JP2019085499A - Manufacturing method of luminophor, luminophor, authenticity discrimination body, memory medium, and mask pattern formation method - Google Patents

Abstract

To propose a manufacturing method of a luminophor capable of easily forming a prescribed pattern, the luminophor, an authenticity discrimination body, a memory medium, a mask pattern formation method.SOLUTION: An electron beam reaction film is formed by applying a compound-containing solution generated by an electron beam reactive compound to a surface of an object for formation (film formation process). Then a luminophor consisting of an organic polymer emitting a light by two-photon excitation can be manufactured by irradiating an electron beam to the electron beam reactive compound (irradiation process). Therefor a prescribed pattern which emits the light by the two-photon excitation (photochemical reaction) can be easily formed since the luminophor generating the photochemical reaction by the two-photon excitation can be formed by irradiation of the electron beam which can conduct fine processing.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method of manufacturing a light emitter, a light emitter, an authenticity discriminator, a memory medium, and a method of forming a mask pattern.

  Heretofore, it has been considered that a pattern is drawn on a printed matter using an ink containing a resin composition that emits fluorescence by two-photon excitation, and the authenticity of the printed matter is discriminated (see, for example, Patent Document 1).

JP, 2011-39979, A

  However, although such a resin composition can emit light by two-photon excitation, it has been necessary to be contained in an ink because a predetermined pattern such as a fine pattern can not be formed only with the resin composition. Therefore, development of a new material capable of easily forming a predetermined pattern without containing it in an ink or the like as well as causing a photochemical reaction by two-photon excitation is also desired.

  Therefore, the present invention has been made in consideration of the above points, and proposes a method of manufacturing a light emitter capable of easily forming a predetermined pattern, a light emitter, an authenticity discriminator, a memory medium, and a method of forming a mask pattern. With the goal.

  The method for producing a light-emitting body according to the present invention comprises the steps of: applying a compound-containing solution generated by an electron beam reactive compound on the surface of an object to form an electron beam reaction film; And an irradiation step of manufacturing a light emitter made of an organic polymer which emits light by two-photon excitation by irradiating the light source.

  The light-emitting body of the present invention is composed of an organic polymer having a transbutadiene-like structure in a part of a polymer having a chain structure and having a cross-linked structure connecting the polymers, and emits light by two-photon excitation It is.

  The true / false discriminator according to the present invention is a true / false discriminator in which light emitters are formed in a predetermined pattern, and the light emitter is the light emitter described above.

  The memory medium of the present invention comprises a recording layer on which an electron beam reaction film which becomes the above-mentioned light emitter by irradiation of an electron beam is formed, and in the recording layer, the electron beam reaction film according to the data to be written. The electron beam is irradiated to a predetermined place of

  In the mask pattern forming method of the present invention, a film forming step of forming an electron beam reaction film as the above light emitting body on a substrate by being irradiated with an electron beam, and a predetermined portion of the electron beam reaction film And the step of irradiating the electron beam reaction film at a portion irradiated with the electron beam as the light emitter, and the solution is used to remove the electron beam reaction film, and the light emitter of the predetermined pattern is And b) forming a pattern on the substrate.

  According to the present invention, since a light emitter capable of emitting light by two-photon excitation can be formed by irradiation of an electron beam which can be finely processed, a light emitter having a predetermined pattern can be easily formed by irradiation of an electron beam.

It is the schematic where it uses for description of the manufacturing method of a light-emitting body. It is the graph which showed the photoluminescence intensity by light emission of one photon excitation and two photon excitation in the light-emitting body of this invention. It is a graph which shows the one-photon excitation emission spectrum in the light-emitting body of this invention, and an electron beam reaction film. It is a graph which shows the two-photon excitation emission spectrum in the light-emitting body and the electron beam reaction film of this invention. It is a graph which shows the intensity | strength difference of a two-photon excitation emission spectrum and a one-photon excitation emission spectrum. FIG. 6A is a graph showing that as the light intensity of ultraviolet light is increased, the photoluminescence intensity of the one-photon excitation light emission spectrum is increased and the spectral shape is different from the two-photon excitation light emission spectrum, and FIG. 2 is a graph showing that a two-photon excitation emission spectrum is emission from a molecule of two or more components. It is a graph which shows the MALDI mass spectrum in the light-emitting body and electron beam reaction film of this invention. It is a graph which shows the absorption spectrum in the light-emitting body of this invention, and an electron beam reaction film. It is a SEM photograph provided for explanation when the electron beam is irradiated to the electron beam reaction film to form a light emitter. It is a two-photon emission photograph provided to the description when light-emitting a light emitter by two-photon excitation. They are a two-photon emission photograph showing a luminous body emitted by two-photon excitation and a one-photon emission photograph showing a luminous body emitted by one-photon excitation. It is a two-photon emission photograph provided for explanation when light is emitted by two-photon excitation of a light emitter formed in a predetermined pattern. It is a graph in which it uses for description of spatial resolution. It is the schematic where it uses for description when irradiating an ultraviolet light to a truth discriminator. It is the schematic where it uses for the explanation when making a true / false discriminator irradiate near infrared pulse light and making it emit light by two photon excitation. FIG. 1 is a schematic view for explaining a memory medium. FIG. 17A is a schematic diagram for explaining a mask pattern forming method (1), FIG. 17B is a schematic diagram for explaining a mask pattern forming method (2), and FIG. 17C is a mask pattern forming method (3 Is a schematic diagram for explaining the

