HK1097565A - Synthesis of nanoparticles - Google Patents

Description

The Technical Standards

The present invention relates to methods for the synthesis of nanoparticles, in particular metal salt nanoparticles, whereby the nanoparticles can be produced both fluorescent and doped.

Metal salt nanoparticles within the meaning of the present invention have a crystal lattice or, in the case of a doping, a host lattice, the cation of which is a metal, in particular a metal of the third subgroup of the periodic table, e.g. lanthanum, or a rare earth metal, and the anion of which, e.g. PO43, is obtained from a suitable anion source, e.g. a free acid of the salts of the nanoparticles to be produced, e.g. lanthanum phosphate nanoparticles.

Err1:Expecting ',' delimiter: line 1 column 166 (char 165)

The hydrothermal synthesis in the above method, however, generally results in a relatively wide particle size distribution and thus poor yields of particles of a certain (desired) size. For example, in the above method, the proportion of particles with diameters below 25 nm is about 20% of recoverable particles, measured in terms of the total amount of crystalline substance obtained by the method. Furthermore, the use of an autoclave due to the high pressures due to the use of water as a synthesis medium is considered to be unfavourable at least for industrial production of the target substance.

However, simplified and more efficient production would be desirable not only for the lanthanum phosphate nanoparticles, but also, in view of the increasing potential for nanoparticles, for a large group of nanoparticles in which the crystal lattice or host lattice may contain in particular compounds from the group of phosphates, halophosphates, arsenates, sulphates, borates, aluminates, gallates, silicates, germanates, oxides, vanadates, niobates, tantalumates, tungstane, molybdate, alkali haliobates, other halogenides, nitrides, sulfides, selenides, sulfoselenides and oxysulfides.

With regard to the specific aspects of nanoparticle doping and the fluorescence of nanoparticles, the above-mentioned publication of 5 July 1999 shows a way of producing inorganic fluorescent dyes which are much more stable in the long term than conventional organic fluorescent dyes.

This is a known substance which exploits the positive property of the durability of the dye due to its inorganic nature, but taking into account the above-mentioned disadvantages of hydrothermal synthesis, in particular high pressure and low yield.

In the further state of the art cited below, fluorescent dyes are used, for example, for the marking of cheques as described in US Patent No. 3,886,083, as security inks as disclosed in Chinese Patent No. CN 1,193,640, for the detection of cracks in surfaces as described in US Patent No. 4,331,871, for the detection of fingerprints, see US Patent No. 4,700,657, for the marking of clear plastic parts such as eyeglass lenses and contact lenses and other products, they are used in the US Patents, US Patent No. 4,238,524, and US Patent No. 5,418,855, and in the field of leakage inspection, WO 920 8 365.

In these publications, however, organic substances are used as fluorescent dyes.

Disadvantages of the organic dyes described are their inadequate stability and the resulting fading, the often small distance between the stimulating and the emitted light, which creates problems in distinguishing the emission light from the stimulating light, the colour of the dyes used which is below normal, which either interferes with the design of the fluorescent product or the safety of the marking, the lack of chemical stability to external influences, which limits the range of use of the dye, and often the lack of transparency of the dyes in relation to clear plastic materials, windows and safety markings on any objects which have a high potential external appeal. Security cards, such as credit cards, credit cards, badges or markings, are also intended to enable customers to identify products without a manufacturer's mark, for example, which are intended to be a valuable tool for identification.

Nanoparticles are also used as potential carriers for fluorescent dyes, as was shown, for example, by the disclosure of WO 9937814, that it is detrimental to bind fluorescent dyes only by binding to the surface of the respective carrier material.

The above-mentioned WO 9937814 describes a way to produce even multi-colored fluorescence. First, polymer microparticles are produced that carry polymer nanoparticles, which in turn are saturated with fluorescent organic dyes from the class commonly known as cyanide dyes. Thus, colored nanoparticles are incorporated into porous microparticles. Several dyes can be used simultaneously to produce different colors in the fluorescence emission of the microparticles. The microparticles and nanoparticles have a non-smooth surface on their respective surface, which is preferred by additional functional groups to increase the bonds.

However, a disadvantage of this method is that it uses organic fluorescent materials which, despite at least partial incorporation into microparticles, are subject to the aforementioned premature ageing and thus show poor long-term stability.

A fundamental disadvantage of the use of organic dyes is that they can be destroyed by inappropriate, excessive stimulation and lose their coloring effect.

Err1:Expecting ',' delimiter: line 1 column 153 (char 152)

Another disadvantage is that these organic fluorescent dyes cannot be used in an appropriate way, i.e. not sufficiently flexible for the specific requirements of many applications for marking objects.

The following shall be used:

Therefore, the purpose of the invention is to enable the organic synthesis of nanoparticles for the groups of substances mentioned at the outset, while avoiding the disadvantages of hydrothermal synthesis.

SUMMARY AND Benefits of the Invention

The method according to the invention, with the characteristics of claim 1, has the advantage over the method described in the above-mentioned publication of achieving a much better yield, due to a much narrower size distribution of the nanoparticles produced, which makes subsequent size selective separation superfluous.

Furthermore, a synoptic theory is revealed, by means of which the universal solution approach can overcome the individual difficulties of synthesis of individual desired nanoparticle groups of substances, each with special solutions according to the invention, immediately recognizable from the synoptic theory.

This claim is made regardless of whether doped or undoped nanoparticles are to be produced. If specifications are given for the synthesis of doped nanoparticles, it should be understood that the manufacturing rule for corresponding undoped nanoparticles can be obtained essentially by replacing the starting material required for doping with an appropriate amount of the starting material for the host lattice material. Furthermore, the term doping is used herein in a very broad sense, so that it is not restricted by a certain percentage of the lattice spaces for the dopant. It therefore also covers, for example, mixed phosphates, or others that have a maximum particle size of two or more nanotubes.

In accordance with the most general aspect of the invention, a method is disclosed for the synthesis of metal salt nanoparticles with a crystal lattice or host lattice, the cation of which, e.g. La3+, is recoverable from a cation source, e.g. LaC13, and the anion of which is recoverable from a class of substance serving as an anion source, the host material containing in particular compounds from the group of phosphates, halophosphates, arsenates, sulphates, borates, silicates, aluminates, gallates, germanium, oxides, vanadates, niobates, tantalum, tungstane, molybdenum, alkalidehalogenates, and other halogenides, nitrides, sulfides, silenides, oxides, and sulfides, which may be characterized by the following steps: (a) Manufacture of a synthetic mixture, at least from: (aa) an organic solvent' containing at least one component containing a phosphor-organic compound which controls the crystal growth of the nanoparticles;or an amine compound, in particular a monoalkylamine, in particular dodecylamine, or a dialkylamine, in particular bis- ((ethylhexyl) amine, in particular for zinc-containing nanoparticles,bb) a cation source, soluble in or at least dispersible in the synthesis mixture, especially a metal salt source, preferably a metal chloride or an alkoxide, andcc) an anion source, soluble in or at least dispersible in the synthesis, of the class of anions, the substance class containing:Other (b) maintain the mixture above a specified minimum synthesis temperature for a synthesis time period appropriate to the temperature, preferably avoiding deposition in the mixture.

Therefore, according to the most general manufacturing aspect of the present invention, a widely applicable solution approach is revealed which allows the synthesis of a wide variety of metal salt nanoparticles and even allows the synthesis of certain semiconductor nanoparticles for the first time.

In addition, fluorescent nanoparticles of very small size of a few nanometres can be produced, which allows their homogeneous incorporation into the finest films, finest coatings, good solubility in liquids without the deposition of certain proportions on the bottom of the liquid typical of larger particle sizes, or homogeneous mixing with the finest dusts without any material change being felt in the respective carrier.

Finally, the manufacturing process for many of the claimed substances is considerably less risky because it can be carried out without overpressure and without the use of an autoclave.

The basic synthesis method may be used preferably (a) For the manufacture of nanoparticles with phosphorus-containing anions, phosphoric acid is used as an anion source, where: Boric acid is used as an anion source for the production of boron-containing nanoparticles, where: For example, tetrabutylammonium dihydrogen phosphate, tetramethylammonium dihydrogen phosphate or triethylammonium dihydrogen phosphate is used to produce nanoparticles containing phosphate anions, tetrabutylammonium dihydrogen phosphate, tetramethylammonium dihydrogen phosphate or triethylammonium dihydrogen phosphate, in the case of nanoparticles containing sulphate anions, tetrabutylammonium hydrogensulphate, tetramethylammonium hydrogensulphate, bisphenol-butylammonium triethylammonium nitrate, or tetramethylammonium nanoparticles containing phosphate, in the case of an anion containing sulphate, is used as a solvent for the synthesis of a compound containing methylammonium triethylammonium sulphate, preferably in the case of an anion containing methylammonium triethylammonium sulphate, in the case of an anion containing methylammonium triethylammonium sulphate, is used as a solvent for the synthesis of a compound containing methylammonium methylammonium triethylammonium sulphate, in the case of methylammonium triethylammonium triethylammonium triethylammonium sulphate, is used as a solvent.

In the case of an organic compound that decomposes at elevated temperatures and gives anions, a predetermined ester of an acid corresponding to the respective anion selected may be used preferably. For phosphates, a phosphoric acid ester may be used, for silicates, a silica acid ester, for borates, a boric acid ester, for sulphates, a sulphuric acid ester, for vanadates, a vanadium acid ester, for tungstenes, a tungsten acid ester may be used.

For halophosphates, for example, a mixture of triethylammonium dihydrogen phosphate and triethylammonium trihydrofluoride can be used, both of which are available on the market.

Highly biodegradable alkoxides may be used as an anion donor in appropriate preference for niobates, tantalum, aluminate, gallate, arsenate and germanate.

For sulphides, besides the metal salts, bistrimethylsilyl sulphide may be used as an anion donor, for selenides bis-trimethylsilyl selenide as appropriate, and for sulfoselenides a corresponding mixture of the above substances.

As the phosphoro-organic compound for the growth control component, at least one of the following may be preferred: (a) Phosphoric acid esters (R1-) (R2-) (R3-O-) P=O ), (b) Phosphoric acid diester (R1-) (R2-O-) (R3-O-) P=O ), (c) Phosphoric acid triester (Trialkylphosphate) (R1-O-) ((R2-O-) (R3-O-) P=O ), (d) Trialkylphosphane (R1-O-) (R2-O-) (R3-O-) P ), in particular Trioctylphosphan (-TOP), (e) Trialkylphosphan oxides (R1-) (R2-) (R3-P=O), in particular Trioctylphosphan oxide (TOPO), contained in the solvent.

The above are only pseudo-structural formulas. The individual oxygen (0) atoms are all bound to the phosphorus atom (P). R1, R2, R3 are first branched or unbranched alkanes with at least one carbon atom or phenyl, toluyl, xylyl, or benzyl groups.

In particular, the esters mentioned in (a) to (c), probably by means of the oxygen atom linked to the phosphorus by a double bond, form a particularly strong bond to many metallic starting compounds which can be used in a useful way in synthesis, thus enabling the synthesis of special nanoparticles of special groups of substances.

In particular, the metal salt particles show even better solubility, dispersibility and tendency to form aggregates when using the esters mentioned in (a) to (c) than when using the other growth control substances.

This phenomenon is probably due to the partial decomposition of the ester at a late stage of the synthesis, when virtually all of the metallic starting compound and anion donor starting substance has already been decomposed into metal salt nanoparticles.

