JPH05501927A - light sensitive recording medium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] light sensitive recording medium Background of the invention The invention generally relates to photosensitive recording media such as photosensitive silver halide emulsions. Regarding.

Photosensitive recording media are used in many different applications and are Logenide emulsions are often used as photographic emulsions. industry The requirements for a commercially successful photographic silver halide emulsion are quite demanding. other These emulsions are highly sensitive or highly fine grained. , has sharpness and wide latitude, and has sufficiently high optical density and sufficiently low It must have a fog density.

Additionally, the emulsion must be highly processable and easy to develop and wash. But at the same time the emulsion can hold or fix the image and its and must be highly resistant to various chemical agents. Besides, Emma The photographic and processability of the emulsion, its stability for a long time before use, and the nature of the emulsion. Highly reliable and reproducible, plus low emulsion production costs That is important.

Many specific photosensitive emulsions that more or less meet these requirements are well known. A few well-known emulsions are dispersed as colloids or in gels. contains particles of silver halide, and either the composition or the nature of the particles is designed to improve or increase the properties of

For example, U.S. Pat. No. 4,484,877 discloses a photosensitive silver halide emulsion. is disclosed, which consists of a silver halide dalein consisting of a core and a shell. The core is Consisting essentially of silver halide containing silver iodide, the shell covers the core and contains the essence It mainly consists of silver bromide, silver chloride or silver chlorobromide.

The shell grows o, 01-0.1 microm thick.

U.S. Pat. No. 4,728,602 discloses silver iodopromide grains consisting of a core and a shell. A photosensitive silver iodopromide emulsion comprising: The core is substantially consists of silver iodopromide containing at least about 5 mole percent silver iodide, and the shell is Iodopromide with a qualitatively lower silver iodide content than the silver iodopromide content of the core. The shell consists essentially of silver bromide. Individual grains of emulsion The relative standard deviation of silver iodide is less than about 20%.

U.S. Pat. No. 4,639,410 discloses silver containing cored dispersed silver halide emulsions. A halide color photographic light sensitive material is disclosed. The shell in the emulsion is Although essentially silver bromide, they may contain silver iodide, silver chloride or silver iodochloride. and the core of each sphere is preferably silver iodopromide. However, it may contain silver halides other than silver iodopromide, such as silver chloride. Wear.

All these emulsions as well as most or all other conventional silver halides Photographic emulsions contain relatively large amounts of silver, and color films contain relatively large amounts of silver. Contains large amounts of dyes and/or dye precursors. Due to the high cost of silver, this less silver and fewer dyes and dye precursors than traditional emulsions It would be highly desirable to provide a silver halide photographic emulsion comprising:

Photosensitive recording media can also be used as optical discs or plates to record data. be done. In these applications, the first beam of light, referred to as the writing beam passes through the recording medium in a pattern consisting of a path or recording medium on a selected area. to represent the stored data. After this change in morphology, The part of the recording medium that was exposed to the writing beam is the part of the recording medium that was not exposed to the writing beam. It can only absorb much more light than the medium.

It is referred to as a reading beam of sufficiently low intensity that it does not change the morphology of the recording medium. The other light beams that are exposed can then pass through the medium. The read beam is When the immersion beam strikes a portion of the recording medium that has been exposed to TrI, it may be reflected or transmitted. , while the read beam is directed to the recording medium that has not been previously exposed to the write beam. When you hit a part, it gets absorbed. In this way, the reading beam is stored on the recording medium. can be used to determine or read data that has been

Until now, optical recording media have not been created using plasmon resonance effects. . The effect is that of increasing the strength of the resulting electromagnetic field. According to the invention, light and significantly improve the sensitivity of the recording medium to other electromagnetic radiation in the optical spectrum. In order to I understood that.

The plasmon resonance effect is exhibited by small particles consisting of an increase in the electromagnetic field at frequencies inside and near the including increased turbulence, absorption and extinction. Extinction is defined as the sum of absorption and scattering . The degree to which a particle exhibits plasmon resonance effects depends on a number of factors, including is the size and shape of the particles, the material or particles, the material being manufactured, and the number of materials. For particles manufactured from . For example, the plasmon resonance effect can be applied to particles with sizes on the order of tens of nanometers. particles, and are therefore commonly referred to as nanoparticles. Because of the above idea, a large number of The nanoparticles consist of materials that are augmented in a selected electromagnetic field frequency range. They are of particular interest because they can be fabricated to exhibit plasmon resonance effects. Plasmon One consequence of the frequency dependence of resonance effects, and hence of absorption and scattering, is that Particles are colored and the result is useful for color photography, color printing, color copying, etc. It is important to be useful. Any frequency that exhibits a plasmon resonance effect of a particle is Also called resonance frequency or plasmon resonance frequency.

Plasmon resonance effects in small metal particles are absorption and scattering phenomena of electromagnetic radiation. It has long been recognized that there is a connection between

Recently, Kerker et al., Phy, Rev. B, 26.4052-4062 (1 In 982), we designed composite nanoparticles consisting of metal and dielectric layers. It was recognized that plasmon resonance can be greatly increased.

It is effective in many ways ranging from nonlinear optomechanical components to photochemical catalysis. allow you to use the fruit.

For example, they can be made of a dielectric material suspended in a medium and surrounded by a shell made of metal. Consider a spherical nanoparticle consisting of a spherical core. much longer than the particle size When electromagnetic radiation of wavelength is incident on the particle, the plasmon resonance effect on it The radiation scattering coefficient a1 of the particle including the effect is given by the following equation.

f is an imaginary number, J=1−, a is the radius of the particle core, b is the radius of the particle, the wavelength of the incident electromagnetic radiation, and the dielectric constant of the ε the law of nature, ε2 is the dielectric constant of the shell, ε is the dielectric constant of the surrounding medium.

In the calculations of this patent, all coefficients of any available magnitude are included. As mentioned above Optical recording media have previously been manufactured to take full advantage of plasmon resonance effects. It had not been done. According to the present invention, selected nanoparticles are provided in an optical recording medium. By this, the plasmon resonance effect can be effectively used to investigate the optical processes occurring in the medium. dramatically increases.

In the present invention, we aim to improve and enhance photographic emulsions and photographic processes. Particles that use various features of the plasmon resonance effect are designed and manufactured to Ru. First, particles are used to increase the electromagnetic field of the silver halide layer of the particles. Increases the intensity and therefore the sensitivity of the silver halide at the point of incidence of light on the emulsion. Increase the strength to a certain level. Second, the amount is much lower than that required for solid silver particles. Manufactured by silver, coated particles are used to increase the absorption and scattering of light by silver. reducing the amount of silver required for photographic emulsions, prints and films. It becomes. Third, coatings that increase frequency-dependent absorption and scattering and thus color Particles can be used to reduce the amount of dye needed for photographic prints and films. It becomes.

Summary of the invention It is an object of the present invention to provide increased optical response in photosensitive media. It is in.

Another object of the invention is to reduce the amount of silver required in photosensitive silver halide emulsions. The goal is to make it less.

Another object of the present invention is to provide the necessary dyes and pigments for photosensitive silver halide emulsions. The goal is to reduce the amount of precursor.

Another object of the invention is to use silver halide coated dielectric particles in a photosensitive recording medium. It's about using it.

Another object of the invention is to produce a silver halide in a photosensitive silver halide emulsion. particles containing a dielectric core coated with a silver halide. Contains a metal shell to increase the sensitivity of the carbonide to light.

Yet another object of the present invention is to combine plasmons to increase the sensitivity of optical recording media. It is based on the use of sound effects.

Another object of the present invention is to provide an optical recording medium with a large number of nanoparticles, each of which This uses the plasmon resonance effect to increase the optical process occurring in the recording medium. It is done as shown.

These and other objectives are achieved by a light sensitive recording medium constructed in accordance with the present invention. It will be done. According to the first embodiment, the medium is a colloid or gel and the colloid is dispersed in Photosensitive silver halide photographic emulsion consisting of a large number of silver halide particles It is. Each of these particles has at least one core surrounded by a shell. One of the core and shell contains silver halide and the other core and shell contain dielectric material. including. Preferably, the core and one of the shells consist essentially of silver halide; and the rest of the shell consists essentially of a dielectric material, and the dielectric material is substantially does not contain silver.

In a second embodiment, the recording medium is applied onto a solid light-reflecting or light-transmitting substrate, the substrate A photosensitive photosensitive material consisting of a colloid and a large number of particles dispersed in the colloid. It is an academic record disc or plate. Each of these particles is surrounded by a shell It includes a core, and at least one of the core and the shell consists essentially of metal. Preferably, Other than the core and shell, these preferred particles consist essentially of a Each core consists essentially of a dielectric material, and each shell of these particles is made of metal.

Other advantages and advantages of the invention are illustrated in the figures which identify and illustrate preferred embodiments of the invention. It will become clear after considering the detailed description given below.

Brief description of the drawing FIG. 1 is a schematic illustration of a photographic emulsion according to the invention.

Figures 2-5 and 5A are either not drawn to scale or the emulsion of Figure 1. Indicates the particles that can be used.

Figures 6-11 are 355 nm, 382 nm, 414 nm, 497 nm, and 6 nm, respectively. Light absorption capacity of solid silver spheres and silver-coated silica spheres at wavelengths of 21 nm and 828 nm Show rate.

Figures 11a-11f show similar wavelength-dependent spectra observed in the scattering and extinction spectra. Indicates the vector.

Figures 12 and 13 also show optical recording media according to the invention.

Figures 14-27, not drawn to scale, are optical recordings of Figures 12 and 13. 3 shows various particles used in the media.

Figures 28-36 can be used to form the particles shown in Figures 2-5 and 14-27. Here are a few ways to do it.

FIG. 37 is a transmission electron micrograph of silver-coated silver bromide nanoparticles.

Figure 38 shows transmission electron microscopy of silver-coated silver bromide nanoparticles treated with ammonia. It's a photo.

Figure 39 shows various optical extinction spectra of silver-coated silver bromide nanoparticles.

(a)-(d) Strets of illuminated solutions of Ag, Br and EDTA at specific concentrations. It is a spectrum. The illumination time increases from a to d.