  An embodiment of the present invention will now be described in detail with reference to the drawings. In the following description, the same elements will be denoted by the same reference symbols, and overlapping descriptions will be omitted.

(1) Outline of the Invention The present invention is characterized in that a light emitter can be formed by irradiating the electron beam reaction film described later with an electron beam, and the light emitter emits light by two-photon excitation. And In this embodiment, any light emitter that emits light by both one-photon excitation and two-photon excitation may be used, but more preferably, it is a light emitter that suppresses light emission by one-photon excitation and emits light only by two-photon excitation. Is desirable. In this case, the light emitter has a molecular structure that is one-photon excitation forbidden (indicating that light emission by one-photon excitation is suppressed) and two-photon excitation permissive (indicating that light is emitted by two-photon excitation).

  Here, first, a method of manufacturing a light emitter will be described. As shown in FIG. 1, a compound-containing solution to be the electron beam reaction film 2 is prepared. For example, a polystyrene solution in which polystyrene is contained in pure water can be used as the compound-containing solution. The polystyrene solution preferably contains 0.01 to 20% by weight of polystyrene. When it is less than 0.01 wt%, it is difficult to form a thin film of polystyrene, and when it is more than 20 wt%, it is desirable that it is 0.01 to 20 wt% because solid polystyrene can not be dissolved in a solvent. Further, the concentration of polystyrene at the time of forming the electron beam reaction film 2 of the optimum film thickness by the casting method is more preferably 0.1 to 5 wt%. When the content of polystyrene is less than 0.1 wt%, the film thickness of the formed electron beam reaction film 2 becomes thin, so that the reaction by the electron beam hardly progresses, and when the content of polystyrene exceeds 10 wt%, the formed electron beam reaction film 2 As described above, it is more preferable that the content of polystyrene is 0.1 to 5 wt%, because the film thickness of C increases and scattering by electron beams greatly contributes and patterning in nanoscale is difficult.

  Next, a polystyrene solution is applied to the surface of the formation target 1 forming the light emitter, and the polystyrene solution is uniformly spread on the surface of the formation target 1 by a casting method or a spin coating method. Next, the film-like polystyrene solution stretched on the surface of the formation target 1 is dried to form the electron beam reaction film 2. Besides the hard substrate, a soft film or the like can be applied as the formation target 1. When the film thickness of the electron beam reaction film 2 is more than 1.0 μm, the scattering of the electron beam contributes and the reaction region by the electron beam spreads, making it difficult to realize nanoscale patterning. Therefore, the film thickness of the electron beam reaction film 2 is desirably 1.0 μm or less in order to realize nanoscale patterning.

  Next, the electron beam reaction film 2 is irradiated with an electron beam to form a light emitter at a position where the electron beam is irradiated. In the present invention, by changing the irradiation condition of the electron beam performed in the manufacturing process, it is possible to form a light emitter which emits light by two-photon excitation.

  Here, the test verified about the irradiation conditions of the electron beam mentioned above is demonstrated below. First, a polystyrene solution of 1 wt% polystyrene and a plurality of substrates made of glass were prepared. Then, a polystyrene solution was applied to each substrate, and the polystyrene solution was extended by a casting method to form a plurality of electron beam reaction films 2. The film thickness of the electron beam reaction film 2 was 900 nm. Subsequently, the irradiation condition (dose amount) of the electron beam was changed for each substrate, and it was confirmed whether to emit light by one-photon excitation or light emission by two-photon excitation with respect to the formed light emitter.

  FIG. 2 is a graph showing the relationship between photoluminescence (PL) intensity and the dose of an electron beam at the time of manufacture. The dose amount of the electron beam is a parameter for evaluating the electron injection amount when the electron beam is irradiated, and can be expressed by the following equation.