This slow decomposition process is likely to result in the separation of alcohol groups from the esters referred to in (a) to (c), resulting in the addition of alcohol to phosphoric acid using a phosphoric acid ester, phosphoric acid and phosphoric acid monester using a phosphoric acid diester, or phosphoric acid monester and diester using a phosphoric acid diester.

All of these decomposition products (except alcohols) contain acidic P-OH groups which are known to form very strong bonds with metal ions, so the coupling of these decomposition products to the nanoparticles may be by binding to the metal ions on the particle surface. In addition, reactive coupling of the alcohol released by decomposition to the particles is also conceivable. e.g. in the case of phosphates containing nanoparticles (such as lanthanum phosphate), the alcohol can be coupled to a phosphate group on the particle surface to form an ester bond.

Finally, it should be noted that we use an analogue decomposition of esters by cleavage of the alcohol groups also for the esters mentioned above as an anion source. However, for this purpose esters are chosen which are thermally unstable, i.e. in which all the alcohol groups are quickly and completely cleaved already in the first stages of synthesis.

Mixtures of the phosphor-organic compounds can also be used to achieve the synthesis of nanoparticles from different groups of substances in a flexible manner.

A further flexible adaptation of the synthesis to the different classes of substances can be achieved by using a mixture consisting of at least one of the above growth-regulating substances and one or more solvents, where the metal complexing properties of these solvents are less than those of the growth-regulating components.

For example, according to a single aspect of the present invention, trialkylphosphate and trialkylphosphane are used as coordinating solvents, which implies the use of relatively large amounts of these substances; for example, 6 litres of triethylhexylphosphate per 1 mol of metal ions (Ce, Tb and La combined) are then used for the synthesis of LaPO4:Ce,Tb nanoparticles, e.g.: 300 ml of Tris-ethylhexylphosphates + 20 mmol of cerchloride + 22,5 mmol of lanthanum chloride + 7,5 mmol of terbium chloride. This corresponds to a ratio of approximately 13: 1.

This is the case, for example, when the failure of the nanoparticles is only partial or only with very large solvent amounts, or when the substances are very expensive or complex to synthesise, as is the case in particular with functionalized trialkylphosphates and phosphates.

Therefore, if a trialkylphosphates or trialkylphosphanes are used as control components in the formation of nanoparticles in a particularly preferred manner, using less than 10 moles per mole of metal ions, preferably 0.9 to 5 moles, and preferably 0.95 to 1.5 moles of control components, the synthesis can be simplified and made cheaper by using lower amounts of the growth control components.

In these cases, solvent mixtures may be used, which therefore contain only a relatively small proportion of trialkylphosphates or trialkylphosphans, the lower limit being slightly less than one mole of trialkylphosphates or trialkylphosphates per mole of metal ions (i.e. 1:1 according to the above nomenclature).

The present invention is intended to select the further components of the solvent mixture in such a way that the boiling point of the mixture is at a temperature which is sufficiently high for the formation of the nanocrystals, here referred to as the minimum temperature of synthesis, and the quantity of the further components is so high that the synthesis seismic is able to keep the nanoparticles formed in the synthesis reaction in solution. The preferred components are those which decompose as little as possible during the reaction time. Particularly preferable are components which, after the end of the reaction, can be distilled under reduced pressure without decomposition by simple laboratory methods, such as oil pump vacuum, not better than 0.01 mbar; water or oil bath, i.e. a distillation temperature not exceeding 200 °C, corresponding to about 480 Kelvin.

In addition, at least one additional, preferably metal complexing, component may be added to the synthesis mixture, preferably to displace crystalline water present in metal salts, in particular a (a) Ether compound, preferably dipentylether, dihexylether, diheptylether, dioctylether, dibenzylether, diisoamylether, ethylene glycoldibutylether, diethylene glycoldibutylether, or diphenyl ether, or/and (b) an alkane compound boiling above the minimum temperature of synthesis, preferably dodecan or hexadecan, (non-metallic complexing), for example for dilution of the reaction mixture, or/and (c) an amine compound, preferably diaminehexy, bis- (ethylhexyl) triaminecty, triamine- (ethylhexyl) triamine.

If R1, R2 or R3 are branched or unbranched alkane chains that contain at least one carboxyl group (-COOH), a carbonic acid ester group (-COOR), amino groups (-NH2) and (-NHR), hydroxyl groups (-OH), cyan groups (-CN), mercaptogroup (-SH), bromine (-Br) and chlorine (-C1) or combinations of these groups, the growth control components can be functionalised very flexibly.

A chloride, such as LaCl3 for lanthanum phosphate nanoparticles, or a bromide, iodide, alkoxide, or acetyl acetonate may be used as the source of the cation preferably.

In further training, the synthesis process according to the invention may include the following additional steps in addition to the basic steps (see above): (a) Prepare a first solution of the cation starting material in a preferably lower alcohol, in particular methanol, preferably using a metal salt which is non-oxidizing and soluble in the synthesis mixture; and (b) Mix the first solution with the existing solvent containing at least one component controlling the crystal growth of the nanoparticles, such as a phosphor-organic compound, to produce the metal complexing synthesis solution;

If the nanoparticles are to be isolated after the completion of the synthesis reaction, the method of the invention contains further optional post-treatment steps: (a) distillation of one or more solvent components of the synthesis mixture, preferably under vacuum, preferably after the end of the synthesis time span, or/andb) cleaning of the nanoparticles of adhesive byproducts by washing with an alcohol, preferably ethanol, or by diafiltration.

The method of the invention may include, in all variations, depending on the acidity of the synthesis mixture and the type of starting materials used, the further step of neutralizing the synthesis mixture to a greater or lesser extent by a base soluble in the synthesis mixture, preferably trihexylamine, triheptylamine, trioctylamine, or trise (2-ethylhexyl) amine, as appropriate.

Preferably, hydrated metal salts can be used as starting materials, as they are often more soluble.The release of small amounts of water during the reaction also accelerates the decomposition of certain anion donor starting compounds, such as alkoxides and esters, thereby increasing the reaction rate.

In addition, several different metal salts may be used in the manufacture of doped nanoparticles, at least one of which is used as a doping material for the nanoparticles to be manufactured.

The invention's range of synthesis variations allows a very wide range of applications, depending on the choice of starting materials and the other components of the synthesis mixture.

By using the solvent components of the invention, such as trialkylphosphate, as a growth control, nanoparticles of the following groups of substances can now be produced for the first time in a narrow size distribution with a low maximum size and high yield without subsequent size selection:

These are the phosphates of the rare earths, the third subgroup and of calcium (Ca), strontium (Sr), barium (Ba), with an upper particle size limit of about 15 nm, preferably 10 nm. The nanoparticles can be produced in such a narrow distribution and at such small sizes only because of their very low propensity to agglomerate, i.e. to grow the particles together, a beneficial effect made possible by the use, for example, of the trialkylphosphates mentioned above in the synthesis.

The next section deals with the synthesis method for and application of fluorescent nanoparticles and aspects of doping in particular.

The nanoparticle material resulting from the synthesis process may contain fluorescent particles which are essentially non-ageing, i.e. have long-lasting luminous properties, are more heat resistant and resistant to other environmental influences than the organic fluorescent dye based substances.

This is achieved mainly by the idea behind this aspect, to produce a complete inorganic nanoparticle of its own, which, after appropriate energetic stimulation, is illuminated by appropriate energy supply, in particular by electromagnetic radiation of corresponding frequency, for example from the infrared (IR), visual (VIS) or ultraviolet (UV) range, or by X-ray radiation and, where appropriate, by matter or electron beams. Embedded in a stable host material, such as a host grid, the light properties are extremely stable, even against difficult physical environmental parameters such as increased pressure, temperature, or fluctuation cycles, as well as fluorescent light, chemical oxidation, photo-oxidation, exposure to organic solvents, acidic or base environments, etc.

This key advantage of the substances of the invention over commercially available organic fluorescent dyes and markers, derived from the inorganic nature of nanoparticles, makes them suitable for use in many applications, including exposed sites.

The following items are at least capable of being designed and used in accordance with the invention: A preferred manufacturing process for nanoparticles of many different groups of substances, in particular inorganically doped nanoparticles, and the process product directly derived from them;a generic quantity of substances, in the sense of products, in whatever physical form it is present, such as powder concentrate, colloid or aerosol;a nanoparticle carrier, hereinafter also abbreviated as NPTS, which carries nanoparticles of the invention, in a spatially homogeneous or inhomogeneous distribution, such that incorporation into the carrier in the sense of a bed or more of a coating with this material is generated;objects that are doped with the carrier/nano-particle and that are doped with the nanoparticle, for example, are intended for testing in a specific direction, for detection of fluorescent phenomena, and for detection of the effects of fluorescent phenomena, as well as for the detection of the effects of a specific process, for example, in the context of a fluorescent family of substances;

For the above items, reference is made to the subsidiary claims.

The sub-claims provide for advantages in further training and improvement of the subject matter of the invention.

The invention relates to the production of fluorescent inorganic nanoparticles in a liquid phase synthesis with an organic solvent to produce colloidal solutions of highly crystalline nanoparticles. These nanoparticles in solution can then be precipitated and dried in further steps of the process. Depending on the solvent used, the source of cations or anion source used for the host lattice and, if necessary, one or more additional sources of cations (preferably metal salts) for the dosing material, the desired nanoparticles and special properties of the nanoparticles are obtained.

In accordance with another aspect of the present invention, a manufacturing process for fluorescent inorganically-doped nanoparticles is disclosed, wherein the nanoparticles in the final product are contained in a host material with at least one dotant, and wherein an organic solvent is used, preferably as described above, for a liquid-acid synthesis of the nanoparticles. The host material is in particular a host lattice containing compounds of the XY entent type, wherein X is a cation of one or more elements of the main groups 1a,2a, 3a; 4a, which is subgroups 2b, 3b, 4b, 5b, 6b, 7b or the lanthanide subgroup of the periodic table, and Y is an anion of one or more of the main groups 3a, 4a, 5a, 6b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 7b, 8b, 8b, 8b, 8b, and 8b, and 8b.

The final product of the inventive step and its modifications is in each case a substance, i.e. a substance for which absolute protection is claimed, independent of the manufacturing process.

Preferably, a host material may contain compounds from the group of sulphides, selenides, sulfoselenides, oxysulphides, borates, aluminates, gallates, silicates, germanates, phosphates, halophosphates, oxides, arsenates, vanadates, niobates, tantalumates, sulphates, tungramates, molybdates, alkali halide and other halogenides or nitrides.

Furthermore, in accordance with the first aspect of the present invention, one or more elements from a set containing elements of the main groups 1a, 2a or A1, Cr, T1, Mn, Ag, Cu, As, Nb, Ni, Ti, In, Sb, Ga, Si, Pb, Bi, Zn, Co and or elements of the lanthanides are used as a dopant.

Preferably, for each fluorescent dye, a pair of coordinated dyes, in particular cer and terbium, with good energy transfer, one acting as an energy absorber, in particular as a UV light absorber and the other as a fluorescent light emitter, may be used.

In principle, the following compounds can be selected as the material for the doped nanoparticles, the following notation listing the host compound to the left of the colon and one or more doping elements to the right of the colon. If chemical elements are separated and bracketed by commas, they can be used optionally. A first selection list is defined as follows, depending on the desired fluorescence property of the nanoparticles to be manufactured, one or more of the compounds to be selected may be used: The term 'specified value' means the value of all the materials of Chapter 9 used, whether or not incorporating a reference material, in the product.The term 'sodium nitrate' means any organic compound with a purity by weight of more than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity by weight of less than 0,5% and a purity of less than 0,5% and a purity of less than 0,5% and a purity of less than 0,5% and a purity of less than 0,5% and a purity of less than 0,5% and of less than 0,5% and a purity of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5% and of less than 0,5%The value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product and the value of all the materials of Chapter 9 used do not exceed 20% of the ex-works price of the product

A second list is defined as follows: The following shall be indicated in the table for the calculation of the amount of the fine-tuning agent:

A third selection list for the doped nanoparticles is defined as follows: "Software" specially designed or modified for the "development", "production" or "use" of equipment specified in 2B201.a. or 2B201.b.

