JP2012094500A - Donor substrate for transfer, and device manufacturing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a donor substrate for transfer which can be enlarged and enables highly accurate fine patterning, without deteriorating characteristics of a thin film such as an organic EL material and the like by impurities.SOLUTION: The donor substrate for transfer includes a supporter having a protrusion, and a photothermal conversion layer formed on the supporter. A reflective layer is provided on the protrusion of the supporter and between the protrusion of the supporter and the photothermal conversion layer.

Description

  The present invention relates to an organic EL element, a transfer donor substrate used for patterning a thin film constituting a device such as an organic TFT, a photoelectric conversion element, and various sensors, and a device using the transfer donor substrate. It relates to a manufacturing method.

  In the organic EL element, electrons injected from a cathode and holes injected from an anode are recombined in an organic light emitting layer sandwiched between both electrodes. Kodak's C.I. W. Since Tang et al. Have shown that organic EL devices emit light with high brightness (see Non-Patent Document 1), many research institutions have studied.

  This light-emitting element is thin and has high luminance light emission under a low driving voltage, and various organic materials are used for the light-emitting layer, so that the three primary colors of red (R), green (G), and blue (B) are used. Therefore, practical use as a color display is progressing. For example, the active matrix type color display shown in FIG. 1 requires a technique for patterning at least the light emitting layers 17R, 17G, and 17B with high precision so as to correspond to the R, G, and B subpixels constituting the pixel. The In order to realize a high-performance organic EL element, a multilayer structure is necessary, and a typical film thickness is 0.1 μm or less, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, It is necessary to sequentially stack an electron injection layer and the like.

  As a thin film fine patterning method, a wet process (coating method) such as an inkjet method or a printing method is known together with a dry process such as mask vapor deposition. In this technique, an organic EL material is formed on a transfer substrate by a wet process, and then transferred to a substrate on which a light emitting element is formed. For example, R, G, and B organic EL materials are separately applied using a separator without forming a photothermal conversion layer on the donor substrate, and the organic EL material on the donor substrate is directly heated and transferred with a laser. Alternatively, a method is disclosed in which a photothermal conversion layer is formed on a donor substrate, R, G, and B organic EL materials are separately applied thereon, and the photothermal conversion layer is irradiated with a laser to perform batch transfer ( For example, see Patent Documents 1 and 2). However, when a photothermal conversion layer is not used, there is a problem that it is necessary to irradiate a high-intensity laser with high alignment accuracy in order to perform sufficient transfer. There is a problem that it is difficult to coat the materials with high accuracy due to the influence of mixing of the organic EL materials. These are problems that make it difficult to increase the size of the substrate.

  As an example of selective transfer, a method is disclosed in which a pattern of a reflective layer is provided on a donor substrate, and a light absorbing layer is provided thereon to transfer only a portion of the material without the reflective layer (for example, (See Patent Document 3). In this method, a reflective layer or a heat insulating layer is laminated as a partition pattern on a support, a transfer material is applied on the entire surface of the donor substrate, and only the inside of the partition pattern is transferred to form a pattern.

  Furthermore, a method of providing a partition pattern on a donor substrate having a photothermal conversion layer and coating the organic EL material with high accuracy is also disclosed (see, for example, Patent Documents 4 to 5). By the way, forming a partition pattern that is a foreign substance other than the transfer material on the donor substrate having the photothermal conversion layer may cause the partition pattern itself to be peeled off and transferred, or impurities may be mixed into the transfer material from the partition pattern. For this reason, it is not preferable. Therefore, in Patent Document 4, the photothermal conversion layer is patterned, and the photothermal conversion layer does not exist below the partition pattern. On the other hand, in Patent Document 5, a light-to-heat conversion layer also exists under the partition pattern. However, the intensity of the irradiation light is reduced by irradiating a relatively wide light so that the transfer material and the partition pattern are simultaneously heated. In addition, even when the partition pattern is heated, peeling or impurities can be prevented from being generated.

JP 2004-87143 A JP 2008-235011 A JP 2009-231275 A JP 2009-146715 A International Publication WO2009 / 154156 Pamphlet

“Applied Physics Letters”, (USA), 1987, 51, 12, 913-915.

  However, in the case of coating the organic EL material on the donor substrate for each emission color, in order to perform patterning with high accuracy and prevent the generation of impurities during the transfer of the material from the donor substrate to the device substrate, It was still insufficient.

  SUMMARY OF THE INVENTION Accordingly, the present invention aims to solve such problems and provide a transfer donor substrate that can be increased in size and highly accurately patterned without deteriorating the properties of thin films including organic EL materials due to impurities. It is.

  The present invention includes a photothermal conversion layer formed on a support substrate and a partition pattern at least partially formed as a convex portion of the support substrate, and a reflective layer and a photothermal conversion on the convex portion of the partition pattern A transfer donor substrate, wherein the transfer layers are laminated in the order of the layers, and a transfer layer is formed on the photothermal conversion layer in the partition pattern.

  According to the transfer donor substrate of the present invention, it is possible to suppress thermal damage to the device in the transfer process of the transfer material, and it is possible to manufacture a device that is finely patterned with high accuracy without deteriorating the device performance. is there.

Sectional drawing which shows an example of the organic EL element by which the light emitting layer was patterned by transcription | transfer using the donor substrate of this invention. Sectional drawing which shows an example of the light emitting layer patterning method of the organic EL element by transcription | transfer using the donor substrate of this invention. The top view which shows an example of the light irradiation method in FIG. Sectional drawing explaining the transcription | transfer using the donor substrate of this invention. Sectional drawing explaining one aspect | mode of the creation process of the donor substrate of this invention. Sectional drawing explaining one aspect | mode of the manufacturing process which performs the simultaneous roughening process of the donor substrate of this invention. The top view explaining another one aspect | mode of the design of the laminated structure of the donor substrate of this invention. Sectional drawing explaining the heat transfer in the reflective layer in the donor substrate of this invention, and a heat insulation layer. Sectional drawing explaining one aspect | mode of the design of the liquid-repellent treatment layer in the donor substrate of this invention. The top view explaining one aspect | mode of the design of the liquid-repellent treatment layer in the donor substrate of this invention.

  FIG. 1 is a diagram showing an example of an organic EL element that can be manufactured using the donor substrate for transfer of the present invention. 2, 3 and 4 of the present invention are a cross-sectional view and a plan view showing an example of the thin film patterning method of the present invention. It should be noted that many figures used in this specification are described by extracting the minimum unit of RGB sub-pixels constituting a large number of pixels in a color display. In order to help understanding, the magnification in the vertical direction (substrate vertical direction) is increased as compared with the horizontal direction (substrate in-plane direction).

  In FIG. 1, an organic EL element (device substrate) 10 includes a support 11, a TFT (including an extraction electrode) 12 formed thereon, a planarization film 13, an insulating layer 14, a first electrode 15, and a hole transport layer 16. , Light emitting layers 17R, 17G, 17B, an electron transport layer 18 and a second electrode 19.

  In FIG. 2, the donor substrate 30 includes a support 31, a support protrusion 32, a photothermal conversion layer 33, a reflective layer 34, a heat insulating layer 35, and a transfer material 37 (an organic EL RGB light emission) existing between the support protrusions. Material coating film). As an example, a structure in which a reflective layer and a heat insulating layer are formed on a support convex portion is shown. Since the support convex part 32 plays a role as a partition for coating the transfer material separately, in the following description, the support convex part, the photothermal conversion layer, the reflective layer, and the heat insulation existing on the support convex part and the upper part thereof. A composite part such as a layer may be referred to as a “partition pattern”.

  In addition, since these are illustrations, the structure of each board | substrate is not limited to these as mentioned later. In a state where the positions of the support protrusions 32 of the donor substrate 30 and the insulating layer 14 of the device substrate 10 are aligned, the two substrates are arranged to face each other. A laser is incident from the support 31 side of the donor substrate 30 and absorbed by the light-to-heat conversion layer 33, and the transfer materials 37R, 37G, and 37B are simultaneously heated and evaporated by the heat generated there, and they are transported by holes of the device substrate 10. By depositing on the layer 16, the light emitting layers 17R, 17G, and 17B are collectively transferred and formed. The entire region of the support convex portion 32 sandwiched between the transfer materials 37R, 37G, and 37B and the partial region of the support convex portion 32 located outside the transfer materials 37R and 37B are heated simultaneously with the transfer material 37. Irradiation with a laser is a feature in the embodiment of FIGS.

  FIG. 3 is a schematic view of the state of laser irradiation in FIG. 2 as viewed from the support 31 side of the donor substrate 30. Since there is a photothermal conversion layer 33 formed on the entire surface, the support protrusion 32 and the transfer materials 37R, 37G, and 37B are not actually visible from the support 31 (glass plate) side, but the positional relationship with the laser is For the sake of explanation, it is shown by a dotted line. The laser beam has a rectangular shape, is irradiated so as to straddle the transfer materials 37R, 37G, and 37B, and is scanned in a direction perpendicular to the arrangement of the transfer materials 37R, 37G, and 37B. The laser beam only needs to be scanned relatively, and the laser may be moved, the set of the donor substrate 30 and the device substrate 20 may be moved, or both.

FIG. 4 is a schematic view of a cross section when the transfer material 37 is transferred with a laser. The laser incident from the support 31 side of the donor substrate 30 can heat the transfer material 37 via the photothermal conversion layer 33 and can be transferred to the donor substrate side. On the other hand, the laser is reflected by the reflective layer 34 at the support protrusion 32. Further, the heat from the reflective layer 34 is hardly transmitted to the photothermal conversion layer 33 on the support convex portion 32 by the heat insulating layer 35. For this reason, it is not heated until the support convex part 32 touches the device side, the organic material used for the insulating layer 14 on the device side is thermally deteriorated, or moisture contained in the insulating layer 14 and residual solvent / Impurities generated by volatilizing or decomposing gas are not mixed into the light emitting layer between the convex portions of the support (within the partition pattern).
In the following, the present invention will be described in more detail.

(1) Irradiation light As a light source of irradiation light, a laser that can easily obtain high intensity and is excellent in shape control of irradiation light can be exemplified as a preferable light source, but an infrared lamp, a tungsten lamp, a halogen lamp, a xenon lamp, a flash lamp A light source such as can also be used. As the laser, a known laser such as a semiconductor laser, a fiber laser, a YAG laser, an argon ion laser, a nitrogen laser, or an excimer laser can be used. Either a continuous wave mode (CW) laser or an intermittent wave mode (pulse) laser may be used. The continuous wave mode laser is effective when used for a transfer material with low heat resistance because the transfer material is slowly heated at a relatively low temperature. Further, the intermittent oscillation mode laser instantly sublimes with high heat, and is effective when it is desired to simultaneously transfer materials having different sublimation temperatures. In this way, the laser can be properly used depending on the characteristics of the transfer material.

