JP4366898B2 - Reflectance detection element, sheet-like image input device, and sheet-like image input method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a reflectance detection element, a sheet-like image input device, and a sheet-like image input method.
[0002]
[Prior art]
In recent years, printing information on hard copy and consuming a large amount of paper has become an environmental problem, so it can be rewritten, does not require much energy to hold the display, and is portable A display medium based on the concept of electronic paper has been proposed, which is a thin liquid crystal display device, an electrochromic display, an organic low molecular weight / high molecular weight recording / erasing with a thermal head described in JP-A-55-154198, etc. A practical application is being considered in a molecular resin matrix display medium, an electrophoretic display device described in US Pat. No. 6,262,833, JP-A Nos. 2000-171839, 2001-201770, and the like.
[0003]
When the above electronic paper is used instead of hard copy, the display data is content as electronic data transmitted via a network such as a LAN (local network), a terminal such as a personal computer, a medium such as a memory, In order to display an image or a document of a hard copy or printed matter on electronic paper, it is necessary to convert it into electronic data once by a scanner or the like, which takes time and is not easy to use. In addition, since there is annoyance of repeating the transmission to the electronic paper for the required number of copies, it has been desired to solve these problems.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to easily and quickly convert analog image data such as hard copy and printed matter into electronic data and use it as electronic paper, and a reflectance detection element, and sheet-like image input using the same. An apparatus and a sheet-like image input method are provided.
[0005]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitutions 1 to 7 .
[0006]
1. On a transparent support, a gate electrode, an insulating layer provided on the transparent support while covering the gate electrode, on the insulating layer, connected source electrode, the drain electrode, the source electrode and the drain, And an organic semiconductor layer having a light transmittance of 350 nm to 850 nm of 10% or more, and a photocharge generation layer, a half mirror, and a light having a light transmittance of 350 nm to 850 nm of 10% or more on the organic semiconductor layer An element for detecting reflectance, wherein the incident control means is arranged in this order.
[0008]
2. Wherein between the organic semiconductor layer and the light charge generating layer, the reflectance detection element according to the 1 light transmittance of 350nm~850nm is characterized by providing more than 10% of the charge transport layer.
[0009]
3. 3. The reflectance detecting element according to 1 or 2 above, wherein the organic semiconductor layer contains a π-conjugated material.
[0010]
4). 4. The reflectance detecting element according to any one of 1 to 3 , wherein a liquid crystal element is used as the light incident control means.
[0011]
5). 5. The reflectance detection element according to any one of 1 to 4, wherein a light blocking layer and a light emitting element are used as the light incident control means.
[0012]
6). 6. A sheet-like image input device comprising the reflectance detection element according to any one of 1 to 5 above.
[0013]
7). 7. A sheet-like image input method using the sheet-like image input device according to 6 .
[0014]
Hereinafter, the present invention will be described in detail.
As a result of various studies on the above-mentioned problems, the present inventors have provided at least a gate electrode on the transparent support as described in claim 1 while covering the gate electrode. An organic semiconductor layer having a light transmittance of 350 nm to 850 nm of 10% or more connecting the source electrode, the drain electrode, and the source electrode and the drain on the insulating layer. By arranging the half mirror and light incident control means in this order on the organic semiconductor layer, analog image data such as hard copy and printed matter can be converted into electronic data easily and quickly and used as electronic paper It has been found that it is possible to provide a reflectance detection element, a sheet-like image input device and a sheet-like image input method using the same, which can be realized.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0016]
<Reflectance detection element>
The configuration of the reflectance detection element according to the present invention will be described with reference to FIGS. 1 (a) and 1 (b).
[0017]
FIG. 1 is a schematic diagram showing an example of the configuration of the reflectance detection element of the present invention. In FIGS. 1A and 1B, a system having a charge generation layer and a charge transport layer is shown, but the effects described in the present invention can be obtained without these layers. In forming the element, it may be formed sequentially from the transparent support side to be a reflectance detection element, and conversely, it may be formed sequentially from the light incident means to be a reflectance detection element.
[0018]
In FIG. 1A, a gate electrode 8 is formed on a transparent support 1, a source electrode 5 and a drain electrode 6 are provided on an insulating layer 7, covered with an organic semiconductor layer 4, and the charge transport layer 3 is formed. The charge generation layer 2 is formed in this order.