(e) any of the above solutions, either treated with ammonia or untreated; are representative spectra observed after the addition of ammonia to Measurements were taken immediately after light exposure with a lighting duration of

Figure 40 shows the calculated quenching efficiency for silver-coated silver bromide nanoparticles.

The diameter of the core particles is 20 nm and the thickness of the silver coating is indicated in nm.

The spectrum marked solid is that of a homogeneous 20 nm diameter silver sphere. .

Figure 41 shows the measured optical extinction spectra of silver-coated silver bromide nanoparticles and two measurements. This is the calculated spectrum. The measured spectrum is divided into two calculated spectra. It's between Tor. In the upper curve, all the silver comes from the reduction of AgBr on the particle surface. It is thought that this happened.

Detailed description of preferred embodiments FIG. 1 shows a first photosensitive recording medium 10 according to the invention. This medium is or gel 12, and a large number of silver halide particles 14 dispersed in the colloid. A photosensitive silver halide photographic emulsion consisting of:

Figure 2-5 shows emulsion 10, designated as 16, 20, 22 and 24, respectively. Four types of particles are shown that can be used. Each of these particles has a small amount surrounded by a shell. contains at least one core, and in each of these particles the core and one of the shells are , contains silver halide, and the rest of the core and shell contain dielectric materials. preferably The core and one of the shells consist essentially of silver halide, and the other core and shell consist essentially of silver halide. qualitatively consisting of a dielectric material, furthermore, the dielectric material is substantially free of silver. . For example, the particle 16 may consist of a core 16a and a shell 16b, the core being essentially dielectric. Consists of materials.

The term "dielectric" material or core as used herein refers to materials that are nonconducting or semiconducting. related. The electrical conductivity of the material ranges from 0, but preferably about lo-40-101 mode. It is. In a preferred embodiment, the electrical conductivity ranges from 10 to 15 mho. In a preferred embodiment, the electrical conductivity ranges from IO'' to 10'. Examples of dielectric materials is glass, glue, cadmium sulfide, gallium arsenide, polydiacetylene, sulfide Lead, titanium dioxide, polymethyl acrylate (PMMA), silver bromide, carbon fiber , sulfide steel, silver sulfide, etc.

The coating (coating or skin or shell) is essentially halogenated. Made of silver. Furthermore, in this particle, the film +6b is a core (core, cor e) placed directly above 16a and substantially completely covering core +6a.

For example, the particles 20 include silver, copper, aluminum, gold, or palladium. The metallization is placed between the dielectric core and the silver halide coating, and the halogen It increases the sensitivity of silver oxide to light. This increased sensitivity is It is produced by the plasmon resonance effect generated by the metal coating. Special , the particle 20 is disposed directly above and below the dielectric core 20a. and metallization 20b covering layer 20b and disposed immediately above layer 20b and covering layer 20b. It consists of a coated silver halide layer of 2°C.

If it is desired to use a gold layer between the dielectric core and the silver halide coating, Alternatively, the metal can be separated from the silver halide as is done in grain 22. Alternatively, it may be desirable to provide space to prevent interference in the development of the latent image. stomach. In particular, the particles 22 are arranged in a dielectric core 22a, directly above the core 22a, and a layer of silver 22b covering the core 22a; A layer 22c of dielectric material, such as a polymer, substantially covering the layer of silver and and a halo disposed immediately above layer 22c and substantially completely covering layer 22c. It consists of a film 22d made of silver germide.

Dielectric substance and silver halide used in emulsion 10 The particles form the core and shell of the particles, respectively, and the emulsion shown in Figure 5 The core 24a and the dielectric core 24a can be used in IO and include silver halide. A fourth particle 24 is shown that includes a coating 24b containing a sexual substance. As shown in Figure 5' For particles 24, in some emulsions the particles have a layer of metal (as shown). to increase the sensitivity of silver halide grains, and also However, if this is done, the grain will also have an attraction between its metal layer and the silver halide core. An electrically conductive material (also not shown) is still coated and used in the development of the latent image. It is desirable to prevent such interference.

Coated nanoparticles that feature plasmon resonance effects and can be used to create photographic emitters. Nanoparticles can be designed and made to improve fusion. nanoparticles (nan) The plasmon resonance effect of oparticc]e) is Image recording performance (writing performance) and image reproduction (reading performance) , reading). Next, that plaz A method by which Mon resonance acting particles can be used in the field of photography will be briefly explained. Than A detailed explanation is given below.

Light from a scene strikes a silver halide photographic emulsion (i l lu minate), which forms very small silver particles in silver halide grains. I will make it happen. The pattern of tiny silver particles forms a latent image. Emma against the light increasing the sensitivity of the laser, i.e. forming a latent image with less light It is often desirable to make emulsions that can Halogen emulsion with coated nanoparticles where there is a silver layer below the silver oxide layer. Silver halide against light by replacing solid silver halide particles in It is possible to increase the sensitivity of Moderate thickness dielectric silver, polymer and halogenated The layered particles with silver undergo the previous plasmon resonance action in the silver halide layer. can be increased. Its intensity is optically enhanced and the same intensity of light is irradiated. more latent image centers in plasmon resonant particles than in solid silver halide. Let it form. In this way, a predetermined amount of silver halide can be produced using the plasmon resonance effect. It can increase the sensitivity to light and improve the image recording performance. Ru.

After exposing a typical silver halide emulsion, small tufts of silver in the latent image Clusters are formed from remaining silver in the grain and/or solution. It acts as a nucleus for the reduction of silver. In black and white photography, the reduced silver absorption Density and dispersion adversely affect the image observed when illuminated with light. color photo In , the reduction of silver is coupled with the formation of color. When illuminated with white light , the dye in the emulsion absorbs certain wavelengths, so that the film absorbs them at certain wavelengths. It may emit or reflect complementary wavelengths, or both. solid silver particles particles are formed after the phenomenon in black-and-white photography, and the particles are more abundant with less silver. They replace coated silver nanoparticles that absorb or scatter a lot of light. I can do it.

The same capacitance can be obtained by coating the surface of dielectric nanoparticles with a light thickness. You can make more absorption with silver. So the amount of silver needed in photography can be done without reducing. Also, the pigments formed during development in color photography. is a plasma that reflects or emits colored light when illuminated with white light. It is replaced by silver-coated nanoparticles with Mon resonance effect. Expensive dyes By replacing the particles, d y e’) with coated particles, the price of the film can be reduced. can be made cheaper. And coated nanoparticles with plasmon resonance action children can be used to reduce the price of both color or black and white photographs. Ru.

Particles are designed to be more effective at plasmon resonance to meet their specific purpose. must be designed to be. Next, the plasma used in the coated nanoparticles About Mon resonance and how to use it in optical recording materials or devices. And more about the advantages of using such resonant particles. explain in detail.

The potential for improvement in recording images is described in (1) below. Ru. Improvements in image reading or reproduction will be described in (2) to (4) below.

An improved particle that absorbs stray light is described in (5). by combining some of the particles The emulsion that is used will be described in (6).

(1) Enhancement by plasmon resonance of light in the silver halide layer in the emulsion The coated nanoparticles with the purpose of used to increase the sensitivity of Such coated particles can be photographed in color. It can be used to record any image in black and white photographs. suitable one Nanoparticles of the type have a dielectric core, a first coating of silver, a second coating of polymer and a halo. It has a second coating of silver germide.

The thickness of the core and coating is determined by the action of light in the appropriate wavelength range in the silver halide layer. must be chosen in such a way as to strengthen it. Emulsions can be created using these particles. It has the advantage of increasing sensitivity and reducing the need for silver. ing.

(2) Coated particles that have an enhancing effect by absorbing light through plasmon resonance can be used as absorbing layer regions in black and white films.

Prior to development, the grains are coated with a layer of silver halide. Through development , the silver halide is reduced to a silver coating, and that coating is used for blasmon resonance. It has the correct thickness. Such nanoparticles are solid silver grains with relatively small amounts of silver. It scatters and absorbs light as efficiently as a child. These particles are photographed reducing the amount of silver required in the emulsion, number of prints and film. I can do it. For black-and-white photography, one must have a plasmon resonance effect at different wavelengths. The particles of the population should be combined in the emulsion. With such particles The advantage is that less silver is required. Also, smaller particles are very good absorbers. It can have an astringent effect, and a thinner layer of grains is packed in, which improves the resolution of the film. degrees can be increased considerably.

(3) increases wavelength-dependent scattering and absorption (i.e., extinction), thus Coated particles that emit colored light are used in photographic films and slides. It can be used to reduce the amount of pigment (dye) required in a process.

For applications where light is emitted through the emulsion, colored light or Formed using either scattering or absorption or any combination thereof I can do what I am forced to do. For example, synchrotron radiation or the color that forms the layer that appears red. - Particles in photographic film or slides emit blue and yellow light when developed. It is a particle that absorbs and scatters while emitting red light. The particles are processed before development. , has a layer of silver halide, and when developed, the silver halide layer The resulting thickness of the coating and the thickness of the other layers absorb and scatter particles as desired. It has a thickness such that With such particles they are expensive dyes. It has the advantage of being a substitute for dyes.

(4) Coated nano that has a plasmon resonance effect that scatters light in a certain spectrum Particles are essential in color printing because they color the light reflected from these particles. It can be used to reduce the amount of dye required. These particles are relatively large The plasmon enhancement effect of large wavelength-dependent scattering and the relatively small wavelength-dependent absorption It has a strengthening effect. Relatively large nanoparticles, e.g. Nanoparticles with diameters in the range 0-200 nanometers or This is a heki that is used because it increases the ratio between them. The particles are halogen-free before development. a layer of silver halide, which layer of silver halide, when developed, forms a layer of the silver coating. thickness and other layer thicknesses such that the particles scatter as desired. ing. For example, particles in a photographic print placed in a layer of emulsion that appears red. The particles are particles that scatter red light when developed. Such particles can also be colored Can be used for copying and color ink.

(5) Coated nanoparticles with a plasmon resonance enhancement effect on light absorption are used in photographic applications. Reduces the amount of silver present in absorbent layers of emulsions, prints and films It can be used for These particles have stronger absorption than scattering and are thus particularly small, e.g. in the range of 5 to 60 nanometers. . Such particles can cause stray light in both black and white or color films. Cary-Lea 5ols currently used to absorb ) can be used as an alternative to Those particles are also added to black and white film. It can also be used as an absorption region. With such particles, less It has the advantage of requiring only small particles.