  The wavelength of the irradiation light is not particularly limited as long as the absorption in the irradiation atmosphere and the support of the donor substrate is small and it is efficiently absorbed in the photothermal conversion layer. Therefore, not only visible light region but also ultraviolet light to infrared light can be used. Considering a suitable support material for the donor substrate, 300 nm to 5 μm can be exemplified as a preferable wavelength region, and 380 nm to 2 μm can be illustrated as a more preferable wavelength region.

  The shape of the irradiation light is not limited to the rectangle illustrated in FIG. The optimum shape can be selected according to the transfer conditions such as linear, elliptical, square, polygonal. Irradiation light may be formed by superposition from a plurality of light sources, or conversely, a single light source may be divided into a plurality of irradiation lights. The scanning speed is not particularly limited, but a range of 0.01 to 2 m / s is generally preferably used. When the light irradiation intensity is relatively small and the damage to the transfer material is reduced by scanning at a lower speed, the scanning speed is preferably 0.6 m / s or less, more preferably 0.3 m / s or less. .

  In the case of divided transfer in which scanning is repeated at the same place, when the overall temperature is lowered by increasing the number of divisions, the scan speed is relatively low in order to reduce the amount of input heat per scan. A high speed of 0.3 m / s or more is preferable. At this time, the number of divisions is preferably 2 to 50 times. This is because if the number of times is too small, the heat of molecules at the time of transfer deteriorates the hole transport layer on the device side. Conversely, if the number of times is too large, not only will the productivity be reduced, but the total amount of heat input will be reduced. This is because the organic molecules on the device side and donor side are deteriorated.

The preferable range of irradiation intensity and heating temperature of the transfer material are uniformity of irradiation light, irradiation time (scanning speed), donor substrate support and photothermal conversion layer material and thickness, reflectivity, partition pattern material and shape It is affected by various conditions such as the material and thickness of the transfer material. In the present invention, the energy density absorbed in the light-to-heat conversion layer is in the range of 0.01 to 10 J / cm ² , and it is a guideline that the irradiation conditions are adjusted so that the transfer material is heated in the range of 220 to 400 ° C. .

(2) Donor Substrate FIG. 5 is a diagram showing one embodiment of a manufacturing process of a donor substrate used in the present invention. First, as shown in FIG. 5A, a reflective layer 34, a heat insulating layer 35, and a resist layer 38 are laminated on the entire surface of a support 31. The resist layer 38 is resistant to an etching solution for etching the heat insulating layer, the reflective layer, and the support. Next, the resist layer is patterned as shown in FIG. When the resist layer 38 is a photoresist, a known photolithography technique can be used. If the resist layer 38 is not photosensitive, a known pattern etching method (or lift-off method) using another photoresist for patterning the resist layer 38 can be used. Alternatively, a stamp method or imprint method in which a mold is pressed against the heat insulating layer 35 formed on the entire surface (a reflective layer 34 when no heat insulating layer is provided), an ink jet method or a nozzle jet method in which a resin material is directly formed by patterning, and various printing methods are used. Utilizing it, the resist layer 38 patterned as shown in FIG. 5B can be formed suddenly.

  Next, as shown in FIG. 5C, the opening of the patterned resist layer 38 is etched in the order of the heat insulating layer 35, the reflective layer 34, and the support 31. In the case where two or more adjacent layers of the heat insulating layer, the reflective layer, and the support can be etched with a common etchant, the layers may be simultaneously etched using such an etchant. In addition, each layer can be etched using different etching solutions. It is possible to peel off the resist layer 38 each time each layer is etched and re-form a resist layer optimal for the etching of the next layer. Here, the same resist layer 38 is used, that is, the resist formed once. It is preferred that layer 38 continue to be utilized until all etching of the thermal insulation layer, reflective layer and support is complete. If the resist layer is re-formed, the positional accuracy may deteriorate each time. However, if the same resist layer is used continuously, the heat insulating layer 35, the reflective layer 34, and the support convex portion 32 are not displaced, and a high-accuracy position is obtained. Togetherness can be achieved.

  When the reflective layer and the heat insulating layer are treated with individual etching solutions, a general acid or alkali can be used as the etching solution for the reflective layer. In particular, when an aluminum alloy is used for the reflective layer, a non-oxidizing etching solution, that is, an etching solution containing a solution of hydrochloric acid, hydrofluoric acid or chloride is desirable. The etchant for the heat insulation layer is not particularly defined as long as it is a composition that can etch the heat insulation layer, but when a glassy material is used for the heat insulation layer, a strong alkali such as potassium hydroxide or sodium hydroxide, or silicon such as hydrofluoric acid. What dissolve | melts a compound can be used. Etching solution containing hydrofluoric acid is used as the etching solution for the support, and the etching rate and etching surface shape can be adjusted by mixing acids such as sulfuric acid, nitric acid, hydrochloric acid, organic acids, and alkalis such as ammonia. It is also possible to form irregularities on the surface of the support in the partition pattern by etching, so that the inside of the partition pattern can be covered with the photothermal conversion layer so that the photothermal conversion layer also has irregularities. A uniform wetted surface can be achieved in the partition pattern when the coating is applied. The surface roughness at this time is preferably such that Rz is 0.05 μm or more, and it is more desirable that the number of irregularities in the surface is larger.

  When an aluminum alloy is used for the reflective layer, the support and the reflective layer can be etched simultaneously with the etching solution containing the above hydrofluoric acid. In addition, it is preferable to use a material that dissolves in hydrofluoric acid such as silicon oxide for the heat insulating layer because the reflective layer, the heat insulating layer, and the support can be etched with the same etching solution.

  Next, as shown in FIG. 5D, the resist layer 38 is peeled off. Next, as shown in FIG. 5E, a photothermal conversion layer is formed on the entire surface, and a liquid repellent treatment is applied to the partition pattern as necessary. Finally, as shown in FIG. 5F, a transfer material 37 is formed between the support convex portions. The transfer material 37 can be roughly classified into a wet method and a dry method. In the wet method, a light emitting material is dissolved in a solvent and applied by ink jet, nozzle, spin coating, spraying or the like. Of these, inkjet and nozzles are preferable because they can be applied to different colors for each section. In the dry method, the light emitting layer can be formed by a vacuum vapor deposition method or the like using a mask having an opening in the partition pattern.

  An ultra-thin film containing a large amount of components insoluble or hardly soluble in the etching solution for etching the support and / or any layer on the support is formed between any of the layers formed on the support. By doing so, the support protrusions can be formed by etching and the space between the support protrusions can be roughened. Here, “slightly soluble in the etching solution” means that the etching rate is 1/10 or less of the etching rate of the support with respect to the etching solution. Hereinafter, such an ultrathin film is referred to as a “roughening film”. When a solvent containing an organic material is applied to a smooth area where roughening treatment is not performed, the solvent tends to concentrate at the base of the partition pattern due to capillary action, and the film thickness of the organic material increases. On the other hand, the smooth portion has low wettability, so that the solvent does not stay in other portions and the film thickness becomes thin. For this reason, in the smooth shape, the film thickness unevenness occurs so that the peripheral part becomes thick in the partition pattern. This phenomenon is improved by the roughening treatment in the partition pattern and the surface wettability is remarkably improved, so that a uniform film is formed when a solvent containing an organic material is applied in the partition pattern. By forming such a uniform film, the film after transfer is also uniform, so that a good light-emitting element with little leakage current and uneven light emission can be obtained.

  FIG. 6 is a cross-sectional view showing an example of a step of performing a roughening process between support protrusions simultaneously with the formation of support protrusions using the roughening film. Although the roughening film 41 is an example provided between the reflective layer 34 and the support 31, the roughening film 41 is provided between the reflective layer 34 and the heat insulating layer 35 or between the heat insulating layer 35 and the resist layer 38. It may be provided.

  As shown in FIG. 6A, a roughening film 41 is provided between the support 31 and the reflective layer 34, and the other processes are performed in the same manner as in FIG. Since the roughening film 41 contains many insoluble or hardly soluble components in the etching solution for etching any one of the reflective layer, the heat insulating layer, and the support, the etching rate in the surface is locally slow. A portion is generated and is etched non-uniformly at a glance including the support 31 under the roughening film 41 as shown in FIG. However, since the roughened film 41 is an extremely thin film, the roughened film 41 is gradually dissolved, and in the process, all the portions are finally removed as shown in FIG. For this reason, the etching surface between support body convex parts can be roughened as a result by the nonuniformity in the middle of an etching. Thereafter, the steps of FIGS. 6D to 6F can be performed in the same manner as the above-described method, and a roughened substrate can be obtained only between the support convex portions which are transfer material forming portions. Even when the roughening film 41 is provided between the reflective layer 34 and the heat insulating layer 35, or when the roughening film 41 is provided between the heat insulating layer 35 and the resist layer 38, the reflective layer 34 and the heat insulating layer 35 are supported by the support. The same effect can be obtained if there is an etching rate equivalent to.

  Generally, it is difficult to roughen the glass used for the support, especially alkali-free glass, using only hydrofluoric acid. After forming the support protrusion as described above, strong acid such as hydrochloric acid, nitric acid / sulfuric acid, etc. In general, the treatment is performed with a special hydrofluoric acid-based etchant mixed with an agent. At this time, there arises a problem that the reflective layer remaining on the support convex portion is abnormally eroded. For this reason, it is difficult to roughen the support with a general roughening solution. If the roughening film is used, it is possible to perform the roughening process simultaneously with the formation of the step using a normal hydrofluoric acid etching solution with little abnormal erosion to the reflective layer.

  Examples of materials insoluble or hardly soluble in hydrofluoric acid used here include copper, silver, gold, platinum, nickel, magnesium, molybdenum, tantalum, and tungsten.

  The roughening film 41 is composed of 30 atomic% (atomic number), more preferably 40 atomic%, of an insoluble or hardly soluble metal in an etching solution for etching the support and / or any layer on the support. It is preferable to include the above. The upper limit is not particularly limited, but if it is too large, the final dissolution and removal becomes difficult. Therefore, the upper limit is preferably 80 atomic% or less, and more preferably 60 atomic%. The other composition is preferably a material that is soluble in the etching solution and has good adhesion to the support and the resist layer. Examples of the composition that are preferable include aluminum, titanium, and zircon. More specifically, when the roughening film 41 is provided between the reflective layer 34 and the support 31 as shown in FIG. 6, (1) the reflective layer 34 and the support 31 are etched with the same etching solution. In this case, it is preferable to contain 30 atomic% or more of an insoluble or hardly soluble metal in the etching solution. (2) When the reflective layer 34 and the support 31 are etched with different etching solutions, the metal is insoluble in the etching solution of the support 31 or It is preferable to contain 30 atomic% or more of a hardly soluble metal. In the case of (2), the roughening film 41 is preferably insoluble in the etching solution for the reflective layer 34. As a method for measuring the composition of the metal constituting the roughening film 41, an analysis method using fluorescent X-rays is preferably used.