[0019]
Regarding the formation of the source electrode 5 and the drain electrode 6, a method of forming a continuous electrode film, cutting by laser ablation or the like to form a gap, and providing the source electrode 5 and the drain electrode 6 is preferably applied. The
[0020]
FIG. 1B is a modified example of FIG. 1C and shows another example in which the source electrode 5 and the drain electrode 6 are connected by the organic semiconductor layer 4. In this case, a production method such as providing the source electrode 5 on the insulating layer 7 and applying the organic semiconductor layer 4 to form the drain electrode 6 is applied.
[0021]
FIG. 2 is a schematic view showing an aspect in which the reflectance detection element of the present invention detects light reflection.
[0022]
2A and 2B, the reflectance detection element 50 is disposed on the recording medium 11a, which is a reflectance measurement target. Here, 11b is an image 11b recorded on the recording medium 11a. Specifically, the image 11b is a toner image such as an electrophotographic image, an ink image produced by inkjet recording, a photographic image, or the like. Incidentally, in the recording medium 11a, the area where the image 11b does not exist is an area where no image is formed.
[0023]
When the reflectance detecting element 50 of the present invention is disposed on the recording medium 11a, incident light 12a, 12b, 12c (here, incident light is 350 nm to 850 nm) that has passed through the light incident control means 10 and the half mirror 9. ) Passes through the charge generation layer 2, the charge transport layer 3, the organic semiconductor layer 4, the insulating layer 7, and the transparent support 1, and is incident on the recording medium 11a and the image 11b.
[0024]
Reflected light (not shown) is generated corresponding to the reflectance with respect to light in the wavelength range of 350 nm to 850 nm of each of the recording medium 11a and the image 11b, which are reflectance measurement targets. Multiple reflections (not shown) are repeated in between.
[0025]
Reflected light is generated by the recording medium 11a and the image 11b, and the reflected light is reflected again by the half mirror 9, so that the reflected light is repeated so that it will be described later according to the intensity of the reflected light. In addition, an optical carrier (not shown) is generated and can be monitored as a current value.
[0026]
Since the recording medium 11a and the image 11b have different reflectivities for light (light having a wavelength range of 350 nm to 850 nm), the resulting current values are different. Therefore, the reflectivity measured by the reflectivity detecting element is different. When the corresponding current value is data-converted, the image 11b can be immediately used as digitally-converted electronic image data.
[0027]
(Optical carrier generation)
The generation of the optical carrier described above will be described.
[0028]
Incident light 12a to 12c that has passed through the half mirror 9 passes through the charge generation layer 2, the charge transport layer 3, the organic semiconductor layer 4, the insulating layer 7, and the transparent substrate 1, and enters the recording medium 11a and the image 11b. .
[0029]
The generation of optical carriers occurs when the incident lights 12a to 12c are first received by the charge generation layer 2, and the incident lights 12a, 12b, and 12c are generated by the charge generation layer 2, the charge transport layer 3, and the organic semiconductor layer 4 respectively. Then, the light passes through the insulating layer 7 and the transparent substrate 1, enters the recording medium 11a and the image 11b, and the reflected light (not shown) on the recording medium 11a and the image 11b is received by the charge generation layer 2.
[0030]
Furthermore, the reflected light partially passes through the charge generation layer 2 and then is reflected again by the half mirror 9, and the reflected light is received by the charge generation layer 2 again. Finally, the spectral sensitivity of the charge generation layer 2 and the incident light (incident light, reflected light from the recording medium 11a or the image 11b, reflected light, reflected light from the half mirror 9 are reflected again. Or the like) is generated in the organic semiconductor layer 4 between the source electrode 5 and the drain electrode 6.
[0031]
Next, the circuit configuration of the reflectance detection element described above will be described with reference to FIG.
FIG. 3 is a schematic diagram showing an example of a circuit configuration of the reflectance detection element of the present invention. In this schematic diagram, the transparent support, the half mirror, and the light incident control means are omitted.
[0032]
In FIG. 3, when the photocarrier is a hole, the photocurrent can be monitored by applying a negative voltage to the gate electrode and applying a bias voltage between the source electrode and the drain electrode. Although depending on the configuration of the element, the gate voltage is preferably 0 V to -50 V, and the bias voltage between the source electrode and the drain electrode is preferably about 0 V to -50 V.
[0033]
When the main carrier is an electron, the polarity may be reversed, and after the photocurrent measurement, the residual charge in the charge generation layer and its vicinity is preferably discharged.
[0034]
<Sheet-like image input device>
Next, the sheet-like image input device of the present invention will be described.