Another feature of the present invention is that the manufacturing process according to the invention uses metal chlorides to obtain the cationic component of the host material or a phosphate salt to obtain its anionic component and adds an acid catcher, preferably an amine, particularly preferably thioctylamine (C24H51N) for synthesis.

This makes it particularly advantageous to produce a host material with a metallic cation and phosphorus as a component of the anionic part of the host lattice.

In addition to the above phosphor-organic compounds phosphoric acid ester, phosphonic acid diester, phosphoric acid triester (trialkyphosphate) as a growth control component, the following chemical substances may be used in preference as solvents or components thereof in the production of the nanoparticles of the invention, according to the above aspect of the present invention: Phosphoric acid amide, preferably hexamethylphosphoric acid triamide, a phosphoramid oxide, preferably Tris-dimethylamino-phosphinoxide, Trisethylhexylphosphat, trialkylphosphine, in particular preferably Trioctylphosphine, here also abbreviated TOP, and preferably Trioctylphosphinoxide, here also abbreviated TOPO, both commercially available from Sigma Aldrich Chemie GmbH, Deisenhofen, Germany, Phosphoramide, preferably Tris-dimethylamino-phosphine, Phosphoric acid, preferably Tris-dimethylamino-phosphinoxide.

The above preferred solvents can be used in a favourable way to obtain LAPO4 as the particularly preferred host material. A LaPO4 host grid can be preferentially doped in such a way that two elements in different relative concentrations are used as doping to each other, one doping element having a local maximum of the absorption spectrum for light, preferably UV light, and the other doping element having a fluorescence emission spectrum having at least one local maximum having a distance △λ/ λ from the absorption maximum of the first doping element of at least 4%, preferably more than 20%.

This method ensures that the doted nanoparticles are excited by non-visible light and emit fluorescent radiation in the visible range of light, so that the stimulation light does not interfere with the emitted fluorescent light. This is particularly useful in the field of safety markings, which will be discussed below.

The process, improved by using the above-mentioned TOP/TOPO as solvent, can be used to obtain the particularly preferred LaPO4 as the host material, which is doped with a first absorbent dotant as a sensitiser, particularly Ce3+ as a selective UV-C absorber, and an emitting second dopant, particularly Tb3+.

If TOP and/or TOPO are used as solvents and a terbium dosage of 0.5 to 30 mol, preferably 5 to 25 mol and particularly 13 to 17 mol is used, with a corresponding mol ratio of 0.13 to 7.5, preferably 0.25 to 4, and preferably 0.9 to 1.1 between lanthanum and cer, and metal chloride salts as the source of the metal, high quality fluorescent nanoparticles can be produced which are particularly useful for high-security marking.

When TOP and/or TOPO are used as solvents during the manufacturing process, the advantages over phosphoric esters are a higher manufacturing temperature of about 530 to about 620 Kelvin, a related better absorption of the doping substance and a resultant audible intensity of the emitted light, which is a decisive factor in the applicability of a fluorescence marker.

Immediately after manufacture, the surface of the nanoparticles is surrounded by a shell consisting of solvent residues of the growth control components, e.g. trioctylphosphine, here also abbreviated TOP, and trioctylphosphinoxide, here also abbreviated TOPO, or one of the others described above, which allows for a simplified handling of the nanoparticles after manufacture, as these surface molecules (solvent residues) provide improved solubility in commercial solvents without changing the particles chemically in a second, more complicated step.

The nanoparticle material obtained from the process can be obtained after precipitation and drying, for example by hot air, as a soft, very fine-grained powder concentrate which can then be embedded in a variety of media, depending on the application case, allowing the nanoparticles to be incorporated into films, for example in the case of aluminium films by rolling, or in the case of polymer films, such as polyethylene or polypropylene, etc., by introduction in the liquid polymer state.

The material of the invention is inorganic and therefore resistant to fading, which makes it suitable for use in extreme conditions, such as temperatures of near zero to about 400 Kelvin, with good yields, without the use of any additional protective material, and in organic and aqueous solvents.

No concentration erosion occurs at high particle concentrations, unlike with organic fluorescence markers.

The material can be adapted to the solvent conditions in various solvents by subsequent chemical modification of the surface.

The nanoparticle material obtained from the process can also be present as a colloid in a carrier liquid, in particular a paint or dye liquid, or as a fine dust/aerosol in a carrier aerosol or gas.

The essential point of the present invention from the point of view of application is the nature of the light emitted by the nanoparticles manufactured in accordance with the invention.

This results in a characteristic property of the nanoparticle type concerned, which results from the specific colour and the specific half-width of the emitted light of the specifically selectable emitter dots or - a plurality of - specifically selectable emitter dots. These properties are currently not possible with any other material than the claimed rare earths.

Err1:Expecting ',' delimiter: line 1 column 145 (char 144)

The main omission is the necessary and specific steps for the doping of nanoparticles. For the rest of the process - synthesis in organic solvent from the starting materials as described above - reference can therefore be made to the description of the manufacturing process for the inorganically doped nanoparticles.

This creates a new possibility of using this quantity of substances, referred to above as phosphorus, as nanoparticles, particularly for the marking of objects, with or without self-doping.

The nanoparticle size ranges from 1 nm to about 1000 nm can be produced specifically, in particular excluding oxygen or water or water vapour during synthesis.

Depending on the control components of the solvent used, a very uniform size of the nanoparticles can be achieved. Even homogeneous small nanoparticles can be manufactured according to the invention in a size range of 1 to 8 nm, preferably in a middle range of 4-5 nm, with a standard deviation of less than 30%, preferably less than about 10%. This allows the nanoparticles to be incorporated into very fine-structured carrier materials without significantly changing the carrier structure as required by the respective application, e.g. when embedded in very thin and/or very soft polymer films. For example, films remain transparent and do not become cloudy as would be the case for larger particles (from about 50 nm onwards).

This is particularly true of nanoparticles from the group of rare earth metals phosphates, or phosphates of major group III, or phosphates of calcium (CA), strontium (Sr), or barium (Ba), The nanoparticles shall have an elongation of not more than 15 nm, preferably not more than 10 nm, along their longest axis and preferably not more than 4 to 5 nm with a standard deviation of less than 30%, preferably less than 10%.

The above-mentioned possibility of producing the phosphorus family as nanoparticles, according to the invention, opens up in particular the use of phosphors, in particular nanoparticles containing phosphates, preferably the use of doped nanoparticles, and in particular the inorganic doped nanoparticles described above as fluorescent markers in general, to mark any object, in particular information media such as CDs, computer components, vehicle components, engine parts, documents, locks, anti-theft devices, objects transparent to visible light such as window bars, eyeglass lenses, contact lenses or transparent screens, and in particular in the field of high-security markings, such as cheques and cheque money, and jewellery, as required and desired.

The invention allows the embedding of the above groups of nanoparticles or nanoparticle carrier materials into labelling articles, either as coating or film coating or as applied paint, to produce labelling of any article in a cost-effective manner, depending on the requirements of the individual case, without affecting the appearance of the article or its haptic or other object-related properties.

The nanoparticles shall preferably be incorporated into or bonded to the labelled object in such a way that the particle or substance of the invention is excitable by a predetermined energy supply, preferably by electromagnetic radiation, in particular radiation with a wavelength less than 300 nm, or by irradiation with particles or electrons, and produces an object externally detectable by fluorescence emission, preferably in the visible range of light, or in the UV or near-IR (NIR) range.

In principle, one or more types of nanoparticles can be selected to meet the specific requirements for the labelling; in particular, one or more excitation spectral ranges can be deliberately selected from their position in the spectrum and their bandwidth; the fluorescence spectrum can also be selected specifically, monochrome, multicolored, visible (VIS), or invisible and detectable only by specific means, etc.

In addition, liquids and gases can be marked for the purpose of testing whether or not such a substance is present anywhere when the NPTS is introduced into the medium in question, which may be relevant in safety checks such as cracking tests on aircraft, pipelines, water pipes and other systems conducting liquids, the advantage being the special distinctive properties of the material, which make the test medium easily traceable.

The material is completely transparent, scatter-free and colourless, allowing it to be used anywhere without being detected.

In the field of product return from the consumer to the manufacturer and the necessary unique marking by the manufacturer, it is also recommended to use a marking which is not visible to the normal viewer but only after stimulation by special forms of energy, such as UV-C light with, for example, a wavelength of 250 nm.

In the field of high-security marking, if desired and so manufactured, for example in the case of Cer/Terbium dosing of LaPO4, the material can only be stimulated to fluorescence by a special W-C lamp of 255 nm wavelength and a corresponding marking made visible.

Such use may be, for example, by incorporating the marker into an open, i.e. transparent, material in the excitation spectral range, preferably in a polymer open in the UV-C range (wavelength < 300 nm), as is the case for commercial polypropylene or polyethylene, etc. Similarly, metal films may be used provided they satisfy this condition.

The excitation wavelength and emission wavelength are advantageously separated by up to 400 nm when using a suitable doping range, which allows for unmistakable detection of the emission wavelength without interfering with the excitation light.

It is also possible to provide print media, such as paper, films, etc., with the nanoparticles of the invention, for example by using appropriate templates and sprays of a carrier liquid, which only after stimulation show corresponding patterns, images, etc., of a certain kind, in color or in multi-color, which are previously invisible.

In the field of optoelectronics, even photocells and other light-sensitive components can be coated with the substance of the invention, since fluorescence occurs only in an area outside the normal operation of the component without interfering with normal operation.

To avoid the need for manual, complex spectral analysis to verify the authenticity of a label, the following automatic detection method is proposed, which is advantageous for quickly and easily identifying whether a particular sample or sample substance is labeled with a given type of nanoparticle: The detection method according to the invention for detecting the fluorescence of a sample substance as being consistent with a given nanoparticle type (reference substance) requires, in its simplest form, a fluorescence emission peak corresponding to the emission peak characteristic of the nanoparticle type. The detection principle essentially consists of the application of up to three interference filters specifically open to a given wavelength.If the apparatus is measuring at about 1-10 nm to the left and right of the main emission line more than 10 - 50%, preferably more than 5 - 20% of the main emission line intensity, a falsification is present. Stimulate the substance with a successful stimulation spectrum known for the specified nanoparticle type, as mentioned above,Filter the main peak spectral range, for example with an appropriately designed interference filter,Filter at least a secondary spectral range next to the main peak, where the specified nanoparticle type is expected to have a maximum low intensity, for example also with an appropriately set interference filter,Quantify the filtered radiation intensities in the specified spectral ranges,For example, with a number of photosensitive elements, such as photocells, each of which is optically directly coupled to a respective interference filter, and determining the ratio of the filtered radiation intensities to each other, for example by evaluating the signal from the photocell, recognise the sample substance as being consistent with the specified nanoparticle type if the ratio of one or more of the near-spectral range beam to the main peak radiation is less than a corresponding given sword wave.

It is advantageous to use the pre-known and thus defined half-width of a major peak of the reference substance to define the sharpness of the reference peak and to determine the threshold as a requirement for authenticity.