(6) Emulsions that combine the above particles and their effects, and the above advantages and effects. Also useful are particles that combine the effects of (1) and (2) are used Examples of particles that are used include dielectric cores, silver coatings, polymeric coatings, and This includes grains coated with silver halide.

The plasmon resonance effect increases the area in the silver halide layer. silver halide When the particles are developed into silver, the plasmon formation of points scattered or absorbed by the particles occurs. provides the advantage (2) above. The particles described in (5) are also in the same emulsion. It can be used in the

In order to achieve the excellent points described in (2), (3) and (4) above, halogenation It is preferable to reduce the silver coating to a relatively smooth silver coating.

[Referring to J5A, a smooth film of reduced silver is formed on the dielectric material. One method is to form the initial particles 16 with sufficient pores to allow ions to pass through. It is pre-coated with polymer 16C having a diameter. For example, the coating 16C is A It is possible to prevent the g' ions from moving to the next surface position of the polymer.

The polymer 16C helps move Ag° ions to the desired site of growth. It is. Such polymeric coatings may be similar to those specifically shown herein. can be created in a similar way.

There are also other methods of forming silver-coated particles independent of the photographic process.

Figures 2-5 only show representative examples of nanoparticles that can be used in carrying out the present invention. and specifically indicates the general relationship between the indicated core and coating. It is. For any nanoparticles used in the present invention, the particles and The core can be of any shape, specifically the particle and core are other than spherical. It may be in the form of For example, the particles and cores may be cylindrical or circular. , may have a filamentous form, and may be in crystalline form. actual core crystal The form can be any shape, for example, these cores Tetragonal crystal type, orthorhombic crystal type, monophyletic crystal type, triclinic crystal type, equiaxed crystal type, hexagonal crystal type, It is possible to be.

Furthermore, an emulsion is a mixture of particles with different sizes and morphologies. Often the emulsion contains a halogen of the type commonly used in photographic emulsions. It can be a silver oxide grain. Furthermore, among the particles used in the present invention, In particular, dielectric materials can be linear or non-linear. It's good to have something like that. In addition, as used herein, the term "metal" Any material with a negative dielectric constant can be mentioned, including superconductors and conductors. polymers, substances with anomalous dispersion of carrier electrons, and free carriers. Highly doped semiconductors whose function determines their dielectric properties include Ru.

The development of Emulsion 10 was partially due to the fact that solids of the same size were formed under the light of various wavelengths. Coated with silver that absorbs and scatters with greater efficiency than silver spheres absorb and scatter This is shown in Figure 6-11, based on the fact that dielectric spheres are formed. ing.

Figure 6-11 shows the light of various wavelengths on solid silver spheres and silver-coated silica spheres. This shows the efficiency of light absorption at wavelengths of 355nm and 382nm, respectively. Efficiency at 14 nm, 497 nm, 621’nm and 828 nm is shown. Ru. Its efficiency is determined by Tone and Ackerman, Abride Optics, Inc., 1981. (Toon and Ackerman.

Applied Optics, 1981) i: computer processing. The light absorption efficiency Q of a particle is determined by its vertical axis in each figure. is plotted along the magnitude parameter X (equal to 2πr/λ ) (where r is the radius of the particle and λ is the wavelength of interest in each figure) is Plotted along the horizontal axis in the figure. Curves 32a, 34 in Figure 6-11 a, 36a, 40a, 42a and 44a show the light absorption efficiency of solid silver spheres It is something. Curves 32b-d, 34b-f, 36b-e, 40b-g, 42b- f and 44b-e indicate the light absorption efficiency of silver-coated silica spheres. In particular, each of these curves covers an entire coated sphere of the diameter of the inner silica core. shows a constant value (indicated in parentheses) for the ratio of the diameter of .

Thus, for example, the value determined from curve 32b of FIG. Consists of an inner silica core with a diameter that is half the overall diameter This is about a spherical object coated with silver, and is determined from curve 36d in Fig. 8. The absorbance values obtained for the inner silica with a diameter of 06 times the diameter of the entire coated sphere are for silver-coated silica spheres consisting of a core of .

For example, Figure 6 shows the original wavelength of 355 nm, approximately 113 nm (X = 1, 0) and an inner silica tube having an outer diameter of For a coated sphere containing a core, the absorption efficiency of the coated sphere is approximately 0.93. Similarly, FIG. 9 shows the wavelength of 497 nm. It has an outer diameter of approximately 79 nm (X = 0.5), which is the outer diameter of the entire coated sphere. Coated spheres containing an inner silica core with a diameter that is 0.07 times the diameter shows that the absorption efficiency of the coated spheres is about 5.22. .

10 and 11 have outer diameters between 1 nanometer and 100 nanometers. For spheres and for light with wavelengths in the range 621 to 828 nanometers, A moderate thickness of silver absorbs many times more light than a solid silver sphere of the same diameter. Spherical particles consisting of an overturned silica core are shown to absorb. for example, Figure 1O shows that under the wavelength of 621 nm, the outer diameter of about 198 nanometers is The absorption efficiency of solid silver spheres with (X=1.0) is about 0.3, and and secondly, an inner part with the same outer diameter and a diameter 09 times the diameter of the entire coated sphere. Coated spheres with silica cores have an absorption efficiency of about 2.0, which is the same This shows that the absorption efficiency is more than 6 times that of a solid eyeball of the same size. There is. FIG. 11 shows that at a wavelength of 828 nm, the outer diameter of approximately 132 (X= 05) that the absorption efficiency of solid silver spheres is about 0.2, and secondly have the same outer diameter and a diameter 0.9 times the diameter of the entire coated sphere. The coated spheres, which grow an internal silica core, have an absorption efficiency of about 58; This represents an absorption efficiency approximately 29 times greater than that of a solid eye of the same size.

Figures 6 and 7 show approximately the wavelengths of ultraviolet light (355 nanometers and 382 nanometers). At wavelengths of absorbs more light than a silver-coated silica core for at least one sphere between This indicates that the However, for some larger spheres, silver Some of the coated particles are much more sensitive to ultraviolet wavelengths than solid optics or absorbers. Absorbs light from a large amount of light. Also, for some larger sized spheres, coated with silver The solid silver particles and solid silver spheres have similar absorption efficiencies. Absorption section of spherical objects The surface is the absorption efficiency of the sphere multiplied by πr2 (where r is the radius of the sphere). Ru.

Similar wavelength-dependent spectra are also observed in the scattering and absorption spectra. Ru. For smaller sized spheres, e.g. 1Onm, the absorption is due to scattering. and coated spheres of larger size, e.g. 200 nm. If the core or coating is moderately large, the scattering will be greater than the absorption. I hear it.

Figures 11a and 11b show the following: (1) λ-dependent spectrum and Q when the particle is small, <<Q,. Figure 11c shows Q when the diameter is ~1100n, ~Q5 It shows. Figures 11d and lle show that the solid spherical shape especially when λ>500 nm The Cabs/Vol of the covered sphere is larger than the Cabs/Vol of the object. It shows.

The light-absorbing pattern of each coated particle is determined by the diameter of the internal silica core and the coating on that core. The desired absorption properties are a function of the thickness of the film and the wavelength of the light impinging on the particles. Make a film emulsion by combining the appropriate amount of coated particles of the given size The coated particles can be obtained for may be combined with other particles. Many times, ``absorption, scattering, or absorbance In order to avoid repeating false statements, in the following description of the synthesis of the properties, , although the method is useful for scattering or absorption spectra as well. It is merely described as an absorption property. One way to synthesize absorption properties takes a large number of coated particles that absorb light over a range of wavelengths of light. , divide the large number of particles into groups according to particle size or coating thickness, and then Make a mixture of particles from these groups and calculate the amount or amount of particles taken from each group weighed. This is done in proportions so that the resulting mixture has the desired absorbency. It is.

For example, if a particular absorption, D(λ), is desired over the visible wavelength range and the initial A large number of coated particles absorb light over this wavelength range, in which case these particles are dispersed in water1, and the dielectric core of the coated particles is about 30 nm. It appears to have a uniform diameter. The coated particle is the thickness of the coating Grouped according to For example, the particles are divided into groups of 14, i.e. 1.5 nm, 1.75 nm, 2. Onm, 2.25nm, 2.5nm, 3.0nm, 3 ．． 5nm, 4.0nm, 4.5nm, 5.0nm,! 3.0nm, 7.0nm, By dividing into groups with film thicknesses of 9.0 nm and 12.0 nm. Wear. The light absorption of each group of particles is expressed as a function of the wavelength of light falling on the particles. and more generally, the absorbency of the first group of particles is A , (λ), where λ is the wavelength of the light hitting the particle. Ru.

The actual absorbency T(λ) of a mixture containing N groups of grains can be expressed as: You can do something like (where a indicates the proportion of particles of the i-th group in the mixture). desired absorbency To achieve this, at (i.e. at, a2, ... aS) is chosen and T(λ ) is approximately equal to or very close to D(λ). It is decided that at or any method could be used to estimate it.

According to one very well-known method, that al is between D(λ) and T(λ) It is estimated so that the sum of the squares of the differences or the integral value C is minimized.

If you follow this method, c-f(D(λ)-Ding(λ))2dλ A set of 81 that minimizes this difference is, for example, a gradient search method (e.g., a practical Pra-ctical Marys Obtimization (Pra-ctical M methods of Optimization) Frefti? -(Fletch (1981)). Therefore, it can be found or estimated as appropriate.

The mixture of coated particles required to achieve the desired absorbency is then: In combining N groups of particles, each weighted by its associated aI, It will be done more.

Another method for obtaining film emulsions with the desired light absorption properties is a series of layers with different particle sizes or types. The purpose is to form a lume emulsion.