[0035]
FIG. 4 is a schematic view showing an aspect of the sheet-like image input device of the present invention. The sheet-like image input of the present invention is based on the active drive constructed based on the elements described in FIGS. The device 20 is shown in model form. (A) shows a side section, and (b) is a plan view.
[0036]
In the figure, a plurality of gate electrodes 8 are arranged in parallel on a transparent support 1, an insulating layer 7 is formed on the gate electrode 8, and a plurality of source electrodes 5 and drain electrodes 6 are formed on the gate electrode 8. Are alternately arranged in the orthogonal direction to form a matrix and connected by the organic semiconductor layer 4, and the charge transport layer 3 and the charge generation layer 2 are disposed in this order on the matrix, and are not shown. In addition, the half mirror and the light incident control means are provided in this order to constitute the reflectance detection element of the present invention.
[0037]
In this configuration, the gate electrode 8 also serves as a scanning line, the area shown in the figure is a unit pixel, and the pixel in the column direction is connected to the common source electrode 5 and drain electrode 6 in the figure.
[0038]
(Half mirror: also called magic mirror)
The half mirror according to the present invention will be described.
[0039]
A half mirror is a kind of mirror, but it is a translucent mirror that does not reflect all the light that hits the mirror, but transmits some of its light. In the present invention, a commercially available half mirror that is usually used for a single-lens reflex distance meter or finder, or used for a part of TTL photometry or the TTL / AF method can be used.
[0040]
The light transmittance of 350 nm to 850 nm of the half mirror according to the present invention is an essential requirement from the viewpoint of achieving the effects described in the present invention, but is preferably 10% to 40%. It is. Moreover, it is preferable that the light reflectance of 350 nm to 850 nm, which is another feature of the half mirror, is 20% or more, and S is more preferably 20% to 60%.
[0041]
Commercially available products can be used for the half mirror according to the present invention showing the light transmittance and light reflectance described above. For example, a new magic mirror (made by Hosaka Glass Co., Ltd.) or the like can be used as the half mirror according to the present invention.
[0042]
(Light incident control means)
The light incident control means according to the present invention will be described.
[0043]
The light incident control means is not particularly limited as long as it controls the switching (on / off) of light incident through the half mirror, but a so-called light shutter function can be used. For example, a liquid crystal shutter, a combination of a light blocking layer and a light emitting element is preferably used.
[0044]
Commercially available liquid crystal shutters can be used as the liquid crystal shutters, and Polymer Dispersed Liquid Crystal: J. Org. W. Doane, N .; A. Vez, B.M. G. Wu, S .; Zumer, Appl. Phys. Lett. 48, 27 (1986), Polymer Network Liquid Crystal, JP-A-2-28284, JP-A-2-55318, etc., Japanese Patent No. 4,193,691. Can be used.
[0045]
As an optical shutter in which a light blocking layer and a light emitting element are combined, for example, a light blocking layer manufactured using black ink or the like can be applied. As a light emitting element, a commercially available organic EL, inorganic EL, fluorescent light can be used. A planar light-emitting body in which a tube, a light-emitting source, a light guide plate, a light scattering plate, and the like are combined can be used.
[0046]
(Equivalent matrix circuit for active drive)
FIG. 5 is a schematic diagram of an equivalent matrix circuit when active driving is performed in the apparatus shown in FIG.
[0047]
In FIG. 5, reference numeral 100 denotes a photodetection unit, and initialization transistors 65-1 to 65 -n connected to, for example, drain electrodes are provided on the signal lines 5-1 to 5 -n. The source electrodes of the transistors 65-1 to 65-n are grounded. The gate electrode is connected to the reset line 651.
[0048]
The scan lines 8-1 to 8-m and the reset line 651 are connected to the scan drive circuit 20. When the readout signal RS is supplied from the scan driving circuit 20 to one of the scan lines 8-1 to 8-m, where p is any value of 1 to m, the scan line 8 The transistors 4- (p, 1) to 4- (p, n) connected to −p are turned on, and photocurrents reflecting carriers generated by the light irradiation are signal lines 5-1 to 5-n. Respectively. The signal lines 5-1 to 5-n are connected to the signal converters 31-1 to 31-n of the signal selection circuit 30. In the signal converters 31-1 to 31-n, the signal lines 5-1 to 5-5 are connected. Voltage signals SV-1 to SV-n proportional to the current value read on -n are generated. The voltage signals SV-1 to SV-n output from the signal converters 31-1 to 31-n are supplied to the register 32.