  When the reflective layer 34 is etched with a solution different from the etchant for the support, it is necessary that the roughening film 41 formed on the support is not dissolved in the etchant for the reflective layer. For this reason, for example, when an aluminum-based alloy that is alkali-dissolved in the reflective layer 34 and an alkali-insoluble titanium-based or zircon-based alloy is used for the roughening film 41 and an alkaline etching solution is used, only the reflective layer 34 is etched. Can be performed. Thereafter, the roughening treatment film 41 and the support 31 are simultaneously etched non-uniformly with a hydrofluoric acid-based etching solution, whereby the roughening treatment and the step formation can be performed simultaneously.

Further, when the roughening film 41 is formed on the reflective layer 34, it is necessary to perform the roughening process with a liquid that can etch the reflective layer 34 and the support 31 at the same time. Due to the etching non-uniformity of the roughening film 41, both the reflective layer 34 and the support 31 can be roughened simultaneously with the etching. In addition, when the reflective layer 34 and the roughening film 41 are etched at the same time, either layer may be abnormally eroded. At this time, it is possible to etch between these layers with the etching solution of the support, but to add a thin layer such as SiO ₂ insoluble in the reflective layer.

  Moreover, it is preferable that the film thickness of a roughening process film is 5 nm or less, and when the density | concentration of an insoluble or a hardly soluble component is high, it is better to make a film thickness thin. Since the roughening film remains on the support convex portion, the decrease in reflectance at the reflective layer 34 can be reduced as the film thickness decreases. The lower limit of the film thickness is not particularly limited, but if it is less than 0.5 nm, the film itself is easily affected by the etching solution, and the film may be etched before the roughening treatment. For this reason, the film thickness is preferably 0.5 nm or more. As another form, the same roughening effect can be obtained by forming the roughening film 41 between the reflective layer 34 and the resist layer 38.

  The support for the donor substrate is not particularly limited as long as it has a low light absorption rate and can stably form a photothermal conversion layer, a partition pattern, and a transfer material thereon. Resin film can be used depending on conditions. Polyester, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyacryl, polysulfone, polyethersulfone, polyphenylene sulfide, polyimide, polyamide, poly Examples include benzoxazole, polyepoxy, polypropylene, polyolefin, aramid resin, and silicone resin.

  In terms of chemical / thermal stability, dimensional stability, mechanical strength, and transparency, a preferred support is a glass plate. Soda lime glass, alkali-free glass, lead-containing glass, borosilicate glass, aluminosilicate glass, low expansion glass, quartz glass and the like can be selected according to the conditions. When the transfer process of the present invention is carried out in vacuum, a glass plate is a particularly preferred support because it is required that gas release from the support is small.

  Moreover, you may coat the surface of glass with various coupling agents, and, thereby, adhesion with a photothermal conversion layer can be improved. As the coupling agent, there are coupling agents such as Si-based, Al-based, Ti-based and Zn-based, and any of them can be used. An aminosilane coupling agent, mercaptosilane coupling agent, or the like is preferably used as a coupling agent having a large adhesion effect with the metal or oxide of the photothermal conversion layer.

  The material of the reflective layer is preferably a material having a high reflectance with respect to light rays incident through the support. Examples of metals having high reflectivity generally include noble metals such as platinum, gold, silver, and copper, aluminum, zinc, and tantalum. Platinum, gold, silver, copper and aluminum are preferable in terms of particularly high reflectance, and aluminum is particularly preferable in terms of easy etching.

  In order to enable simultaneous etching of the support and the reflective layer under optimum conditions by adjusting the hydrofluoric acid, the reflective layer preferably contains aluminum and a hydrofluoric acid resistant metal. Examples of the hydrofluoric acid-resistant metal include noble metals, nickel, magnesium, and the like. By including these metals, the solubility (etching rate) of the aluminum alloy in hydrofluoric acid can be adjusted. In addition, as a material that dissolves in hydrofluoric acid but has a low speed, there are metals having high heat resistance such as molybdenum, tantalum, and tungsten. The inclusion of these metals is preferable because not only the solubility of the reflective layer in hydrofluoric acid can be adjusted, but also the heat resistance of the reflective layer itself can be improved.

  When the above metal is added in a large amount, the hydrofluoric acid resistance of the reflective layer is improved, but the light reflectance is also lowered. For this reason, the reflective layer preferably contains 70 atomic% or more of aluminum, more preferably 85 atomic% or more. Moreover, a preferable upper limit is 95 atomic%. The remaining composition preferably contains one or more selected from the group consisting of noble metals, nickel, magnesium, molybdenum and tungsten. When the aluminum content in the reflective layer is 85 to 95 atomic%, it is preferable because an optimum partition bank shape can be obtained under conditions close to the etching rate for hydrofluoric acid of general glass as a support.

  Further, the reflective layer may not be a single layer, and may be a plurality of metal layers. The thickness of the reflective layer is not particularly specified, but is preferably 50 nm or more and 2 μm or less from the viewpoint of reflecting a sufficient amount of light and reducing the internal stress of the reflective layer. The method for forming the reflective layer is not particularly limited. When an inorganic material is used, known techniques such as vacuum deposition, EB deposition, sputtering, ion plating, CVD, laser ablation, and plating method are used. Known techniques such as spin coating, slit coating, and dip coating can be used. In the case of producing a reflective layer made of a mixture of two or more substances, the method is not particularly defined, and examples thereof include a co-evaporation method having a multi-component crucible and a hearth and a sputtering film forming method using a mixture sputtering target. A wet process such as an alloy plating method can also be used. A sputtering method using an alloy target is preferable because the additive concentration can be easily controlled to be constant. For example, when an alloy film containing 70 atomic% aluminum and 30 atomic% copper is manufactured, a sputtering target mixed with the above atomic ratio may be prepared and sputter deposition may be performed. In the co-evaporation method, a reflective layer having a target mixing ratio can be obtained by always setting the deposition rate in terms of the number of atoms of aluminum and copper to 7: 3. As a method for measuring the composition of the metal constituting the reflective layer, an analysis method using fluorescent X-rays is preferably used. This is because many kinds of elements can be compared quantitatively.

  When the reflectance of the reflective layer is low, heat of absorption from incident light is generated and the reflective layer may be heated to some extent. Therefore, it is preferable that a heat insulating layer is provided between the reflective layer and the photothermal conversion layer. The heat insulating layer is for preventing the heat from being transmitted to the upper part of the partition pattern even if a small amount of heat is generated in the reflective layer. For this reason, it is preferable that the material has a low thermal conductivity and a large specific heat. An organic material or an inorganic material may be used, and an organic / inorganic hybrid material may be used. Oxides such as silicon dioxide, zirconia, and titania, and nitrides such as silicon nitride, zirconium nitride, and titanium nitride have a thermal conductivity of about one-tenth that of the metal of the reflective layer, which is preferable. The film of the heat insulating layer is preferably amorphous rather than single crystal, and more preferably amorphous. This is because the lower the crystallinity, the smaller the heat transfer and the more the heat transfer can be suppressed. In addition, defects can be formed by appropriately containing impurities, and the above crystallinity can be suppressed. Carbon and heat-resistant organic materials can also be used.

  In the case where the heat insulating layer, the reflective layer, and the support are etched simultaneously, it is desirable that the etching rate of each etching layer is close, and the heat insulating layer is preferably made of the same or close material as the support. Therefore, it is possible to use silicon dioxide containing aluminum oxide, calcium oxide, magnesium oxide, boron oxide, strontium oxide, or the like.

  The thickness of the heat insulating layer is not particularly limited as long as it does not transmit a small amount of heat generated in the reflective layer to the device side, but a thicker one is preferable. However, a heat insulating layer that is too thick is preferably 2 μm or less because peeling problems are likely to occur and the process for producing a thick film is burdened. On the other hand, when the film thickness is too thin, the function as a heat insulating layer cannot be sufficiently achieved. For this reason, when providing a heat insulation layer, it is desirable to set it as thickness 20 nm or more.

  An example of the embodiment of the transfer donor substrate of the present invention is shown in FIG. 7, and further, the role of the reflective layer and the heat insulating layer in this patent will be described in more detail from the state of heat transfer in the reflective layer and the heat insulating layer shown in FIG. To do. 8A to 8D are cross-sectional views in which a portion where the partition pattern is in contact with the insulating layer of the device substrate is enlarged. White arrows indicate the incidence and reflection of light rays, black arrows indicate heat transfer, and oblique lattice portions indicate damaged portions due to heat transfer from the partition pattern.

  FIG. 8D shows a conventional technique in which only a light-to-heat conversion layer is formed without forming a reflective layer in a partition pattern. In this case, since light is directly incident on the photothermal conversion layer above the partition pattern, the photothermal conversion layer is heated. The photothermal conversion layer is heated to a temperature sufficient for sublimation of the light emitting material, and a considerable amount of thermal damage occurs at the interface in contact with the insulating layer in contact therewith. Since the hole transport layer material is laminated on the upper part of the insulating layer, or the insulating layer material itself is in contact with the upper part of the partition pattern, these materials sublimate and decompose under the influence of heat to generate impurities. , Entering the inside of the EL element and lowering the performance.

  On the other hand, FIG. 7 (a) is a basic shape of the donor substrate of the present invention, which includes a support having a convex portion and a photothermal conversion layer formed on the support, A reflective layer is provided on the convex portion between the light-to-heat conversion layer. In the case of FIG. 7 (a), as shown in FIG. 8 (a), many incident rays are reflected by the reflective layer, so the reflective layer itself is not heated to a high temperature, and the reflective layer with high heat transfer rate. Heat transmitted to the device side through the photothermal conversion layer can be greatly suppressed. However, when the light reflectivity of the reflective layer is relatively low, the temperature of the reflective layer rises to some extent, and the insulating layer may be slightly damaged by the heat.

  In FIG. 7B, a heat insulating layer is provided between the reflective layer and the photothermal conversion layer. As shown in FIG. 8B, the reflective layer absorbs part of the light and generates heat. Even so, the heat is hardly transmitted to the photothermal conversion layer 33 due to the presence of the heat insulating layer 35. Therefore, almost no heat is transferred to the insulating layer of the device substrate opposed to the device substrate. FIG. 8C shows a case where the reflectance of the reflective layer is further increased, and the heat generated in the reflective layer can be greatly reduced. It is preferable that 50% or more of the incident light is reflected by the reflective layer.

