stronger reducing agent, the concentration of silver nitrate is reduced rapidly which shortens the time during which new nuclei form and grow concurrently yielding a monodispersed population of silver nanoparticles.

Particles formed by reduction must have their surfaces stabilized to prevent undesirable particle agglomeration (when multiple particles bond together), growth, or coarsening. The driving force for these phenomena is the minimization of surface energy (nanoparticles have a large surface to volume ratio). This tendency to reduce surface energy in the system can be counteracted by adding species which will adsorb to the surface of the nanoparticles and lowers the activity of the particle surface thus preventing particle agglomeration according to the DLVO theory and preventing growth by occupying attachment sites for metal atoms. Chemical species that adsorb to the surface of nanoparticles are called ligands. Some of these surface stabilizing species are: NaBH₄ in large amounts, poly(vinyl pyrrolidone) (PVP), sodium dodecyl sulfate (SDS), and/or dodecanethiol.

Once the particles have been formed in solution they must be separated and collected. There are several general methods to remove nanoparticles from solution, including evaporating the solvent phase or the addition of chemicals to the solution that lower the solubility of the nanoparticles in the solution. Both methods force the precipitation of the nanoparticles.

Polyol process

The polyol process is a particularly useful method because it yields a high degree of control over both the size and geometry of the resulting nanoparticles. In general, the polyol synthesis begins with the heating of a polyol compound such as ethylene glycol, 1,5-pentanediol, or 1,2-propylene glycol7. An Ag⁺ species and a capping agent are added (although the polyol itself is also often the capping agent). The Ag⁺ species is then reduced by the polyol to colloidal nanoparticles. The polyol process is highly sensitive to reaction conditions such as temperature, chemical environment, and concentration of substrates. Therefore, by changing these variables, various sizes and geometries can be selected for such as quasi-spheres, pyramids, spheres, and wires. Further study has examined the mechanism for this process as well as resulting geometries under various reaction conditions in greater detail.

Seed-mediated growth

Seed-mediated growth is a synthetic method in which small, stable nuclei are grown in a separate chemical environment to a desired size and shape. Seed-mediated methods consist of two different stages: nucleation and growth. Variation of certain factors in the synthesis (e.g. ligand, nucleation time, reducing agent, etc.), can control the final size and shape of nanoparticles, making seed-mediated growth a popular synthetic approach to controlling morphology of nanoparticles.

The nucleation stage of seed-mediated growth consists of the reduction of metal ions in a precursor to metal atoms. In order to control the size distribution of the seeds, the period of nucleation should be made short for monodispersity. The LaMer model illustrates this concept. Seeds typically consist small nanoparticles, stabilized by a ligand. Ligands are small, usually organic molecules that bind to the surface of particles, preventing seeds from further growth. Ligands are necessary as they increase the energy barrier of coagulation, preventing agglomeration. The balance between attractive and repulsive forces within colloidal solutions can be modeled by DLVO theory. Ligand binding affinity, and selectivity can be used to control shape and growth. For seed synthesis, a ligand with medium to low binding affinity should be chosen as to allow for exchange during growth phase.

The growth of nanoseeds involves placing the seeds into a growth solution. The growth solution requires a low concentration of a metal precursor, ligands that will readily exchange with preexisting seed ligands, and a weak or very low concentration of reducing agent. The reducing agent must not be strong enough to reduce metal precursor in the growth solution in the absence of seeds. Otherwise, the growth solution will form new nucleation sites instead of growing on preexisting ones (seeds). Growth is the result of the competition between surface energy (which increases unfavorably with growth) and bulk energy (which decreases favorably with growth). The balance between the energetics of growth and dissolution is the reason for uniform growth only on preexisting seeds (and no new nucleation). Growth occurs by the addition of metal atoms from the growth solution to the seeds, and ligand exchange between the growth ligands (which have a higher bonding affinity) and the seed ligands.

Range and direction of growth can be controlled by nanoseed, concentration of metal precursor, ligand, and reaction conditions (heat, pressure, etc.). Controlling stoichiometric conditions of growth solution controls ultimate size of particle. For example, a low concentration of metal seeds to metal precursor in the growth solution will produce larger particles. Capping agent has been shown to control direction of growth and thereby shape. Ligands can have varying affinities for binding across a particle. Differential binding within a particle can result in dissimilar growth across particle. This produces anisotropic particles with nonspherical shapes including prisms, cubes, and rods.

Light-mediated growth

Light-mediated syntheses have also been explored where light can promote formation of various silver nanoparticle morphologies.

Silver mirror reaction

The silver mirror reaction involves the conversion of silver nitrate to Ag(NH3)OH. Ag(NH3)OH is subsequently reduced into colloidal silver using an aldehyde containing molecule such as a sugar. The silver mirror reaction is as follows:

2(Ag(NH₃)₂)⁺ + RCHO + 2OH⁻ → RCOOH + 2Ag + 4NH₃.

The size and shape of the nanoparticles produced are difficult to control and often have wide distributions. However, this method is often used to apply thin coatings of silver particles onto surfaces and further study into producing more uniformly sized nanoparticles is being done.

Ion implantation

Ion implantation has been used to create silver nanoparticles embedded in glass, polyurethane, silicone, polyethylene, and poly(methyl methacrylate). Particles are embedded in the substrate by means of bombardment at high accelerating voltages. At a fixed current density of the ion beam up to a certain value, the size of the embedded silver nanoparticles has been found to be monodisperse within the population, after which only an increase in the ion concentration is observed. A further increase in the ion beam dose has been found to reduce both the nanoparticle size and density in the target substrate, whereas an ion beam operating at a high accelerating voltage with a gradually increasing current density has been found to result in a gradual increase in the nanoparticle size. There are a few competing mechanisms which may result in the decrease in nanoparticle size; destruction of NPs upon collision, sputtering of the sample surface, particle fusion upon heating and dissociation.

The formation of embedded nanoparticles is complex, and all of the controlling parameters and factors have not yet been investigated. Computer simulation is still difficult as it involves processes of diffusion and clustering, however it can be broken down into a few different sub-processes such as implantation, diffusion, and growth. Upon implantation, silver ions will reach different depths within the substrate which approaches a Gaussian distribution with the mean centered at X depth. High temperature conditions during the initial stages of implantation will increase the impurity diffusion in the substrate and as a result limit the impinging ion saturation, which is required for nanoparticle nucleation. Both the implant temperature and ion beam current density are crucial to control in order to obtain a monodisperse nanoparticle size and depth distribution. A low current density may be used to counter the thermal agitation from the ion beam and a buildup of surface charge. After implantation on the surface, the beam currents may be raised as the surface conductivity will increase. The rate at which impurities diffuse drops quickly after the formation of the nanoparticles, which act as a mobile ion trap. This suggests that the beginning of the implantation process is critical for control of the spacing and depth of the resulting nanoparticles, as well as control of the substrate temperature and ion beam density. The presence and nature of these particles can be analyzed using numerous spectroscopy and microscopy instruments. Nanoparticles synthesized in the substrate exhibit surface plasmon resonances as evidenced by characteristic absorption bands; these features undergo spectral shifts depending on the nanoparticle size and surface asperities, however the optical properties also strongly depend on the substrate material of the composite.

Biological synthesis

The biological synthesis of nanoparticles has provided a means for improved techniques compared to the traditional methods that call for the use of harmful reducing agents like sodium borohydride. Many of these methods could improve their environmental footprint by replacing these relatively strong reducing agents. The commonly used biological methods are using plant or fruit extracts, fungi, and even animal parts like insect wing extract. The problems with the chemical production of silver nanoparticles is usually involves high cost and the longevity of the particles is short lived due to aggregation. The harshness of standard chemical methods has sparked the use of using biological organisms to reduce silver ions in solution into colloidal nanoparticles.

In addition, precise control over shape and size is vital during nanoparticle synthesis since the NPs therapeutic properties are intimately dependent on such factors. Hence, the primary focus of research in biogenic synthesis is in developing methods that consistently reproduce NPs with precise properties.

Fungi and bacteria

Bacterial and fungal synthesis of nanoparticles is practical because bacteria and fungi are easy to handle and can be modified genetically with ease. This provides a means to develop biomolecules that can synthesize AgNPs of varying shapes and sizes in high yield, which is at the forefront of current challenges in nanoparticle synthesis. Fungal strains such as Verticillium and bacterial strains such as Klebsiella pneumoniae can be used in the synthesis of silver nanoparticles. When the fungus/bacteria is added to solution, protein biomass is released into the solution. Electron donating residues such as tryptophan and tyrosine reduce silver ions in solution contributed by silver nitrate. These methods have been found to effectively create stable monodisperse nanoparticles without the use of harmful reducing agents.