[0049]
In the register 32, the supplied voltage signal is sequentially selected and converted into a digital optical signal for one scanning line (for example, 12 bits to 14 bits) by the A / D converter 33. The control circuit 40 Scanning is performed by supplying a readout signal RS to each of the lines 8-1 to 8-m via the scanning drive circuit 20, and a digital signal for each scanning line is taken in to generate an optical signal.
[0050]
This optical signal is supplied to the control circuit 40. Note that the reset signal RT is supplied from the scanning drive circuit 20 to the reset line 651 to turn on the transistors 65-1 to 65-n, and the readout signal RS is supplied to the scanning lines 8-1 to 8-m. When the transistors 4- (1, 1) to 4- (m, n) are turned on, the stored carriers are emitted through the transistors 65-1 to 65-n, and the light detection unit 100 is initialized. be able to.
[0051]
A memory unit 41 and an operation unit 42 are connected to the control circuit 40, and the operation of the sheet-like image input device 20 in FIG. 4 is controlled based on an operation signal PS from the operation unit 42. Further, the optical signal data DS can be input from the control circuit 40 to the display unit 43.
[0052]
Reference numeral 44 denotes a power source (external power source), and 45 denotes a connector, through which the sheet-like image input device 20 shown in FIG. 4 is integrated with other devices to exchange optical signal data DFE, for example, image formation. be able to.
[0053]
(Sheet-like image input device capable of detecting full-color images)
FIG. 6 is a schematic diagram illustrating an example of a sheet-like image input device capable of detecting a full-color image. For example, on the light incident surface side of the sheet-like image input device 20 shown in FIG. 4, for example, an arrangement as shown in FIG. 6 (R is a red filter, G is a green filter, and B is a blue filter) is repeated. By providing a sheet-like image input device capable of detecting a full-color image can be configured.
[0054]
The color separation filter is provided to separate the image information into the three primary colors and can have various configurations. For example, yellow, green, and cyan filters are arranged in a mosaic pattern or a stripe pattern. And a method of arranging filters of three colors of red, green, and blue in a mosaic or stripe form. Examples of a method for arranging the color separation filters in a mosaic form include a lattice arrangement method typified by a Bayer arrangement, an arrangement in which triangles, hexagons, and circles are spread. The arrangement of each color may be regular or may be arranged at random.
[0055]
Various known methods can be used for manufacturing the color separation filter. As a representative method for producing a color separation filter, a pigment dispersion method for obtaining a monochromatic pattern by forming a photosensitive resin layer in which a pigment is dispersed on a substrate and patterning the layer is a material for dyeing on the substrate. After applying a water-soluble polymer material and patterning it into a desired shape by a photolithography process, the resulting pattern is immersed in a dyeing bath to obtain a colored pattern. The pigment is dispersed in a thermosetting resin. And by repeating printing three times, R, G, and B are applied separately, and then a printing method in which a colored layer is formed by thermosetting the resin, and a coloring liquid containing a dye is inkjet-transparent substrate There is an ink jet method in which a colored pixel portion is formed by discharging the colored liquid and drying the colored liquid.
[0056]
Hereinafter, materials used for the configuration of the reflectance detection element of the present invention will be described.
<< Material for source and drain electrodes >>
The material for the source electrode and drain electrode of the reflectance detection element of the present invention is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, Tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver Paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / Copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc., especially platinum, gold, silver, copper, aluminum, indium, ITO And carbon are preferred. Alternatively, a known conductive polymer whose conductivity has been improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrene sulfonic acid, or the like is also preferably used. Among them, those having low electrical resistance at the contact surface with the semiconductor layer are preferable.
[0057]
<Material for gate electrode>
The gate electrode according to the present invention is preferably a transparent electrode. Here, the term “transparent” means that the light transmittance at 350 nm to 850 nm is preferably 50% or more, and more preferably, the light transmittance is in the range of 50% to 99%.
[0058]
As the gate electrode forming material according to the present invention, when the side having the gate electrode is a light incident surface, the gate electrode is made of indium oxide, tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped oxide. By using a transparent conductive film such as tin, ITO, or an In ₂ O ₃ —ZnO-based amorphous transparent conductive film, the transparent electrode can be configured.