Dose amount = (irradiation current [A] x irradiation time [s]) / irradiation area [m ² ]

  In the one-photon emission (emission by one-photon excitation) measurement, a light source emitting an ultraviolet light laser (excitation wavelength: 375 nm, light intensity 1 μW) was used. On the other hand, in the two-photon emission (emission by two-photon excitation) measurement, a mode-locked titanium-sapphire laser (central wavelength: 800 nm, pulse width: <60 fs, light intensity 600 μW) emitting near-infrared pulsed light was used as a light source. Then, ultraviolet light and near infrared pulsed light were irradiated to each light emitter whose dose amount of electron beam was changed, and it was confirmed whether each light emitter emitted light. The results are shown in FIG.

In FIG. 2, “TPL” indicates photoluminescence intensity by two-photon excitation, and “PL” indicates photoluminescence intensity by one-photon excitation. As shown in FIG. 2, it was confirmed that in the region where the dose of the electron beam is 110 μC / cm ² or more and 770 μC / cm ² or less, it is possible to form a light emitter that emits light by two-photon excitation. Also, in the region where the dose of electron beam is 110 μC / cm ² or more and 770 μC / cm ² or less, although light emission by one-photon excitation also occurs when irradiated with an ultraviolet light laser with a light intensity of 1 μW, light emission by two-photon excitation It was confirmed that the light emission by one-photon excitation was suppressed.

It was also confirmed that, in the region where the dose of the electron beam is 110 μC / cm ² or more and 770 μC / cm ² or less, the photoluminescence intensity by two-photon excitation is increased as the dose is increased. In addition, in the region where the dose of the electron beam is 110 μC / cm ² or more and 770 μC / cm ² or less, it can be confirmed that the photoluminescence intensity by one-photon excitation is slightly increased as the dose is increased. The

However, in the above, it has been described that a light emitting body that emits light by two-photon excitation can be manufactured in a region where the dose of electron beam is 110 μC / cm ² or more and 770 μC / cm ² or less. / cm ² or more desirably less than 30MC / cm ^2. When the dose of the electron beam was 30 mC / cm ² or more, light emission by two-photon excitation was not observed. This is because the polymer molecules are fragmented by the electron beam being irradiated more than necessary. Therefore, the dose of the electron beam capable of producing a light emitter characterized by emitting light by two-photon excitation is preferably less than 30 mC / cm ² .

In addition, when the dose of the electron beam is less than 110 μC / cm ² , the dose of the electron beam is insufficient, and the generation of the target molecule is suppressed. Therefore, it is preferable that the dose of the electron beam capable of producing a light emitter characterized by emitting light by two-photon excitation is 110 μC / cm ² or more. More preferably, it is desirable to be 110 μC / cm ² or more and 10 mC / cm ² or less. The reason is that, within the above range, the two-photon excitation light emission intensity tends to increase monotonically with respect to the dose of the electron beam.

Next, in Example 1, as described above, an electron beam reaction film is actually formed of a polystyrene solution containing 1 wt% of polystyrene, and the electron beam reaction film (sample) before the electron beam irradiation and the electron beam irradiation The presence or absence of one-photon excitation light emission was confirmed for the electron beam reaction film (sample). The electron beam was irradiated at an irradiation current of 40 pA, an irradiation time of 8 s, an irradiation area of 2.77 × 10 ⁻⁶ cm ² , and a dose of 110 μC / cm ² . When ultraviolet light is irradiated to the electron beam reaction film before the electron beam irradiation and the electron beam reaction film (that is, the light emitter) after the electron beam irradiation, the photoluminescence intensity is measured, as shown in FIG. The results were obtained.

  In FIG. 3, "without irradiation" indicates before electron beam irradiation, and "with irradiation" indicates after electron beam irradiation. From FIG. 3, in the sample before electron beam irradiation, a peak was observed at 300 to 350 nm, and it was confirmed that light was emitted by one-photon excitation by ultraviolet light. On the other hand, in the sample after electron beam irradiation, the result is shown that the peak of the emission intensity is significantly reduced compared to the sample before electron beam irradiation.

  Next, mode-locked titanium-sapphire lasers (center wavelength: 750-820 nm, pulse width: <60 fs) were used to confirm the presence or absence of two-photon excitation light emission for each of the samples before and after the electron beam irradiation. As a light source, near-infrared pulse light was irradiated, and the photoluminescence intensity was measured. As a result, the result as shown in FIG. 4 was obtained. In FIG. 4, “TPL intensity” shown on the vertical axis indicates the emission intensity by the two-photon excitation process using near infrared pulsed light.

  From FIG. 4, in the sample after electron beam irradiation (“a1” in FIG. 4), it was possible to observe an emission peak derived from two-photon excitation similar to the cathode luminescence spectrum in the vicinity of 500 nm.