A method has been found of reducing silver ions by the introduction of the fungus Fusarium oxysporum. The nanoparticles formed in this method have a size range between 5 and 15 nm and consist of silver hydrosol. The reduction of the silver nanoparticles is thought to come from an enzymatic process and silver nanoparticles produced are extremely stable due to interactions with proteins that are excreted by the fungi.

Bacterium found in silver mines, Pseudomonas stutzeri AG259, were able to construct silver particles in the shapes of triangles and hexagons. The size of these nanoparticles had a large range in size and some of them reached sizes larger than the usual nanoscale with a size of 200 nm. The silver nanoparticles were found in the organic matrix of the bacteria.

Lactic acid producing bacteria have been used to produce silver nanoparticles. The bacteria Lactobacillus spp., Pediococcus pentosaceus, Enteroccus faeciumI, and Lactococcus garvieae have been found to be able to reduce silver ions into silver nanoparticles. The production of the nanoparticles takes place in the cell from the interactions between the silver ions and the organic compounds of the cell. It was found that the bacterium Lactobacillus fermentum created the smallest silver nanoparticles with an average size of 11.2 nm. It was also found that this bacterium produced the nanoparticles with the smallest size distribution and the nanoparticles were found mostly on the outside of the cells. It was also found that there was an increase in the pH increased the rate of which the nanoparticles were produced and the amount of particles produced.

Plants

The reduction of silver ions into silver nanoparticles has also been achieved using geranium leaves. It has been found that adding geranium leaf extract to silver nitrate solutions causes their silver ions to be quickly reduced and that the nanoparticles produced are particularly stable. The silver nanoparticles produced in solution had a size range between 16 and 40 nm.

In another study different plant leaf extracts were used to reduce silver ions. It was found that out of Camellia sinensis (green tea), pine, persimmon, ginko, magnolia, and platanus that the magnolia leaf extract was the best at creating silver nanoparticles. This method created particles with a disperse size range of 15 to 500 nm, but it was also found that the particle size could be controlled by varying the reaction temperature. The speed at which the ions were reduced by the magnolia leaf extract was comparable to those of using chemicals to reduce.

The use of plants, microbes, and fungi in the production of silver nanoparticles is leading the way to more environmentally sound production of silver nanoparticles.

A green method is available for synthesizing silver nanoparticles using Amaranthus gangeticus Linn leaf extract.

Products and functionalization

Synthetic protocols for silver nanoparticle production can be modified to produce silver nanoparticles with non-spherical geometries and also to functionalize nanoparticles with different materials, such as silica. Creating silver nanoparticles of different shapes and surface coatings allows for greater control over their size-specific properties.

Anisotropic structures

Silver nanoparticles can be synthesized in a variety of non-spherical (anisotropic) shapes. Because silver, like other noble metals, exhibits a size and shape dependent optical effect known as localized surface plasmon resonance (LSPR) at the nanoscale, the ability to synthesize Ag nanoparticles in different shapes vastly increases the ability to tune their optical behavior. For example, the wavelength at which LSPR occurs for a nanoparticle of one morphology (e.g. a sphere) will be different if that sphere is changed into a different shape. This shape dependence allows a silver nanoparticle to experience optical enhancement at a range of different wavelengths, even by keeping the size relatively constant, just by changing its shape. This aspect can be exploited in synthesis to promote change in shape of nanoparticles through light interaction. The applications of this shape-exploited expansion of optical behavior range from developing more sensitive biosensors to increasing the longevity of textiles.

Triangular nanoprisms

Triangular-shaped nanoparticles are a canonical type of anisotropic morphology studied for both gold and silver.

Though many different techniques for silver nanoprism synthesis exist, several methods employ a seed-mediated approach, which involves first synthesizing small (3-5 nm diameter) silver nanoparticles that offer a template for shape-directed growth into triangular nanostructures.

The silver seeds are synthesized by mixing silver nitrate and sodium citrate in aqueous solution and then rapidly adding sodium borohydride. Additional silver nitrate is added to the seed solution at low temperature, and the prisms are grown by slowly reducing the excess silver nitrate using ascorbic acid.

With the seed-mediated approach to silver nanoprism synthesis, selectivity of one shape over another can in part be controlled by the capping ligand. Using essentially the same procedure above but changing citrate to poly (vinyl pyrrolidone) (PVP) yields cube and rod-shaped nanostructures instead of triangular nanoprisms.

In addition to the seed mediated technique, silver nanoprisms can also be synthesized using a photo-mediated approach, in which preexisting spherical silver nanoparticles are transformed into triangular nanoprisms simply by exposing the reaction mixture to high intensities of light.

Nanocubes

Silver nanocubes can be synthesized using ethylene glycol as a reducing agent and PVP as a capping agent, in a polyol synthesis reaction (vide supra). A typical synthesis using these reagents involves adding fresh silver nitrate and PVP to a solution of ethylene glycol heated at 140 °C.

This procedure can actually be modified to produce another anisotropic silver nanostructure, nanowires, by just allowing the silver nitrate solution to age before using it in the synthesis. By allowing the silver nitrate solution to age, the initial nanostructure formed during the synthesis is slightly different than that obtained with fresh silver nitrate, which influences the growth process, and therefore, the morphology of the final product.

Coating with silica

In this method, polyvinylpyrrolidone (PVP) is dissolved in water by sonication and mixed with silver colloid particles. Active stirring ensures the PVP has adsorbed to the nanoparticle surface. Centrifuging separates the PVP coated nanoparticles which are then transferred to a solution of ethanol to be centrifuged further and placed in a solution of ammonia, ethanol and Si(OEt₄) (TES). Stirring for twelve hours results in the silica shell being formed consisting of a surrounding layer of silicon oxide with an ether linkage available to add functionality. Varying the amount of TES allows for different thicknesses of shells formed. This technique is popular due to the ability to add a variety of functionality to the exposed silica surface.

Metrology

A number of reference materials are available for silver nanoparticles. NIST RM 8017 contains 75 nm silver nanoparticles embedded in a cake of the polymer polyvinylpyrrolidone to stabilize them against oxidation for a long shelf life. They have reference values for mean particle size using dynamic light scattering, ultra-small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy; and size distribution reference values for the latter two methods. The BAM-N001 certified reference material contains silver nanoparticles with a specified size distribution with a number-weighted median size of 12.6 nm measured by small-angle X-ray scattering and transmission electron microscopy.

Use

Catalysis

Using silver nanoparticles for catalysis has been gaining attention in recent years. Although the most common applications are for medicinal or antibacterial purposes, silver nanoparticles have been demonstrated to show catalytic redox properties for dyes, benzene, and carbon monoxide. Other untested compounds may use silver nanoparticles for catalysis, but the field is not fully explored.

NOTE: This paragraph is a general description of nanoparticle properties for catalysis; it is not exclusive to silver nanoparticles. The size of a nanoparticle greatly determines the properties that it exhibits due to various quantum effects. Additionally, the chemical environment of the nanoparticle plays a large role on the catalytic properties. With this in mind, it is important to note that heterogeneous catalysis takes place by adsorption of the reactant species to the catalytic substrate. When polymers, complex ligands, or surfactants are used to prevent coalescence of the nanoparticles, the catalytic ability is frequently hindered due to reduced adsorption ability. However, these compounds can also be used in such a way that the chemical environment enhances the catalytic ability.

Supported on silica spheres – reduction of dyes

Silver nanoparticles have been synthesized on a support of inert silica spheres. The support plays virtually no role in the catalytic ability and serves as a method of preventing coalescence of the silver nanoparticles in colloidal solution. Thus, the silver nanoparticles were stabilized and it was possible to demonstrate the ability of them to serve as an electron relay for the reduction of dyes by sodium borohydride. Without the silver nanoparticle catalyst, virtually no reaction occurs between sodium borohydride and the various dyes: methylene blue, eosin, and rose bengal.

Mesoporous aerogel – selective oxidation of benzene

Silver nanoparticles supported on aerogel are advantageous due to the higher number of active sites. The highest selectivity for oxidation of benzene to phenol was observed at low weight percent of silver in the aerogel matrix (1% Ag). This better selectivity is believed to be a result of the higher monodispersity within the aerogel matrix of the 1% Ag sample. Each weight percent solution formed different sized particles with a different width of size range.