[0059]
(Method of forming electrode)
As a method for forming an electrode, a conductive thin film formed using a conductive material described above as a raw material using a method such as vapor deposition or sputtering, a method for forming an electrode using a known photolithography method or a lift-off method, aluminum, There is a method of etching on a metal foil such as copper using a resist by thermal transfer, ink jet or the like.
[0060]
Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from the coating film by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.
[0061]
The conductive fine particles include platinum, gold, silver, nickel, chromium, copper, iron, tin, tantalum, indium, cobalt, palladium, tellurium, rhenium, iridium, and aluminum having a particle diameter of 1 nm to 50 nm, preferably 1 nm to 10 nm. , Ruthenium, germanium, molybdenum, tungsten, zinc, and the like can be used, but platinum, gold, silver, copper, cobalt, chromium, iridium, nickel, palladium, molybdenum having a work function of 4.5 eV or more is particularly preferable. And metal fine particles such as tungsten.
[0062]
As a method for producing such a metal fine particle dispersion, metal ions are reduced in a liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, metal vapor synthesis method, colloid method, coprecipitation method, etc. Examples of the chemical production method for producing metal fine particles include colloidal methods described in JP-A-11-76800, JP-A-11-80647, JP-A-319538, JP-A-2000-239853, JP-A-2001-254185, It is a dispersion produced by a gas evaporation method described in JP 2001-53028 A, JP 2001-35814 A, JP 2001-35255 A, JP 2000-124157 A, JP 2000-123634 A, and the like. After these dispersions are applied and formed into an electrode pattern, the solvent is dried, and heat treatment is performed at a temperature in the range of 100 ° C. to 300 ° C., preferably 150 ° C. to 200 ° C., thereby thermally fusing the metal fine particles. By doing so, an electrode can be formed.
[0063]
《Insulating layer》
Although various insulating films can be used as the insulating layer according to the present invention, an inorganic oxide film having a high relative dielectric constant is particularly preferable. Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. However, nitrides such as silicon nitride and aluminum nitride can also be used.
[0064]
Examples of the method for forming the film include a vacuum process, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and a spray process. Wet processes such as coating methods, spin coating methods, blade coating methods, dip coating methods, casting methods, roll coating methods, bar coating methods, die coating methods, and other wet processes such as printing and ink jet patterning methods, etc. Can be used depending on the material.
[0065]
The wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor, for example, A so-called sol-gel method in which a solution of an alkoxide body is applied and dried is used.
[0066]
Among these, the following atmospheric pressure plasma method and sol-gel method are preferable.
The method for forming an insulating film by plasma film formation under atmospheric pressure is a process in which a reactive gas is discharged under atmospheric pressure or a pressure near atmospheric pressure to excite reactive gas to form a thin film on a substrate. The method is described in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, 2000-147209, 2000-185362, and the like. Accordingly, a highly functional thin film can be formed with high productivity.
[0067]
In addition, as an organic compound film, polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photo cation polymerization type photo curable resin, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, Also, cyanoethyl pullulan or the like can be used. As the method for forming the organic compound film, the wet process is preferable.
[0068]
An inorganic oxide film and an organic oxide film can be laminated and used together. The film thickness of these insulating films is preferably in the range of 50 nm to 3 μm, more preferably in the range of 100 nm to 1 μm.
[0069]
<Organic semiconductor layer>
The material for forming the organic semiconductor layer according to the present invention will be described.
[0070]
In the present invention, since the photocharge (carrier) generated in the organic semiconductor layer can be reflected as a current value flowing between the source electrode and the drain electrode, the carrier may be either an electron or a hole. Is a p-type, the main carrier (also referred to as main carrier) of the photocurrent between the source electrode and the drain electrode is preferably a hole, and when the organic semiconductor layer is n-type, the main carrier (also referred to as main carrier) is an electron. Is preferred.