  FIG. 7C shows a structure in which an antireflection layer 35 'is formed on the entire surface. The antireflection layer is a layer for reducing the reflectance of incident light and increasing the light absorption rate in the light-to-heat conversion layer, and a laminate of optical thin films is preferably used. As a result, multiple interference is generated, and the reflectance of incident light is reduced. In the embodiment of FIG. 7C, the light-heat conversion efficiency of the light-heat conversion layer is increased, so that the amount of incident light can be reduced. This means that the amount of light incident on the reflective layer is also reduced, so that the temperature rise of the reflective layer can be greatly reduced.

  FIG. 7D shows a case where a heat insulating layer is further formed in FIG. Thereby, even if some heat is generated in the reflective layer, heat is not transferred to the outermost surface of the partition pattern, so that thermal damage can be further reduced to the device substrate side. The antireflection layer 35 'may also serve as a heat insulating layer on the partition pattern.

  Of these structures, FIG. 7C and FIG. 7D show the antireflection layer on the entire surface of the substrate in the process immediately before the formation of the photothermal conversion layer in the preparation process of FIG. 7A and FIG. 7B. It can be created by forming.

  The greater the reflectance of the reflective layer and the smaller the reflectance of the light-to-heat conversion layer, the more efficiently heat is converted in the light-to-heat conversion layer, and the transfer of the luminescent material is promoted, while heat transfer through the partition pattern is reduced. Thereby, the damage to an EL element is reduced and a high-performance device is obtained. For this reason, it is desirable that the value of “reflectance in the reflective layer” / “reflectance in the photothermal conversion layer” (hereinafter referred to as “reflectance ratio”) is large.

  In addition, the reflectance in this specification is shown as a ratio with respect to incident light energy of total reflected light energy including diffuse reflection. Specifically, it can be measured as follows. First, regarding the reflectance of the reflective layer, the reflective layer provided on the donor substrate is formed on another support with the same film thickness as that provided on the donor substrate. Next, laser light is incident at an angle of 45 degrees from the support side, and the reflected light energy is measured with a laser power meter (UP-15K manufactured by GENTEC). Then, the reflected light energy is divided by the incident light energy to obtain the reflectance of the reflective layer. The same applies to the light-to-heat conversion layer, but the reflectance in the light-to-heat conversion layer is the reflectance when the light-to-heat conversion layer and the anti-reflection layer are integrated when an anti-reflection layer is used. The incident light used for the measurement may be in the range of the wavelength of the light used when the transfer material is transferred using the donor substrate of the present invention, and is in the range of 300 nm to 3 μm.

  Generally, the heat resistance of an organic material used for an insulating layer of a device substrate is 150 ° C. to 200 ° C., while the sublimation temperature of the light emitting layer is 150 ° C. to 300 ° C. In order to suppress the temperature of the partition pattern in contact with the insulating layer of the device substrate and prevent the insulating layer of the device substrate from being decomposed to improve device characteristics, measurement is performed using light having a wavelength of at least one of 300 nm to 3 μm. The reflectance ratio calculated from the “reflectance in the reflective layer” and “reflectance in the photothermal conversion layer” is preferably 1.5 or more, and should be further increased when used as a light-emitting material for high-temperature sublimation. Is preferred. The larger the reflectance ratio, the better. However, there are also restrictions on materials constituting the reflective layer, the photothermal conversion layer, and the antireflection layer, and it is usually 10 or less, and 5 or less depending on the type of preferred material. The method for adjusting the reflectance ratio is not particularly limited, but it is effective to change the material composition or form an antireflection layer.

  The thickness of the antireflection layer is set to a value close to a quarter of the wavelength in order to cancel the reflected light by causing interference by the phase reversed with the wavelength of the incident light and the reflected light. As a result, multiple reflection occurs in the antireflection layer, and the reflected light has the effect of canceling out the incident light due to interference. For this reason, the thickness of the antireflection layer is preferably within 25% of the error with respect to the length of one quarter of the incident wavelength, and more preferably within 15%. The material preferably has a low refractive index relative to glass, and fluorides such as magnesium fluoride, lithium fluoride, calcium fluoride, and strontium fluoride are preferable for glass. In general, when an antireflection layer is produced from a laminated film, the reflectance of a wide range of wavelengths can be lowered by adjusting the thickness and refractive index of each film. For this reason, the antireflection layer in the partition pattern does not need to be a single layer, and may be a two-layer film or a laminated film of more layers.

  When the light emitting layer is formed in the partition pattern by a coating method, since the light emitting material is dissolved in the solvent, the amount of liquid injected into the partition is considerably thicker than the target thickness. An example is as follows. In general, the dry film thickness of the light emitting layer is 20 to 60 nm, and it is necessary to apply a solution containing a light emitting material in an amount corresponding to the thickness. Since the solubility of the luminescent material in the solvent is about 0.5 to 3% by weight, the luminescent material solution applied to the partition pattern is approximately 30 to 200 times the dry film thickness. Therefore, the height of the partition pattern needs to be 30 to 200 times higher than the thickness of the light emitting layer. The height of the partition pattern at this time is at least 0.6 to 12 μm. However, since the liquid is instantly biased in the partition pattern at the time of application of the solution, it may be practically 3 to 15 μm in height. preferable.

  From this, when it is going to form a division pattern only by a reflection layer as described in patent document 3, it will be a preferable aspect that the thickness of reflection layer itself shall be 3 micrometers or more. On the other hand, when the reflective layer is formed thick, the film is elongated in the case of sputtering film formation, and in the case of vapor deposition film formation, stress is generated with the substrate by contraction. For this reason, the thick reflective layer is easily peeled off from the substrate due to internal stress, and it is difficult to form a fine pattern.

  Even if the photothermal conversion layer is heated to a high temperature, it is necessary to keep the temperature rise (thermal expansion) of the support itself within an allowable range. Therefore, the heat capacity of the support is preferably sufficiently larger than that of the photothermal conversion layer. Therefore, the thickness of the support is preferably 10 times or more the thickness of the photothermal conversion layer. The allowable range depends on the size of the transfer region and the required accuracy of patterning, but cannot be generally shown. For example, when the photothermal conversion layer rises from room temperature by 300 ° C. and the support is heated by the thermal diffusion, When it is desired to suppress the temperature rise of the support itself to 3 ° C. or less, which is 1/100 of the temperature rise of the photothermal conversion layer, when the volume heat capacity of the photothermal conversion layer and the support is approximately the same, the support The thickness of is preferably 100 times or more the thickness of the photothermal conversion layer. In addition, when it is desired to suppress the temperature rise of the support itself to 1 ° C. or less which is 1/300 of the temperature rise of the photothermal conversion layer, the thickness of the support is 300 times or more the thickness of the photothermal conversion layer. More preferably it is. In a typical case where the volumetric heat capacity of the light-to-heat conversion layer is about twice that of the support, the thickness of the support is preferably 200 times or more, and more than 600 times the thickness of the light-to-heat conversion layer. Is more preferable.

  The support needs to be opposed to the partition pattern of the donor substrate and the insulating layer of the device substrate by applying pressure uniformly in the direction of the device substrate from the opposite side of the surface on which the photothermal conversion layer is formed. At this time, it is desirable to bring the support into surface contact with a transparent rigid body. This is because, by bringing the rigid body into contact with the portion in contact with the support, heat transfer occurs from the support relative to the rigid body, and the temperature increase of the entire donor substrate can be suppressed. Since this rigid body needs to transmit light, a transparent material with high thermal conductivity such as glass or sapphire is desirable. In order to improve the heat absorption efficiency of the support by contact between the support and the transparent rigid body, it is also possible to insert a cushion material having a high thermal conductivity between the transparent rigid body and the support. By doing so, even if the size is increased, the amount of dimensional displacement due to thermal expansion is small, and high-precision patterning becomes possible.

  The photothermal conversion layer is not particularly limited as long as it is a material / configuration that efficiently absorbs light to generate heat and is stable against the generated heat. For example, a thin film in which carbon black, graphite, titanium black, an organic pigment, metal particles or the like are dispersed in a resin, or an inorganic thin film such as a metal thin film can be used. In the present invention, since the photothermal conversion layer may be heated to about 300 ° C., the photothermal conversion layer is preferably composed of an inorganic thin film having excellent heat resistance. It is particularly preferred that Metallic materials include tungsten, tantalum, niobium, manganese, molybdenum, titanium, chromium, gold, silver, copper, platinum, iron, zinc, aluminum, cobalt, nickel, magnesium, vanadium, zirconium, silicon, carbon, and so on. An alloy thin film or a laminated thin film thereof can be used.

  As described above, an antireflection layer can be formed on the support side of the photothermal conversion layer as necessary. Further, an antireflection layer may be formed on the surface of the support on the light incident side. As these antireflection layers, optical interference thin films using a difference in refractive index are preferably used. Silicon, silicon oxide, silicon nitride, zinc oxide, magnesium oxide, titanium oxide, magnesium fluoride, lithium fluoride, calcium fluoride, A simple substance such as strontium fluoride, a mixed thin film, or a laminated thin film thereof can be used.

  Since the light-to-heat conversion layer needs to provide sufficient heat for evaporation of the transfer material, it is preferable that the heat capacity of the light-to-heat conversion layer is greater than that of the transfer material. Accordingly, the thickness of the photothermal conversion layer is preferably thicker than the thickness of the transfer material, and more preferably 5 times or more the thickness of the transfer material. The numerical value is preferably 0.02 to 2 μm, more preferably 0.1 to 1 μm. Since the photothermal conversion layer preferably absorbs 90% or more, more preferably 95% or more of the irradiation light, it is preferable to design the thickness of the photothermal conversion layer so as to satisfy these conditions. When forming the transfer auxiliary layer, it is preferable to design the transfer auxiliary layer so that the heat generated in the light-to-heat conversion layer is thin in a range that satisfies the required functions so as not to hinder efficient transfer of the heat to the transfer material. .

  The planar shape of the photothermal conversion layer is not particularly limited as long as it is formed in a portion where the transfer material exists. As exemplified above, it may be formed on the entire surface of the donor substrate or may be patterned. Since the light-to-heat conversion layer has a high light absorption rate, it is preferable to form a position mark on the donor substrate at an appropriate position inside and outside the transfer region using the light-to-heat conversion layer.

  As a method for forming the photothermal conversion layer and the transfer auxiliary layer, a known technique such as spin coating, slit coating, vacuum deposition, EB deposition, sputtering, ion plating, or the like can be used. When patterning, a known photolithography method or laser ablation can be used.

  The shape of the partition pattern is not limited to the lattice structure already illustrated in FIG. 3. For example, when three types of transfer materials 37 R, 37 G, and 37 B are formed on the donor substrate 30. The planar shape of the partition pattern may be a stripe extending in the y direction.