Silver alloy – synergistic oxidation of carbon monoxide

Au-Ag alloy nanoparticles have been shown to have a synergistic effect on the oxidation of carbon monoxide (CO). On its own, each pure-metal nanoparticle shows very poor catalytic activity for CO oxidation; together, the catalytic properties are greatly enhanced. It is proposed that the gold acts as a strong binding agent for the oxygen atom and the silver serves as a strong oxidizing catalyst, although the exact mechanism is still not completely understood. When synthesized in an Au/Ag ratio from 3:1 to 10:1, the alloyed nanoparticles showed complete conversion when 1% CO was fed in air at ambient temperature. The size of the alloyed particles did not play a big role in the catalytic ability. It is well known that gold nanoparticles only show catalytic properties for CO when they are ~3 nm in size, but alloyed particles up to 30 nm demonstrated excellent catalytic activity – catalytic activity better than that of gold nanoparticles on active support such as TiO₂, Fe₂O₃, etc.

Light-enhanced

Plasmonic effects have been studied quite extensively. Until recently, there have not been studies investigating the oxidative catalytic enhancement of a nanostructure via excitation of its surface plasmon resonance. The defining feature for enhancing the oxidative catalytic ability has been identified as the ability to convert a beam of light into the form of energetic electrons that can be transferred to adsorbed molecules. The implication of such a feature is that photochemical reactions can be driven by low-intensity continuous light coupled with thermal energy.

The coupling of low-intensity continuous light and thermal energy has been performed with silver nanocubes. The important feature of silver nanostructures that are enabling for photocatalysis is their nature to create resonant surface plasmons from light in the visible range.

The addition of light enhancement enabled the particles to perform to the same degree as particles that were heated up to 40 K greater. This is a profound finding when noting that a reduction in temperature of 25 K can increase the catalyst lifetime by nearly tenfold, when comparing the photothermal and thermal process.

Biological research

Researchers have explored the use of silver nanoparticles as carriers for delivering various payloads such as small drug molecules or large biomolecules to specific targets. Once the AgNP has had sufficient time to reach its target, release of the payload could potentially be triggered by an internal or external stimulus. The targeting and accumulation of nanoparticles may provide high payload concentrations at specific target sites and could minimize side effects.

Chemotherapy

The introduction of nanotechnology into medicine is expected to advance diagnostic cancer imaging and the standards for therapeutic drug design. Nanotechnology may uncover insight about the structure, function and organizational level of the biosystem at the nanoscale.

Silver nanoparticles can undergo coating techniques that offer a uniform functionalized surface to which substrates can be added. When the nanoparticle is coated, for example, in silica the surface exists as silicic acid. Substrates can thus be added through stable ether and ester linkages that are not degraded immediately by natural metabolic enzymes. Recent chemotherapeutic applications have designed anti cancer drugs with a photo cleavable linker, such as an ortho-nitrobenzyl bridge, attaching it to the substrate on the nanoparticle surface. The low toxicity nanoparticle complex can remain viable under metabolic attack for the time necessary to be distributed throughout the bodies systems. If a cancerous tumor is being targeted for treatment, ultraviolet light can be introduced over the tumor region. The electromagnetic energy of the light causes the photo responsive linker to break between the drug and the nanoparticle substrate. The drug is now cleaved and released in an unaltered active form to act on the cancerous tumor cells. Advantages anticipated for this method is that the drug is transported without highly toxic compounds, the drug is released without harmful radiation or relying on a specific chemical reaction to occur and the drug can be selectively released at a target tissue.

A second approach is to attach a chemotherapeutic drug directly to the functionalized surface of the silver nanoparticle combined with a nucelophilic species to undergo a displacement reaction. For example, once the nanoparticle drug complex enters or is in the vicinity of the target tissue or cells, a glutathione monoester can be administered to the site. The nucleophilic ester oxygen will attach to the functionalized surface of the nanoparticle through a new ester linkage while the drug is released to its surroundings. The drug is now active and can exert its biological function on the cells immediate to its surroundings limiting non-desirable interactions with other tissues.

Multiple drug resistance

A major cause for the ineffectiveness of current chemotherapy treatments is multiple drug resistance which can arise from several mechanisms.

Nanoparticles can provide a means to overcome MDR. In general, when using a targeting agent to deliver nanocarriers to cancer cells, it is imperative that the agent binds with high selectivity to molecules that are uniquely expressed on the cell surface. Hence NPs can be designed with proteins that specifically detect drug resistant cells with overexpressed transporter proteins on their surface. A pitfall of the commonly used nano-drug delivery systems is that free drugs that are released from the nanocarriers into the cytosol get exposed to the MDR transporters once again, and are exported. To solve this, 8 nm nanocrystalline silver particles were modified by the addition of trans-activating transcriptional activator (TAT), derived from the HIV-1 virus, which acts as a cell-penetrating peptide (CPP). Generally, AgNP effectiveness is limited due to the lack of efficient cellular uptake; however, CPP-modification has become one of the most efficient methods for improving intracellular delivery of nanoparticles. Once ingested, the export of the AgNP is prevented based on a size exclusion. The concept is simple: the nanoparticles are too large to be effluxed by the MDR transporters, because the efflux function is strictly subjected to the size of its substrates, which is generally limited to a range of 300-2000 Da. Thereby the nanoparticulates remain insusceptible to the efflux, providing a means to accumulate in high concentrations.

Antimicrobial

Introduction of silver into bacterial cells induces a high degree of structural and morphological changes, which can lead to cell death. As the silver nanoparticles come in contact with the bacteria, they adhere to the cell wall and cell membrane. Once bound, some of the silver passes through to the inside, and interacts with phosphate-containing compounds like DNA and RNA, while another portion adheres to the sulfur-containing proteins on the membrane. The silver-sulfur interactions at the membrane cause the cell wall to undergo structural changes, like the formation of pits and pores. Through these pores, cellular components are released into the extracellular fluid, simply due to the osmotic difference. Within the cell, the integration of silver creates a low molecular weight region where the DNA then condenses. Having DNA in a condensed state inhibits the cell's replication proteins contact with the DNA. Thus the introduction of silver nanoparticles inhibits replication and is sufficient to cause the death of the cell. Further increasing their effect, when silver comes in contact with fluids, it tends to ionize which increases the nanoparticles' bactericidal activity. This has been correlated to the suppression of enzymes and inhibited expression of proteins that relate to the cell's ability to produce ATP.

Although it varies for every type of cell proposed, as their cell membrane composition varies greatly, It has been seen that in general, silver nanoparticles with an average size of 10 nm or less show electronic effects that greatly increase their bactericidal activity. This could also be partly due to the fact that as particle size decreases, reactivity increases due to the surface area to volume ratio increasing.

Silver nanoparticles have been shown to have synergistic antibacterial activity with commonly used antibiotics such as; penicillin G, ampicillin, erythromycin, clindamycin, and vancomycin against E. coli and S. aureus. Furthermore, synergistic antibacterial activity has been reported between silver nanoparticles and hydrogen peroxide causing this combination to exert significantly enhanced bactericidal effect against both Gram negative and Gram positive bacteria. This antibacterial synergy between silver nanoparticles and hydrogen peroxide can be possibly attributed to a Fenton-like reaction that generates highly reactive oxygen species such as hydroxyl radicals.

Silver nanoparticles can prevent bacteria from growing on or adhering to the surface. This can be especially useful in surgical settings where all surfaces in contact with the patient must be sterile. Silver nanoparticles can be incorporated on many types of surfaces including metals, plastic, and glass. In medical equipment, it has been shown that silver nano particles lower the bacterial count on devices used compared to old techniques. However, the problem arises when the procedure is over and a new one must be done. In the process of washing the instruments a large portion of the silver nano particles become less effective due to the loss of silver ions. They are more commonly used in skin grafts for burn victims as the silver nano particles embedded with the graft provide better antimicrobial activity and result in significantly less scarring of the victim.These new applications are direct decedents of older practices that used silver nitrate to treat conditions such as skin ulcers. Now, silver nanoparticles are used in bandages and patches to help heal certain burns and wounds. An alternative approach is to use AgNP to sterilise biological dressings (for example, tilapia fish skin) for burn and wound management.