[0071]
As an organic semiconductor material constituting the organic semiconductor layer according to the present invention, a π-conjugated material is used. For example, polypyrroles such as polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-disubstituted pyrrole), polythiophene, poly (3-substituted thiophene), poly (3,4- Di-substituted thiophene), polythiophenes such as polybenzothiophene, polyisothianaphthenes such as polyisothianaphthene, polychenylene vinylenes such as polychenylene vinylene, and poly (p-phenylene vinylene) such as poly (p-phenylene vinylene). Phenylene vinylenes), polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (aniline) such as poly (2,3-substituted aniline), polyacetylenes such as polyacetylene, and polydiacetylenes such as polydiacetylene , Polyazulenes such as polyazulene, polypyrene, etc. Polypyrazoles, polycarbazoles such as polycarbazole and poly (N-substituted carbazole), polyselenophenes such as polyselenophene, polyfurans such as polyfuran and polybenzofuran, and poly (p-phenylene) such as poly (p-phenylene) Phenylene) s, polyindoles such as polyindole, polypyridazines such as polypyridazine, naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, pyrene, dibenzopyrene, chrysene, perylene, coronene, terylene, ovalene, Derivatives (triphenodioxazine, triphenodithiazine) in which a part of carbon of polyacenes such as quaterylene and circumanthracene and polyacenes are substituted with atoms such as N, S and O and functional groups such as carbonyl groups Hexacene-6,15-quinone, etc.), polyvinylcarbazole, polyphenylene sulfide, or the like can be used polycyclic condensate described in polyvinylene sulfide polymer and JP-like de 11-195790.
[0072]
Further, for example, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (α, which is a thiophene hexamer having the same repeating unit as those polymers. Oligomers such as 3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives can also be preferably used.
[0073]
Further, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A-11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethylbenzyl) Along with naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (1H, 1H-perfluorooctyl), N, N′-bis (1H, 1H-perfluorobutyl) and N, N′- Dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimide derivatives, naphthalene 2,3,6,7 tetracarboxylic acid diimides and other naphthalene tetracarboxylic acid diimides, and anthracene 2,3,6,7-tetracarboxylic acid Condensed-ring tetracarboxylic acids such as anthracene tetracarboxylic acid diimides such as diimide Examples include diimides, fullerenes such as C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , and C ₈₄ , carbon nanotubes such as SWNT, merocyanine dyes, and dyes such as hemicyanine dyes.
[0074]
Among these π-conjugated materials, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituent thereof, or two or more of these are used as a repeating unit, and the number n of the repeating units is 4 to 4 At least one selected from the group consisting of an oligomer of 10 or a polymer in which the number n of repeating units is 20 or more, a condensed polycyclic aromatic compound such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanine. Species are preferred, and π-conjugated polymers are particularly preferred.
[0075]
Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. Organic molecular complexes such as can also be used. Furthermore, (sigma) conjugated polymers, such as polysilane and polygermane, and organic-inorganic hybrid material as described in Unexamined-Japanese-Patent No. 2000-260999 can also be used.
[0076]
In the present invention, for example, a material having a functional group such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanoethylene, and tetracyanoquinodimethane are used in the organic semiconductor layer. And materials that can accept electrons, such as derivatives thereof, materials that have functional groups such as amino groups, triphenyl groups, alkyl groups, hydroxyl groups, alkoxy groups, and phenyl groups, substituted amines such as phenylenediamine , So-called doping, containing materials that serve as donors of electrons, such as anthracene, anthracene, benzoanthracene, substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and its derivatives, tetrathiafulvalene and its derivatives, etc. Processing Good.
[0077]
The doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Accordingly, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant. Either an acceptor or a donor can be used as the dopant used in the present invention.
[0078]
As this acceptor, a halogen such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF, Lewis acid such as PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BC 1 ₃ , BBr ₃ , SO ₃ , HF HC1, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H and other protic acids, acetic acid, formic acid, amino acids and other organic acids, FeCl ₃ , FeOCl, TiCl ₄ , Transition metals such as ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoCl ₅ , WF ₅ , WCl ₆ , UF ₆ , LnCl ₃ (Ln = La, Ce, Nd, Pr, and other lanthanoids and Y) Examples thereof include compounds, electrolyte anions such as Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₅ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , and sulfonate anions.
[0079]
As donors, alkali metals such as Li, Na, K, Rb, and Cs, alkaline earth metals such as Ca, Sr, and Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy , Ho, Er, Yb, and other rare earth metals, ammonium ions, R ₄ P ⁺ , R ₄ As ⁺ , R ₃ S ⁺ , acetylcholine, and the like.