  Since light in the visible region is not usually observed from polystyrene, it can be presumed to be from the reaction product generated by the irradiation of the electron beam. In addition, in the sample ("b1" in FIG. 4) before electron beam irradiation, the emission peak derived from two-photon excitation was not able to be observed.

  Next, for the sample after electron beam irradiation (Example 1) described above, the emission spectrum (two-photon excitation emission spectrum) by two-photon excitation when irradiated with near-infrared pulse light and the ultraviolet light when irradiated Regarding the emission spectrum (one-photon emission spectrum) by one-photon excitation, the intensity difference of the photoluminescence intensity was examined. The luminous body of Example 1 was irradiated with near-infrared pulse light having a light intensity of 600 μW, and was irradiated with ultraviolet light having a light intensity of 1 μW. As a result, the results shown in FIG. 5 were obtained.

  In this case, weak light emission by one-photon excitation was observed. In addition, the ratio (intensity ratio) of the photoluminescence intensity was examined for the photoluminescence intensity when light was emitted by two-photon excitation and the photoluminescence intensity when light was emitted by one-photon excitation at a wavelength position of 600 nm. . As a result, it has been confirmed that the photoluminescence intensity when light is emitted by two-photon excitation is about 80 times as large as the photoluminescence intensity when light is emitted by one-photon excitation.

  Moreover, when each emission spectrum shown in FIG. 5 was normalized by each peak intensity, a result as shown in FIG. 6A was obtained. It was confirmed that the photoluminescence intensity by one-photon excitation can be controlled by the excitation light intensity because the emission intensity also increases as the ultraviolet light intensity increases.

  Further, as shown in FIG. 6A, in the emission spectrum when light was emitted by two-photon excitation, emission peaks were observed at around 480 nm and at around 500 nm, respectively, and it was confirmed that the emission peaks gradually decrease. On the other hand, in the light emission spectrum when light was emitted by one-photon excitation, it was confirmed that the light emission peak was observed at around 480 nm, and the light was gradually reduced from there.

  Thus, it was confirmed that the emission spectrum (two-photon excitation emission spectrum) at the time of light emission by two-photon excitation and the emission spectrum at the time of light emission by one-photon excitation were different. Since the shape of the emission spectrum by two-photon excitation and one-photon excitation is different, light emission by two-photon excitation is selected by selecting, for example, 600 nm as the detection wavelength, where the intensity ratio of photoluminescence intensity by two-photon excitation and one-photon excitation is large. It is also possible to detect only

  FIG. 6B shows an outline obtained by component fitting of the two-photon excitation emission spectrum shown in FIG. 6A with a Gaussian waveform. From FIG. 6B, the two-photon excitation emission spectrum is a spectrum constituted by light emission from at least two or more component molecules, and “one-photon, two-photon excitation permissible molecule” and “one-photon excitation forbidden, two-photon excitation permissible molecule respectively It could be confirmed that

  Next, with respect to the sample before electron beam irradiation and the sample after electron beam irradiation, the MALDI (Matrix Assisted Laser Desorption / Ionization) mass spectrum was examined respectively, and results as shown in FIG. 7 were obtained.

  The mass difference Δm of the periodic peak observed in the mass spectrum with the adjacent peak is 104, which corresponds to the mass of the monomer. This periodicity was maintained in both of the mass spectra before and after the electron beam irradiation, and it was confirmed that the skeleton of polystyrene was retained also in the sample after the electron beam irradiation.

  Next, the electron absorption spectra of the sample before the electron beam irradiation and the sample after the electron beam irradiation were examined, and the results shown in FIG. 8 were obtained. It was confirmed that the sample before electron beam irradiation ("b2" in FIG. 8) had an absorption peak near 260 nm, and the sample after electron beam irradiation ("a2" in FIG. 8) had an absorption peak near 280 nm . Such a long wavelength shift of the absorption peak suggests the formation of a conjugated system.

  From the above results, it can be inferred that the crosslinking reaction proceeds with polystyrene and a conjugated structure is generated by irradiating the polystyrene with an electron beam. Thus, it has been confirmed that the light emitting material has an excitation characteristic of emitting light by two-photon excitation by being an organic polymer having a molecular structure having a crosslinked structure and a conjugated structure.

Next, the electron beam reaction film produced as Example 1 mentioned above was linearly irradiated with an electron beam at a dose of 635 μC / cm ² at intervals of about 20 μm using a scanning electron microscope. Thereafter, the electron beam reaction film after immersion in a chloroform solution was confirmed by a SEM (Scanning Electron Microscope) photograph, and results as shown in FIG. 9 were obtained. It was confirmed that the structure of the portion irradiated with the electron beam was left undissolved in the chloroform solution.