  The height of the support protrusion is not particularly limited, and the transfer material is preferably not in direct contact with the transfer surface of the device substrate, and the gap between the transfer material of the donor substrate and the transfer surface of the device substrate is 1-100 μm is desirable, and considering the liquid height in the process of applying the light emitting layer and the etchable height of the support, it is preferable to keep it in the range of 3-15 μm. It is preferably thicker than the thickness, 1-100 μm, more preferably 3-15 μm. Further, when applying the transfer material in the partition pattern, it is necessary to apply the solvent so that the solvent does not overflow from the partition pattern. For this purpose, the support protrusion is preferably thicker, and more preferably 4 μm or more. By making the support protrusion with such a thickness face the device substrate, it becomes easy to keep the gap between the transfer material of the donor substrate and the transfer surface of the device substrate at a constant value, and also the evaporated transfer The possibility of material entering into other compartments can be reduced.

  The sectional shape of the partition pattern is preferably a forward tapered shape in order to facilitate the evaporation transfer material to be uniformly deposited on the device substrate. As illustrated in FIG. 2, when a pattern such as the insulating layer 14 exists on the device substrate 10, the width of the insulating layer 14 is preferably wider than the width of the partition pattern. Further, it is preferable that the alignment pattern is arranged so that the width of the partition pattern is within the width of the insulating layer 14 at the time of alignment. In this case, even if the partition pattern is thin, the donor substrate 30 and the device substrate 10 can be held in a desired gap by increasing the thickness of the insulating layer 14. The typical width of the partition pattern is 5 to 50 μm and the pitch is 25 to 300 μm. However, the partition pattern may be designed to an optimum value depending on the application, and is not particularly limited.

  It is preferable that a liquid repellent treatment layer 36 is provided on the outermost surface of the partition pattern to retain the solution in which the transfer material is dissolved in the partition pattern by making the solution repellent. The liquid repellent treatment layer preferably has a large contact angle with respect to the solvent used for dissolving the transfer material, preferably 40 ° or more, and more preferably 60 ° or more. The thinner the liquid repellent layer, the smaller the absolute amount of impurities that may be eluted from it. However, if the layer is too thin, the effect of the liquid repellent treatment may be impaired. Therefore, the preferred thickness of the liquid repellent layer is from 0.5 nm to 100 nm, and in the case of a monomolecular film described later, it is preferably from 1 nm to 5 nm. The liquid repellent treatment layer does not necessarily need to be a continuous film, as long as it has a function of repelling the solution on the partition pattern and partitioning the coating.

  9 and 10 are a sectional view and a plan view showing a state in which the liquid repellent treatment layer 36 is formed on the partition pattern. (A) shows a case where the liquid repellent treatment layer is designed wider than the partition pattern, and the transfer material can be used effectively because the solvent after application stays in the partition pattern and is not applied onto the partition pattern. (B) is a case where the liquid repellent treatment layer is designed only near the upper part of the partition pattern. Since the transfer material wets and spreads also on the edge portion of the partition pattern, a large amount of material is used. Since the uniformity can be increased, the film thickness uniformity after transfer can be improved. Either of these cases can be selected depending on the situation. Since the solvent is repelled by the liquid repellent treatment layer, it is possible to prevent the solvent applied in the partition pattern from spreading on the partition pattern and entering (mixing colors) into adjacent partitions. This is also true when the interval between the partition patterns is narrowed. Therefore, the transfer material can be accurately applied in each partition pattern, and multicolor coating can be performed particularly in a highly accurate and extremely narrow pattern that could not be achieved in the past. Further, since the partition pattern can be designed to be narrower than the width of the insulating layer on the device side, there is a great advantage that the transfer material can be transferred onto the device substrate more uniformly than in the past.

  As a specific method for providing the liquid repellent treatment layer, various low surface energy organic films, in particular, fluorine-containing organic material layers are formed on the partition pattern to provide a liquid repellent function on the top surface of the partition pattern. It is desirable to have it. As an example of the treatment layer preparation method, fluorine-containing polymer material such as (1) silicone resin, (2) vinyl fluoride resin, acrylic resin or polyimide resin containing fluorine in the skeleton on the surface of the barrier layer on the partition pattern (3) Forming a layer such as a coupling agent containing fluorine. In particular, a silane coupling agent containing fluorine in the molecular structure forms a monomolecular film on the barrier layer and does not occlude impurities inside the resin unlike a polymer material. For this reason, the impurities that dissolve in the solvent when the transfer material is applied are overwhelmingly less than other organic polymer films and silicone films, which is particularly preferable. In addition, the liquid-repellent treatment layer made of a polymer material does not have strong adhesion to the barrier layer, so that peeling may occur when it is repeatedly used. In this way, impurities contained in the polymer material itself may be gradually eluted due to penetration of heat or solvent, and may be mixed into the transfer material and deteriorate the performance of the organic EL element. On the other hand, in the case of a silane coupling agent containing fluorine, a monomolecular film that has a liquid repellent function and is chemically bonded to the material surface of the barrier layer firmly covers the barrier layer, so that the solvent penetrates through the peeling portion. Does not occur, and impurity elution is greatly suppressed.

When the coupling agent containing fluorine is represented by a chemical structural formula, a compound represented by the following formula is given as a typical structure. In particular, a coupling agent having a linear perfluoroalkyl group is preferable because adhesion to the barrier layer is increased and durability is improved.
(1) CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(2) CF ₃ CH ₂ SiCl ₃
(3) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃
(4) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
(6) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (CH ₃ ) Cl ₂
(8) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂
(9) (CH ₃ ) ₃ SiOSO ₂ CF ₃
(10) CF ₃ CON (CH ₃ ) SiCH ₃
(11) CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(12) CF ₃ CH ₂ OSi (OCH ₃ ) ₃
(13) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(14) CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(15) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(16) CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(17) CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃
A method for producing the liquid repellent treatment layer on the partition pattern is not particularly limited, and examples include a method in which a photosensitive resist is applied on the entire surface of the barrier layer, and the openings are processed by opening only the partition pattern. It is also possible to apply a liquid repellent material to a film or glass, and paste the liquid repellent material on the film or glass onto the partition pattern of the donor substrate by facing the donor substrate with an untreated liquid repellent barrier layer. . As other methods, a liquid repellent treatment agent is applied to the entire surface including the partition pattern, and only the inside of the partition pattern is irradiated locally with a laser to decompose and remove the liquid repellent treatment agent, or UV light is irradiated through a mask. There are various methods such as a method of decomposing and removing the liquid repellent component and a method of applying only to the upper part of the partition pattern by using an inkjet method or a nozzle coating method using a solvent.

(3) Transfer material The transfer material is a material for forming a thin film constituting a device such as an organic EL element, an organic TFT, a photoelectric conversion element, and various sensors. The transfer material may be either an organic material or an inorganic material including a metal. When heated, the transfer material evaporates, sublimates, or ablates, or uses an adhesive change or a volume change to change from a donor substrate to a device substrate. Anything can be used as long as it can be transferred to the head. Further, the transfer material may be a precursor of the thin film forming material, and the transfer film may be formed by being converted into the thin film forming material by heat or light before or during the transfer.

  The thickness of the transfer material varies depending on the function and the number of transfers. For example, when transferring a donor material (electron injection material) such as lithium fluoride, a thickness of 1 nm is sufficient, and in the case of an electrode material, the thickness may be 100 nm or more. . In the case of the light emitting layer which is a suitable patterning thin film of the present invention, the thickness of the transfer material is preferably 10 to 100 nm, and more preferably 20 to 50 nm.

  The method for forming the transfer material is not particularly limited, and a dry process such as vacuum evaporation or sputtering can be used. However, as a method that can easily cope with an increase in size, at least a solution composed of the transfer material and a solvent is placed in the partition pattern. It is preferable to transfer after applying and drying the solvent. Examples of the coating method include inkjet, nozzle coating, electropolymerization and electrodeposition, offset and flexographic printing, lithographic printing, relief printing, gravure, screen printing, and other various printing methods. In particular, in the present invention, it is important to accurately form a fixed amount of transfer material in each partition pattern. From this viewpoint, inkjet can be exemplified as a particularly preferable method.

  Without the partition pattern, the RGB organic EL material layers formed from the coating liquid are in contact with each other, and the boundary is not uniform, and a mixed layer is formed in no small amount. In order to prevent this, it is difficult to make the film thickness of the boundary region the same as the center when the gap is formed so as not to contact each other. In any case, since this boundary region cannot be transferred because it causes a reduction in device performance, it is necessary to selectively transfer a region narrower than the organic EL material pattern on the donor substrate. Accordingly, the width of the organic EL material that can actually be used is narrowed, and when an organic EL display is manufactured, the pixel has a small aperture ratio (the area of the non-light-emitting region is large). In addition, because the transfer must be performed excluding the boundary area, batch transfer is not possible. Therefore, it is necessary to irradiate R, G, and B sequentially and transfer them independently, and the high accuracy of high-intensity laser irradiation. Alignment is required. From the viewpoint of solving such a problem, a method of performing batch transfer by the above method using a donor substrate having a transfer material formed from a partition pattern and a coating liquid can be exemplified as a particularly preferable embodiment of the present invention.

  When applying a solution consisting of a transfer material and a solvent to the coating method, generally adding a surfactant, dispersant, etc., adjusts the viscosity, surface tension, dispersibility, etc. of the solution to make an ink. Often to do. However, in the present invention, if these additives are present as a residue in the transfer material, there is a concern that they will be taken into the transfer film during transfer and adversely affect device performance as impurities. Therefore, it is preferable to minimize the addition or unintentional mixing of these impurities, and it is preferable to prepare the solution so that the purity of the transfer material after drying is 95% or more, and further 98% or more. Such adjustment is possible by setting the ratio of the transfer material in the components other than the solvent in the ink to 95% by weight or more.

  As the solvent, known materials such as water, alcohol, hydrocarbon, aromatic compound, heterocyclic compound, ester, ether, ketone and the like can be used. In the ink jet method suitably used in the present invention, a solvent having a relatively high boiling point of 100 ° C. or higher, more preferably 150 ° C. or higher is used, and the solubility of the organic EL material is excellent. Examples of suitable solvents include methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), γ-butyllactone (γBL), ethyl benzoate, tetrahydronaphthalene (THN), xylene, cumene and the like.

  When the transfer material satisfies all the solubility, transfer resistance, and device performance after transfer, it is preferable to dissolve the original transfer material in a solvent. When the transfer material is poor in solubility, the solubility can be improved by introducing a soluble group with respect to a solvent such as an alkyl group into the transfer material. When a soluble group is introduced into a prototype of a transfer material that excels in device performance, the performance may deteriorate. In that case, for example, the soluble material can be eliminated by heat at the time of transfer to deposit the original material on the device substrate.