If the sub-area is only covered on one side of the main peak, there is a threshold, or generally two if sub-areas are covered on both sides of the main peak.

It is advantageous to filter and evaluate two or more subspectral regions in addition to the main peak, which can contribute to increased detection confidence.

The advantage of the two options is that the signal collection and evaluation effort is low, since the signal from the photocell can be easily and cheaply digitized and evaluated by computer.

In another variant of the detection method, a special image, if any, such as barcodes or more complex images or patterns of the fluorescent source are additionally captured, for example, by a CCD camera and evaluated by appropriate state-of-the-art imaging logic.

The detection device corresponding to the method is essentially based on the functional characteristics described above, and portable detectors can also be manufactured, since all elements of the detection system are small and easy to manufacture or are commercially available, except for the programming logic for signal analysis.

In addition to the aforementioned use for marking purposes, the substances of the invention can be used as a protective layer against hard UV radiation and as a transducer of hard UV radiation into visible light, provided that they absorb energy in the hard UV range and emit energy in the visible range, thus significantly increasing the sensitivity of commercial detectors in this energy range.

When used with solar panels, for example, if the light-recording surface has a coating according to the invention with the conversion properties described above, hard UV radiation can be converted into visual light and thus contribute to an increase in the efficiency of the collector.

The following shall be added:

Examples of implementations of the invention are shown in the drawings and further described in the description below.

It shows: Fig. 1a schematic block diagram for an embodiment of a detector device according to the invention according to a simpler form;Fig. 2a block diagram according to Fig. 1 for a more complex embodiment;Fig. 3a schematic emission spectrum of a reference substance and a sample substance, and measurement points in the detection evaluation;Fig. 4a schematic surface molecules of a doped nanoparticle according to the manufacturing process in TOP/TOPO solvent;Fig. 5 shows, for example, the absorption (excitation wavelength) and fluorescence spectrum (wavelength) of LaCePO4:Tb in CH3;Cl

The following is a description of the examples of exercises:

The following is a detailed description of a preferred embodiment of a manufacturing process of the invention for the exemplary manufacture of LaPO4Ce:Dy.

The following shall be added:

(a) In a first 50 ml main flask with an intensive cooler, temperature sensor and a heating sponge, 20 ml of commercially available TOP (90%) are filled and evaporated at about 323 Kelvin (K) for one hour by stirring. (b) In a second flask, 2 g of TOPO and 2.3 ml of TOP are mixed and the TOPO is melted under slight heating to produce a homogeneous mixture. (c) In a third flask, the salts LaCl3 (0.001 mol), CeCl3 (0.0012 mol) and DyCl3 (0.00024 mol) are dissolved in 3 ml of methanol and then transferred to the TOP/POTO mixture. (d) Then 0.00283 HPO4 is added to the above 50 ml flask at 32 mol of Kelvin and stirred under vacuum.(e) The methanol from the salt, TOP/TOPO, methanol mixture is then distilled under vacuum at room temperature and the remaining solution is transferred to the first flasks. (f) The temperature is then raised to 533 Kelvin and stirred overnight. The resulting nanoparticles can then be dissolved in 30 ml of toluene and cut with 20 ml of methanol. This results in a substance which can then be dried, for example, under controlled supply of hot air, at about 310 Kelvin, to produce a dry substance.

The following is a description of a preferred embodiment of a manufacturing process of the invention for the exemplary production of LaPO4Ce:Tb:

The following is the list of the products covered by the exemption:

(a) In a 50 ml main flask with an intensive cooler, temperature sensor with a heating fungus, 20 ml of Trisethylhexylphosphat are filled and evaporated at about 323 K 1h under stirring. (b) In a second flask, 10 ml of Trisethylhexylphosphat and 3.2 ml of Trioctylamine are mixed and infused with 0.0028 mol H3PO4. (c) In a third flask, the salts LaCl3 (0.001 mol), CeCl3 (0.0012 mol) and TbCl3 (0.00024 mol) are dissolved in 3 ml of methanol and then transferred to the main flask. (d) When the metal salts have completely dissolved in methanol, the mixture is transferred to the main flask and the methanol is removed from 323 K.

Err1:Expecting ',' delimiter: line 1 column 316 (char 315)

The following is the list of active substances:

To heat transport, add 50 ml of 1,6-hexandiol to the space between the outlet and the glass. Then close the autoclave, carefully evacuate twice and re-fill each time with nitrogen or argon (or another noble gas). Finally, heat the autoclave for up to 57 hours (= 53 minutes and 4 minutes at this temperature). Cool the autoclave, decompress the water, first cool the part of the glass, then release the contents of the glass. The isopropanol is concentrated in 100 ml of isopropanol, which is then cooled to 60 g/l.

The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

Synthesis of Y3Al5O12, Nd nanoparticles (not visible, infrared luminescence):

For heat transport, add 50 ml of 1,6-hexandiol to the space between the autoclave wall and the glass. Then close the autoclave, evacuate carefully twice and refill each time with nitrogen or argon (or another noble gas). Finally, raise the autoclave to 573 kJ and heat it for 4 to 12 hours. Cool the autoclave part off, then release the decanter, which first dissolves the isopropanol content in 60 g/l of the isopropanol. The isopropanol is centrifuged in a small solution of 60 g/l of water and then cooled to 1250 g/l.

The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

The following is the list of the substances which are to be used in the manufacture of the product:

For heat transport, add 50 ml of 1,6-hexandiol to the space between the autoclave wall and the glass. Then close the autoclave, evacuate carefully twice and refill each time with nitrogen or argon (or another noble gas). Finally, heat the autoclave to 573 °C and heat it for 4 hours. Then, remove the decanter, then release the decanter. The contents of the glass are centrifuged with 60 ml of isopropanol, which is 60-250 ml of isopropanol. The water is then cooled to 12000 ml.

Properties of the substance: yellow, not colourless; can also be excited by violet light.

The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

The following table shows the results of the analysis:

Dissolve 3.78 g (10.4 mmol) Ga ((NO3) 3 · 6 H2O, 2.68 g (5.9375 mmol) Gd ((NO3) 3 · 6 H2O and 142 mg (0.3125 mmol) Tb ((NO3) 3 · 6 H2O in 20 ml of water by stirring. Pour this solution on a set into a solution of 10 ml 25% ammonia water in 40 ml of water (not inverted). The pH must be greater than 10, otherwise add more ammonia. Decentrifuge the precipitate, then decant. Stir the precipitate 5 times in 50-100 ml of water and then 5 times in 50-100 ml of methanol, wash, refine and decant.Heat to 373 K under vacuum until all methanol and water are distilled. Blow inert gas (e.g. nitrogen or argon) and boil for 16 hours under inert gas flow. Let the approach cool and transfer to a glass for the autoclave. Place the glass in the autoclave and loosen it with a glass cap. For heat transport, give 50 ml of 1.6-hexandiol into the space between the autoclave wall and glass.The autoclave is cooled, the contents of the glass are dissolved in 100-250 ml of isopropanol, the precipitate is decentrifuged and washed several times with isopropanol, then washed with water until peptation (= small particles dissolve again) begins, the colloidal solution is centrifuged for 60 min at 12000 g and the precipitate of Gd3Ga5O12 is separated from the supernatant by decanting. The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

The following is the list of the active substances in the active substance:

• 6 H2O and 136 mg (0.3125 mmol) Nd(NO3) 3 • 6 H2O dissolve in 20 ml of water by stirring. Pour this solution on a set into a solution of 10 ml 25% ammonia water in 40 ml of water (not vice versa. The pH must be greater than 10, otherwise add more ammonia. Decentrify the precipitation, then decant. Stir the precipitation 5 times in 50-100 ml of water and then 5 times in 50-100 ml of methanol, wash, scrape and decant.The 6-hexandiol is then heated to 373 K under vacuum until all methanol and water are distilled. The 6-hexandiol is then aerated with inert gas (e.g. nitrogen or argon) and boiled for 16 hours under inert gas flow. The approach is cooled and transferred to a glass for the autoclave. The glass is placed in the autoclave and loosely closed with a glass cap. For heat transport, 50 ml of 1.6-hexandiol is given to the space between the autoclave and the glass wall.The precipitate is centrifuged and washed several times with isopropanol. Then washed with water until peptation (= small particles dissolve again) begins. Centrifuge the colloidal solution for 60 min at 12000 g and separate the precipitate of the Y3Al5O12:Nd nanoparticles from the supernatant by decanting. The reaction also works with 1,4-butandiol instead of 1,6-heksandiol, but the effect on small particles is worse.

The following is the list of the active substances in the active substance:

Dissolve 3.90 g (10.4 mmol) Al(NO3) 3 · 9 H2O, 2.27 g (5.9375 mmol) Y(NO3) 3 · 6 H2O and 136 mg (0.3125 mmol) Ce(NO3) 3 · 6 H2O in 20 ml of water by stirring. Pour this solution on a set into a solution of 10 ml 25% ammonia water in 40 ml of water (not vice versa). The pH must be greater than 10, otherwise add more ammonia.The 6-hexandiol is then heated to 373 K under vacuum until all methanol and water are distilled. The 6-hexandiol is then aerated with inert gas (e.g. nitrogen or argon) and boiled for 16 hours under inert gas flow. The approach is cooled and transferred to a glass for the autoclave. The glass is placed in the autoclave and loosely closed with a glass cap. For heat transport, 50 ml of 1.6-hexandiol is given to the space between the autoclave and the glass wall.The autoclave is cooled, the contents of the glass are dissolved in 100-250 ml of isopropanol: the precipitate is decentrifuged and washed several times with isopropanol, then washed with water until the peptization (small particles dissolve again) is frozen. The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

The following is the list of the active substances in the active substance:

Dissolve 3.90 g (10.4 mmol) Al(NO3) 3 · 9 H2O, 2.27 g (5.9375 mmol) Y(NO3) 3 · 6 H2O and 139 mg (0.3125 mmol) Eu(NO3) 3 · 6 H2O in 20 ml of water by stirring. Pour this solution on a set into a solution of 10 ml 25% ammonia water in 40 ml of water (not vice versa). The pH must be greater than 10, otherwise add more ammonia. Decentrify the precipitation, then decant. Stir the precipitation 5 times in 50-100 ml of water and then 5 times in 50-100 ml of methanol, wash, centrify and decant.The 6-hexandiol is then heated to 373 K under vacuum until all methanol and water are distilled. The 6-hexandiol is then aerated with inert gas (e.g. nitrogen or argon) and boiled for 16 hours under inert gas flow. The approach is cooled and transferred to a glass for the autoclave. The glass is placed in the autoclave and loosely closed with a glass cap. For heat transport, 50 ml of 1.6-hexandiol is given to the space between the autoclave and the glass wall.The autoclave is cooled, the contents of the glass are dissolved in 100-250 ml of Is,opropanol. The precipitate is decentrifuged and washed several times with isopropanol. Then washed with water until peptation (= small particles dissolve again) begins. The colloidal solution is centrifuged for 60 min at 12000 g and the precipitate of the Y3Al5O12:Eu nanoparticles is separated from the supernatant by decantation.

Luminating and doped zinc silicate: For the purposes of heading 2926, the expression 'metallic compounds' means compounds which are not chemically defined.

In a second PE vessel, dissolve 8 g NaOH in 80 ml of water. Add 1,042 g (5 mMol) SiO2H5) 4 (tetraxylan) or 0.761 g (5 mMol=SiOCH3) 4 (tetramethoxylan) and stir overnight. 48 mg (0.3 mmol) KMnO4 in a small amount of water. Transfer all three to the autoclave, dissolve to 190 parts, dissolve the autoclave and dissolve 30 ml (N2O2H2O2 or 5 g/90 g/n) of water. The solution is then heated to a small temperature and dissolves in water for about 60 minutes.