They also show promising application as water treatment method to form clean potable water. This doesn't sound like much, but water contains numerous diseases and some parts of the world do not have the luxury of clean water, or any at all. It wasn't new to use silver for removing microbes, but this experiment used the carbonate in water to make microbes even more vulnerable to silver. First the scientists of the experiment use the nanopaticles to remove certain pesticides from the water, ones that prove fatal to people if ingested. Several other tests have shown that the silver nanoparticles were capable of removing certain ions in water as well, like iron, lead, and arsenic. But that is not the only reason why the silver nanoparticles are so appealing, they do not require any external force (no electricity of hydrolics) for the reaction to occur. Conversely, post-consumer silver nanoparticles in waste water may adversely impact biological agents used in waste water treatment.

Consumer Goods

Household applications

There are instances in which silver nanoparticles and colloidal silver are used in consumer goods. Samsung for example claimed that the use of silver nanoparticles in washing machines would help to sterilize clothes and water during the washing and rinsing functions, and allow clothes to be cleaned without the need for hot water. The nanoparticles in these appliances are synthesized using electrolysis. Through electrolysis, silver is extracted from metal plates and then turned into silver nanoparticles by a reduction agent. This method avoids the drying, cleaning, and re-dispersion processes, which are generally required with alternative colloidal synthesis methods. Importantly, the electrolysis strategy also decreases the production cost of Ag nanoparticles, making these washing machines more affordable to manufacture. Samsung has described the system:

[A] grapefruit-sized device alongside the [washer] tub uses electrical currents to nanoshave two silver plates the size of large chewing gum sticks. Resulting in positively charged silver atoms-silver ions (Ag⁺)-are injected into the tub during the wash cycle.

Samsung's description of the Ag nanoparticle generating process seems to contradict its advertisement of silver nanoparticles. Instead, the statement indicates that laundry cycles. When clothes are run through the cycle, the intended mode of action is that bacteria contained in the water are sterilized as they interact with the silver present in the washing tub. As a result, these washing machines can provide antibacterial and sterilization benefits on top of conventional washing methods. Samsung has commented on the lifetime of these silver-containing washing machines. The electrolysis of silver generates over 400 billion silver ions during each wash cycle. Given the size of the silver source (two “gum-sized” plate of Ag), Samsung estimates that these plates can last up to 3000 wash cycles.

These plans by Samsung were not overlooked by regulatory agencies. Agencies investigating nanoparticle use include but are not limited to: the U.S. FDA, U.S. EPA, SIAA of Japan, and Korea's Testing and Research Institute for Chemical Industry and FITI Testing & Research Institute. These various agencies plan to regulate silver nanoparticles in appliances. These washing machines are some of the first cases in which the EPA has sought to regulate nanoparticles in consumer goods. Samsung stated that the silver gets washed away in the sewer and regulatory agencies worry over what that means for wastewater treatment streams. Currently, the EPA classifies silver nanoparticles as pesticides due to their use as antimicrobial agents in wastewater purification. The washing machines being developed by Samsung do contain a pesticide and have to be registered and tested for safety under the law, particularly the U.S. Federal Insecticide, Fungicide, and Rodenticide Act. The difficulty, however behind regulating nanotechnology in this manner is that there is no distinct way to measure toxicity.

In addition to the uses described above, the European Union Observatory for Nanomaterials (EUON) has highlighted that silver nanoparticles are used in colourants in cosmetics, as well as pigments. A recently published study by the EUON has illustrated the existence of knowledge gaps regarding the safety of nanoparticles in pigments.

Health and safety

The U.S. National Institute for Occupational Safety and Health derived a recommended exposure limit (REL) for silver nanomaterials (with <100 nm primary particle size) of 0.9 μg/m³ as an airborne respirable 8-hour time-weighted average (TWA) concentration. This is in comparison to its REL of 10 μg/m³ as an 8-hour TWA for total silver (including metal dust, fumes, and soluble compounds). It was found that the unbound silver cation is the ultimate toxicant, and ions formed extracellularly drive toxicity after exposure to Ag nanoparticles.

Although silver nanoparticles are widely used in a variety of commercial products, there has only recently been a major effort to study their effects on human health. There have been several studies that describe the in vitro toxicity of silver nanoparticles to a variety of different organs, including the lung, liver, skin, brain, and reproductive organs. The mechanism of the toxicity of silver nanoparticles to human cells appears to be derived from oxidative stress and inflammation that is caused by the generation of reactive oxygen species (ROS) stimulated by either the Ag NPs, Ag ions, or both.For example, Park et al. showed that exposure of a mouse peritoneal macrophage cell line (RAW267.7) to silver nanoparticles decreased the cell viability in a concentration- and time-dependent manner. They further showed that the intracellular reduced glutathionine (GSH), which is a ROS scavenger, decreased to 81.4% of the control group of silver nanoparticles at 1.6 ppm.

Modes of toxicity

Since silver nanoparticles undergo dissolution releasing silver ions, which is well-documented to have toxic effects, there have been several studies that have been conducted to determine whether the toxicity of silver nanoparticles is derived from the release of silver ions or from the nanoparticle itself. Several studies suggest that the toxicity of silver nanoparticles is attributed to their release of silver ions in cells as both silver nanoparticles and silver ions have been reported to have similar cytotoxicity. For example, In some cases it is reported that silver nanoparticles facilitate the release of toxic free silver ions in cells via a "Trojan-horse type mechanism," where the particle enters cells and is then ionized within the cell. However, there have been reports that suggest that a combination of silver nanoparticles and ions is responsible for the toxic effect of silver nanoparticles. Navarro et al. using cysteine ligands as a tool to measure the concentration of free silver in solution, determined that although initially silver ions were 18 times more likely to inhibit the photosynthesis of an algae, Chlamydomanas reinhardtii, but after 2 hours of incubation it was revealed that the algae containing silver nanoparticles were more toxic than just silver ions alone. Furthermore, there are studies that suggest that silver nanoparticles induce toxicity independent of free silver ions. For example, Asharani et al. compared phenotypic defects observed in zebrafish treated with silver nanoparticles and silver ions and determined that the phenotypic defects observed with silver nanoparticle treatment was not observed with silver ion-treated embryos, suggesting that the toxicity of silver nanoparticles is independent of silver ions.

Protein channels and nuclear membrane pores can often be in the size range of 9 nm to 10 nm in diameter. Small silver nanoparticles constructed of this size have the ability to not only pass through the membrane to interact with internal structures but also to become lodged within the membrane. Silver nanoparticle depositions in the membrane can impact regulation of solutes, exchange of proteins and cell recognition. Exposure to silver nanoparticles has been associated with "inflammatory, oxidative, genotoxic, and cytotoxic consequences"; the silver particulates primarily accumulate in the liver. but have also been shown to be toxic in other organs including the brain. Nano-silver applied to tissue-cultured human cells leads to the formation of free radicals, raising concerns of potential health risks.

Allergic reaction: There have been several studies conducted that show a precedence for allergenicity of silver nanoparticles.
Argyria and staining: Ingested silver or silver compounds, including colloidal silver, can cause a condition called argyria, a discoloration of the skin and organs.In 2006, there was a case study of a 17-year-old man, who sustained burns to 30% of his body, and experienced a temporary bluish-grey hue after several days of treatment with Acticoat, a brand of wound dressing containing silver nanoparticles. Argyria is the deposition of silver in deep tissues, a condition that cannot happen on a temporary basis, raising the question of whether the cause of the man's discoloration was argyria or even a result of the silver treatment. Silver dressings are known to cause a "transient discoloration" that dissipates in 2–14 days, but not a permanent discoloration.
Silzone heart valve: St. Jude Medical released a mechanical heart valve with a silver coated sewing cuff (coated using ion beam-assisted deposition) in 1997. The valve was designed to reduce the instances of endocarditis. The valve was approved for sale in Canada, Europe, the United States, and most other markets around the world. In a post-commercialization study, researchers showed that the valve prevented tissue ingrowth, created paravalvular leakage, valve loosening, and in the worst cases explantation. After 3 years on the market and 36,000 implants, St. Jude discontinued and voluntarily recalled the valve.

Silicon photonics

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Silicon_photonics

Silicon photonics is the study and application of photonic systems which use silicon as an optical medium. The silicon is usually patterned with sub-micrometre precision, into microphotonic components. These operate in the infrared, most commonly at the 1.55 micrometre wavelength used by most fiber optic telecommunication systems. The silicon typically lies on top of a layer of silica in what (by analogy with a similar construction in microelectronics) is known as silicon on insulator (SOI).