  Next, the electron beam reaction film irradiated with this electron beam is irradiated with near infrared pulsed light using a mode-locked titanium sapphire laser (center wavelength: 800 to 820 nm, pulse width: <60 fs) as a light source, and two photons When confirmed by the luminescence photograph, the result as shown in FIG. 10 was obtained. From FIG. 10, it was confirmed that light was emitted linearly in accordance with the portion irradiated with the electron beam.

  Next, using the mode-locked titanium-sapphire laser (center wavelength: 750 to 820 nm, pulse width: <60 fs) as a light source, near-infrared pulsed light with a light intensity (laser intensity) of 600 μW is irradiated. Light was emitted by two-photon excitation, and photons were measured by a two-photon detector. Further, ultraviolet light having an excitation wavelength of 375 nm and a light intensity of 1 μW was irradiated to cause the light emitter of Example 1 to emit light by one-photon excitation, and photons were measured by a photodetector.

  As a result, the results shown in FIG. 11 were obtained. In FIG. 11, “TPL” indicates a two-photon emission photograph and “PL” indicates a one-photon emission photograph. As shown in FIG. 11, in the two-photon excitation, the photon count number of the excitation light was 258 kcps. In “PL” in FIG. 11, the portion emitting light in the two-photon emission photograph of “TPL” slightly emitted light. In this one-photon excitation, the photon count number of the excitation light was 6.4 kcps. From the above, it has been confirmed that the light emission by one-photon excitation is suppressed as compared to the light emission by two-photon excitation.

Next, in order to confirm that a nanoscale optical pattern can be produced, an electron beam reaction film produced as the above-mentioned Example 1 was subjected to a dose of 1900 μC / cm ² using a scanning electron microscope and an interval of about 10 μm. The electron beam was irradiated in the form of a grid. Next, the electron beam reaction film irradiated with this electron beam is irradiated with near infrared pulsed light using a mode-locked titanium sapphire laser (center wavelength: 750 to 820 nm, pulse width: <60 fs) as a light source, and two photons When confirmed by the luminescence photograph, the result as shown in FIG. 12 was obtained. From FIG. 12, according to the location which irradiated the electron beam, it was light-emitted in the grid | lattice form, and it confirmed that the nanoscale optical pattern could be produced.

  When the photoluminescence intensity was measured along the white line a across the light emitter in FIG. 12 in order to investigate the spatial resolution, the result as shown in FIG. 13 was obtained. “Spatial resolution” in FIG. 13 indicates a device function, and “Line profile” indicates photoluminescence intensity along a white line a across the light emitters. When the full width at half maximum (FWHM) was examined to evaluate the width of the light emitter, the device function was 0.33 μm and the width of the light emitter was 0.94 μm. This also confirms that nanoscale optical patterns can be produced.

(2) Molecular structure of the light emitter of the present invention formed on the basis of polystyrene Next, after forming an electron beam reaction film with a polystyrene solution, the electron beam reaction film is irradiated with an electron beam to form a light emitter The molecular structure of the reaction will be described below. Here, from the results of FIG. 7 and FIG. 8, it can be inferred that the crosslinking reaction proceeds with polystyrene and the conjugated structure is generated by irradiating the polystyrene with the electron beam. The formation from polystyrene to an organic polymer having a crosslinked structure and a conjugated structure is described below, focusing on the molecular structure of part of the polymer.

  When polystyrene is irradiated with an electron beam, it is presumed that the elimination reaction of hydrogen occurs in a part of the polymer having a chain structure of polystyrene as shown in the following Chemical Formula 1 to Chemical Formula 6. That is, the hydrogen of the side chain is eliminated to generate a carbon-carbon double bond in the main chain.

  As a result, a part of the polymer having a chain structure has, as a conjugated structure, at least a part of the main chain of the polymer alternately having a carbon double bond and a single bond as shown in It becomes a trans butadiene-like structure which has benzene in a side chain. It is generally known that trans butadiene is a molecule that permits two-photon excitation, and has the property of emitting light in the visible range. Also in the organic polymer to be the light-emitting body of the present invention, it is presumed that two-photon excitation is permitted by generating a molecular structure similar to trans butadiene in a part of the polymer by being irradiated with an electron beam.

  Here, the trans-butadiene-like structure may be any structure as long as it maintains the backbone of trans-butadiene having a chain structure having carbon double bonds and single bonds alternately in the main chain. Here, by using polystyrene as the starting material, as shown in chemical formula 6, as a conjugated structure, it becomes a trans butadiene similar structure having benzene in the side chain, but the starting material changes, and chemical formula 6 Will produce different trans butadiene-like structures.