11. Luminescent and doped barium silicate: For lead-doped BaSiO3 (((2-at.%):

The clear solution is added to the tetraethoxylan. The glass is rinsed with another 50 ml of 0.1 M BaOH) 2 solution, which are also added to the PE bottle. The solution is stirred for 60 min in the well-sealed PE bottle. The suspension is then filled in an autoclave teflon and heated in the autoclave at 543 K overnight. The water is then heated from the bottom of the tank and cooled by centrifuging the water with a small amount of water. The solution is then dissolved in a teflon tank at 12000 nanometers.

12. Luminescent and calcium silicate For lead-doped CaSiO3 (((2-at.%):

Weigh 1.042 g (5 mmol) of Si (OC2H5) 4 in a 100 ml Erlenmeyer flask, fill and stir with 40 ml ethanol. Bring 50 ml of water with HNO3 to pH 4.5 and add to the stirred solution. Close the flask and stir overnight. When the solution has remained clear, fill a 250 ml round flask with 40 ml of water and hang it. Mark the position of the mini- flask on the glass wall with a waterproof pen, pour out the water and fill the solution from the Erlenmeyer flask. At 313 K temperature, press the solution to about 40 ml (mark !) in the rotary evaporator bath, so that the alcohol is removed.1.157 g (4.9 mMol) Ca(NO3) 2 · 4 H2O and 33 mg (0.1 mMol) Pb(NO3) 2 dissolve in 30 ml of water. Bring this solution and the silicate solution gently to pH 6.0 with diluted KOH. Then add the Ca/Pb solution to the silicate solution and fill in a glass autoclave vessel. Heat overnight in the autoclave at 543 K under stirring.

The following shall be reported in the table: The following requirements shall be met:

Heat the solution in the autoclave (Teflon vessel) under stirring for one hour to 543 K. Filter the precipitate and dissolve it in 100 ml of 0.5 M HNO3 (= 0.5 M HNO3) re-inserted with 6.87 De 2010 solution (60%) (Monsanto) (20'Mol) of NaOH, stir for 60 min. Then stir with 1 M NaVO4 (NaOH. 40-100!) 5 ml of NaOH and bring the pH down to 15 g/mL. This reduces the concentration of the solution to 60 g/mL. The resulting solution is centrifuged with a small amount of water and dissolved in a small amount of water (up to 12 min.

Other, of a kind used for the manufacture of semiconductor devices The rule:

779 mg (3.3 mMol) Ca(NO3) 2 • 4 H2O are dissolved in 150 ml of water, the solution is triticated and brought to pH 12 with NaOH. 990 mg (3 mmol) Na2WO4 • 2 H2O are dissolved in 150 ml of water, the solution is brought back to pH 12. The solutions are mixed in autoclave vessels, the pH is brought to the old value if necessary, and heated overnight in the autoclave at 543 K under stirring. The precipitation obtained is decentrifuged and washed with water.

The following shall be added to the list of substances: The test shall be carried out on the vehicle in which the test is performed.

The solution is heated overnight to 533 KC in the autoclave at 70 per cent saturation under agitation. The solution is then washed with water until peptization (= small particles dissolve again) The colloidal solution is boiled for 60 min at 12000 nanometres and the lower part of the supernatant is separated from the surface by centrifuging.

16. Luminescent and doped calcium molybdate The following shall be reported for the product:

708 mg (3.0 mmol) Ca(NO3) 2•4 H2O and 74 mg (0.167 mmol) Eu(NO3) 3•6 H2O are dissolved in 30 ml of water. 618 mg (3.5 mmol Mo) (NH4) 6Mo7O24•4 H2O are dissolved in 30 ml of water and with 1 M NaOH at pH 8. In a Teflon autoclave vessel, the Ca/Eu solution is added to the molybdate solution, the pH, if necessary, is brought to the old value of the molybdate solution and heated overnight in the autoclave at 543 K under hot tubes. The precipitation obtained is decentrifuged and washed with water (= with a mixture of water and water).

The following is added to the list of substances which are to be classified in the Annex to this Regulation: For the manufacture of K8Ta6O19· 16 H2O (Mw = 1990.07 g/mol):

Preheat the oven to 773 K. Fill 25 g KOH and 5 g Ta2O5 in a silver jug (not glass) and heat (to a clear boiling point) in the oven for 30 min. In the meantime, heat 500 ml of water for boiling. Remove the jug from the oven, cool it, and leach the melt cake several times with a little hot water (total about 50-100 ml if sufficient). Fill the solution in a PE bottle (not glass !) Filter the solution into a PE bottle through a wrinkle filter and plastic funnel. For product failures, transfer the solution to the same volume of ethanol (technical) up to four times. The resulting solution will work if the required quantity is reached.

The following shall be used for the calculation of the maximum level of the test substance:

Dissolve 5 H20 and 109 mg (0.25 mmol) Tb in 20 ml of water and give 1 M KOH to 14 ml in a Teflon autoclave vessel. Dissolve 1.66 g K8Ta6O19 · 16 H2O (5 mMol Ta) and 1 ml 1 M KOH in 35 ml of water and give the lanthanide solution. Heat the solution in the autoclave (teapot) under stirring for one hour to 543 K. Filter the precipitate and transfer it to 200 ml 0.5 HNO3 (pH 0.3) mixed with 6.87 g Dequest 2010 solution (60%) (20 KOol) for 60 min. Then with more than 1 m 80 (H. 1 ml 200 ml KOol) dissolve it to a pH of 455 m/min. and bring it to a complete boil-off at approximately 12.00 o'clock and stirring it at about 45 °C.

The precipitate is stirred with 40 ml of water and dispersed in the ultrasonic bath for 2 min. Then centrifuged and decanted at 4500 U/min for 15 min. (peptization?).

Manufacture of other products of heading No 7302

300 ml of Tris- (ethylhexyl) phosphate are rinsed with nitrogen without oxygen and added to 100 ml of dry methanol with a solution of 10.48 g of CaCl2 . 2 H2O (71.25 mmol) and 836 mg EuCl2 (3.75 mmol). Under vacuum, the methanol and crystalline water are distilled at 303 to 313 K. Then 4.90 g (50 mmol) of crystalline phosphoric acid are added to a mixture of 65.5 ml (150 mmol) trioctylamine and 150 ml Tris- (ethylhexyl) phosphate and the remaining solution is given to a mixture of water and water. The solution is evaporated several times and evaporated with four nitrates to minimise oxidation of Eu3+. The final solution is then cooled to 473 K. Once the mixture is cooled, a portion of the methanol is added to the mixture and cooled to 448 °C.

Manufacture of other materials of heading No 7302

300 ml of Tris- (ethylhexyl) phosphate are rinsed with nitrogen without oxygen and dissolved with a solution of 9.78 g CaCl2 .2 H2O (70 mmol), 223 mg EuCl2 (1 mmol) and 503 mg MnCl2 (4 mmol) in 100 ml of dry methanol. Under vacuum, the methanol and crystalline water are distilled at 303 to 313 K. Then 4.90 g (50 mmol) crystalline phosphoric acid is dissolved in a mixture of 65.5 ml (150 mmol) trioxy and 150 ml Tris- (ethylhexyl) phosphate and dissolved to the remaining solution. The solution is then heated four times and dissolved with nitrogen to minimise evaporation of Eu3+. The solution is dissolved in a quantity of 473 mmol (50 mmol) of methanol and dissolved in a solution of 448 mL of methanol, so that the solution is heated to a temperature of 443 °C. The solution is then dissolved in a solution of 443 mL of methanol and dissolved in a solution of 443 mL of methanol.

The following is a list of the main components of the new technology:

For heat transport, 50 ml of 1,6-hexandiol are added to the space between the autoclave wall and the glass. Then the autoclave is closed, carefully evacuated twice and recharged with nitrogen or argon (or another noble gas) each time. Finally, the autoclave is heated to 573 °C and kept at this temperature for 4 hours (= once. First, the autoclave is cooled, the pressure is off, then the Eufrate is off. The contents of the glass are decanted in 100 ml of Nianopropanol.

The reaction also works with 1,4-butandiol instead of 1,6-hexandiol, but the yield on small particles is worse.

Other exemplary forms of manufacture in accordance with the invention are:

The following are to be classified in heading 8401:

Mix 2.5 tetraethyl orthosilicate with 40 ml ethanol and mix 7.5 ml of 0.8 M tetrabutylammonium hydroxide solution in methanol. Stir with 0.9 ml water and stir overnight with the mixture closed. Then mix the solution with about 20 ml dihexyl ether and distil the alcohols in the rotary evaporator at about 30 °C bath temperature.

Dissolve 1.3 g (9.5 mMol) ZnCl2 and 99 mg (0.5 mMol) MnCl2 · 4 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. Distillate the methanol under vacuum. Stir under vacuum and add 16.6 ml (38 mmol) of trioctylamine and the above tetrabutylammonium silicate solution in dihexyl ether. Then heat to about 200 °C under nitrogen and stir overnight. Distillate the solvent (especially dihexyl ether) from the solution under vacuum. If desired, the residual raw product can be removed from the by-products by washing with small amounts of ethanol, diafiltration or other usual methods as indicated above.

The following shall be reported for the following materials:

Mix 2.5 tetraethyl orthosilicate with 40 ml ethanol and mix 7.5 ml of 0.8 M tetrabutylammonium hydroxide solution in methanol. Stir with 0.9 ml water and stir overnight with the mixture closed. Then mix the solution with about 20 ml dihexyl ether and distil the alcohols in the rotary evaporator at about 30 °C bath temperature.

Dissolve 1.3 g (9.5 mMol) ZnCl2 and 99 mg (0.5 mMol) MnCl2 · 4 H2O in a small amount of methanol and add 50 ml bis- ((2-ethylhexyl) amine. Distillate the methanol under vacuum. Add the above solution of tetrabutylammonium silicate solution to dihexyl ether by stirring. Heat to about 200 °C under nitrogen and stir overnight. Distil the solvent (especially dihexyl ether) from the solution under vacuum. The remaining raw material can be purified by diafiltration (filter pore size: 5000-10,000 Daltons) against toluene in a stirring cell and then isolated by a narrowing of the diafiltrated solution at the rotary evaporator.

Lead-doped calcium silicate nanoparticles:

Mix 2.5 tetraethyl orthosilicate with 40 ml ethanol and mix 7.5 ml of 0.8 M tetrabutylammonium hydroxide solution in methanol. Stir with 0.9 ml water and stir overnight with the mixture closed. Then mix the solution with about 20 ml of dibenzyl ether and distil the alcohols in the rotary evaporator at about 30 °C bath temperature.

Dissolve 1.67 g (9 .5 mMol) Ca (CH3COO) 2 · H2O and 222 mg (0.5 mMol) Pb (CH3COO) 2 · 3 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dibenzyl ether. Distillate the methanol under vacuum. Add 16.6 ml (38 mmol) trioctylamine and the above solution of tetrabutylammonium silicate to dibenzyl ether by stirring. Heat to about 250 °C with nitrogen and stir overnight. The solution is then purified against toluene by diafiltration (filter pore size: 5000-10,000 Daltons) in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following shall be indicated in the table:

Mix 2.5 tetraethyl orthosilicate with 40 ml ethanol and mix 7.5 ml of 0.8 M tetrabutylammonium hydroxide solution in methanol. Stir with 0.9 ml water and stir overnight with the mixture closed. Then mix the solution with about 20 ml of dibenzyl ether and distil the alcohols in the rotary evaporator at about 30 °C bath temperature.