12 and 13 refer generally to 50a and 50b, respectively, and also refer to the present invention. 2 illustrates two embodiments of the second type of light-sensitive recording medium according to the invention; . This medium is a light-sensitive optical recording disk or plate; , a solid substrate 52 that reflects or emits light, and a substrate 52 supported by the substrate. This includes a large number of particles 54. The particles 54 are as shown in FIG. may be carried directly by the substrate 52, or as shown in FIG. Similarly, particles 54 are dispersed in a colloid or gel 56 applied onto a substrate. I can do it. Each particle 54 includes a core surrounded by a skin; At least one of the core and the skin consists essentially of metal. Like or the core and the rest of the coating consist essentially of dielectric material; More specifically, preferably the core of each of these particles is made of an essentially dielectric material. It has become. The coating of each particle is made of metal.

To record data in a 50a or 50b medium, a light beam, that is Also called a write beam, A light beam of sufficient intensity to alter the morphology of the coated particles 54, e.g. , such as those modified by dissolving the silver coating or dielectric core. The beam is caused to pass over the recording medium in the desired pattern and its path or selection changes the morphological structure of the particle over a defined region, thereby preserving represents the data. Because of this change in morphology, the light beam Is the part of the media exposed to the light beam the part of the media not exposed to the light beam? It has the ability to absorb less light than it absorbs.

Another light beam, also known as the read beam, ), but this strength is sufficiently low that it does not change the morphology and structure of the particles 54. Or it can then be passed over a recording medium.

The light beam hits a part of the recording medium that has been previously exposed to the light beam. The lead beam is then exposed to a light beam. It is absorbed when it hits a part of the recording medium that is not covered. Of this method, A system can be used to determine or read data stored in a recording medium. can. As appreciated by those skilled in the art, the In any nanoparticle, the particle and core may have any suitable shape. Specifically, the particles and core must be cylindrical or circular. It may be in solid, filamentous or crystalline form. Also, The light beam alters these particles in a variety of specific ways to produce the desired result. Used to tighten. Furthermore, regarding the particles 54 containing a dielectric substance, , a suitable dielectric material may also be used, in particular the dielectric material may be linear or It may be non-linear. In addition, as used herein, the term "metal" '' can be any material with a negative dielectric constant, which is super Electric conductors, conductive polymers, substances with irregular dispersion of carrier electrons, and Heavily toped semiconductors that define free carrier behavior or dielectric properties I can give my body away.

A suitable or preferred method for use in the recording medium shown in FIGS. 12 and 13. In forming and selecting new particles, it is helpful to keep the following considerations in mind.

l) There are significant plasmon resonance effects exhibited by certain particles (resonant vibrations and At wavelengths of light (also known as particles), the electromagnetic field surrounding the particles is enhanced.

ll) Heat generated by electromagnetic fields or the absorption of these fields inside or outside the particle. The surrounding particles change the particles so that they absorb or scatter less light. Ru.

1) I) Plasma represented by dielectric layered particles made of small metals The Summon effect depends on the size and dielectric constant of these layers, and on the physical structure of the particles. Only a relatively small change in the structure causes the particle to absorb or scatter light. They can be made to vary considerably in the manner or degree of rolling.

iv) Magnetic materials can be used up to or beyond the Curie point of the material. When heated, it becomes non-magnetic.

Based on the above facts, the particles for the recording media 50a and 50b are, on the one hand, Significantly alters the ability of particles to absorb or scatter light using a light beam. On the one hand, the ability of particles to absorb or scatter light in a light beam It is possible to make it so that it does not change noticeably where there is no difference.

For example, for the first general group of particles, the particle has a core and a can include a layer of one substance and a layer of a second substance; Each layer is made of a material different from that of the other layers, and its light The beam allows these two substances to react with each other and determines the dielectric constant of the particle's original substance. It is possible to form a third material with a different dielectric constant. FIG. 14 shows the core 60 a shows a particle 60 containing a first layer 60b and a second layer 60c; One of the layers 60b and 60C is a dielectric material, such as an oxide, and The other of these layers 60b and 60c is a metal, such as silver. light The energy of the beam causes layers 60b and 60c to react with each other to form dielectric silver oxide. to form. A different particle is shown at 62 in Figure 15, and this particle is 62a and a dielectric layer 62b formed thereon. The particles 62 formed are , since it does not have a metal layer, this particle does not exhibit plasmon resonance effects.

Therefore, the light absorption and reflection properties of particles 62 are the same as the light absorption and reflection properties of particles 60, respectively. It is very different from radiation.

As another example, FIG. 16 shows a core 64a and first and second layers 64b, 64c. 64, each of the latter two layers each containing one type of attractant. It is made up of electrically conductive substances. The light beam causes these dielectric materials to react with each other and the ice A dielectric constant different from that of the material used for a forming the layers 64b and 64c. form a third dielectric substance with This changed particle is shown at 66 in Figure 17. It is shown. The particles are formed from the core 66a and the dielectric material 66b formed. It has become.

Concerning the second general particle of lath, which is represented by particle 70 in Figure 8, The particle consists of a core 70a and one or more layers 70b and 70c. One of these layers is made of monomer. Light beam is that thing Polymerization of the monomer layer transforms the layer into a solid phase, which has a dielectric constant of the monomer. It has a dielectric constant different from . The formed particles are shown at 72 in FIG. and the particles are shown as having a core 72a, a first layer 72b and a polymer layer 7. It consists of 2c. layer of monomer 70c at low temperature to create the particles 70 itself. Preferably, it is formed or applied onto the core 70a of the particle.

Regarding the third general particle, the light beam changes the shape of the particle. It is used to change the absorption or reflection of light. for example, FIG. 20 shows a spherical shape consisting of a core 74a, a first shell 74b, and a second outer skin 74c. This shows a particle 74 that does not have a particle size. Is the light beam absorbed by the particle 74? The energy causes the shell 74C to melt and then interact with the medium in which the particles are suspended. Surface tension between the remaining shell 74b causes the shell and core to become spherical. Figure 21 Particles formed at 76 are shown. The particles then have a core 76a and a shell 7 It consists of 6b. The plasmon resonance effect exhibited by particle 76 is is different from the plasmon resonance effect shown by The light absorption and reflection properties are different from those of the latter particles.

For the fourth common particle, the light beam melts the outer layer of the particle. This molten material is then used to transfer the particles to the substrate on which they are supported or to the substrate. It mixes with the dielectric constant of the medium surrounding the particle and changes its dielectric constant. for example , FIG. 22 shows a core 80a and coatings 80b and 80c dispersed in a medium 82. A particle 80 that has been removed is shown. In use, the light beam melts the coating 80c. , the material from the coating mixes with the medium 82. The result of this process is shown in Figure 23. The core 84a and the coating 84b are dispersed in a medium 86. Particles 84 are shown. represented in the medium 86 by particles 84 The plasmon resonance effect is caused by the plasmon resonance exhibited by the particles 80 in the medium 82. The sound effect is different. As a result, the light absorption or The light reflection property is the light absorption property or light reflection property of the particle 80 in the medium 82, respectively. It's different.

For the fifth class of particles, the light beam melts the outer layer of the particle. used to change the structure of the inner layer of the particle, e.g. from amorphous to crystalline. or convert crystalline substances into amorphous substances. Figure 24 shows this type of particle; This includes a core 90a and coatings 90b and 90c. The light beam is the outer skin By melting the film 90c and changing the structure of the inner film 90b, grains shown as 92 in FIG. 25 are formed. It is composed of a core 92a and a film 92b. to particle 92 The plasmon resonance effect produced is therefore different from that exhibited by particle 90. As a result, the light absorption and light reflection properties of these two particles are different.

The seventh class of particles contains a layer of magnetized material and is Energy is used to raise the temperature of this material by more than one curie point of that material. There, the object is no longer magnetic. For example, Figure 26 shows this general A type of particle 94 is shown, which has a core 94a made of magnetic material. and a film 94b made of metal.

In implementation, the light beam is arranged such that the particles are at the level of one or more curie points in the core 94a. 94 so that its core is no longer magnetic.

As another example, a particle 96 including a core 96a and two coatings 96b and 96c may be used as shown in FIG. 7. The core 96a is made of a dielectric material, and the coating 96b is made of a dielectric material. It is metal, and the film 96c is a magnetic material. In the recording medium 50a or 50b Then, the light beam raises the temperature of the film 96C at one or more points of Curi. The coating is no longer magnetic.

As will be understood by those skilled in the art, reversible methods may be used to record media 50a and By changing the particles of 50b, a system that can be written and read many times is created. for example, The coated sphere is a single Curie dot (a type of curie used in optical discs). only to raise the temperature to about +50°C (about +50°C in magnetic materials) The magnetic field can be used to increase the magnetic domain. It can also be used to set the orientation of the beam. The second method is reversible.

The above-mentioned changes caused by the light beam or other similar changes changes that are absorbed by the light or the recording medium or emitted through the recording medium. change the extent to which The particles in the recording medium 50a or 50b are, for example, optical placed on the surface, as in a disk, or distributed throughout it. It's good to be closed. When the particles are dispersed throughout, the Preference is given to particles of such density. In addition, metals are dielectric layered grains reacting with to form another dielectric material, e.g. grains 60. children are particularly useful for forming volume phase holograms. monomer The particles whose polymerization process is initiated by the light beam are also polymerized. It is particularly useful for forming luminous phase holograms.

The sensitizer used in ordinary photographic emulsions is the one used in the photographic emulsion of the present invention. in which the coating used on the outside or inside of the silver halide layer Can be used with other spheres.

Furthermore, the silver halide emulsion of the present invention can be prepared using various known chemical methods. can be processed by conventional sensitization methods. For example, the emulsion is active Sulfur-containing compounds that can react with gelatin and silver (e.g. thiosulfates) sulfur sensitization method using Reducing agent substances (e.g., stannous 5alts), amines, (such as dorazine derivatives, formamidine sulfinic acid or silane compounds) reduction sensitization method or noble metal compounds (e.g., total complex salts, metals belonging to group , for example, complex salts with pt, rr or Pd). It can be processed as follows.

Gelatin can be used as a protective colloid for preparing the silver halide emulsion of the present invention. Wear. However, for example, gelatin derivatives; graft polymers of gelatin and other heavy Aggregates: proteins such as albumin and casein; hydroxyethyl cellulose , carboxymethylcellulose, cellulose sulfate esters, etc. Derivatives, sugar derivatives such as sodium alginate and starch derivatives: Polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly-N-vinylpyro Lydone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl various synthetic hydrophilic polymers such as imidazole and polyvinylpyrazole; Other hydrophilic colloids can also be used, such as synthetic hydrophilic copolymers;

Regarding gelatin, there are gelatin hydrolysis products and gelatin enzymatic degradation products. Similarly, lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin are Can be used.