  When transferring a transfer material into which a soluble group has been introduced, the transfer material has a soluble group in the solvent at the time of application to prevent the generation of gas and the incorporation of desorbed material into the transfer film. It is preferable to transfer the transfer material after converting or eliminating the soluble group by. For example, when a material having a benzene ring or an anthracene ring is taken as an example, a material having a soluble group as represented by formulas (1) to (2) can be irradiated with light to be converted into a prototype material. Moreover, as shown in formulas (3) to (6), an intramolecular cross-linking structure such as an ethylene group or a diketo group is introduced as a soluble group, and the process returns to the original material by a process of eliminating ethylene and carbon monoxide therefrom. It can also be made. The conversion or elimination of the soluble group may be in a solution state before drying or in a solid state after drying. However, in consideration of process stability, it is preferably performed in a solid state after drying. Since the original molecule of the transfer material is often nonpolar, the molecular weight of the desorbed material is small so that the desorbed material does not remain in the transfer material when the soluble group is removed in the solid state. It is preferably polar (repulsive to the nonpolar prototype molecule). In order to remove oxygen and water adsorbed in the transfer material together with the desorbed material, it is preferable that the desorbed material easily reacts with these molecules. From these viewpoints, it is particularly preferable to convert or eliminate the solubilizing group in the process of eliminating carbon monoxide. This technique can be applied to condensed polycyclic hydrocarbon compounds as well as condensed polycyclic hydrocarbon compounds such as naphthacene, pyrene, and perylene. Of course, these may be substituted or unsubstituted.

(4) Device substrate The support of the device substrate is not particularly limited, and the materials exemplified for the donor substrate can be used. In order to prevent the patterning accuracy from deteriorating due to the difference in thermal expansion due to temperature change when the transfer material is transferred with both facing each other, the difference in thermal expansion coefficient between the support of the device substrate and the donor substrate is 10 ppm / ° C. The following is preferable, and it is more preferable that these substrates are made of the same material. The glass plate exemplified as a particularly preferred support for the donor substrate can also be exemplified as a particularly preferred support for the device substrate. Both thicknesses may be the same or different.

  The device substrate may be composed of only a support during transfer, but it is general that a structure necessary for the device configuration is formed on the support in advance. For example, in the organic EL element shown in FIG. 1, the insulating layer 14 and the hole transport layer 16 can be formed by a conventional technique and used as a device substrate.

  A structure such as the insulating layer is not essential, but when the device substrate and the donor substrate are opposed to each other, the partition pattern of the donor substrate is prevented from coming into contact with the underlying layer formed on the device substrate and being damaged. Therefore, it is preferably formed in advance on the device substrate. For the formation of the insulating layer, the materials exemplified as the partition pattern of the donor substrate, the film formation method, and the patterning method can be used. With respect to the shape, thickness, width, and pitch of the insulating layer, the shape and numerical values exemplified in the partition pattern of the donor substrate can be exemplified.

(5) Transfer process The donor substrate and the device substrate are opposed to each other in a vacuum, and the transfer space can be taken out into the atmosphere while keeping the transfer space in a vacuum, and transfer can be performed. For example, the region surrounded by the partition pattern of the donor substrate and / or the insulating layer of the device substrate can be held in a vacuum. In this case, a vacuum sealing function may be provided at the periphery of the donor substrate and / or the device substrate. When a base layer of a device substrate, for example, a hole transport layer is formed by a vacuum process, a light emitting layer is patterned by the present invention, and an electron transport layer is also formed by a vacuum process, the donor substrate and the device substrate are opposed to each other in a vacuum. The transfer is preferably performed in a vacuum. In this case, for example, a method of aligning the donor substrate and the device substrate with high accuracy in a vacuum and maintaining the facing state is, for example, vacuum dropping / pasting of a liquid crystal material used in a liquid crystal display manufacturing process. A known technique such as a matching step can be used. Also, regardless of the transfer atmosphere, the donor substrate can be radiated or cooled during transfer, and when the donor substrate is reused, the donor substrate can be used as an endless belt. By using a photothermal conversion layer formed of a good conductor such as metal, the donor substrate can be easily held by an electrostatic method.

  In the present invention, since vapor deposition mode transfer is preferable, it is preferable to pattern a single transfer film in one transfer. However, by using the peeling mode and the ablation mode, for example, by forming a stacked structure of an electron transport layer / a light emitting layer on a donor substrate, and transferring it to the device substrate while maintaining the stacked state, The light-emitting layer / electron transport layer transfer film can be patterned once.

  The transfer atmosphere may be atmospheric pressure or reduced pressure. For example, in the case of reactive transfer, transfer can be performed in the presence of an active gas such as oxygen. In the present invention, since reduction of transfer damage of the transfer material is one of the problems, it is preferable to be in an inert gas such as nitrogen gas or under vacuum. By appropriately controlling the pressure, it is possible to promote uniformity of film thickness unevenness during transfer. From the viewpoint of reducing damage to the transfer material, reducing impurities mixed into the transfer film, and lowering the evaporation temperature, vacuuming is particularly preferable.

  One of the problems of the conventional method in which the thin film formed by the coating method is directly used as the functional layer of the organic EL element is the film thickness unevenness. In the present invention, even when the transfer material is formed by the coating method, the same film thickness unevenness may occur. However, in the vapor deposition mode, which is the preferred transfer method in the present invention, the transfer material is loosened to the molecular (atomic) level during transfer. Since the film is evaporated on the device substrate and deposited on the device substrate, the film thickness unevenness of the transfer film is reduced. Therefore, for example, at the time of application, the transfer material is particles made of molecular aggregates such as pigment, and even if the transfer material is not a continuous film on the donor substrate, it is evaporated and loosened to the molecular level during transfer. By doing so, a transfer film excellent in film thickness uniformity can be obtained on the device substrate.

  Next, a method for manufacturing a device using the patterning method of the present invention will be described. In the present invention, the device includes an organic EL element, an organic TFT, a photoelectric conversion element, various sensors, and the like. In the organic TFT, various electrodes such as an organic semiconductor layer, an insulating layer, a source, a drain, and a gate can be patterned according to the present invention. In an organic solar cell, an electrode and the like can be patterned. Below, the organic EL element is mentioned as an example and the manufacturing method is demonstrated.

  FIG. 1 is a cross-sectional view showing an example of a typical structure of the organic EL element 10 (display). An active matrix circuit including the TFT 12 and the planarization layer 13 is formed on the support 11. The element portion is the first electrode 15 / hole transport layer 16 / light emitting layer 17 / electron transport layer 18 / second electrode 19 formed thereon. An insulating layer 14 that prevents a short circuit from occurring at the electrode end and defines a light emitting region is formed at the end of the first electrode. The device configuration is not limited to this example, for example, only one light emitting layer having a hole transport function and an electron transport function may be formed between the first electrode and the second electrode, The hole transport layer may be a hole injection layer and a hole transport layer, and the electron transport layer may be a multilayer structure of an electron transport layer and an electron injection layer, and the light emitting layer has an electron transport function. The electron transport layer may be omitted. Moreover, you may laminate | stack in order of 1st electrode / electron transport layer / light emitting layer / hole transport layer / second electrode. In addition, these layers may be a single layer or a plurality of layers. Although not shown, after the second electrode is formed, a protective layer, a color filter, sealing, or the like may be performed using a known technique or the patterning method of the present invention.

  In a color display, at least the light emitting layer needs to be patterned, and the light emitting layer is a thin film that is preferably patterned in the present invention. The insulating layer, the first electrode, the TFT, and the like are often patterned by a known photolithography method, but may be patterned by the present invention. Moreover, when it is necessary to pattern at least one layer, such as a positive hole transport layer, an electron carrying layer, and a 2nd electrode, you may pattern by this invention. It is also possible to pattern only the R and G of the light emitting layer according to the present invention, and form the entire surface of the B light emitting layer and the R and G electron transporting layer thereon.

  As an example of manufacturing the organic EL element shown in FIG. 1, the first electrode 15 is patterned by photolithography, the insulating layer 14 is patterned by a known technique using a photosensitive polyimide precursor material, and then the hole transport layer is formed. 16 is formed on the entire surface by a known technique using a vacuum deposition method. Using this hole transport layer 16 as a base layer, the light emitting layers 17R, 17G, and 17B are patterned thereon according to the present invention shown in FIG. On top of this, if the electron transport layer 18 and the second electrode 19 are formed on the entire surface by a known technique using a vacuum deposition method or the like, the organic EL element can be completed.

  The light emitting layer may be a single layer or a plurality of layers, and the light emitting material of each layer may be a single material or a mixture of a plurality of materials. From the viewpoint of luminous efficiency, color purity, and durability, the light emitting layer preferably has a single layer structure of a mixture of a host material and a dopant material. Therefore, the transfer material for forming the light emitting layer is preferably a mixture of a host material and a dopant material.

  When the transfer material described below is used when the transfer material is arranged in the partition pattern, the transfer material can be formed by applying and drying a mixed solution of the host material and the dopant material. You may apply | coat the solution of host material and dopant material separately. Even if the host material and the dopant material are not uniformly mixed at the stage of forming the transfer material, they may be mixed uniformly at the time of transfer. Further, the concentration of the dopant material in the light emitting layer can be changed in the film thickness direction by utilizing the difference in evaporation temperature between the host material and the dopant material during transfer.

Examples of light-emitting materials include anthracene derivatives, naphthacene derivatives, pyrene derivatives, various metal complexes such as quinolinol complexes such as tris (8-quinolinolato) aluminum (Alq ₃ ) and benzothiazolylphenol zinc complexes, bisstyrylanthracene derivatives, tetraphenyl Butadiene derivatives, coumarin derivatives, oxadiazole derivatives, benzoxazole derivatives, carbazole derivatives, distyrylbenzene derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, rubrene, quinacridone derivatives, Phenoxazone derivatives, perinone derivatives, perylene derivatives, coumarin derivatives, chrysene derivatives, pyromethene derivatives, iridium complex materials called phosphorescent materials Low molecular weight material or the like, polyphenylene vinylene derivatives, polyparaphenylene derivatives, can be exemplified a polymer material such as a polythiophene derivative. In particular, examples of materials excellent in light emission performance and suitable for the patterning method of the present invention include anthracene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, pyromethene derivatives, and various phosphorescent materials.

  The hole transport layer may be a single layer or a plurality of layers, and each layer may be a single material or a mixture of a plurality of materials. A layer called a hole injection layer is also included in the hole transport layer. From the viewpoint of hole transportability (low driving voltage) and durability, an acceptor material that promotes hole transportability may be mixed in the hole transport layer. Therefore, the transfer material for forming the hole transport layer may be made of a single material or a mixture of a plurality of materials. When the transfer material is arranged in the partition pattern, it can be formed by various methods as with the light emitting layer.