• Add 16 ml (38 mmol) of trioctylamine and the above solution of tetrabutylammonium silicate in dizyl ether. Then heat to about 250 °C under nitrogen and stir overnight. The solution is then purified against toluene by diafiltration (filter pore size: 5000-10,000 Daltons) in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following is added to the list of substances which are to be classified in the Annex to this Regulation:

Mix 2.5 tetraethyl orthosilicate with 40 ml ethanol and mix 7.5 ml of 0.8 M tetrabutylammonium hydroxide solution in methanol. Stir with 0.9 ml water and stir overnight with the mixture closed. Then mix the solution with about 20 ml of dioctyle ether and distil the alcohols in the rotary evaporator at about 30 °C bath temperature.

Dissolve 2.88 g (9.5 mmol) YCl3 · 6 H2O and 187 mg (0.5 mMol) TbCl3 · 6 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dibene diethyl ether. Distillate the methanol under vacuum. Add 16.6 ml (38 mmol) trisi- (((2-ethylhexyl) amine and the above solution of tetrabutylammonilicate solution in diethyl ether by stirring. Heat to about 250 °C with nitrogen and stir overnight at this temperature. The solution is then purified against toluene by diafiltration (filter pore size: 5000-10,000 Daltons) in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following shall be reported in the table:

The following table shows the total number of substances in the test chemical: Dissolve methanol slightly and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexylether. Add 16.6 ml (38 mmol) of trioctylamine and 14.0 ml of 1 ml of boric acid H3BO3 solution to dihexylether (14 mmol) after stirring, then heat to approximately 200 °C with nitrogen and stir overnight. Distil the solvent (especially dihexyl ether) from the solution under vacuum. If desired, the residual raw product can be removed from the by-products by washing with small amounts of ethanol, diafiltration or other usual methods as indicated above.

InBO3:Tb Nanoparticles:

Dissolve 2.78 g (9.5 mMol) InCl3 · 4 H2O and 187 mg (0.5 mmol) TbCl3 6 H2O in a little ethanol. Dissolve and add 4.6 g (12 mmol) Trioctylphosphanoxide (TOPO) in 40 ml of dioctylether. Distillate the methanol and the released crystalline water under vacuum. Add 16.6 ml of Tris- ((2-ethylhexyl) amine and 14.0 ml of 1 ml of boric acid H3BO3 solution in dioctylated ether (14 mmol) to the cloudy solution, then heat to approximately 280 °C with nitrogen and stir overnight at this temperature.

The following shall be reported in the table:

The total volume of the solution is approximately 2.88 g (9.5 mMol) YCl3 • 6 H2O and 183 mg (0.5 mMol) EuCl3. Dissolve the ethanol slightly and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. Add 12,9 ml (38 mmol) of trihexylamine and 14,0 ml of 1 ml of boric acid H3BO3 to dihexy-ether (14 mmol) by stirring, then heat to about 200 °C with nitrogen and stir overnight. If desired, the residual raw material can be removed from the solution by washing with small amounts of ethanol, by diafiltration or other usual methods as described above.

The following is the list of the substances which are to be classified in the product:

1.38 g As2O5 in approximately 40 ml of methanol, 1.0 ml of water and 3.8 ml of 0.8 M solution of tetrabutylammonium hydroxide are added to the methanol and stirred overnight, then the solution is added to about 20 ml of dihexyl ether and the alcohols are distilled at about 30 °C bath temperature in the rotary evaporator.

Dissolve 3,528 g (9.5 mmol) LaCl3 • 7 H2O and 183 mg (0.5 mmol) EuCl3 • 6 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. Add 16.6 ml (38 mmol) of trioctylamine and arsenate solution above, stirring, then heating to about 200 °C with nitrogen and stirring overnight. If desired, the raw product can be removed from the solution by washing with small amounts of ethanol, by diafiltration or other usual methods.

The following shall be indicated in the table:

Dissolve 3,528 g (9.5 mMol) LaCl3· 7 H2O and 183 mg (0.5 mMol) EuCl3· 6 H2O in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexylether. Add a solution of 3.77 g Na2HAsO4 · 7 H2O (12 mmol) to 40 ml of Tris[2-(2-methoyethoxy) ethyl]amine (a complex-forming agent for Na-ions) after stirring, then heat to about 200 °C with nitrogen and stir overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following shall be reported for the following categories of materials:

Dissolve 2.88 g (9.5 mMol) YCl3, · 6 H2O and 177 mg (0.5 mMol) CeCl3 · 6 H2O in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexylether. Add a solution of 2.14 g Na2HPO4 · 2 H2O (12 mmol) to 40 ml of Tris[2-(2-methoyethoxy) ethyl]amine (a complex-forming Na-ion) after stirring, then heat to about 200 °C with nitrogen and stir overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

YPO4: Dy nanoparticles 32.

Dissolve 2.88 g (9.5 mMol) YCl3 6 H2O and 188 mg (0.5 mMol) DyCl3 6 H2O in a little methanol and add 3.3 ml (12 mmol) of triisobutyl phosphate and 40 ml of dihexylether. Solve 2.14 g Na2HPO4 · 2 H2O (12 mmol) in a mixture of 10 ml 15-Crown-5 kronenether (a complex-forming Na-ion) and 20 ml dihexylether and stir the solution to metallic salt, then heat to about 200 °C with nitrogen and stir overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent pressing of the diafiltrated solution on the rotary evaporator.

In 2S3Nanoparticles:

Dissolve and add 4.6 g (12 mmol) of trioctylphosphanoxide (TOPO) to 40 ml of dioctylether. Distillate the methanol and the released crystalline water under vacuum. 667 mg NaHS · H2O (9 mmol) together with 5 ml 15-Crown-5 kronenether (a complex-forming Na-ion) are dissolved in 20 ml ethylene glycol dibutylether and agitated to a metal salt solution, then heated to about 200 °C under nitrogen and agitated overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

BaSO4 is a nanoparticle:

Dissolve 3.165 g (9.5 mMol) BaBr2 • 2 H2O and 177 mg (0.5 mmol) CeCl3 • 6 H2O in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexylether. 1.66 g NaHSO4 · H2O (12 mmol) together with 5 ml 15-Crown-5 kronenether (a complex-forming Na-ion) are dissolved in 20 ml ethylene glycoldibutylether and agitated to a metal salt solution, then heated to about 200 °C under nitrogen and agitated overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following shall be indicated in the table:

Dissolve 6 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. 2.05 g tetrabutylammonium hydrogen sulphate (CH2CH2CH2CH2) 4NHSO4 (12 mmol) are dissolved in 20 ml of dihexyl ether and agitated with 16.6 ml (38 mmol) of trioctylamine to a metal salt solution, then heated to about 200 °C with nitrogen and stirred overnight. The solution is then purified by diafiltration (filter pore size: 5000-10,000 Daltons) against ethanol in a stirring cell and the nanoparticles are isolated by subsequent straining of the diafiltrated solution at the rotary evaporator.

The following shall be reported for the following categories of materials:

Dissolve 1.485 g (4 mmol) LaCl3 · 7 H2O, 1.676 g (4.5 mmol) CeCl3 · 7 H2O and 538 mg (1.5 mMol) NdCl3 · 6 H2O in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexylether. 645 mg triethylamine trishydrofluoride ((CH2CH2) 4N · 3 HF (4 mmol) is dissolved in 20 ml of dihexylether and stirred with 16.6 ml (38 mmol) of trioctylamine to a metal saline solution, then heated to about 200 °C with nitrogen and stirred overnight. If desired, the residual raw material can be removed from the solution by washing with small amounts of ethanol, by diafiltration or other usual methods as described above.

The following shall be reported for the following categories of materials:

Dissolve 1.96 g (4 mMol) La (CH3COCHCOCH3) 3 · 3 H2O, 2.21 g (4.5 mMol) Ce (CH3COCHCOCH3) 3 · 3 H2O and 765 mg (1.5 mMol) Tb (CH3COCHCOCH3) 3 · 3 H2O in a small amount of methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. Dissolve 0.5 ml of hydrofluoropyridine complex (C5H5N) · x HF with approximately 70% HF by weight in 20 ml of dihexylether and stir to obtain the solution of metal acetyl ketones, then heat to about 200 °C with nitrogen and stir overnight. If desired, the residual raw product can be removed by washing with small amounts of ethanol or by diafiltration as described above.

The following shall be indicated in the table:

2.10 g (7.9 mmol) Y ((CH3CHOCH3) 3, 630 mg (1.8 mMol) Yb ((CH3CHOCH3) 3) and 103 mg (0.3 mMol) Er ((CH3CHOCH3) 3) dissolve in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. Dissolve 1.1 g of hydrofluoro-2,4,6-trimethylpyridine complex (approximately 11-12 mMol HF per gram) in 20 ml of dihexyl ether and stir to obtain the solution of the metallic propyllates, then heat to approximately 200 °C with nitrogen and stir overnight. If desired, the residual raw product can be removed by washing with small amounts of ethanol or by diafiltration as described above.

The following is the list of the substances which are to be classified in the product:

Dissolve 2.50 g (7.9 mMol) La ((CH3CHOCH3) 3, 630 mg (1.8 mMol) Yb ((CH3CHOCH3) 3) and 103 mg (0.3 mMol) Er ((CH3CHOCH3) 3) in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of dihexyl ether. 645 mg triethylamine trishydrofluoride (CH2CH2) 4N - · 3 HF (4 mmol) is dissolved in 20 ml of dihexylether and agitated to a solution of metallic propyllates, then heated to approximately 200 °C with nitrogen and stirred overnight. If desired, the residual raw product can be removed by washing with small amounts of ethanol or by diafiltration as described above.

The following shall be reported for the following categories of materials:

Dissolve 3.11 g (9.8 mMol) Ce(CH3CHOCH3) 3 and 64 mg (0.2 mMol) Nd(CH3CHOCH3) 3 in a little methanol and add 3.3 ml (12 mmol) of tributyl phosphate and 40 ml of disopentylether. Disperse 0.5 ml of 48% hydrochloric acid (12 mMol HF) in 20 ml of disopentylether and stir the solution of the metal propyllates, then boil the solution overnight under nitrogen. If desired, the residual raw product can be removed by washing with small amounts of ethanol or by diafiltration as described above.

End of the explicit manufacturing examples.

As can be seen from the examples above, the principle underlying the present invention can be applied very broadly to produce a variety of substances with specifically selectable properties.

If TOP and/ or TOPO are used as solvents during manufacture, the resulting The advantages of a higher production temperature, of about 530 Kelvin and above, a related better absorption of the doping substance and a resultant sound intensity of the emitted light, which can be a decisive factor for the applicability of a fluorescent marker.

As shown schematically in Figure 4, immediately after manufacture, the surface 47 of the nanoparticles is surrounded by a shell consisting of solvent residues, in particular Trioctylphosphine 48 (TOP) and Trioctylphosphinoxide 49 (TOPO), of which only one is shown in the figure, which allows for a simplified handling of the nanoparticles after manufacture, since these surface molecules (solvent residues) provide improved solubility in commercial solvents without changing the particles in a second, cumbersome chemical step.

The substance resulting from the above steps of the manufacturing process may also be dried as described above and crushed into a fine powder up to about 30 nm average grain size if necessary.

The following are detailed descriptions of the detection methods and devices, using the figures.

In the other figures, in particular Fig. 1 and Fig. 2, the same reference marks refer to the same or similar functional components.