To stabilize the photographic properties of emulsions, and to stabilize photographic materials such as silver halide-containing emulsions. The silver halide-containing compound of the present invention is used to prevent fogging during manufacturing, storage, and processing steps. A variety of compounds can be added to photographic emulsions. antifoggant and stabilizer Examples of oxidizing agents include benzothiazinium salts, dinitroimidazoles, and nitrobenes. Zoimidazoles; Chlorobenzimidazoles; Bromobenzimidazoles :Mercaptothiazoles; Mercaptothiadiazoles, aminotriazoles Benzotriazoles, Nitrobenzotriazoles: Mercaptotetrazo Moles; mercaptopyrimidines, mercaptotriazines, oxazolinthio thioketo compounds such as triazaindenes, tetraazaindenes, and azaindenes, such as azaindenes: benzenethiosulfonic acid: ben Examples include zenesulfinic acid and benzenesulfonic acid amide.

photographic materials for increased sensitivity and contrast, or silver halide-containing emulsions; In order to accelerate the development of the silver halide emulsion of the present invention, an agent may be further added to the silver halide containing photographic emulsion of the present invention. esters, esters, amines, thioether compounds.

Thiomorpholines, quaternary ammonium salt compounds 7 Urethane derivatives: urea derivatives polyalcohols such as derivatives, imidazole derivatives, and 3-fisibriton derivatives. Kylene oxides and derivatives thereof may be included.

The silver halide-containing photographic emulsion of the present invention includes cyanine dyes, merocyanine dyes, Complex cyanine dyes, complex merocyanine dyes, holo-polar cyanine dyes, hemi- Methine dyes such as cyanine dyes, styryl dyes, hemioxonol dyes spectral sensitization. Particularly useful dyes include cyanine dyes, merocyanine complex melon dyes, and complex melon dyes.

Regarding these dyes, viroline ring, oxapurine ring, thiazoline ring, pyroline ring, Basic heterocycles such as ole ring, oxazole ring, tetrazole ring, pyridine ring, etc. Any conventional cyanine dye ring can be used. The aforementioned rings include the indolenine ring, the penzo Intorunine ring, indole ring, benzoxazole ring, naphthoxazole ring, Aromatic carbonization such as henzoselenazole ring, benzimidazole ring, and quinoline ring It can also be fused with hydrogen rings.

Pyrazolin-5-one ring, thiohydantoin ring, 2-thioxazolidine-2,4 -dione ring, thiazolidine-2,4-dione ring, rhodanine ring, thiobarbital ring A 5- or 6-membered heterocycle with a ketomethylene structure, such as a merocyanide ring, is It can be used as a ring in merocyanine dyes and complex merocyanine dyes.

These sensitizing agents can be used alone or in combination. Combination of sensitizers Combined use is often used for over-sensitization.

The silver halide-containing photographic emulsion of the present invention further includes a dye having a spectral sensitizing effect. or the substance itself does not absorb visible light or should not be used at the same time as the above-mentioned sensitizers. It is also possible to contain a substance that exhibits an excessive sensitizing effect when used.

Photographic materials using the silver halide-containing emulsion of the present invention may have For various purposes, it is also possible to include water-soluble dyes as filter dyes. Ru. Examples of such dyes include oxonal dyes and hemioxonol dyes. , styryl dyes, merocyanine dyes, cyanine dyes, and ab dyes.

Among these dyes, oxonol dyes, hemioxonol dyes, merosia Nin dyes are useful.

Photographic materials such as the silver halide-containing emulsions of the present invention include a silver halide emulsion layer and other Stilbenes, triazines, oxazoles, and coumarin in the hydrophilic colloid layer. It is also possible to contain a bleaching agent. These substances are water-soluble and water-insoluble. If they are insoluble in water, they can be used by dispersing them.

In the present invention, known anti-fading agents are used alone or simultaneously with color image sensitizers. Can be used in combination. Photographs using the silver halide-containing emulsion of the present invention True materials also contain hydroquinone derivatives and aminofluoride as anti-color cast agents. Containing phenol derivatives, gallic acid derivatives, and ascorbic acid derivatives You can do something like that.

The silver halide-containing photographic emulsion of the present invention can be used as a material for black-and-white photographs, as well as for multilayer, multicolor photographic materials. It can also be used for food. On the support of multilayer natural color photographic materials there is usually a red At least one layer is sensitive to color, and at least one layer is sensitive to green. , there is at least one blue-sensitive silver halide emulsion layer. sensitive to red One layer usually contains cabra, which produces cyano dyes, and the green-sensitive layer contains mabra. The blue-sensitive layer contains a cabra that produces a zenta dye, and a blue-sensitive layer that produces a yellow dye. Includes Kabra. However, other combinations can be used if desired.

Regarding Kabra, which produces a yellow color, benzoylacetanilide compounds and pivalo Known closed ketomethylene caps such as ylacetanilide compounds, etc. You can use type A. Regarding Kabra, which produces magenta color, pyrazolone compounds , indacylon compounds, cyanoacetyl compounds, and pyrazolone Particularly useful are the series compounds. Regarding Kabra, which produces cyan color, phenol Compounds having a ureido group, naphthol compounds, and couplers having a ureido group can be used.

DIR Kabra (development inhibitor free Kabra) can also be used in the present invention.

Photographic materials using the silver halide-containing emulsion of the present invention include (apart from Dl Cabra). ) Contains compounds that can release development inhibitors as development progresses. can be set. Furthermore, Kabras which can liberate development accelerating substances, Fogging agents used in the development process can also be used in the present invention.

Photographic materials such as the silver halide-containing emulsions of the present invention include allyl-substituted benzotriazo compounds, 4-thiazindone compounds, benzophenone compounds, cinnamic acid Purple compounds such as ester compounds, butadiene compounds, and benzoxide compounds External radiation absorbers can be included in the hydrophilic colloid layer. In the present invention , UV absorbers can be used.

In addition, couplers that absorb ultraviolet light (e.g., naphthol-based cyan-coloring couplers) UV absorbing polymers can be used in the present invention. These UV absorption Agents can be mordanted into specific layers of the photographic material.

Photographic materials such as the silver halide-containing emulsions of the present invention can be processed using known processing methods. Any known processing solution can be used. Processing temperature typically ranges from 18°C to 50°C However, it may be lower than 18°C or higher than 50°C.

In order to develop photographic materials, a development process that produces a silver image (black and white) is required depending on the purpose. color photographic processing, which is a development process that produces a dye image, is used. can.

The color developer used to develop the photographic material of the present invention is generally a color developer. Consists of an alkaline aqueous solution containing imaging reagents. Color developing reagents are Phenyle diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-B- Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-B-hyde Droxyethylaniline, 3-methyl-4-amino-N-ethyl-N-B-meta sulfoamide ethylaniline, 4-amino-3-methyl-N-ethyl-N- Contains aromatic-grade amino color developing reagents such as B-methoxyethylaniline). nothing.

The photographic emulsion layer is usually bleached after color development. The bleaching process is done at the same time as the fixing process. Alternatively, it is performed separately from the fixing process. Bleach is iron (■): Kobal h (m>nicro) Mu (■); Steel (■); Peracids: Cattle non-chemicals such as ferricyanide and nitrosation Compounds dinichromates; organic complex salts of iron (I) and cobalt (III), ethyl Diaminetetraacetic acid, nitrotriacetic acid, 1,3-diamino-2-propatol tetraacetic acid aminobocarboxylic acids such as acids, citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids, persulfates, permanganates: nitrosophenols, etc. Contains polyvalent metal compounds. Among these substances, potassium ferinoanide , ethylenediaminetetraacetic acid iron (I) sodium salt, ethylenediaminetetraacetic acid iron (I) sodium salt, ethylenediaminetetraacetic acid iron (I) DI) ammonium salts are particularly useful. Iron(III) ethylenediaminetetraacetate Complex salts are useful as bleaching and fixing solutions.

Suitable methods for preparing coated particles for use in the recording material of the invention include: You can also use something like that. For example, as shown in FIG. 28, particles 16 in FIG. Dielectric particles coated with silver halide are generally negatively charged colloids. An aqueous solution containing dielectric particles, positively charged silver ions, and l\ chlorides was prepared. , halogenation by reacting halogen derived from halides with silver ions. The process consists of depositing and growing silver to completely cover individual dielectric particles. and prepared. The dielectric is dispersed in a solution at a specific concentration, followed by the addition of silver ions. Moreover, it is desirable to further add a halide.

A preferred method is to adjust the pH of the solution after adding the dielectric particles to the solution; and then maintained at a level slightly higher than 2 (more preferably between about 3 and 5).

In this method, the dielectric particles are either negatively charged or negatively charged when they are added to the solution. There is no need to Instead, by adding particles to the solution and making the aqueous solution acidic. The dielectric particles become negatively charged. Additionally, the preferred method The initial concentration of silver ions in the solution is relatively low, less than IO-'M, and the halogen concentration in the solution is The initial concentration of the genide is slightly higher, for example 10%, than the concentration of silver ions in the solution. The solution is stirred at a constant speed while the halide is added to the solution.

Silver ions may be added to the solution in the form of. For example, silver ions can be converted into soluble salts. It can be added in some form (for example in the form of silver nitrate). Similarly, the halogen added to the solution Chemicals include sodium bromide, sodium chloride, potassium bromide, or similar compounds. Any suitable halide, such as alkali halides like similar compounds But that's fine. Furthermore, suitable dielectric materials for use in the aforementioned method may be It may be linear or non-linear, and may have any suitable shape or size. For example, It may be an electric particle or a spherical silica particle. Firstly dielectric particles or these silica particles, secondly silver ions are added to the solution in the form of silver nitrate, and thirdly halides are added to the solution. When sodium bromide is present, the reaction between silver derived from silver nitrate and bromine derived from sodium bromide occurs. silver bromide is formed and deposits on the silica particles to form a layer.