  In addition, when polystyrene is irradiated with an electron beam, as described above, a part of the polymer of polystyrene becomes a trans-butadiene-like structure, and the other part of the polymer is represented by Chemical Formula 1, Chemical Formula 2, Chemical Formula 7 and Chemical Formula 7 As shown in Formula 8, it is presumed that a crosslinking reaction occurs. That is, the hydrogen of the side chain is eliminated in a part of the polymer, and a single bond is formed between the carbon at the site where hydrogen is eliminated in one polymer and the carbon at the site where hydrogen is eliminated in the other polymer .

  As a result, an organic polymer having a transbutadiene-like structure in a part of the polymer having a chain structure and having a crosslinked structure connecting the polymers having a chain structure is produced as shown in I can guess that. The light emitter is presumed to emit light by two-photon excitation by having such a molecular structure.

(3) Action and Effect From the above, in the present invention, the compound-containing solution (polystyrene solution) generated by the electron beam reactive compound (polystyrene) is applied to the surface of the object to form an electron beam reactive film (film formation Process). Then, by irradiating the electron beam reaction film with an electron beam, it is possible to manufacture a light emitter made of an organic polymer that emits light by two-photon excitation (irradiation step). Therefore, since a light emitter which causes a photochemical reaction by two-photon excitation can be formed by irradiation of an electron beam which can be finely processed, a predetermined pattern which emits light (photochemical reaction) by two-photon excitation can be easily formed.

  The light emitter thus produced is composed of an organic polymer having a transbutadiene-like structure in a part of the polymer having a chain structure and having a crosslinked structure connecting the polymers. An organic polymer produced from an electron beam reaction film formed with a polystyrene solution has a trans-butadiene-like structure having carbon double bonds and single bonds alternately in part of the main chain and benzene in the side chain. Since a light emitter having such a molecular structure can be formed by an electron beam, it can easily form a predetermined pattern that emits light (photochemical reaction) by two-photon excitation.

(4) True and False Discriminator Next, the true and false discriminator using the above-described light emitter will be described below. For example, banknotes, passports, stock certificates, gift certificates, income stamps, various tickets, and other securities etc. have monetary value, and therefore, it is required to provide authenticity determination technology. Also, even for documents that do not have monetary value, it may be necessary to identify counterfeit products and genuine products. In this case, as shown in FIG. 14, the true / false discriminator 6 using the light emitter described above is formed for the true / false discriminating object 5 which needs to discriminate between a counterfeit product and a genuine product. As a result, it is possible to determine whether the genuine / false discriminator 5 is a counterfeit or a genuine article based on whether the true / false discriminator 6 emits light by two-photon excitation.

  In the case of this embodiment, as the authenticity determination object 5, for example, a paper medium such as a business card or a document, a film made of resin, or other various materials can be used. The true / false discriminating object 5 has an electron beam reaction film 7 formed in a predetermined shape, such as a quadrilateral, at a predetermined position on the surface. The electron beam reaction film 7 is irradiated in advance with an electron beam of a predetermined pattern by an electron beam irradiation apparatus, and a light emitter is formed at the irradiation spot of the electron beam.

  As a result, as shown in FIG. 14, in the case of the true / false discriminating object 5, even if the ultraviolet light is irradiated, for example, the light emission by the one-photon excitation in the light emitter is suppressed. On the other hand, as shown in FIG. 15, when the near infrared pulse light is irradiated to the true / false discriminating object 5, the luminous body 8 emits light by two-photon excitation. A judge who determines whether the object 5 for authenticity discrimination is a counterfeit product or a genuine product is based on the fact that light emission is caused by two-photon excitation in the authenticity discriminator 6 and the object 5 for authenticity discrimination is a genuine product It can be determined that

  Such a true / false discriminator 6 can be manufactured by the same manufacturing method as the method of manufacturing the light-emitting body described above in “(1) Outline of the present invention”. For example, a compound-containing solution (polystyrene solution) generated by an electron beam reactive compound (polystyrene) is applied to the surface of the true / false discrimination object 5 to be formed to form an electron beam reaction film (film forming step) .

  Then, the electron beam reaction film is irradiated with an electron beam in a predetermined pattern to form a light emitter made of an organic polymer which emits light by two-photon excitation. Thereby, the true / false discriminator 6 in which the light emitters 8 emitting light by two-photon excitation are formed in a predetermined pattern can be formed.

  In the above configuration, since the true / false discriminator 6 can form the light emitter 8 by an electron beam, it can easily form a predetermined pattern that emits light (photochemical reaction) by two-photon excitation.