  As a hole transport material, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-diphenyl-4,4′-diamine (NPD) and N, N′-biphenyl-N, N′— Biphenyl-1,1′-diphenyl-4,4′-diamine, N, N′-diphenyl-N, N ′-(N-phenylcarbazolyl) -1,1′-diphenyl-4,4′-diamine Such as aromatic amines, N-isopropylcarbazole, pyrazoline derivatives, stilbene compounds, hydrazone compounds, low molecular materials such as oxadiazole derivatives and heterocyclic compounds represented by phthalocyanine derivatives, and these low molecules Examples thereof include polymer materials such as polycarbonate having a compound in the side chain, styrene derivative, polyvinyl carbazole, and polysilane. Examples of the acceptor material include low molecular weight materials such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), hexaazatriphenylene (HAT) and its cyano group derivative (HAT-CN6). In addition, metal oxides such as molybdenum oxide and silicon oxide that are thinly formed on the surface of the first electrode can also be exemplified as hole transport materials and acceptor materials.

  The electron transport layer may be a single layer or a plurality of layers, and each layer may be a single material or a mixture of a plurality of materials. A layer called a hole blocking layer or an electron injection layer is also included in the electron transport layer. From the viewpoint of electron transport properties (low drive voltage) and durability, the electron transport layer may be mixed with a donor material that promotes electron transport properties. A layer called the electron injection layer is often discussed as this donor material. The transfer material for forming the electron transport layer may be made of a single material or a mixture of a plurality of materials. When the transfer material is arranged in the partition pattern, it can be formed by various methods as with the light emitting layer.

As the electron transporting material, condensed polycyclic aromatic derivatives such as quinolinol complexes, naphthalene, anthracene, such as Alq ₃ and 8 quinolinolato alert lithium (Liq), typified by 4,4'-bis (diphenyl) biphenyl Styryl aromatic ring derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, benzoquinolinol complexes, hydroxyazole complexes, azomethine complexes, various metal complexes such as tropolone metal complexes and flavonol metal complexes, heterocycles containing electron-accepting nitrogen Examples thereof include low molecular materials such as compounds having an aryl ring structure, and polymer materials having these low molecular compounds in the side chain.

  Examples of the donor material include alkali metals and alkaline earth metals such as lithium, cesium, magnesium, and calcium, various metal complexes such as quinolinol complexes, and oxides and fluorides such as lithium fluoride and cesium oxide. be able to. An electron transport material or a donor material is one of materials that easily change in performance due to the combination with each of the RGB light emitting layers, and is exemplified as another preferable example that is patterned by the present invention.

  It is preferable that at least one of the first electrode and the second electrode is transparent in order to extract light emitted from the light emitting layer. In the case of bottom emission in which light is extracted from the first electrode, the first electrode is transparent, and in the case of top emission in which light is extracted from the second electrode, the second electrode is transparent. When the transfer material is arranged in the partition pattern, it can be formed by various methods as with the light emitting layer. Also, at the time of transfer, reactive transfer can be performed, for example, by reacting a transfer material with oxygen. As the transparent electrode material and the other electrode, conventionally known materials can be used as described in JP-A-11-214154, for example.

  The organic EL element in the present invention is not generally limited to the active matrix type in which the second electrode is formed as a common electrode. For example, the organic EL element is formed of a stripe electrode in which the first electrode and the second electrode intersect each other. It may be a simple matrix type or a segment type in which the display unit is patterned so as to display predetermined information. Examples of these applications include televisions, personal computers, monitors, watches, thermometers, audio equipment, automobile display panels, and the like.

  The patterning method of the present invention is applicable not only to organic EL elements but also to devices such as organic TFTs, photoelectric conversion elements, and various sensors. For example, as exemplified by Japanese Patent Application Laid-Open Nos. 2003-304014, 2005-232136, and 2004-266157 as conventional techniques for organic TFTs, a semiconductor precursor material is formed on a device substrate. Although a method for forming a semiconductor layer by converting after direct application has been disclosed, it is possible to obtain the same effect as an organic EL element by forming this semiconductor layer by the patterning method of the present invention. It is.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these Examples.

Example 1
A donor substrate was prepared as follows. An alkali-free glass substrate OA-10 was used as a support, and after cleaning / UV ozone treatment, aluminum was formed as a reflective layer on the entire surface by sputtering to a thickness of 0.2 μm. Next, as a metal layer as a metal resist material for forming a partition pattern, 0.005 μm of chromium and then 0.2 μm of copper were laminated and formed by sputtering. Photoresist (PMER-300RH manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied and dried thereon, and exposed and developed so that a portion to be a partition pattern remained. The metal resist layer in the opening was etched with 1 wt% diluted sulfuric acid to which 0.5 wt% of hydrogen peroxide was added, and the photoresist was peeled off to form a metal resist having the same shape as the partition pattern. Thereafter, a portion of the reflective layer where the metal resist material does not exist and the support were etched with a 5 wt% hydrofluoric acid solution to form a step of 5 μm on the support. Thereafter, the metal resist was peeled off by dipping in an etching solution containing 0.5 wt% hydrogen peroxide and 1 wt% sulfuric acid. At this time, the aluminum of the reflective layer under the metal resist on the convex portion of the substrate was also etched, and an infinite number of spots infiltrated with the etching solution was generated, resulting in a disadvantage that light was transmitted. In this way, although there was a defect, a portion where the metal resist was present became a convex portion, and a support having a reflective layer formed on the convex portion was obtained. Thereafter, the surface was cleaned / UV ozone cleaned, and then tantalum was sputtered to a thickness of 0.4 μm as a photothermal conversion layer on the entire surface.

  A xylene solution containing 0.5 wt% of the following RD-1 with respect to the following RH-1 and having a total of 1 wt% of RH-1 and the following RD-1 is applied by an ink jet method between the convex portions of the support, 80 The solvent was removed by vacuum drying at 0 ° C. to form a 40 nm thick film.

The device substrate was produced as follows. A non-alkali glass substrate (manufactured by Geomat Co., Ltd., sputtering film-formed product) on which an ITO transparent conductive film was deposited to 140 nm was cut into 38 × 46 mm, and ITO was etched into a desired shape by a photolithography method. Next, after applying and drying polyimide resin (PW-1000: manufactured by Toray Industries, Inc.), the insulating layer is formed by curing with a hot plate under conditions of exposure, development, and 200 ° C. for 5 minutes in accordance with the convex portion of the donor substrate. Produced. The height of this insulating layer was 1.8 μm, the cross section was a forward tapered shape, and the width was 30 μm. Openings exposing ITO with a width of 70 μm and a length of 270 μm were arranged at a pitch of 100 and 300 μm inside the pattern of the insulating layer. This substrate was subjected to UV ozone treatment, installed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 3 × 10 ⁻⁴ Pa or less. By a resistance heating method, 50 nm of TPD232 (Aujek: LT-N216) and then 10 nm of NPD were stacked on the entire surface of the light emitting region by vapor deposition as a hole transport layer.

Next, the convex part of the donor substrate and the insulating layer of the device substrate were aligned and held in a vacuum of 3 × 10 ⁻⁴ Pa or less, and then taken out into the atmosphere. The transfer space defined by the insulating layer and the convex portion was kept at a reduced pressure. In this state, a CW laser with a central wavelength of 1060 nm is irradiated from the glass substrate side of the donor substrate so that a part of the transfer material and a part of the convex part are heated at the same time, and the transfer material is the underlayer of the device substrate. Transferred onto the hole transport layer. The laser intensity was about 300 W / mm ² , the scanning speed was 1.25 m / s, and repeated scanning was performed by overlapping the lasers so as to be transferred over the entire light emitting region.

The device substrate after the luminescent material transfer was placed in the vacuum vapor deposition apparatus again and evacuated until the degree of vacuum in the apparatus was 3 × 10 ⁻⁴ Pa or less. E-1 shown below as an electron transport layer was deposited on the entire surface of the light emitting region by resistance heating. Next, lithium fluoride was deposited at a thickness of 0.5 nm as a donor material (electron injection layer), and aluminum was deposited at a thickness of 100 nm as a second electrode to produce an organic EL device having a 5 mm square light emitting region. When a constant current of ^2.5 mA / cm ² was passed through this element and the luminance was measured with a spectrophotometer CS-1000 (manufactured by Minolta), it showed an initial luminance of 5.0 cd / A, and the current continued to flow under the same conditions. The luminance half time after that was 100 hours. Note that the luminance half-life is significantly lower than those in Examples 2 to 4 and the like. This seems to be because the laser light leaks at the defective part of the metal resist during transfer, the part of the partition pattern in contact with the device is heated, the resin on the device side is damaged, and impurities are mixed in the light emitting layer. .

Examples 2-4
The material of the reflective layer is an aluminum alloy containing 15 atomic% silver and 85 atomic% aluminum, and the film thickness is 0.2 μm (Example 2), 0.4 μm (Example 3) as shown in Table 1. A substrate was prepared in the same manner as in Example 1 except that the values were changed to 0 μm (Example 4). When a constant current of 2.5 mA / cm ² was passed through the device, the initial luminance was 6.0, 6.1, and 6.3 cd / A, respectively, and the luminance half-lives were 1500 hours, 1500 hours, and 2000 hours, respectively. there were. When the reflective layer is thick, it is considered that it has a heat insulating effect due to the heat capacity of the reflective layer itself. For this reason, heat transfer to the device substrate was reduced, and the uneven light emission state also showed good results.

  The element ratio of the metal layer of the reflective layer was measured using a fluorescent X-ray analyzer SEA-2120 manufactured by Seiko Instruments Inc. Example 2 will be described as an example. First, a 0.2 μm film was made of 100% silver, the surface of the film was measured with a fluorescent X-ray analyzer, and the detected silver peak was taken as 100%. Next, the silver peak detected on the surface of the alloy film with a fluorescent X-ray analyzer was compared with the peak of the pure silver film, and the ratio was defined as the concentration of silver atoms in the film [atomic%]. In Examples 3 and 4, the same measurement was performed by changing the thickness of the pure silver film to 0.4 μm and 1.0 μm, respectively.

  In the following examples, the same evaluation was performed by substituting another metal instead of silver, and the concentration of the metal in the alloy film was calculated.

Examples 5-7
The reflective layer is made of an aluminum alloy containing silver, and the silver concentration is changed to 5 atomic% (Example 5), 25 atomic% (Example 6), and 35 atomic% (Example 7). A substrate was prepared in the same manner as in 1. In the case of containing 35 atomic% of silver when treated with an etching solution of hydrofluoric acid, the etching did not progress uniformly in the reflective layer, and part of the film residue was generated around the metal resist. Since the etching of the support did not proceed in the portion where the film residue occurred, a step could be formed, but the width was narrower than the design value. When a constant current of 2.5 mA / cm ² was passed through these elements, the initial luminance was 6.2, 6.0, 6.0 cd / A, respectively, and the luminance half-time was 2000 hours, 1500 hours, 1000 hours, respectively. Met. There was little heat transfer to the device substrate, and the uneven light emission showed good results.