Silicon photonic devices can be made using existing semiconductor fabrication techniques, and because silicon is already used as the substrate for most integrated circuits, it is possible to create hybrid devices in which the optical and electronic components are integrated onto a single microchip. Consequently, silicon photonics is being actively researched by many electronics manufacturers including IBM and Intel, as well as by academic research groups, as a means for keeping on track with Moore's Law, by using optical interconnects to provide faster data transfer both between and within microchips.

The propagation of light through silicon devices is governed by a range of nonlinear optical phenomena including the Kerr effect, the Raman effect, two-photon absorption and interactions between photons and free charge carriers. The presence of nonlinearity is of fundamental importance, as it enables light to interact with light, thus permitting applications such as wavelength conversion and all-optical signal routing, in addition to the passive transmission of light.

Silicon waveguides are also of great academic interest, due to their unique guiding properties, they can be used for communications, interconnects, biosensors, and they offer the possibility to support exotic nonlinear optical phenomena such as soliton propagation.

Applications

Optical communications

In a typical optical link, data is first transferred from the electrical to the optical domain using an electro-optic modulator or a directly modulated laser. An electro-optic modulator can vary the intensity and/or the phase of the optical carrier. In silicon photonics, a common technique to achieve modulation is to vary the density of free charge carriers. Variations of electron and hole densities change the real and the imaginary part of the refractive index of silicon as described by the empirical equations of Soref and Bennett. Modulators can consist of both forward-biased PIN diodes, which generally generate large phase-shifts but suffer of lower speeds, as well as of reverse-biased PN junctions. A prototype optical interconnect with microring modulators integrated with germanium detectors has been demonstrated. Non-resonant modulators, such as Mach-Zehnder interferometers, have typical dimensions in the millimeter range and are usually used in telecom or datacom applications. Resonant devices, such as ring-resonators, can have dimensions of few tens of micrometers only, occupying therefore much smaller areas. In 2013, researchers demonstrated a resonant depletion modulator that can be fabricated using standard Silicon-on-Insulator Complementary Metal-Oxide-Semiconductor (SOI CMOS) manufacturing processes. A similar device has been demonstrated as well in bulk CMOS rather than in SOI.

On the receiver side, the optical signal is typically converted back to the electrical domain using a semiconductor photodetector. The semiconductor used for carrier generation has usually a band-gap smaller than the photon energy, and the most common choice is pure germanium. Most detectors utilize a PN junction for carrier extraction, however, detectors based on metal–semiconductor junctions (with germanium as the semiconductor) have been integrated into silicon waveguides as well. More recently, silicon-germanium avalanche photodiodes capable of operating at 40 Gbit/s have been fabricated. Complete transceivers have been commercialized in the form of active optical cables.

Optical communications are conveniently classified by the reach, or length, of their links. The majority of silicon photonic communications have so far been limited to telecom and datacom applications, where the reach is of several kilometers or several meters respectively.

Silicon photonics, however, is expected to play a significant role in computercom as well, where optical links have a reach in the centimeter to meter range. In fact, progress in computer technology (and the continuation of Moore's Law) is becoming increasingly dependent on faster data transfer between and within microchips. Optical interconnects may provide a way forward, and silicon photonics may prove particularly useful, once integrated on the standard silicon chips. In 2006, Intel Senior Vice President - and future CEO - Pat Gelsinger stated that, "Today, optics is a niche technology. Tomorrow, it's the mainstream of every chip that we build." In 2010 Intel demostrated a 50 Gbps connection made with silicon photonics.

The first microprocessor with optical input/output (I/O) was demonstrated in December 2015 using an approach known as "zero-change" CMOS photonics. This is known as fiber-to-the-processor. This first demonstration was based on a 45 nm SOI node, and the bi-directional chip-to-chip link was operated at a rate of 2×2.5 Gbit/s. The total energy consumption of the link was calculated to be of 16 pJ/b and was dominated by the contribution of the off-chip laser.

Some researchers believe an on-chip laser source is required. Others think that it should remain off-chip because of thermal problems (the quantum efficiency decreases with temperature, and computer chips are generally hot) and because of CMOS-compatibility issues. One such device is the hybrid silicon laser, in which the silicon is bonded to a different semiconductor (such as indium phosphide) as the lasing medium. Other devices include all-silicon Raman laser or an all-silicon Brillouin lasers wherein silicon serves as the lasing medium.

In 2012, IBM announced that it had achieved optical components at the 90 nanometer scale that can be manufactured using standard techniques and incorporated into conventional chips. In September 2013, Intel announced technology to transmit data at speeds of 100 gigabits per second along a cable approximately five millimeters in diameter for connecting servers inside data centers. Conventional PCI-E data cables carry data at up to eight gigabits per second, while networking cables reach 40 Gbit/s. The latest version of the USB standard tops out at ten Gbit/s. The technology does not directly replace existing cables in that it requires a separate circuit board to interconvert electrical and optical signals. Its advanced speed offers the potential of reducing the number of cables that connect blades on a rack and even of separating processor, storage and memory into separate blades to allow more efficient cooling and dynamic configuration.

Graphene photodetectors have the potential to surpass germanium devices in several important aspects, although they remain about one order of magnitude behind current generation capacity, despite rapid improvement. Graphene devices can work at very high frequencies, and could in principle reach higher bandwidths. Graphene can absorb a broader range of wavelengths than germanium. That property could be exploited to transmit more data streams simultaneously in the same beam of light. Unlike germanium detectors, graphene photodetectors do not require applied voltage, which could reduce energy needs. Finally, graphene detectors in principle permit a simpler and less expensive on-chip integration. However, graphene does not strongly absorb light. Pairing a silicon waveguide with a graphene sheet better routes light and maximizes interaction. The first such device was demonstrated in 2011. Manufacturing such devices using conventional manufacturing techniques has not been demonstrated.

Optical routers and signal processors

Another application of silicon photonics is in signal routers for optical communication. Construction can be greatly simplified by fabricating the optical and electronic parts on the same chip, rather than having them spread across multiple components. A wider aim is all-optical signal processing, whereby tasks which are conventionally performed by manipulating signals in electronic form are done directly in optical form. An important example is all-optical switching, whereby the routing of optical signals is directly controlled by other optical signals. Another example is all-optical wavelength conversion.

In 2013, a startup company named "Compass-EOS", based in California and in Israel, was the first to present a commercial silicon-to-photonics router.

Long range telecommunications using silicon photonics

Silicon microphotonics can potentially increase the Internet's bandwidth capacity by providing micro-scale, ultra low power devices. Furthermore, the power consumption of datacenters may be significantly reduced if this is successfully achieved. Researchers at Sandia, Kotura, NTT, Fujitsu and various academic institutes have been attempting to prove this functionality. A 2010 paper reported on a prototype 80 km, 12.5 Gbit/s transmission using microring silicon devices.

Light-field displays

As of 2015, US startup company Magic Leap is working on a light-field chip using silicon photonics for the purpose of an augmented reality display.

Artificial intelligence

Silicon photonics has been used in artiificial intelligence inference processors that are more energy efficient than those using conventional transistors. This can be done using Mach-Zehnder interferometers (MZIs) which can be combined with nanoelectromechanical systems to modulate the light passing though it, by physically bending the MZI which changes the phase of the light.

Physical properties

Optical guiding and dispersion tailoring

Silicon is transparent to infrared light with wavelengths above about 1.1 micrometres. Silicon also has a very high refractive index, of about 3.5. The tight optical confinement provided by this high index allows for microscopic optical waveguides, which may have cross-sectional dimensions of only a few hundred nanometers. Single mode propagation can be achieved, thus (like single-mode optical fiber) eliminating the problem of modal dispersion.

The strong dielectric boundary effects that result from this tight confinement substantially alter the optical dispersion relation. By selecting the waveguide geometry, it is possible to tailor the dispersion to have desired properties, which is of crucial importance to applications requiring ultrashort pulses. In particular, the group velocity dispersion (that is, the extent to which group velocity varies with wavelength) can be closely controlled. In bulk silicon at 1.55 micrometres, the group velocity dispersion (GVD) is normal in that pulses with longer wavelengths travel with higher group velocity than those with shorter wavelength. By selecting a suitable waveguide geometry, however, it is possible to reverse this, and achieve anomalous GVD, in which pulses with shorter wavelengths travel faster. Anomalous dispersion is significant, as it is a prerequisite for soliton propagation, and modulational instability.