(5) Memory Medium Next, a memory medium using the light emitter described above will be described below. As shown in FIG. 16, in the memory medium 10, a recording layer 10b made of an electron beam reaction film is provided on the surface of the substrate 10a. The electron beam reaction film to be the recording layer 10 b can be manufactured by the same manufacturing method as the method for manufacturing the electron beam reaction film described in the above-mentioned “(1) Outline of the present invention”. For example, a compound-containing solution (polystyrene solution) generated by an electron beam reactive compound (polystyrene) is applied to the surface of the substrate 10a to be formed to form an electron beam reactive film (film forming step).

  Data can be written to the recording layer 10 b of the memory medium 10 by a writing device (not shown) that emits an electron beam. In this case, the writing apparatus includes an electron beam irradiation unit (not shown) for irradiating an electron beam, and irradiates the recording layer 10b with the electron beam irradiated from the electron beam irradiation unit. At this time, the writing device selects a portion where the electron beam reaction film is irradiated with the electron beam according to the data to be written. As a result, the portion of the recording layer 10b not irradiated with the electron beam is maintained as the electron beam reaction film 11b, and the light emitter 11a is formed in the portion irradiated with the electron beam.

  The data written to the recording layer 10 b can be read by the detection device 12. The detection device 12 includes a light source 13 which emits two photons, and irradiates the two photons emitted from the light source 13 to the recording layer 10 b through the semitransparent mirror 15 and the lens 16. Here, near-infrared pulse light can be used as two photons. The recording layer 10 b emits light by two-photon excitation when near-infrared pulse light is irradiated to the formation portion of the light emitter 11 a. On the other hand, in the formation portion of the electron beam reaction film 11 b where the light emitter 11 a is not formed, light emission by two-photon excitation does not occur even when near-infrared pulsed light is irradiated.

  The visible light L2 emitted by the light emitter 11a of the recording layer 10b is received by the light detection unit 14 through the lens 16 and the semitransparent mirror 15 of the detection device 12. Thus, the detection device 12 can reproduce data based on the presence or absence of the reception of the visible light L2 from the recording layer 10b.

  In the above configuration, the memory medium 10 can form the light emitters 11a only at predetermined positions of the recording layer 10b by irradiating the recording layer 10b with the electron beam, so that a predetermined pattern of light emission (photochemical reaction) by two-photon excitation Can be easily formed. In the light emitter 11a formed by the irradiation of the electron beam, the visible light L2 is emitted by two-photon excitation. Therefore, the visible light L2 can be detected as a writing position of data based on the visible light L2.

  Here, the case where the hard disk-like substrate 10a is applied as the substrate on which the recording layer is formed has been described, but the present invention is not limited to this, for example, substrates of other various shapes such as quadrilateral or Alternatively, a flexible film may be applied as a substrate.

(6) Method of Forming Mask Pattern Next, a method of forming a mask pattern using the light emitting body described above will be described below. In the above-mentioned “(1) Outline of the present invention”, the light emitter formed by irradiating the electron beam reaction film with the electron beam is not removed even if it is immersed in, for example, a chloroform solution. On the other hand, the electron beam reaction film not irradiated with the electron beam can be removed by immersion in a chloroform solution. By using such characteristics of the electron beam reaction film and the light emitter, a mask pattern can be manufactured on the substrate.

  The electron beam reaction film used when manufacturing the mask pattern can be manufactured by the same manufacturing method as the method of manufacturing the electron beam reaction film described above in “(1) Outline of the present invention”. For example, as shown in FIG. 17A, a compound-containing solution (polystyrene solution) generated by an electron beam reactive compound (polystyrene) is applied to the surface of a substrate 21 to be formed to form an electron beam reactive film 22a (film Formation process).

  Next, by irradiating a predetermined portion of the electron beam reaction film 22a with an electron beam, as shown in FIG. 17B, the light emitter 22c is formed only at the portion irradiated with the electron beam, and the electron beam reaction patterned on the substrate 21 The film 22b is formed. Next, the light emitter 22c formed on the substrate 21 and the patterned electron beam reaction film 22b are immersed in a chloroform solution to remove only the electron beam reaction film 22b, as shown in FIG. 17C, and the light emitter 22c is left (pattern formation step).

  As a result, only the light emitters 22c having a predetermined pattern can be left on the surface of the substrate 21. Therefore, the light emitters 22c formed in the predetermined pattern can be used as a mask pattern.