FIG. 29 shows the coating 20b on the particle 20 and the coating 22b on the particle 22. , which shows an outline of the method for preparing a metal coating in the form of dielectric particles. This method is common , negatively charged colloidal dielectric particles, metal ions, and 3 to 7 carbon atoms. secondary alcohols containing carbon atoms and alkyl ketones containing from 3 to 7 carbon atoms. Prepare an aqueous solution and remove oxygen from the solution.

Exposure of the solution to ultraviolet light causes metal ions to attach to the dielectric particles and complete individual dielectric particles. It consists of the following steps: forming a metal coating that covers the entire surface. dielectric particles, metal particles The concentration of on, isopropanol, acetone and the time of exposure of the solution to UV light are constant. It is desirable to form a uniform film on the dielectric particles with the calculated thickness. Yes.

When the term lower alkyl is used alone or in combination herein, When used, it means containing 1 to 7 carbon atoms. These alkyl The groups may be linear or branched, and include methyl, ethyl, and propyl groups. group, isopropyl group, butyl group, 5ec-butyl group, isobutyl group, t-butyl group group, pentyl group, amyl group, hexyl group, heptyl group, or similar Base included. As used here, secondary alkanols are lower alkyl alcohols. It corresponds to a hydroxyl group or is bonded to a secondary carbon. to secondary alkanols contains isopropanol, 5ec-butanol, or similar be caught.

A preferred alkyl ketone is acetone.

In the method described above, the ketone (acetone) or It absorbs ultraviolet energy and reacts with secondary alcohol (isopropanol), It is thought to generate alkyl secondary (isopropyl) radicals. these The radicals act as strong reducing agents and attach metal ions to dielectric particles. Make it into metal molecules. Dielectric particles, metal ions, secondary alcohols, and ketones in aqueous solution The order of addition is not strict. For example, if you add a secondary alcohol and a ketone to the solution, The dielectric particles may be dispersed in the solution, and then metal ions may be added.

In a preferred method, after adding the dielectric particles to the solution, such as the method shown in FIG. Adjust the pH of the solution to a level slightly above 2 (more preferably about 3). to 5). In this method, once dielectric particles are added to the solution, Dielectric particles do not need to be negatively charged; by making the aqueous solution acidic, Dielectric particles become negatively charged.

Furthermore, the initial concentration of metal ions in solution is relatively low, with 2 ;The initial concentrations of acetone and isopropanol in the solution are almost the same; This is considerably higher than the initial concentration of metal ions, about 400 times. moreover, It is advisable to stir the solution during exposure to UV light.

Using the methods described above, a large number of special types of metal coatings can be prepared. use The types of metals that can be produced are transition metals, lanthanides, and group 3A metals. Especially good Preferred metals include Group 8 and Group IB metals, especially copper, silver, and gold. , iron, nickel, palladium, platinum, cobalt, iron, iridium, Tenium, aluminum, or similar metals are preferred. especially desirable The most important metals are copper, silver, gold, nickel, palladium, and platinum.

In order to prepare silver-coated dielectric particles, gold-coated particles, and palladium-coated particles, we The most desirable option is to use the law. To further supply metal ions into the solution A suitable method may be as follows. For example, water-soluble silver nitrate These metal ions can be supplied by adding neutral metal salts to the solution. Ru.

Furthermore, the suitable dielectric used in the above method may be , may be linear or non-linear, and may be of any suitable shape or size. for example , dielectric particles or spherical silica particles. These silica particles are used as dielectric particles. When used as a solution and metal ions in the form of silver nitrate are added to the solution, ultraviolet light or acetone Working together with sopropatol, silver ions adhere to the silica particles and form a metallic silver coating. form.

Example 1 The following example describes a method of making metal coated non-conductive particles.

Make an aqueous solution by mixing the following solutions in a 50ml beaker.

(1) O, OIM AgN0. 0.5m1 (2) 0.50M Low porosity 81 02 particles 0. The diameter of 5m1 particles can be easily changed to other sizes, or A 20 nanometer one is chosen.

(3) Pure isopropanol 1.5ml (4) Pure acetone 1. 5m l All chemicals are of reagent grade quality unless otherwise noted. Add the above mixture to 16 ml of distilled water. dilute with m1 and adjust the pH to 4-5 by adding dropwise 0.01M nitric acid solution. This p In the H range, silica particles become negatively charged and attach positively charged silver ions to their surface. let After mixing thoroughly for 1 minute using a magnetic stirrer, the sample was placed in a Transfer to a UV photolysis vessel prepared for careful deoxygenation by bubbling with nitrogen gas for an hour. melt It is important that there is no oxygen in the liquid. A 450 watt Hg-Xe lamp was applied to the sample. The mixture was irradiated for 1 hour using a lamp and continued to be stirred gently using a magnetic stirrer. The color of the solution, The resulting thickness of the coating can be controlled by adjusting the duration of irradiation with UV light. I can do it. This is the basis for the production of silver-coated silica particles in this example.

Silver-coated non-conductive particles can also be produced by a method using photoreduction of silver halide. One of them is outlined in Figure 30. In this method, silver halide coating is used. The non-conducting particles made, for example, by the method described above in connection with FIG. The silver halide coating on each individual grain is exposed to metallic silver. coating.

However, rather than the more integrated method outlined in Figure 31, silver-coated non-conducting particles Used in manufacturing. In this method, non-conductive particles are mixed with silver ions, halides, electrically Dispersed in a solution containing a hole scavenger and reacts with silver ions or halogens of halides. Then apply a coating of silver halide that completely covers the non-conducting particles. The solution is exposed to ultraviolet light to change the silver halide coating to a silver coating. Ru. Concentration of non-conducting particles, silver ions, halides, and electron hole scavengers in solution and the length of time the solution is exposed to ultraviolet light to achieve a uniform, preselected thickness. A thin coating is created on the non-conductive particles.

In this way, the initial concentration of silver ions in solution is equal to that of the initial concentration of halide in solution. It is preferable that the concentration of the former be greater than that of the latter; for example, the concentration of the former may be approximately 5 times that of the latter. stomach. Silver ions may be in any suitable form in solution, such as silver nitrate, in aqueous solution. may be added to the solution in the form of salts soluble in Similarly, the halide added to the solution is , alkali halides, e.g. sodium bromide. These include thorium, sodium chloride, potassium bromide, and potassium chloride. even more appropriate Non-conducting materials are used in this method, linear or non-linear, and of suitable shape and size. It's fine. For example, the non-conductive particles may be spherical silica particles. (1) Non-electronic conductive particles or silica particles, (11) added to the solution in the form of silver ions or silver nitrate; (iii) When the halide is sodium bromide, silver from silver nitrate or bromide It reacts with bromide from sodium to form silver bromide, which is resistant to ultraviolet light in the presence of EDTA. The silver bromide coating is reduced to metallic silver.

In the above method, it is preferable that the light source includes ultraviolet light. Light source, 1l50-550n It is desirable to include a range of wavelengths. The preferred wavelength is 200-4001 m.

Furthermore, the intensity of the light used is between 50 watts and 1. Desired range of 5 kilowatts The preferred strength is 250-1000 watts. Particularly preferred strength is 35 0-550 watts, with an intensity of about 450 watts being most preferred.

Example 2 Metallic silver on SiOz particles is obtained by photoreduction of silver halide, and its halogen Silver oxide is typically blocked by the presence of excess Ag' ions.Hole (h+) scavengers , EDTA is added to the solution. 0.002M NaBr solution 1 solution 1 solution 19ml In addition, the solution is made by mixing the following in a 50ml beaker:

(1) 0. OIM AgNOx 1m1 (2) 0.50M Low porosity 5102 Particle 0. 5ml Particle diameter can be easily changed to other sizes or 12 ml Nometer.

(3) 0.02M EDTA 1m1 (4) Distilled water 16ml After mixing well, the solution was transferred to a 1 cm UV quartz cell and 375 Watt tungsten Expose to a halogen light source. Under these conditions, colloidal AgBr is more than 350 nm. It absorbs only a small amount of light, so a large amount of light is not actually absorbed. Idea of reduction method The mechanism by which this happens is as follows.

AgBr　・−・−AgBr　(e−+h”)AgBr+e−〜−−+　Ag '+Br-EDTA+h"--...→Product Br-+Ag" (excess) --The irradiation time, which is on the order of AgBr minutes, determines the color of the silver-coated silica particles. Melt.

This color is the result of the thickness of the silver layer and ranges from yellow to purplish-grey.

Once the silver-coated silica spheres are removed, they are purified by dialysis to produce todenol. placed in a sodium sulfate micellar solution or microemulsion.

A variation of the method described above can be used to create metal coatings other than silver on nanoparticles. Metallic silver on non-conducting particles acts as a catalyst to separate metal ions from other metal ions in solution. Taking advantage of the fact that it will act to help grow a metallic coating on the particles It is something to do. In this variant, outlined in Figure 32, a solution containing non-conducting particles is prepared. Then, silver halide is formed on the grains, and at least the silver halide is exposed to light. A portion is converted to metallic silver, and metal ions are added to the solution to separate individual non-conducting particles into the solution. It creates a coating that completely covers the metal, and the metallic silver on the particles acts as a catalyst. Acts as a catalyst to accelerate the formation of metal coatings. These metal ions are suitable added to the solution by a method, such as a conventional photographic developer or added to release metal ions. It will be done.

To aid the growth of a metal coating on a non-conducting particle, place a small amount on the particle. Therefore, the method described above requires only a small amount of metallic silver to be deposited on the non-conducting particles. The amount of silver halide is sufficient. On the other hand, a complete coating of silver halide on a non-conductive particle coatings may be created, with only a small amount of halogenation on individual particles. Changes to silver or metallic silver. In another variant, the silver halide coating is non-electroconductive. The conductor grains may be completely covered, and a small amount of silver halide from the solder may cover the individual grains. It turns into metallic silver on the particles, and a small amount of metallic silver remains on the non-conducting particles. Used to help form a metal coating that completely covers the silver halide. So The resulting product is a first layer of silver that more or less completely covers the non-conducting pores. coating, a second coating of metal that completely covers the silver halide layer It consists of

The following example describes a coating of silver on a nonconductive strip of silver bromide. EDTA Silver bromide nanoparticles that are present and briefly exposed to strong UV light are silver-coated silver bromide nanoparticles. 50 Watts to 1 with the same optical absorption spectrum as calculated by the child distribution. ．． 5 kilowatts, preferably 250-550 watts, most preferably 350- It means a light intensity of 550 watts.