In order for the silicon photonic components to remain optically independent from the bulk silicon of the wafer on which they are fabricated, it is necessary to have a layer of intervening material. This is usually silica, which has a much lower refractive index (of about 1.44 in the wavelength region of interest), and thus light at the silicon-silica interface will (like light at the silicon-air interface) undergo total internal reflection, and remain in the silicon. This construct is known as silicon on insulator. It is named after the technology of silicon on insulator in electronics, whereby components are built upon a layer of insulator in order to reduce parasitic capacitance and so improve performance.

Kerr nonlinearity

Silicon has a focusing Kerr nonlinearity, in that the refractive index increases with optical intensity. This effect is not especially strong in bulk silicon, but it can be greatly enhanced by using a silicon waveguide to concentrate light into a very small cross-sectional area. This allows nonlinear optical effects to be seen at low powers. The nonlinearity can be enhanced further by using a slot waveguide, in which the high refractive index of the silicon is used to confine light into a central region filled with a strongly nonlinear polymer.

Kerr nonlinearity underlies a wide variety of optical phenomena. One example is four wave mixing, which has been applied in silicon to realise optical parametric amplification, parametric wavelength conversion, and frequency comb generation.

Kerr nonlinearity can also cause modulational instability, in which it reinforces deviations from an optical waveform, leading to the generation of spectral-sidebands and the eventual breakup of the waveform into a train of pulses. Another example (as described below) is soliton propagation.

Two-photon absorption

Silicon exhibits two-photon absorption (TPA), in which a pair of photons can act to excite an electron-hole pair. This process is related to the Kerr effect, and by analogy with complex refractive index, can be thought of as the imaginary-part of a complex Kerr nonlinearity. At the 1.55 micrometre telecommunication wavelength, this imaginary part is approximately 10% of the real part.

The influence of TPA is highly disruptive, as it both wastes light, and generates unwanted heat. It can be mitigated, however, either by switching to longer wavelengths (at which the TPA to Kerr ratio drops), or by using slot waveguides (in which the internal nonlinear material has a lower TPA to Kerr ratio). Alternatively, the energy lost through TPA can be partially recovered (as is described below) by extracting it from the generated charge carriers.

Free charge carrier interactions

The free charge carriers within silicon can both absorb photons and change its refractive index. This is particularly significant at high intensities and for long durations, due to the carrier concentration being built up by TPA. The influence of free charge carriers is often (but not always) unwanted, and various means have been proposed to remove them. One such scheme is to implant the silicon with helium in order to enhance carrier recombination. A suitable choice of geometry can also be used to reduce the carrier lifetime. Rib waveguides (in which the waveguides consist of thicker regions in a wider layer of silicon) enhance both the carrier recombination at the silica-silicon interface and the diffusion of carriers from the waveguide core.

A more advanced scheme for carrier removal is to integrate the waveguide into the intrinsic region of a PIN diode, which is reverse biased so that the carriers are attracted away from the waveguide core. A more sophisticated scheme still, is to use the diode as part of a circuit in which voltage and current are out of phase, thus allowing power to be extracted from the waveguide. The source of this power is the light lost to two photon absorption, and so by recovering some of it, the net loss (and the rate at which heat is generated) can be reduced.

As is mentioned above, free charge carrier effects can also be used constructively, in order to modulate the light.

Second-order nonlinearity

Second-order nonlinearities cannot exist in bulk silicon because of the centrosymmetry of its crystalline structure. By applying strain however, the inversion symmetry of silicon can be broken. This can be obtained for example by depositing a silicon nitride layer on a thin silicon film. Second-order nonlinear phenomena can be exploited for optical modulation, spontaneous parametric down-conversion, parametric amplification, ultra-fast optical signal processing and mid-infrared generation. Efficient nonlinear conversion however requires phase matching between the optical waves involved. Second-order nonlinear waveguides based on strained silicon can achieve phase matching by dispersion-engineering. So far, however, experimental demonstrations are based only on designs which are not phase matched. It has been shown that phase matching can be obtained as well in silicon double slot waveguides coated with a highly nonlinear organic cladding and in periodically strained silicon waveguides.

The Raman effect

Silicon exhibits the Raman effect, in which a photon is exchanged for a photon with a slightly different energy, corresponding to an excitation or a relaxation of the material. Silicon's Raman transition is dominated by a single, very narrow frequency peak, which is problematic for broadband phenomena such as Raman amplification, but is beneficial for narrowband devices such as Raman lasers. Early studies of Raman amplification and Raman lasers started at UCLA which led to demonstration of net gain Silicon Raman amplifiers and silicon pulsed Raman laser with fiber resonator (Optics express 2004). Consequently, all-silicon Raman lasers have been fabricated in 2005.

The Brillouin effect

In the Raman effect, photons are red- or blue-shifted by optical phonons with a frequency of about 15 THz. However, silicon waveguides also support acoustic phonon excitations. The interaction of these acoustic phonons with light is called Brillouin scattering. The frequencies and mode shapes of these acoustic phonons are dependent on the geometry and size of the silicon waveguides, making it possible to produce strong Brillouin scattering at frequencies ranging from a few MHz to tens of GHz.Stimulated Brillouin scattering has been used to make narrowband optical amplifiers as well as all-silicon Brillouin lasers. The interaction between photons and acoustic phonons is also studied in the field of cavity optomechanics, although 3D optical cavities are not necessary to observe the interaction. For instance, besides in silicon waveguides the optomechanical coupling has also been demonstrated in fibers and in chalcogenide waveguides.

Solitons

The evolution of light through silicon waveguides can be approximated with a cubic Nonlinear Schrödinger equation, which is notable for admitting sech-like soliton solutions. These optical solitons (which are also known in optical fiber) result from a balance between self phase modulation (which causes the leading edge of the pulse to be redshifted and the trailing edge blueshifted) and anomalous group velocity dispersion. Such solitons have been observed in silicon waveguides, by groups at the universities of Columbia, Rochester, and Bath.

CZTS

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/CZTS

CZTS
Names
CZTS crystal structure. Orange: Cu, grey: Zn/Fe, blue: Sn, yellow: S.
Other names copper zinc tin sulfide
Identifiers
CAS Number	12158-89-3
Properties
Chemical formula	Cu₂ZnSnS₄
Molar mass	439.471 g/mol
Appearance	Greenish black crystals
Density	4.56 g/cm³
Melting point	990 °C (1,810 °F; 1,260 K)
Band gap	1.4–1.5 eV
Structure
Crystal structure	Tetragonal
Lattice constant	a = 0.5435 nm, c = 1.0843 nm, Z = 2

Copper zinc tin sulfide (CZTS) is a quaternary semiconducting compound which has received increasing interest since the late 2000s for applications in thin film solar cells. The class of related materials includes other I₂-II-IV-VI₄ such as copper zinc tin selenide (CZTSe) and the sulfur-selenium alloy CZTSSe. CZTS offers favorable optical and electronic properties similar to CIGS (copper indium gallium selenide), making it well suited for use as a thin-film solar cell absorber layer, but unlike CIGS (or other thin films such as CdTe), CZTS is composed of only abundant and non-toxic elements. Concerns with the price and availability of indium in CIGS and tellurium in CdTe, as well as toxicity of cadmium have been a large motivator to search for alternative thin film solar cell materials. The power conversion efficiency of CZTS is still considerably lower than CIGS and CdTe, with laboratory cell records of 11.0 % for CZTS and 12.6 % for CZTSSe as of 2019.

Crystal structure

CZTS is a I₂-II-IV-VI₄ quaternary compound. From the chalcopyrite CIGS structure, one can obtain CZTS by substituting the trivalent In/Ga with a bivalent Zn and IV-valent Sn which forms in the kesterite structure.

Some literature reports have identified CZTS in the related stannite structure, but conditions under which a stannite structure may occur are not yet clear. First-principle calculations show that the crystal energy is only 2.86 meV/atom higher for the stannite than kesterite structure suggesting that both forms can coexist. Structural determination (via techniques like X-ray diffraction) is hindered by disorder of the Cu-Zn cations, which are the most common defect as predicted by theoretical calculations and confirmed by neutron scattering. The near random ordering of Cu and Zn may lead to misidentification of the structure. Theoretical calculations predict the disorder of the Cu-Zn cations to lead to potential fluctuations in the CZTS and could therefore the cause for the large open circuit voltage deficit, the main bottle neck of state-of-the-art CZTS devices. The disorder can be reduced by temperature treatments. However, other temperature treatments alone do not seem to be able to yield highly ordered CZTS. Other strategies need to be developed to reduce this defect, such as tuning of the CZTS composition.