  In the above configuration, the electron beam reaction film 22a can easily form a predetermined pattern because the light emitters 22c are formed only at the portions irradiated with the electron beam. At this time, by making the light emitter 22c on the substrate 21 emit light by two-photon excitation, the pattern shape of the light emitter 22c formed on the substrate 21 is confirmed before or after removal of the patterned electron beam reaction film 22b. You can also

  In addition, although the case where the hard board | substrate 21 was applied as a base | substrate was described, this invention may apply not only this but other various base | substrates, such as a soft film.

(7) Other Embodiments The present invention is not limited to the present embodiment, and various modifications can be made within the scope of the present invention. For example, in the memory medium in the embodiment described above, a light emitter 11a is formed by an electron beam on the electron beam reaction film 11b to be the recording layer 10b, and data is read based on light emission by two-photon excitation in the light emitter 11a. Although the case has been described, the present invention is not limited to this. For example, as described in the above-mentioned “(6) mask pattern forming method”, the electron beam reaction film may be removed by immersion in a chloroform solution to form a recording layer in which only a light emitter of a predetermined pattern is left.

  in this case. In the recording layer of the memory medium, a recess is formed in the region from which the electron beam reaction film is removed, and the light emitter of a predetermined pattern remains in a convex shape. In the memory medium, asperities formed in the recording layer can be read out and detected by light or the like, and data can be read out based on the detection result.

  Further, in the above-described embodiment, a case is described where polystyrene is applied as an electron beam reactive compound in which a light emitter that emits light by two-photon excitation is formed by being irradiated with an electron beam. Not limited to. Various materials other than polystyrene can be used as the electron beam reactive compound, as long as a light emitting body comprising an organic polymer having a transbutadiene-like structure in a chain structure and a crosslinked structure in which chain structures are crosslinked can be formed. good.

  In addition, as the light emitter, a light emitter comprising an organic polymer having a transbutadiene-like structure in a chain structure and a crosslinked structure in which chain structures cross each other is described, but as a transbutadiene-like structure, for example, Besides the molecular structure in which hydrogen in the side chain of trans butadiene is replaced by benzene etc., a structure similar to trans stilbene (trans stilbene similar structure) similar to that of trans stilbene consisting of benzene, similar to conjugated polyene It includes the structure (conjugated polyene-like structure).

  The trans stilbene-like structure is a structure similar to trans stilbene in which carbon is substituted at the phenyl group of stilbene.

  The conjugated polyene analog structure is a structure similar to a conjugated polyene in which carbon or benzene is constituted in the side chain of polyene.

2, 7, 11b, 22a, 22b Electron beam reaction film 6 true / false discriminator 8, 11a, 22c luminous body 10 memory medium

Claims (10)

A film forming step of forming an electron beam reaction film by applying a compound-containing solution generated by an electron beam reaction compound on the surface of an object to be formed;
And irradiating the electron beam reaction film with an electron beam to produce a light emitter made of an organic polymer which emits light by two-photon excitation. In the film forming step,
The method according to claim 1, wherein the electron beam reactive compound is polystyrene, and the compound-containing solution is a polystyrene solution in which 0.01 to 20 wt% of the polystyrene is contained. The manufacturing method of the light-emitting body of Claim 1 or 2 whose irradiation dose of the said electron beam in the said irradiation process is 110 micro C / cm < ² > or more and less than 30 mC / cm < ² >.   The manufacturing method of the light-emitting body of any one of Claims 1-3 which forms the said light-emitting body of the said predetermined pattern by irradiating the said electron beam to a predetermined pattern at the said irradiation process.   A light emitter comprising an organic polymer having a trans-butadiene-like structure in a part of a polymer having a chain structure and having a crosslinked structure connecting the polymers, and emitting light by two-photon excitation.   The light-emitting body according to claim 5, wherein the trans-butadiene-like structure has carbon double bonds and single bonds alternately in part of its main chain and benzene in its side chain.   The light emitter according to claim 5 or 6, which emits light by one-photon excitation. A true / false discriminator in which a light emitter is formed in a predetermined pattern,
The true-false discriminator, wherein the light-emitting body is the light-emitting body according to any one of claims 5 to 7.   A recording layer provided with an electron beam reaction film as a light emitter according to any one of claims 5 to 7 by being irradiated with an electron beam, the recording layer comprising the recording layer according to data to be written. A memory medium, wherein the electron beam is irradiated to a predetermined portion of an electron beam reaction film. A film forming step of forming an electron beam reaction film to be a light emitter according to any one of claims 5 to 7 by irradiating an electron beam on a substrate,
Irradiating the electron beam to a predetermined portion of the electron beam reaction film, and irradiating the electron beam reaction film at a portion irradiated with the electron beam as the light emitter;
And D. removing the electron beam reaction film using a solution to form the light emitter of a predetermined pattern on the substrate.

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