With shorter irradiation times, the plasmon resonant polar This is consistent with theory as long as the wavelength shifts to longer wavelengths and increases with coating thickness or light irradiation. . The resonance maximum of the distribution of coated particles can be shifted to 600-700 nm.

Example 3 Silver bromide colloid is made by quickly mixing equal amounts of AgNOs and N a B r solutions. Ru. Growth stabilizer (SDS) and electron donor (EDTA) are added immediately after precipitation.

Typically, the final concentration is 1X10-'M Br-1IXIO-'mAg'', 5X 10-'M (SDS), 5xl O-'M EDTA. The concentration of SDS is , well below the critical micellization concentration (10-”M). Expose to light from a 450 watt Hg-Xe lamp per second. The spectrum is blue at the shortest irradiation. Ru. With longer irradiations the solution is orange.

Adding ammonia to the irradiation solution dissolves AgBr by forming a complex with Ag3. As a result, it turns yellow, a color characteristic of small metallic silver colloids.

The particle size distribution was characterized using a transmission electron microscope (JEOL 1200EX). It will be done. A typical photomicrograph is shown in (Figure 198). Limited microscopic photographic material A size distribution consistent with is a lognormal distribution.

N (r) = No exp (-((In (r)-In (rm))/In (s)) 2) (1) rm is lnm or less, and S is 4-4.5 nm. Within range. The size distribution determined by TEM appears to change significantly upon irradiation with light. I can't see it.

After adding ammonia to the irradiated material, only small particles with a diameter of 5 nm or less were detected. seen in EM (Fig. 19b). The most appropriate interpretation is that through irradiation, a portion of AgBr The larger particles are AgBr/Ag complexes.

Examples of optical absorption spectra measured immediately after irradiation are shown in Figures 20a)-d).

The irradiation time and/or the concentration of EDTA and therefore the reduction of Ag+ are determined from a) to d). It is increasing as time goes by. As the irradiation time increases, the absorption peak shifts to shorter wavelengths. to This result is consistent with theory as long as the thickness of the coating increases with irradiation. Figure 20e) The spectrum of the ammoniated solution shown in represents homogeneous silver nanoparticles. . The general shape of the above spectra can be easily reproduced. At comparative irradiation time, Br- Absent, the color manifestation of the given material can be ignored.

The theoretical optical absorption spectra of the individual silver coating methods are shown in FIG. coating thickness , the theoretical absorption spectrum shifts from red to blue as the ratio of the radius to the radius increases. Ru. This data shows that as the irradiation time increases, the absorption maximum or the actual spectrum shifts to blue. This is because the film thickness should increase with irradiation time. Compound The spectrum is very sensitive to coating thickness. Variations in the diameter of the scar and the thickness of the coating Therefore, the measured spectrum is considerably broader than the spectrum shown in Figure 21. It is.

The magnitude of the absorption spectrum also characterizes the silver-coated particles. For example, 700nm The absorption cross section per unit volume of silver at a wavelength of For silver-coated nanoparticles with a suitable ratio of 0 to 100%, it is 100 times larger than that of a solid eyeball.

The fact that the theoretical absorption is so large confirms that the particles are coated with silver. It will help you chew. However, the size distribution is wide, so be careful when making comparisons. must be considered.

Here, we start with the size distribution of the grains described by the above formula and perform trial and error. Find the coating thickness distribution that matches the measured spectrum, and determine the size of the spectrum. It was found that the values were within the range expected from the initial concentrations of Ag' and Br-. Ta.

The assumptions made in the calculation of the spectrum are as follows.

1. Reduced silver exists in the form of a smooth film on the surface of spherical AgBr particles. Exists. The absorption efficiency is calculated using the separation of variable solutions for concentric spheres based on the arithmetic method. calculated.

2. The size distribution of thin particles is described by the lognormal distribution in the above equation.

The value of NO is determined by placing the total amount of all particles before irradiation in a distribution comparable to the amount of AgBr. Ta. The initial total amount of AgBr is calculated by solving the ion equilibrium equation including the Ag”-EDTA complex. Temeta.

3 The size distribution of the coating thickness is glassian, typically with a standard deviation of 22-8n. There is a difference.

4. The silver coating is formed by reduction of silver halide in the initial grains or by A from solution. is produced by the reduction of g'''. Calculations are made for each of the two cases. Ta.

5 Total absorption is calculated by numerically integrating the distribution of the radius of the scar and the thickness of the coating. .

be (λ) = Nn (rc) Ng (t) Q (rc, t.

mc, mt, λ) πr” drcdt (2) Here, Nn is the size of the shin cloth, and Ng is the size distribution of the coating.

Q is the absorption efficiency, mc is the refractive index of the film, and mt is the refractive index of the coating.

Typically the integral over the shin was rm2~r=18.

6 The refractive index of silver was determined by Hagemann et al., J. OP, SocAm. 65, 742-744 (1975) and Kerker, JOP, Soc, A. m, B,, 1327-1329 (1985L data alone or very Combines the Drude model, which takes into account the increase in electron dispersion on the surface of thin films. I calculated it. Johnson and Chr i s t ry, Phy, Refractive index data of Rev., Dan, 6.4370-4379 (1972) Using. A linear interpolation method was used to obtain refractive index values for points not included in the data.

7. The refractive index of AgBr is White, J, Opt, Soc, Am.

the Photographic Process”, M aMillan (1977) p, 2+6 data were combined.

FIG. 41 shows an actually measured spectrum and two calculated spectra. on the top curve , the Ag in the film is thought to come from the solution, that is, the AgBr concentration When the film grows larger, the size does not become smaller. In the bottom curve, Ag in the coating is thought to come only from the reduction of AgBr on the surface of the particles, and therefore When it grows, it shrinks. The measured curve is between the two calculated spectra. Therefore, the magnitude of the plasmon enhanced absorption is within the range of the calculated values.

The main parameters that allow the distribution to be matched to the spectrum are l) coating thickness and standard deviation; 2) range of numerical integration for differences and coatings; 2) size distribution and range of integration for wrinkles; 3) Silver refractive index data, the fraction of reduced silver coming from solution. The calculated space The vector is very sensitive to the distribution of the selected wrinkles and coatings, and the range of integrals. have also defined the size distribution. The calculated spectrum depends on the refractive index of the silver used. ing. However, by changing the size distribution, similar spectra or Obtained in different models. The effect of different assumptions about the source of Ag on the coating is shown in Figure 4. Found in 0. In a preliminary experiment without excess silver, a space similar to that seen in Figure 39d was obtained. kutle was obtained.

I'm not trying to restrict you, but the silver film is made up of many small silver particles. I believe that. The coating may also contain AgBr or not, and may have large It is homogeneous enough to have a refractive index similar to silver. When treated with solution or ammonia , the coating will be broken into many small particles, so the bonds between the particles will be relatively weak.

Perhaps we should consider that the spectrum can be explained by non-spherical silver particles. A Ammonia, which dissolves gBr but not Ag, changes the spectrum from small solid particles. The fact that particles are not very exotic in TEM makes this Disagree with the hypothesis. Also, it does not appear to be related to either the particle shape or the color of the solution.

Prediction of the surface-plasmon resonance frequency and the fact that absorption becomes stronger at longer wavelengths , the Ag-AgBr colloidal complex pair was experimentally confirmed. Ag is on AgBr Particles are scattered so that it covers smoothly.

Silver-coated non-conductive particles undergo chemical reduction of silver ions by hydroquinone at high temperatures. It can also be created using the method. The next example is outlined in FIG. Explain how.

Example 4 Add 100 ml of silica solution (particle diameter 7 nm) purified by overnight dialysis to 250 ml bottles. 0.01MAgNO3 solution was added dropwise while stirring gently. Adjust H to 4.0 to final concentrations shown in the table below. After about 2 minutes, 001M melted in your mouth. A sufficient quantity of quinone is added in a similar manner. The reduction to metallic silver takes about 5 minutes and gradually takes place. occurs, with a color change from pale yellow to dark brown. The rate of silver precipitation by this method is It can be controlled by changing the temperature from 85-95°C (= a clear solution is obtained every time). , cool and purify by dialysis.

Example 5 The following table summarizes the experimental conditions, including the final concentrations (in molar), and was performed in four different sets. Ta.

I I[I[[IV S102 1% 1% 1% 1% AgN0. 5.0XI0 1.0Kari0 1.5XI0 2.0XlO Hydroxy Non 5.0X10 1.0X10 1.5X10 2.0XIO of precipitated silver The amount increases from ■ to ■, which is evident from the color of the solution (light yellow to dark brown). electric Child microscopy also provided clear support. The optical absorption spectrum has a single peak at approximately 4001 m. This shows the existence of a peak.

Electron microscope results Solution I appears smaller, more distinct, and darker, with a size of 110-3 Consisting of particles in the 0n range. For solutions ■, ■, ■, the particle size is 440-1O0 It turns out that the particle size is n, and the particles are either dark or have elongated spherical shapes. Final The size distribution is partially due to the variable size of the silica particles and is It was found to be 77-11n.

In all of the above methods, after the coated particles have been created, the solution created by dialysis is Sodium dodesol sulfate micellar solution or microemulsion You can put it inside. Additional coatings of silver halide, metals, or polymers, Additions may be made until the desired final shape is reached. The polymer going of these particles is is easily made in solution by the well-known emulsion polymerization method, and the monomer and appropriate amounts of initiator are added.

For example, the following method, outlined in FIG. It shows how it is done.

The following stock aqueous solutions are prepared:

(r) O, IM K12 PO.

(II) 0. 1M Na0H (I) 2% solution of sodium salt of styrene sulfonic acid, Na5S (copolymer (IV) )K2S20. 3% solution of All solutions are made with double-distilled water and all chemicals are reagent grade.