Material properties

Carrier concentrations and absorption coefficient of CZTS are similar to CIGS. Other properties such as carrier lifetime (and related diffusion length) are low (below 9 ns) for CZTS. This low carrier lifetime may be due to high density of active defects or recombination at grain boundaries. Defect formation in CZTS is prevalent due to low defect formation energies of zinc-copper antisite defects and copper vacancies. These defects create 'effective' charge in the crystal structure, which is stabilized by the aggregation of different defects that compensate for the charge disparity to become effectively neutral. As a result, electron-trapping states are formed, which enables recombination. Having deep-level defect states lowers the open-circuit voltage and the conversion efficiency of a CZTS solar cell.

Many secondary phases are possible in quaternary compounds like CZTS and their presence can affect the solar cell performance. Secondary phases can provide shunting current paths through the solar cell or act as recombination centers, both degrading solar cell performance. From the literature it appears that all secondary phases have a detrimental effect on CZTS performance, and many of them are both hard to detect and commonly present. Common phases include ZnS, SnS, CuS, and Cu₂SnS₃. Identification of these phases is challenging by traditional methods like X-ray diffraction (XRD) due to the peak overlap of ZnS and Cu₂SnS₃ with CZTS. Other methods like Raman scattering are being explored to help characterize CZTS.

Fabrication

CZTS has been prepared by a variety of vacuum and non-vacuum techniques. They mostly mirror what has been successful with CIGS, although the optimal fabrication conditions may differ. Methods can be broadly categorized as vacuum deposition vs. non-vacuum and single-step vs. sulfization/selenization reaction methods. Vacuum-based methods are dominant in the current CIGS industry, but in the past decade there has been increasing interest and progress in non-vacuum processes owing to their potential lower capital costs and flexibility to coat large areas.

The record-holding CZTS solar cells is made by spin coating a hydrazine-based slurry. Due to its reducing character, hydrazine can stabilize sulfide and selenide anions in solution without adding impurities into the mix. To prevent defect formation, copper-poor and zinc-rich solutions were used.

A particular challenge for fabrication of CZTS and related alloys is the volatility of certain elements (Zn and SnS) which can evaporate under reaction conditions. Once CZTS is formed, element volatility is less of a problem but even then CZTS will decompose into binary and ternary compounds in vacuum at temperatures above 500 °C. This volatility and difficulty of preparing a single-phase material has resulted in the success of many traditional vacuum methods. Currently the best CZTS devices have been achieved through certain chemical methods which allow CZTS formation at low temperatures avoiding volatility problems.

A continuous flow process using ethylene glycol as a solvent has been developed at Oregon State University which may be suitable for industrial scale mass production.

Motivation for development

CIGS and CdTe are two of the most promising thin-film solar cells and have recently seen growing commercial success. Despite continued rapid cost reduction, concerns about material price and availability as well as toxicity have been raised. Although current material costs are a small portion of the total solar cell cost, continued rapid growth of thin-film solar cells could lead to increased material price and limited supply.

For CIGS, indium has been subject to growing demand because of the rapid expansion of indium tin oxide (ITO) used in flat screen displays and mobile devices. The demand coupled with limited supply helped prices quickly climb to over $1000/kg before the global recession. While processing and capital equipment make up the majority of the costs for producing a CIGS solar cells, the price of the raw material is the lower bound for future costs and could be a limiting factor in decades ahead if demand continues to increase with limited supply. Indium exists mostly in low concentration ore deposits and is therefore obtained mainly as a byproduct of zinc mining. Growth projections based on many assumptions suggest that indium supply could limit CIGS production to the range of 17–106 GW/yr in 2050. Tellurium is even scarcer than indium, although demand has also been historically lower. Tellurium abundance in the earth's crust is similar to that of gold, and projections of future availability range from 19 to 149 GW/yr in 2050.

CZTS (Cu₂ZnSnS₄) offers to alleviate the material bottlenecks present in CIGS (and CdTe). CZTS is similar to the chalcopyrite structure of CIGS but uses only earth-abundant elements. Raw materials are about five times cheaper than those for CIGS, and estimates of global material reserves (for Cu, Sn, Zn and S) suggest we could produce enough energy to power the world with only 0.1% of the available raw material resources. In addition, CZTS is non-toxic, unlike CdTe and to a lesser extent CIGS (although selenium is sometimes alloyed with CZTS and CdS is sometimes used as the n-type junction partner). In addition to these economical and environmental benefits, CZTS exhibits much greater radiation hardness than other photovoltaic materials, making it an excellent candidate for use in space.

Development of solar cells

CZTS was first created in 1966 and was later shown to exhibit the photovoltaic effect in 1988. CZTS solar cells with efficiency up to 2.3% were reported in 1997, as well as CZTSe devices. The solar cell efficiency in CZTS was increased to 5.7% in 2005 by optimizing the deposition process. Recently, a 3.4% bifacial device, using In substituted CZTS (CZTIS) absorber material and transparent conducting back contact was reported in 2014, which can produce photocurrent on either side of illumination; later, the device efficiency based on this bifacial configuration has been boosted to 5.8% in 2016. Additionally, it has been demonstrated that sodium has an enhancing effect on the structural and electrical properties of CZTS absorber layers. These improvements, alongside the beginnings of CIGS production on a commercial scale in the mid-2000s catalyzed research interest in CZTS and related compounds.

Since 1988 CZTS was considered as an alternative to CIGS for commercial solar cell systems. The advantage of CZTS is the lack of the relatively rare and expensive element indium. The British Geological Survey Risk List 2011 gave indium a "relative supply risk index" of 6.5, where the maximum was 8.5.

In 2010, a solar energy conversion efficiency of about 10% was achieved in a CZTS device. CZTS technology is now being developed by several private companies. In August 2012, IBM announced they had developed CZTS solar cell capable of converting 11.1% of solar energy to electricity.

In 2013 Rajeshmon et al. reported an efficiency of 1.85% on spray pyrolysed CZTS/In₂S₃ solar cell.

In November 2013, the Japanese thin-film solar company Solar Frontier announced that in joint research with IBM and Tokyo Ohka Kogyo (TOK), they had developed a world-record setting CZTSSe solar cell with a 12.6% energy conversion efficiency.

In 2018, CZTS nanoparticles were used as a hole transport layer for perovskite solar cells as a method to increase device stability and affordability, yielding a reported conversion efficiency of 9.66%.

Stellar parallax

From Wikipedia, the free encyclopedia

Stellar parallax is the apparent shift of position (parallax) of any nearby star (or other object) against the background of distant stars. By extension, it is a method for determining the distance to the star through trigonometry, the stellar parallax method. Created by the different orbital positions of Earth, the extremely small observed shift is largest at time intervals of about six months, when Earth arrives at opposite sides of the Sun in its orbit, giving a baseline distance of about two astronomical units between observations. The parallax itself is considered to be half of this maximum, about equivalent to the observational shift that would occur due to the different positions of Earth and the Sun, a baseline of one astronomical unit (AU).

Stellar parallax is so difficult to detect that its existence was the subject of much debate in astronomy for hundreds of years. Thomas Henderson, Friedrich Georg Wilhelm von Struve, and Friedrich Bessel made first successful parallax measurements in 1832–1838, for the stars Alpha Centauri, Vega, and 61 Cygni.

Parallax method

Principle

Throughout the year the position of a star S is noted in relation to other stars in its apparent neighborhood:

Stars that did not seem to move in relation to each other are used as reference points to determine the path of S.

The observed path is an ellipse: the projection of Earth’s orbit around the Sun through S onto the distant background of non-moving stars. The farther S is removed from Earth’s orbital axis, the greater the eccentricity of the path of S. The center of the ellipse corresponds to the point where S would be seen from the Sun:

The plane of Earth’s orbit is at an angle to a line from the Sun through S. The vertices v and v' of the elliptical projection of the path of S are projections of positions of Earth E and E’ such that a line E-E’ intersects the line Sun-S at a right angle; the triangle created by points E, E’ and S is an isosceles triangle with the line Sun-S as its symmetry axis.