[0080]
As a method for doping these dopants, either a method of preparing an organic semiconductor thin film in advance and then introducing the dopant later, or a method of introducing the dopant when forming the organic semiconductor thin film can be used. As doping of the former method, gas phase doping using a dopant in a gas state, liquid phase doping in which a solution or liquid dopant is brought into contact with the thin film, and diffusion doping in which a solid state dopant is brought into contact with the thin film Examples of solid phase doping can be given. In liquid phase doping, the efficiency of doping can be adjusted by applying electrolysis. In the latter method, a mixed solution or dispersion of an organic semiconductor compound and a dopant may be simultaneously applied and dried. For example, when using a vacuum evaporation method, a dopant can be introduce | transduced by co-evaporating a dopant with an organic-semiconductor compound. When a thin film is formed by a sputtering method, a dopant can be introduced into the thin film by sputtering using a binary target of an organic semiconductor compound and a dopant. Still other methods include chemical doping such as electrochemical doping, photoinitiated doping, and physical methods such as ion implantation shown in the publication “Industrial Materials”, Vol. 34, No. 4, p. 55 (1986). Any of the chemical dopings can be used.
[0081]
(Method for producing organic semiconductor layer (organic thin film))
These organic semiconductor layers (organic thin films) can be prepared by vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, plasma polymerization, electrolysis Examples include polymerization methods, chemical polymerization methods, spray coating methods, spin coating methods, blade coating methods, dip coating methods, cast methods, roll coating methods, bar coating methods, die coating methods, and LB methods, which can be used depending on the material. . However, among these, in terms of productivity, spin coating methods, blade coating methods, dip coating methods, roll coating methods, bar coating methods, die coating methods, etc. that can easily and precisely form thin films using organic semiconductor solutions. Liked.
[0082]
(Thickness of organic semiconductor layer)
The thickness of the thin film made of these organic semiconductors is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the thickness of the active layer made of the organic semiconductor. Although it changes with semiconductors, 1 micrometer or less is preferable, More preferably, it is 10 nm-300 nm.
[0083]
<Charge generation layer>
The charge generation layer according to the present invention will be described.
[0084]
In the present invention, since the photocharge (carrier) generated in the organic semiconductor layer is reflected as a current value flowing between the source electrode and the drain electrode, the carrier may be either an electron or a hole. In the case of the type, the main carrier of the photocurrent between the source electrode and the drain electrode is preferably a hole, and when the organic semiconductor layer is n-type, the main carrier is preferably an electron.
[0085]
In addition, from the viewpoint of increasing the amount of photocharge (carrier) at the time of light incidence, it is preferable to provide a charge generation layer between the organic semiconductor layer and the half mirror, and more preferably, a light transmittance of 350 nm to 850 nm. It is to provide a charge generation layer of 10% or more, and particularly preferably to provide a charge generation layer having a transmittance of 50% to 90%.
[0086]
The charge generation layer is an azo pigment such as Sudan Red or Diane Blue as a charge generation material, a quinone pigment such as pyrenequinone or anthanthrone, an indigo pigment such as indigo or thioindigo, an azurenium salt pigment, copper phthalocyanine, a metal phthalocyanine, a titanyl phthalocyanine And a phthalocyanine pigment such as a binder resin such as polyester, polycarbonate, polystyrene, polyvinyl butyral, polyvinyl acetate, acrylic resin, polyvinyl pyrrolidone, ethyl cellulose, cellulose acetate butyrate and the like.
[0087]
That is, the charge generating material and binder resin are, for example, hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate. Alcohols such as methanol, ethanol, propanol, butanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; ethers such as tetrahydrofuran and 1,4-dioxane; amines such as pyridine and diethylamine; N, N-dimethyl Nitrogen compounds such as amides such as formamide; other fatty acids and phenols; ball mills, homomixers, sand mills, ultrasonic dispersions in one or more solvents such as sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate Etc. To prepare a coating solution, which dip, spray, blade, applied by the method of coating a roll or the like can be formed and dried.
[0088]
The binder resin in the charge generation layer: the charge generation material is preferably adjusted to a mass ratio of about 0 to 10: 1 to 50, and the thickness of the formed charge generation layer is preferably adjusted to a range of 0.01 μm to 10 μm. The film thickness range is 0.05 μm to 1.0 μm.
[0089]
A known silver halide may be used as the charge generating material. Spectral sensitized silver halide grains having sensitivity to blue, green and red (BGR) light may be mixed and contained in the charge generation layer.
[0090]
<Charge transport layer>
The charge transport layer according to the present invention will be described.
[0091]
As a configuration of the reflectance detection element of the present invention, it is possible to improve the mobility of photoelectric charges (carriers) generated by incident light and to make the element with a high response speed between the charge generation layer and the organic semiconductor layer. It is preferable to provide a charge transport layer, more preferably a charge transport layer having a light transmittance of 350 nm to 850 nm of 10% or more, particularly preferably a light transmittance of 50% in the wavelength range of 350 nm to 850 nm. ˜90% charge transport layer is provided.