Transfer 131.6 ml of a 1% solution of silver-coated silica particles to a three-necked flask. melt Stir 8 ml of solution ■ followed by 6.4 ml of solution ■ using a magnetic stirrer. Add while doing so. Attach a condenser and a platinum thermometer to the flask, and set it to a temperature controller and thermostat. Adjust the temperature of the flask to 65 °C by combining the heating mantle. child At a temperature of , nitrogen gas is constantly bubbled through the mixture and 30 ml of styrene are added. 15 After 10 minutes, add 10 ml of solution ①, and after another 20 minutes, add 4 ml of solution N. Add. Depending on the desired polymer film thickness, 25ml of a 1% solution of hydroquinone 1 is added to terminate the reaction, suspended, and further purified by dialysis.

Example 6 Coating carbon fibers with copper is a highly reducing and short-lived 1-hydroxy-1-methylene This is done by photochemical reduction of Cu″3 using ruethyl radicals. These radicals are , 450 watts of Hg-Xe It is created by irradiation with a UV source from a lamp. Expressing the reaction, (CH,)　2co→　(CH,)2C○(CH,), Co”+(CH,), C HOH → 2 (CH2’I 2COH2(CH3)2 COH+Cu” -+ 2 (CH2)2 CO+Cu+2H"nCu-+Cun Using two different solutions (IXIO-2M and lXl0-3) of Cu- of different coating thicknesses. Both solutions are 1M acetone, 1M propanol. -2. Contains carbon fiber. The irradiation time was 2 hours.

When these coated fibers are washed with distilled water and observed under an optical microscope, they are very impressive. The smooth coating visibly reveals the metallic luster of copper. copper on this fiber The amount was determined using atomic absorption spectroscopy after removing the coating with 1M nitric acid. this fiber The presence of copper above was also confirmed using energy dispersive spectroscopy (EDS), and shows the peak. The thickness of the coating can be controlled by the copper concentration of the solution and the irradiation time. . It can be easily changed from 0 nanometers to microns.

The methods described above can be used in various combinations to create particles of desired shape.

For example, FIG. 35 outlines a method for making particles 20 of FIG. First, metal coating 31. Further, a coating 20c of silver halide is applied on the metal layer 2Ob, for example, as shown in FIG. Create according to the method shown. Similarly, FIG. 36 shows how to make particles 22 of FIG. Outline. In this method, a metal coating 22b is first applied on a non-conductive layer 22a. 29, and then apply polyurethane on coating 22b. silver halide layer 22 on coating 22c. d is made in the manner described above in connection with FIG.

It is clear that the invention described here has been successful in fulfilling the purpose all stated. However, people who are familiar with the technology will be able to come up with many modifications and specifics. The true intent of the appended claims, including any modifications or embodiments that fall within the scope of the invention. It will be accepted that he intends to do so.

FIG.I FIG, 4 FIG, 5 FIG.7 0.5 1.0 +, 5 2. OX → FIG.8 FIG.9 xnm FIG, 1la 200.003000040000500.00600.00700.0080 0.0O900,00 month (nm) F IG, Ilb λ depth 4!4nm FIG, 16 FIG, l7 FIG, 20 FIG, 21 FIG, 22 FIG, 23 FIG, 24 FIG, 25 FIG. 31 FIG. 32 FIG. 33 FIG. 34 FIG. 35 FIG. 36 FIG. 37 FIG. 38 FIG. 41 Procedural amendment April 27, 1992

Claims (33)

[Claims] 1. In a photosensitive silver halide emulsion for photography, the emulsion comprises: colloid and Consisting of a large number of silver halide grains dispersed in the colloid, each of the grains includes a core surrounded by a skin, and one of the core and the skin is essentially The core and the other of the coatings are essentially dielectric. The photographic emulsion is characterized in that it consists of a sexual substance. 2. 2. The photographic material according to claim 1, wherein the dielectric material is substantially free of silver atoms. emulsion. 3. Each of the particles further includes a layer of metal disposed between the core of the particle and the coating. The photographic emulsion according to claim 1, wherein the photographic emulsion contains: 4. Each of the particles further comprises a layer of metal and one of the core and coating of the particle. 4. The photographic emulsion according to claim 3, comprising a layer of a polymeric substance disposed in the photographic emulsion. hmm. 5. The core of each particle consists of an essentially dielectric material, and the coating of each particle consists of an essentially dielectric material. 2. The photographic emulsion according to claim 1, wherein said emulsion comprises silver halide. 6. Each of the particles further includes a metal disposed between the core and the coating of the particle. 6. The photographic emulsion according to claim 5, comprising a layer of. 7. Each of the particles is further disposed between the layer of metal and the coating. 7. A photographic emulsion according to claim 6, which comprises a layer of polymeric material. 8. a layer of metal in each particle substantially completely covers the core of the particle; wherein the layer of polymeric material in each particle is substantially completely covered by the metal of the particle. 8. The photographic emulsion according to claim 7, which is coated with a layer of. 9. Each of the particles further includes a polymeric coating extending around the coating of the particle. The photographic emulsion according to claim 1, which is a photographic emulsion. 10. Each of the particles further includes a polymeric coating extending around the coating of the particle. 3. The photographic emulsion according to claim 2, which comprises: 11. Each of the particles further includes a polymeric coating extending around the coating of the particle. 6. The photographic emulsion according to claim 5, which comprises: 12. In a photosensitive silver halide emulsion for photography, the emulsion is , colloid and consisting of a large number of silver halide grains, each of which contains i) essentially a core consisting of a dielectric material; ii) consisting essentially of a metal; iii) a first coating completely covering the particle and disposed directly on the core of the particle; consisting essentially of a polymeric material and disposed immediately above the first coating of the particle. and a second coating essentially completely covering the first coating; and iv) consisting essentially of silver halide and immediately above the second coating of the grain; a third coating disposed and essentially completely covering the second coating; A photographic emulsion characterized by being 13. 13. The dielectric material of the core is essentially silver-free. Photographic emulsion. 14. 14. The method of claim 13, wherein the first coating of each particle consists essentially of silver. Photographic emulsion. 15. The photographic emul according to claim 9, wherein the core of each particle is made of silica. John. 16. Uses enhanced plasmon resonance effects to enhance absorption and scattering processes. Its uses. 17. In a light-sensitive recording medium, the medium is a solid that reflects or emits light. a colloid applied onto the substrate; It consists of a large number of particles dispersed in the colloid, each of which is covered by a film. a core surrounded by A recording medium characterized by being made of metal. 18. the other of the core and the coating consists essentially of a dielectric material The recording medium according to claim 17. 19. The core of each particle consists essentially of a dielectric material, and the coating of each particle consists essentially of a dielectric material. each of the particles is further disposed immediately above the coating of the particles and is made of a metal. Claim 1 comprising a layer of polymeric material covering the film qualitatively completely. 8. Recording medium according to 8. 20. In a light-sensitive optical recording medium, the recording medium comprises a support medium, It consists of a number of particles supported by the support medium, each particle having a core and a skin. comprising a membrane, the core and one of the membranes consisting essentially of metal; A recording medium used as a signature. 21. A claim in which the core and other parts of the coating essentially consist of a dielectric material. Item 20. Recording medium according to item 20. 22. Each of the grains further comprises another coating consisting essentially of silver halide. The recording medium according to claim 21. 23. In a light-sensitive recording medium, the medium is a solid that reflects or emits light. Substrate; a colloid applied onto the substrate; and It consists of a large number of particles dispersed in the colloid, each of which has i) a core consisting essentially of dielectric material; ii) disposed immediately above and substantially covering the core, and further comprising gold; iii) a coating disposed immediately above the coating and substantially extending the coating; from a coating consisting essentially of a polymeric material. A recording medium characterized by being 24. 24. The recording medium according to claim 23, wherein the film of each particle is made of silver. 25. A solid light-reflecting or light-emitting substrate and a substance supported by the substrate. Storage or reading of data on types of optical recording media that have a large number of particles In the extrusion method, the method writes a given putter onto the written medium. a recording medium for representing data stored in the recording medium through the beam; a step of changing the morphological structure of the particles over a selected region of the particle; The process of passing a readout beam over a medium and reading out the data stored there. , where the particles are nanoparticles, each nanoparticle containing multiple layers. the plurality of layers have a core surrounded by a coating, and the core and the coating A method characterized in that one of the metals consists essentially of metal. 26. One layer of each nanoparticle contains a first material having a first dielectric constant. and another layer of each nanoparticle contains a second material with a second dielectric constant. The process of passing a light beam onto the recording medium involves using a light beam. the first substance and second substance of each of the plurality of nanoparticles to react with each other using and a third substance having a third dielectric constant different from the first and second dielectric constants. 26. The method of claim 25, comprising the step of forming. 27. One layer of each nanoparticle is a monomer body, and a light beam is placed on the recording medium. A light beam is used to pass a large number of nanoparticles over a selected area. The method according to claim 25, which comprises a step of polymerizing each monomer layer. Law. 28. The process of passing a light beam onto the recording medium is selected using a light beam. A claim in which the morphology of each of the plurality of nanoparticles changes over a region 25. The method described in 25. 29. The nanoparticles are suspended in a medium having a dielectric constant, and a laser beam is placed on the recording medium. The step of passing the particle beam is selected using changes in the morphology of the particle. 26. The method of claim 25, wherein the dielectric constant of the medium is varied over the region. 30. The step of passing a light beam onto the recording medium is to pass a light beam onto the recording medium. The layer is melted and a number of nanoparticles are separated from each other over selected areas. 26. The method according to claim 25, wherein the morphology of the layer is changed. 31. The step of passing a light beam onto the recording medium is one step using a light beam. and construct each separate layer of a large number of nanoparticles over a selected area. 26. The method according to claim 25, wherein the method changes the structure. 32. Each layer of the nanoparticles is made of a magnetized substance, and the recording medium The process of passing a light beam over the selected area using the light beam The method according to claim 32, which demagnetizes a substance in which a large number of nanoparticles are magnetized. Law. 33. Each layer of the nanoparticles is made of a magnetized substance, and the recording medium The process of passing a light beam over an externally applied magnetic field Then, the write beam is applied while aligning the domains of the magnetic material along the direction of the magnetic field. the particle or any magnetic region surrounding the particle using a magnetic field. 26. The method according to claim 25, further comprising the step of heating to a curie temperature of .