Any stars that did not move between observations are, for the purpose of the accuracy of the measurement, infinitely far away. This means that the distance of the movement of the Earth compared to the distance to these infinitely far away stars is, within the accuracy of the measurement, 0. Thus a line of sight from Earth's first position E to vertex v will be essentially the same as a line of sight from the Earth's second position E' to the same vertex v, and will therefore run parallel to it - impossible to depict convincingly in an image of limited size:

Since line E'-v' is a transversal in the same (approximately Euclidean) plane as parallel lines E-v and E'-v, it follows that the corresponding angles of intersection of these parallel lines with this transversal are congruent: the angle θ between lines of sight E-v and E'-v' is equal to the angle θ between E'-v and E'-v', which is the angle θ between observed positions of S in relation to its apparently unmoving stellar surroundings.

The distance d from the Sun to S now follows from simple trigonometry:

tan(½θ) = E-Sun / d,

so that d = E-Sun / tan(½θ), where E-Sun is 1 AU.

The more distant an object is, the smaller its parallax.

Stellar parallax measures are given in the tiny units of arcseconds, or even in thousandths of arcseconds (milliarcseconds). The distance unit parsec is defined as the length of the leg of a right triangle adjacent to the angle of one arcsecond at one vertex, where the other leg is 1 AU long. Because stellar parallaxes and distances all involve such skinny right triangles, a convenient trigonometric approximation can be used to convert parallaxes (in arcseconds) to distance (in parsecs). The approximate distance is simply the reciprocal of the parallax: $d (pc) \approx 1 / p (arcsec) .$ For example, Proxima Centauri (the nearest star to Earth other than the Sun), whose parallax is 0.7685, is 1 / 0.7685 parsecs = 1.301 parsecs (4.24 ly) distant.

Variants

Stellar parallax is most often measured using annual parallax, defined as the difference in position of a star as seen from Earth and Sun, i.e. the angle subtended at a star by the mean radius of Earth's orbit around the Sun. The parsec (3.26 light-years) is defined as the distance for which the annual parallax is 1 arcsecond. Annual parallax is normally measured by observing the position of a star at different times of the year as Earth moves through its orbit.

The angles involved in these calculations are very small and thus difficult to measure. The nearest star to the Sun (and also the star with the largest parallax), Proxima Centauri, has a parallax of 0.7685 ± 0.0002 arcsec. This angle is approximately that subtended by an object 2 centimeters in diameter located 5.3 kilometers away.

Derivation

For a right triangle,

\tan p = \frac{1 au}{d},

where $p$ is the parallax, 1 au (149,600,000 km) is approximately the average distance from the Sun to Earth, and $d$ is the distance to the star. Using small-angle approximations (valid when the angle is small compared to 1 radian),

\tan x \approx x radians = x \cdot \frac{180}{π} degrees = x \cdot 180 \cdot \frac{3600}{π} arcseconds,

so the parallax, measured in arcseconds, is

p^{″} \approx \frac{1 au}{d} \cdot 180 \cdot \frac{3600}{π} .

If the parallax is 1", then the distance is

d = 1 au \cdot 180 \cdot \frac{3600}{π} \approx 206, 265 au \approx 3.2616 ly \equiv 1 parsec .

This defines the parsec, a convenient unit for measuring distance using parallax. Therefore, the distance, measured in parsecs, is simply $d = 1 / p$ , when the parallax is given in arcseconds.

Error

Precise parallax measurements of distance have an associated error. This error in the measured parallax angle does not translate directly into an error for the distance, except for relatively small errors. The reason for this is that an error toward a smaller angle results in a greater error in distance than an error toward a larger angle.

However, an approximation of the distance error can be computed by

δ d = δ (\frac{1}{p}) = | \frac{\partial}{\partial p} (\frac{1}{p}) | δ p = \frac{δ p}{p^{2}}

where d is the distance and p is the parallax. The approximation is far more accurate for parallax errors that are small relative to the parallax than for relatively large errors. For meaningful results in stellar astronomy, Dutch astronomer Floor van Leeuwen recommends that the parallax error be no more than 10% of the total parallax when computing this error estimate.

History of measurement

Early theory and attempts

Stellar parallax is so small that it was unobservable until the 19th century, and its apparent absence was used as a scientific argument against heliocentrism during the early modern age. It is clear from Euclid's geometry that the effect would be undetectable if the stars were far enough away, but for various reasons, such gigantic distances involved seemed entirely implausible: it was one of Tycho Brahe's principal objections to Copernican heliocentrism that for it to be compatible with the lack of observable stellar parallax, there would have to be an enormous and unlikely void between the orbit of Saturn and the eighth sphere (the fixed stars).

James Bradley first tried to measure stellar parallaxes in 1729. The stellar movement proved too insignificant for his telescope, but he instead discovered the aberration of light and the nutation of Earth's axis, and catalogued 3,222 stars.

19th and 20th centuries

Measurement of annual parallax was the first reliable way to determine the distances to the closest stars. In the second quarter of the 19^th century, technological progress reached to the level which provided sufficient accuracy and precision for stellar parallax measurements. The first successful stellar parallax measurements were done by Thomas Henderson in Cape Town South Africa in 1832–1833, where he measured parallax of one of the closest stars, Alpha Centauri. Between 1835 and 1836, astronomer Friedrich Georg Wilhelm von Struve at the Dorpat university observatory measured the distance of Vega, publishing his results in 1837. Friedrich Bessel, a friend of Struve, carried out an intense observational campaign in 1837–1838 at Koenigsberg Observatory for the star 61 Cygni using a heliometer, and published his results in 1838. Henderson published his results in 1839, after returning from South Africa.

Those three results, two of which were measured with the best instruments at the time (Fraunhofer great refractor used by Struve and Fraunhofer heliometer by Bessel) were the first ones in history to establish the reliable distance scale to the stars.

A large heliometer was installed at Kuffner Observatory (In Vienna) in 1896, and was used for measuring the distance to other stars by trigonometric parallax. By 1910 it had computed 16 parallax distances to other stars, out of only 108 total known to science at that time.

Being very difficult to measure, only about 60 stellar parallaxes had been obtained by the end of the 19th century, mostly by use of the filar micrometer. Astrographs using astronomical photographic plates sped the process in the early 20th century. Automated plate-measuring machines and more sophisticated computer technology of the 1960s allowed more efficient compilation of star catalogues. In the 1980s, charge-coupled devices (CCDs) replaced photographic plates and reduced optical uncertainties to one milliarcsecond.

Stellar parallax remains the standard for calibrating other measurement methods (see Cosmic distance ladder). Accurate calculations of distance based on stellar parallax require a measurement of the distance from Earth to the Sun, now known to exquisite accuracy based on radar reflection off the surfaces of planets.

Space astrometry

In 1989, the satellite Hipparcos was launched primarily for obtaining parallaxes and proper motions of nearby stars, increasing the number of stellar parallaxes measured to milliarcsecond accuracy a thousandfold. Even so, Hipparcos is only able to measure parallax angles for stars up to about 1,600 light-years away, a little more than one percent of the diameter of the Milky Way Galaxy.

The Hubble telescope WFC3 now has a precision of 20 to 40 microarcseconds, enabling reliable distance measurements up to 3,066 parsecs (10,000 ly) for a small number of stars. This gives more accuracy to the cosmic distance ladder and improves the knowledge of distances in the Universe, based on the dimensions of the Earth's orbit.

As distances between the two points of observation are increased, the visual effect of the parallax is likewise rendered more visible. NASA's New Horizons spacecraft performed the first interstellar parallax measurement on 22 April 2020, taking images of Proxima Centauri and Wolf 359 in conjunction with earth-based observatories. The relative proximity of the two stars combined with the 6.5 billion kilometer (about 43 AU) distance of the spacecraft from Earth yielded a discernible parallax of arcminutes, allowing the parallax to be seen visually without instrumentation.

The European Space Agency's Gaia mission, launched 19 December 2013, is expected to measure parallax angles to an accuracy of 10 microarcseconds for all moderately bright stars, thus mapping nearby stars (and potentially planets) up to a distance of tens of thousands of light-years from Earth. Data Release 2 in 2018 claims mean errors for the parallaxes of 15th magnitude and brighter stars of 20–40 microarcseconds.

Radio astrometry

Very long baseline interferometry in the radio band can produce images with angular resolutions of about 1 milliarcsecond, and hence, for bright radio sources, the precision of parallax measurements made in the radio can easily exceed those of optical telescopes like Gaia. These measurements tend to be sensitivity limited, and need to be made one at a time, so the work is generally done only for sources like pulsars and X-ray binaries, where the radio emission is strong relative to the optical emission.

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