[0092]
The charge transport layer formed adjacent to the charge generation layer is applied and dried using an applicator, bar coater, dip coater or the like obtained by dissolving the charge transport material alone or in a binder resin together with a binder resin. Obtained.
[0093]
Examples of charge transport materials include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxazolone derivatives, Benzothiazole derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, styryl compounds, amine derivatives, distyryl compounds (above p-type) ), Benzoquinone compounds, anthraquinone compounds, naphthoquinone compounds, naphthalenediimide compounds, fluorenone compounds, thiopyran compounds Compound, indane compounds, indanedione type compounds include cyclopentadiene compound and these nitro derivatives, cyano derivatives, dicyano-methylene derivative, malonic ester derivative, a Fueniruimino derivative (or n-type) and the like.
[0094]
Examples of the binder resin for forming the charge transport layer include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, and polycarbonate. Resins, silicon resins, melamine resins, and copolymer resins containing two or more of these resin repeating units, or high molecular organic semiconductors such as polyvinyl carbazole in addition to these insulating resins, The solvent for dissolving and dispersing the charge transport material and the binder resin can be selected from the above-mentioned solvents for forming the charge generation layer.
[0095]
The charge transporting material is 20 to 200 parts by weight, preferably 30 to 150 parts by weight per 100 parts by weight of the binder resin, and the thickness of the charge transporting layer is preferably about 5 to 50 μm.
[0096]
As the coating method of the composition of each layer, further known coating methods such as dipping, spin coating, knife coating, bar coating, blade coating, squeeze coating, reverse roll coating, gravure roll coating, curtain coating, spray coating, die coating, etc. An application method that can be used and can be applied continuously or thinly is preferably used.
[0097]
《Transparent support》
The transparent support according to the present invention will be described.
[0098]
The transparent support is composed of glass or a flexible resin sheet. For example, a polymer film can be used as the sheet. Examples of the polymer film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples thereof include films made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. By using such a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.
[0099]
The transparent support according to the present invention preferably has a light transmittance of 350 nm to 850 nm of 10% or more, more preferably 30% or more, and particularly preferably 50 or more.
[0100]
【The invention's effect】
According to the present invention, an analog image data such as a hard copy or printed matter can be easily and quickly converted into electronic data and used as electronic paper, a reflectance detection element, a sheet-like image input device using the same, and We were able to provide a sheet-like image input method.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of a configuration of a reflectance detection element of the present invention.
FIG. 2 is a schematic view showing an aspect in which the reflectance detection element of the present invention detects light reflection.
FIG. 3 is a schematic diagram showing an example of a circuit configuration of a reflectance detection element of the present invention.
FIG. 4 is a schematic diagram showing an aspect of a sheet-like image input device of the present invention.
FIG. 5 is a schematic diagram of an equivalent matrix circuit when active driving is performed in the apparatus shown in FIG. 4;
FIG. 6 is a schematic diagram illustrating an example of a sheet-like image input apparatus capable of detecting a full-color image.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Transparent support 2 Charge generation layer 3 Charge transport layer 4 Organic-semiconductor layer 5 Source electrode 6 Drain electrode 7 Insulating layer 8 Gate electrode 9 Half mirror 10 Light incident control means 50 Reflectance detection element

Claims (7)

On a transparent support, a gate electrode, an insulating layer provided on the transparent support while covering the gate electrode, on the insulating layer, connected source electrode, the drain electrode, the source electrode and the drain, And an organic semiconductor layer having a light transmittance of 350 nm to 850 nm of 10% or more, and a photocharge generation layer, a half mirror, and a light having a light transmittance of 350 nm to 850 nm of 10% or more on the organic semiconductor layer An element for detecting reflectance, wherein the incident control means is arranged in this order. 2. The reflectance detection element according to claim 1, wherein a charge transport layer having a light transmittance of 350 nm to 850 nm of 10% or more is provided between the organic semiconductor layer and the photocharge generation layer . The reflectance detection element according to claim 1, wherein the organic semiconductor layer includes a π-conjugated material. 4. The reflectance detecting element according to claim 1, wherein a liquid crystal element is used as the light incident control means . 5. The reflectance detecting element according to claim 1, wherein a light blocking layer and a light emitting element are used as the light incident control means . A sheet-like image input device comprising the reflectance detection element according to claim 1. A sheet-like image input method using the sheet-like image input device according to claim 6.

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