With reference to the drawings in general and in particular to Fig. 1, an embodiment of a detector device according to the invention, according to a basic form, contains three interference filters 10, 12, 14, three photophones 16, 18, 20, each coupled to the interference filters, a processing unit 22 for signals from the photophones and a display device 24, for example a display.

The test substance 28 shall be examined for the presence of a marking on it which can be recognised as being consistent with a given nanoparticle type which in turn has a peak fluorescence emission.

This is the case of LaPO4Ce:Tb, whose absorption and fluorescence spectra are illustrated in Figure 5, details of which are given below.

The radiation schematically shown by arrows in Fig. 1 initially stimulates a mark, if any, on the sample substance 28 in the form of nanoparticles possibly inorganically doped therein.

In the case of the terbium fluorescein emission, filter 12 passes only through the narrow wavelength range of the maximum of the main peak, i.e. a wavelength range of 543 nm + 2 nanometres. The interference filter is set to transmit a similarly narrow wavelength range. In the case of the latter, it transmits a narrow wavelength range of 530 + 10/- nanometres + 1 nanometres/wavelength, thus shortening the main wavelength range and thus covering the main wavelength range.

The interference filter 14 is set in the same way as filters 10 and 12, except that it covers the longer-wave sub-spectral range by 550 nanometres.

As shown in Fig. 1, the light passing through the interference filters hits the photosensitive surface of the photocells 16, 18 and 20, where a more or less large current is generated, depending on the intensity, which is greater the more light falls on the photosensitive surfaces.

The processing unit 22 is equipped with three input ports 23a, 23b, 23c which receive the currents from the photocells. The currents from the three photocells are first digitized in the processing unit 22 at a specified sample rate of, say, 10 kilohertz and stored in a dedicated storage area of the unit 22 which is large enough to cover a specified time window of measured values of, say, one second or more.

The next step is to make meanings over the time window for all three signals from photocells 16, 18 and 20. These meanings are now given as A, B and C. The mean of A corresponds to the mean of photocell 16, the mean of B of photocell 18 and the mean of C of photocell 20.

In the case of light emission, the value of B is accepted as evaluated in an exemplary range between 50 and 500. If the range is below 50, it is assumed that the test substance emits too little light in the main peak range in absolute terms to be tested by the detection method of the invention with acceptable tolerance. If the value is above 500, it has exceeded the permissible measurement range and cannot be evaluated immediately. In such a case, the emission source 26 must first be corrected to a lower intensity. This can be done, for example, by an automated feedback between the unit 22 source and a control for the light 26 but this connection is not marked for reasons of better visibility.

The B value for sample substance 28 is now between 50 and 500. It can now be concluded that the sample substance is at least to some extent in the narrow wavelength range of the main peak maximum emitted significantly. Thus, sample substance 28 could have a marking corresponding to the reference substance. To ensure or exclude this, the following two ratios are formed: A/B and C/B. The intensities of the sub-spectral ranges from photocells 16 and 20 are thus placed in relation to the intensity of the main peak, respectively.

The present invention only recognizes the sample as authentic if both ratios are less than a specified threshold value, since only in this case is there an emission spectrum of the test substance with a similarly sharp emission peak to the reference substance, and if at least one of the ratios is greater than this threshold, the sample is recognized as non-authentic and an equivalent output is generated in the display device 24.

The threshold can be advantageously approximated to 50% if the sub-spectral ranges are measured at wavelengths corresponding to the half-width of the reference peak.

Thus, for example, if B is 300, the test substance is only verified as authentic if both A and C are below 150. For safety reasons, a certain tolerance range can still be defined in one direction or another.

The advantage of evaluating only intensity ratios rather than absolute values is that the method is independent of the absolute values of the amount of radiation captured, which largely eliminates the need for advanced measurement methods and allows the distance between the sample and the filters to be varied within certain limits without distorting the result, as long as the distances of the three filters to the surface of the sample are equal.

In Figure 3, when evaluating the dashed emission line, the results of the test substance 28 for the A/B ratio would be about 90% and for the C/B ratio about 105%.

Figure 2 shows a representation to illustrate the detection method and the corresponding device in a slightly more complex variant.

The main difference between the two is that, instead of photonic cells, CCD cameras 30, 32 and 34 are now coupled to the interference filters 10, 12 and 14 instead of or simultaneously with the photonic cells. In the case of simultaneous coupling, the following steps can be performed in addition to those described above to ensure additional marking verification. In this case, after successful initial testing (see above), the images received by the CCD cameras with pattern recognition algorithms as known in the art are identified by a reference map, which is defined as the one provided in a specified sample processing unit. 22 A corresponding sample is only validated if the sample is validated and the sample is processed in a specified range of samples.

In the other case, if, apart from the CCD cameras, no photosensitive element absorbs the light of the interference filters, the luminous intensity of the images taken by the CCD cameras is evaluated in the sense of the quantification of the signals described above, with subsequent quantification.

Although the present invention has been described above by a preferred embodiment, it is not limited to this but can be modified in a variety of ways.

In particular, UV-absorbing substances of the invention may be used to shield or eliminate UV light or as converters of visible light, for example as an admixture in sunscreen or as a coating to increase the efficiency of solar systems, in particular photovoltaic systems, and to protect the systems from premature aging caused by UV light.

A new and diverse field of application for the groups of substances of the invention also results from the use of nanoparticles containing one or more substances of the phosphorus family, in particular tungsten, tantalum, gallate, aluminate, borate, vanadate, sulfoxide, silicate, halogen compounds for the production of light in devices or luminaires of any kind, and lamps. This enables LEDs, display devices, screens of any kind to be used by default. However, the use of such "phosphorus nanoparticles" is particularly useful when the properties of the nanoparticles are similar, providing a special advantage for the particular surface area concerned. For example, nanoparticles may be used in a special way, for example, in the production of light in a large or medium size, or in the production of nanoparticles, which may be economically viable only in the specific case described in the present invention.

Claims (58)

1. a method for the synthesis of metal salt nanoparticles, with a crystal lattice or host lattice, the cation of which is recoverable from a cation source and the anion of which is recoverable from a class of substances serving as an anion source, where the host material may contain in particular compounds from the group of phosphates, halophosphates, arsenates, sulphates, borates, aluminates, gallates, silicates, germanates, oxides, vanadates, niobates, tantalum, tungsten, molybdate, alkali halide, other halogenates, nitrides, sulphides, silenides, sulphene phosphides and oxysulfides, characterised by the steps: Other

   (a) Manufacture of a synthetic mixture, at least from: Other

   (aa) an organic solvent containing at least one component controlling the crystal growth of the nanoparticles, in particular a component containing a phosphoro-organic compound or a monoalkylamine, in particular dodecylamine, or a dialkylamine, in particular bis- (ethylhexyl) amine;

   (bb) a cation source, a cation source that is soluble in the synthetic mixture or at least dispersed in it, in particular a metal salt source, preferably a metal chloride or an alkoxide or metal acetate; and

   (cc) an anionic source, soluble in the synthetic mixture or at least dispersible in the synthetic mixture, of the class of substances, the class of which contains: Other

   (aa) free acids of the salts of the metal salt nanoparticles to be manufactured; or

   (bbb) salts soluble in the synthetic mixture or at least dispersed in it, in particular salts with organic cation, or metal salts, the latter preferably alkali metal salts; or

   (ccc) organic compounds which release the anion from an elevated minimum temperature of synthesis, depending on the choice of the salt of the nanoparticles to be produced, and a suitable anion donor from the class of substances; and

   (b) Keep the mixture above a specified minimum temperature of synthesis for a synthesis time appropriate to the temperature.
2. The method described in claim 1, wherein Other

   (a) For the manufacture of nanoparticles with phosphorus-containing anions, phosphoric acid is used as an anion source, where: For the manufacture of nanoparticles with boron-containing anions, boric acid is used as the anion source, whereas for the manufacture of fluorine-containing nanoparticles, fluoric acid is used as the anion source, whereas

   (b) in the case of the use of a salt of the anionic class which is difficult to dissolve in the synthesis mixture, a complexing agent is added to the metal component of the metal salt for its easier solubility for synthesis, a crown ether for alkali metal salts being preferred.
3. The method according to the above claim, whereby at least one of the following is used as the phosphoro-organic compound for the growth control component: Other

   (a) phosphoric acid esters (R1-) (R2-) (R3-O-) P=O ),

   (b) phosphoric acid diester, (R1-) (R2-O-) (R3-O-) P=O),

   (c) Phosphoric acid triester, (trialkylphosphate) (R1-O-) ((R2-O-) (R3-O-) P=O),

   (d) Trialkylphosphane (R1-) (R3-) (R3-) (P), in particular trioctylphosphane (TOP),

   (e) Trialkylphosphanoxides (R1-) (R2-) (R3-) P=O), in particular trioctylphosphanoxide (TOPO), where R1, R2, R3 are branched or unbranched alkane chains with at least one carbon atom, or phenyl, toluene, xylolyl or benzyl groups; or

   (f) a phosphoramide, preferably Tris (dimethylamino) phosphane, or

   (g) a phosphorus peroxide, preferably Tris (dimethylamino) phosphanoxide,

   Other The solvent is not soluble in water.
4. A process according to the above claim using a trialkylphosphates or trialkylphosphanes as the control component in the formation of the nanoparticles, using less than 10 moles per mole of metal ions, preferably 0,9 to 5 moles, and preferably 0,95 to 2 moles of control component.
5. The method according to one of the above claims, adding at least one additional component, preferably a metal complexing component, to the synthesis mixture, preferably to displace crystalline water present in metal salts starting compounds, in particular a Other

   (a) Ether compound, preferably dipentylether, dihexylether, diheptylether, dioctylether, dibenzylether, diisoamylether, ethylene glycoldibutylether, diethylene glycoldibutylether or diphenyl ether, and/or

   (b) an alkane compound boiling above the minimum temperature of synthesis, preferably dodecan or hexadecan, or

   (c) an amine compound, preferably dihexylamine, bis (2-ethylhexyl) amine, trioctylamine, tris (2-ethylhexyl) amine.
6. The method described in claim 3, wherein R1, R2 or R3 are branched or unbranched alkane chains containing at least one carboxyl group (-COOH), a carbonic acid ester group (-COOR), amino groups (-NH2) and (-NHR), a hydroxyl group (-OH), a cyan group (-CN), a mercaptogroup (-SH), a bromine (-Br) and a chlorine (-Cl) or combinations thereof.
7. The method described in claim 3 using mixtures of the organo-phosphorus compounds.
8. A process according to one of the above claims using at least one of chlorides, bromides, iodides, alkoxides, metal acetates, or acetyl acetonate as the starting material as the cation source.
9. The following requirements shall apply to the process:

   (a) the preparation of a primary solution of the cation starting material in an alcohol, preferably of a lower grade, especially methanol, preferably using a metal salt which is non-oxidizing and soluble in the synthetic mixture; and

   (b) Mix the first solution with the solvent of claim 1 or 2 to produce the metal complexing synthetic mixture;

   (c) Heating of the synthesis mixture under inert gas, particularly nitrogen.
10. The method of the above claim, including the step of preferably distilling the lower alcohol from the synthetic mixture during synthesis.
11. Processes according to one of the above requirements, including the next step: Other

    Distillate one or more solvent components of the synthesis mixture, preferably under vacuum, preferably after the end of the synthesis time.
12. Processes according to one of the above requirements, including the next step: Other

    Cleaning the nanoparticles of adhesive byproducts by washing with an alcohol, preferably ethanol, or by diafiltration.
13. Processes according to one of the above requirements, including the next step: Other

    Neutralize the synthetic mixture with a base soluble in the synthetic mixture, preferably trihexylamine, triheptylamine, trioctylamine, trise (((2-ethylhexyl) amine.
14. A process according to one of the above claims using a hydrated metal salt as the starting material.
15. A process according to one of the above claims used to synthesize fluorescent nanoparticles.
16. A process according to one of the above claims using several different cation sources, in particular metal salt starting compounds, at least one of which is used as a doping material for the nanoparticles to be manufactured.
17. The method of claim 1, wherein the crystal lattice or, in the case of a doping, the host lattice contains compounds of type XY, wherein X is a cation of one or more elements of the main groups 1a,2a, 3a, 4a, subgroups 2b, 3b, 4b, 5b, 6b, 7b or lanthanides of the periodic table, and Y is either a polyatomic anion from one or more elements of the main groups 3a, 4a, 5a, subgroups 3b, 4b, 5b, 6b, 7b, and 8b and elements of the main groups 6a, 6a, and 7 or a single atomic anion from the main group 5a, 6a or 7a of the periodic table.
18. A process according to one of the above claims using a phosphoric acid ester, in particular a trialkylphosphate, and preferably tributylphosphate, as the growth control component of the solvent to produce LaPO4 nanoparticles.
19. a process according to one of the above claims, using as a doping agent one or more elements: from a batch containing elements of the main groups 1a, 2a or Al, Cr, Tl, Mn, Ag, Cu, As, Nb, Ni, Ti, In, Sb, Ga, Si, Pb, Bi, Zn, Co and or elements of the lanthanides.
20. A method according to one of the above claims using as doping two elements in different relative concentrations to each other, one doping element having a local maximum of the absorption spectrum for light, preferably UV light, and the other doping element having a fluorescence emission spectrum having at least a local maximum, having a distance Δλ/ λ from the absorption maximum of the first doping element of at least 4%, preferably more than 20%.
21. The method according to the above claim, using cer and terbium as dopants and LaPO4 as the host material.
22. A process according to any of the foregoing claims 1 to 19, whereby nanoparticles are synthesized with any of the following: Other

    The term 'specified value' means the value of the value of all the materials used in the manufacture of the product, whether or not they are used in the manufacture of the product, and the value of the products used in the manufacture of the product, if the value of the products is not known to be known.The value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product and the value of all the materials of Chapter 9 used do not exceed 20% of the ex-works price of the productThe following are the main components of the test chemical:
23. A process according to any of the foregoing claims 1 to 19, whereby nanoparticles are synthesized with any of the following: Other

    The following shall be indicated in the table for the calculation of the amount of the fine:
24. A process according to any of the foregoing claims 1 to 19, whereby nanoparticles are synthesized with any of the following compounds: MgF2:Mn; ZnS:Mn; ZnS:Ag; ZnS:Cu; CaSiO3:A; CaS:A; CaO:A; ZnS:A; Y2O3:A or MgF2:A (A = lanthanides).
25. a process according to one of the above claims, in particular claim 21, using a terbium dosage in the range of 0,5 to 30 mol%, preferably 5 to 25 mol and preferably 13 to 17 mol, wherein lanthanum and cer are respectively in a molar ratio of 0.13 to 7.5, preferably 0.25 to 4, and preferably 0.9 to 1.1, and metal chloride salts are used as metal sources.
26. The method described in claim 1 for the synthesis of semiconductor (HL) nanoparticles, in particular III-V or II-VI semiconductors.
27. Nanoparticles produced by the process specified in any of the above claims.
28. Substance containing nanoparticles as defined in the above claim.
29. Substance containing nanoparticles, containing a crystal lattice or, in the case of a doping, a host lattice, where: Host grid contains compounds of type XY, where X is a cation of one or more elements of major groups 1a, 2a, 3a, 4a, subgroups 2b, 3b, 4b, 5b, 6b, 7b or lanthanides of the periodic table, and Y is either a polyatomic anion of one or more elements of major groups 3a, 4a, 5a, subgroups 3b, 4b, 5b, 6b, 7b, and 8b and elements of major groups 6a, and or 7, or a single anion of major groups 5a, 6a or 7a of the periodic table, and containing one or more elements of the group containing elements of the main groups 1a, 2a or Al, Cr, Tl, Mn, Ag, Cu, As, Nb, Ni, Ti, In, Sb, Ga, Si, Pb, Bi, Zn, Co and or elements of the lanthanides.
30. a. A substance according to the above claim, the grating being in particular compounds of one of the following groups: Other

    "Technology" according to the General Technology Note for the "development" or "production" of equipment, equipment or "software" specified in 2B201.
31. A substance according to one of the two claims above, whereby the dosage contains two elements in predetermined relative concentrations, one of which has a local maximum of the absorption spectrum for light, in particular W-light, and the other has a fluorescence emission spectrum having at least a local maximum, with a distance Δλ/λ of the absorption maximum of the first dosage element from the first of at least 4%.
32. The 'C' value is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, excluding the 'C' value, which is the value of all the components of the product, including the 'C' value, including the value of all the components of the product, including the 'C' value, including the value of all the components of the product, including the components of the product, including the value, including the value of the components, including the value of the components, including the components, including the value of the components, including the components, including the components, including, the parts, including, the parts of the parts, including, parts, and parts of the parts, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and components, and componentsThe value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product and the value of all the materials of Chapter 9 used do not exceed 20% of the ex-works price of the productThe following are the main components of the product: - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of a single layer of polyethylene, - the product is made of polyethylene, - the product is made of polyethylene, - the product is made of polyethylene, the product is made of polyethylene, the product is made of polyethylene, the product is made of polyethylene, the product is made of polyethylene, the product is made of polyethylene, the product is made of polyethylene, the product is the product is made of polyethylene, the product is the product is the product is made of polyethylene. The data collected by the laboratory are used to determine the quantity of nanoparticles used.
33. "Software" specially designed or modified for the "development", "production" or "use" of equipment specified in 1B001.b., 1B001.c., 1B001.d., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001.e., 1B001, 1B001.e., 1B001, 1B001.e., 1B001, 1B001.e., 1B001, 1B001, 1B001.e, 1B001, 1B001, 1B001, 1B001, 1B001, 1B001, 1B001, 1B001, 1B002, 1B002, 1B001, 1B002 and 1B002 and 1B002 and 1B002 are not specified in this specification, but not in this specification.
34. "Software" specially designed or modified for the "development", "production" or "use" of equipment specified in 1B001.b., 1B001.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B101.c., 1B111.c., 1B111.c., 1B111.c., and 1B111.c.
35. Substance according to claim 29, the host grid containing a lanthanum or lanthanide compound, in particular LaPO4, and containing lanthanide group dotants.
36. Substance according to the above claim, containing two dotanes, in particular cer and terbium, one acting as an energy absorber, in particular as a UV light absorber and the other as a fluorescent light emitter.
37. Substance according to any of the above claims 29 to 36, preferably containing nanoparticles from the group of rare earth metals phosphates, or phosphates of major group III, or phosphates of calcium (Ca), strontium (Sr), or barium (Ba), The nanoparticles shall have an extension of not more than 15 nm, preferably not more than 10 nm, along their longest axis and preferably not more than 4 to 5 nm with a standard deviation of less than 30%, preferably less than 10% each.
38. Nanoparticle carrier material, in particular a carrier film, a carrier liquid, in particular a carrier paint or carrier dye, or aerosol-containing doped nanoparticle as claimed 27 or a substance as claimed 28 to 37.
39. Nanoparticle carrier as defined above, where the nanoparticles are embedded in a polymer, preferably a polymer film, in particular polyethylene or polypropylene.
40. Polymer film containing doped nanoparticles as defined in claim 27 or a substance as defined in claims 28 to 37.
41. a labelling of a substance in which the nanoparticles produced by the process described in claims 1 to 26 or a substance described in claims 27 to 37 are incorporated in such a way that the particle or substance is excitable by a predetermined energy supply, preferably electromagnetic radiation, in particular radiation with a wavelength of less than 300 nm, or radiation with particles or electrons, and produces an externally detectable fluorescent emission, preferably in the visible range of light in the UV range or near infrared (NIR) range, from the substance.
42. An article according to the above claim, incorporating a nanoparticle carrier according to one of claims 38 or 39 or a polymer film according to claim 40.
43. Substance according to the above claim containing a coating with a nanoparticle carrier.
44. Use of nanoparticles containing one or more substances of the phosphorus family, in particular use of tungsten, tantalum, borate, vanadate, sulfoxides, silicates, gallates, aluminates, halogen compounds for the marking of objects, in particular banknotes, data carriers, computer components, vehicle components, engine parts, documents, locks, anti-theft devices, objects transparent to visible light, jewellery or works of art, or for the making of fingerprints.
45. Use of doped nanoparticles for the labelling of the above claim.
46. Use of nanoparticles as claimed 27 or a substance as claimed 28 to 38 for the labelling as claimed 44.
47. Use of nanoparticles according to claim 27 or a substance according to any of claims 28 to 38 to label liquids or gases.
48. Use of a UV light absorbing substance according to claim 36 to convert UV light into another form of energy.
49. Use of a UV-absorbing substance as claimed by claim 36 as a convertor into visible light.
50. Use of nanoparticles containing one or more substances of the phosphorus family, in particular use of tungsten, tantalum, borate, vanadate, sulfoxides, silicates, gallates, aluminates, halogen compounds for the production of light in equipment or luminaires.
51. Use of doped nanoparticles as claimed 27 or a substance as claimed 28 to 39 for light production in devices or luminaires.
52. The use of doped nanoparticles as claimed 27 or a substance as claimed 28 to 39 or a polymer film as claimed 40 to produce images visible only after appropriate stimulation.
53. Detection method to detect the fluorescence of a test substance (28) as consistent with that of a reference substance of a specified nanoparticle type with a peak fluorescence emission (40), including the steps: Other

    The test chemical (28) is stimulated by a method of stimulation known to be successful for the specified nanoparticle type.

    Filters of the main peak spectral range of the test substance (28),

    Filter at least one sub-spectral range next to the main peak (40), where the specified nanoparticle type is expected to have little or no intensity relative to the main peak intensity,

    quantify the filtered radiation intensities in the specified spectral ranges; and

    Determine one or more relationships between the filtered radiation intensities;

    Assess the conformity of test substance (28) with reference substance on the basis of the ratios.
54. Detection procedure according to the above claim, which filters and evaluates two or more subspectral ranges other than the main peak (40)
55. detection procedure according to one of the two claims above, including the steps, to capture and evaluate the image of the source of fluorescence radiation.
56. A device for performing the detection procedure described in claim 53, containing: a device (26) to stimulate the test substance (28) with a known successful stimulation spectrum for the specified nanoparticle type, a device (12) to filter the main peak spectral range of the test substance (28), a device (10,14) to filter at least one sub-spectral range adjacent to the main peak (40), where the specified nanoparticle type is expected to have a low or no intensity relative to the main peak intensity, a device (16,18,20) for quantifying the filtered radiation intensities in the specified spectral ranges, a device (22) to determine one or more ratios of filtered radiation intensities, a device (22,24) to assess the conformity of test substance (28) with reference substance by means of the ratios.
57. Device according to the above claim, incorporating a device (16,20,22,24) to filter and evaluate two or more sub-spectral areas other than the main peak (40)
58. a width of not more than 50 mm, a device (30,32,34) to capture the image of the fluorescent source, and a device (22,24) to evaluate the image of the fluorescent source.