Examples 8-11
The reflective layer is made of an aluminum alloy containing copper, and the concentration of copper is 5 atomic% (Example 8), 15 atomic% (Example 9), 25 atomic% (Example 10), and 35 atomic% (Example 11). A substrate was prepared in the same manner as in Example 1 except that each change was made. In the case of containing 35 atomic% of copper when treated with an etching solution of hydrofluoric acid, etching did not progress uniformly in the reflective layer, and some film residue was generated. Since the etching of the support did not proceed in the portion where the film residue occurred, a step could be formed, but the width was narrower than the design value. When a constant current of 2.5 mA / cm ² was passed through these elements, the initial luminances were 6.2, 6.2, 6.0, 6.0 cd / A, respectively, and the luminance half-time was 2000 hours and 2000 hours, respectively. The time was 1500 hours and 1000 hours. There was little heat transfer to the device substrate, and the uneven light emission showed good results.

Examples 12-15
The reflective layer is made of an aluminum alloy containing molybdenum, and the concentration is changed to 5 atomic% (Example 12), 15 atomic% (Example 13), 25 atomic% (Example 14), and 35 atomic% (Example 15), respectively. A substrate was prepared in the same manner as in Example 1 except that. When 35 atomic% of molybdenum is contained when treated with an etching solution of hydrofluoric acid, the etching does not proceed uniformly in the reflective layer, and a part of the film remains, and only a step having a width narrower than the design value is formed as in the seventh embodiment. could not. When a constant current of 2.5 mA / cm ² was passed through these elements, initial luminances of 6.0, 5.7, 5.5, 5.5 cd / A were exhibited, respectively, and the luminance half-times were 1000 hours and 500 hours, respectively. Hours, 200 hours, 200 hours. The luminance of Examples 13 to 15 was lower than that of Example 12 and the luminance half time was also shorter than that of Example 12 because of the low heat transfer to the device substrate due to the low reflectance of the reflective layer. The state of uneven luminescence showed good results.

Examples 16-21
The material of the reflective layer is an aluminum alloy containing 15 atomic% of metal other than aluminum, and the metal species is tantalum (Example 16), tungsten (Example 17), gold (Example 18), platinum (Example 19), A substrate was prepared in the same manner as in Example 1 except that nickel (Example 20) and magnesium (Example 21) were used. In Example 21 containing magnesium, the etching solution penetrated when the metal resist material was removed by etching, and the same defects as in Example 1 occurred. When a constant current of ^2.5 mA / cm ² was passed through these elements, the initial luminance of 5.8, 5.8, 6.0, 6.0, 5.9 cd / A was obtained for the elements of Examples 16 to 20. The luminance half-lives were 300 hours, 300 hours, 1500 hours, 1000 hours, and 500 hours, respectively. There was little heat transfer to the device substrate, and the uneven light emission showed good results. On the other hand, the element of Example 21 seems to have the same reason as that of the element of Example 1, but the luminance decreased a little to 5.5 cd / A, and the luminance half time also decreased to 200 hours.

Examples 22-25
After forming the reflective layer over the entire surface, SiO ₂ is formed over the entire surface as a heat insulating layer, and the film thickness is 0.05 μm (Example 22), 0.2 μm (Example 23), 0.4 μm (Example 24), 1 The substrate was formed in the same manner as in Example 1 except that the thickness was set to 0.0 μm (Example 25), and the heat-insulating layer was etched at the same time as the reflective layer and the support in the portion where no metal resist material was present. When a constant current of ^2.5 mA / cm ² was passed through these elements, Example 22 showed an initial luminance of 6.2 cd / A, and Examples 23 to 25 showed an initial luminance of 6.4 cd / A. In Example 22, it was 2000 hours, and in Examples 23 to 25, it was 3000 hours. This is probably because the thicker the heat insulating layer, the more difficult the heat is transmitted to the device side, which prevents the contamination of impurities from the device substrate. All the devices showed good results in the state of uneven light emission.

Example 26
A substrate was prepared in the same manner as in Example 24 except that the reflective layer was an aluminum alloy containing 15 atomic% of molybdenum. When a constant current of 2.5 mA / cm ² was passed through this device, an initial luminance of 6.2 cd / A was exhibited, and the luminance half time was 2000 hours. Heat was not transmitted to the device substrate, and the light emission unevenness also showed good results. Although the reflectance is lower than that of Example 13, it can be seen that by increasing the thickness of the heat-insulating layer, heat propagation can be suppressed and good element performance is exhibited.

Example 27
After peeling off the metal resist material in Example 2, a step of forming MgF ₂ with a film thickness of 0.194 μm on the entire surface to form a heat insulating layer on the convex portion and an antireflection layer between the convex portion and the convex portion, Thereafter, a substrate was prepared in the same manner as in Example 2 except that a photothermal conversion layer was formed. As a result, the reflection of light rays is suppressed in the partition pattern surrounded by the convex portions, and the reflectance of the photothermal conversion layer is reduced by the antireflection layer, and the incident light is absorbed well. It could be reduced to cm ² . When a constant current of 2.5 mA / cm ² was passed through the device, the initial luminance was 6.4 cd / A, and the luminance half time was 6000 hours. Heat was not transmitted to the device substrate, and the light emission unevenness also showed good results. This is a much better result than Example 2 having the same reflective layer composition, and it is considered that the heat conduction is suppressed by the formation of the heat insulating layer. Further, the durability is improved compared to Example 23 in which a heat insulating layer is added to Example 2, and it is considered that heat transfer is further suppressed by reducing the laser intensity of transfer.

Example 28
In Example 2, an element was prepared in the same manner except that an alloy of 40 atomic% silver and 60 atomic% aluminum was formed to a thickness of 2 nm as a roughening film, and a reflective layer was formed thereon. As a result, the etched surface could be roughened simultaneously with the formation of the step. The roughness of the roughening treatment part was Rz: 0.3 μm defined by JIS B0601: 2001, and the uniformity of film thickness unevenness after coating was good. For this reason, the film thickness uniformity after transfer was also improved.

Comparative Example 1
In this comparative example, a substrate without a step is used, and a reflective layer is used as a partition pattern. An alkali-free glass substrate OA-10 was used as a support, and after cleaning / UV ozone treatment, aluminum was formed as a reflective layer on the entire surface by sputtering to a thickness of 0.2 μm. A photoresist (PMER-300RH manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied and dried thereon, and exposed and developed so that a portion to be a partition pattern remained. The aluminum layer in the opening was etched with a ferric chloride solution, and the photoresist was peeled off to form a reflective layer having the same shape as the partition pattern. Thereafter, the surface was cleaned / UV ozone cleaned, and then tantalum was sputtered to a thickness of 0.4 μm as a photothermal conversion layer on the entire surface.

When the xylene solution used in Example 1 was applied between the reflective layers of the support by the inkjet method, the ink liquid overflowed into the adjacent partition pattern when the liquid was applied by the inkjet method, and the light emitting layer in the partition pattern The film thickness was uneven. In addition, it was observed that the insulating layer of the device substrate was melted at the portion in contact with the partition pattern of the donor substrate even in the process of transferring by laser. Due to these influences, the initial luminance of the device characteristics was only 3.0 cd / m ² and the durability was 5 hours or less.

Comparative Example 2
Example 1 except that the metal resist layer is laminated on the support without forming the reflective layer in Example 1, the subsequent steps are performed to form irregularities on the support, and tantalum of the photothermal conversion layer is formed on the entire surface. A substrate was produced in the same manner as described above. When a constant current of 2.5 mA / cm ² was passed through this element, an initial luminance of 2.0 cd / A was shown. Moreover, the upper part of the insulating layer of the device substrate was heated and thermally deformed. From this, heat is transmitted to the device substrate side, and it is considered that the hole transport layer on the insulating layer and the decomposed material of the insulating material are scattered in the partition pattern and the performance is deteriorated.

10 Organic EL elements (device substrates)
11 Support 12 TFT (including extraction electrode)
13 Planarization layer 14 Insulating layer 15 First electrode 16 Hole transport layer 17 Light emitting layer 18 Electron transport layer 19 Second electrode 20 Device substrate 30 Donor substrate 31 Support body 32 Support convex part 33 Photothermal conversion layer 34 Reflection layer 35 Heat insulation Layer 35 ′ Antireflection layer 36 Liquid repellent treatment layer 37 Transfer material 38 Resist layer 39 Partition pattern 40 Partition pattern inside 41 Roughening treatment film

Claims (10)

For transfer, comprising a support having a convex part and a photothermal conversion layer formed on the support, and a reflective layer provided between the photothermal conversion layer on the convex part of the support Donor substrate. The donor substrate for transfer according to claim 1, wherein the reflective layer is a metal layer, and the metal contains 70 atomic% or more of aluminum. The transfer donor substrate according to claim 2, wherein the metal includes one or more of copper, silver, gold, platinum, nickel, magnesium, molybdenum, tantalum, and tungsten. The donor substrate for transfer according to any one of claims 1 to 3, wherein a value of "reflectance in reflection layer" / "reflectivity in photothermal conversion layer" is 1.5 or more. The donor substrate for transfer according to any one of claims 1 to 4, wherein a heat insulating layer is provided between the reflective layer and the photothermal conversion layer. A total of 30 atomic% or more of metals insoluble or hardly soluble in the etching solution for etching the support and / or any layer on the support, between any of the layers formed on the support, The donor substrate for transfer described in any one of Claims 1-5 in which the layer whose film thickness is 5 nm or less is formed. For transfer, comprising a support having a convex part and a photothermal conversion layer formed on the support, and a reflective layer provided between the photothermal conversion layer on the convex part of the support A method for producing a donor substrate, wherein a convex portion of a support and a reflective layer thereon are formed by forming a reflective layer on the support, and then pattern-etching the support and the reflective layer using the same resist film. A process for producing a donor substrate for transfer, wherein A support having a convex part and a light-to-heat conversion layer formed on the support, wherein a reflective layer is provided between the light-to-heat conversion layer on the convex part of the support, and the reflective layer And a heat insulating layer provided between the photothermal conversion layer and a transfer donor substrate, wherein the convex portion of the support and the reflective layer thereon and the heat insulating layer are formed on the support. A method for producing a donor substrate for transfer, comprising forming a layer and then pattern-etching the support, the reflective layer, and the heat insulating layer using the same resist film. Between the support and the resist film, a total of 30 atomic% or more of insoluble or hardly soluble metal is contained in the etching solution for etching the support and / or any layer on the support, and the film thickness is 5 nm or less. The method for producing a donor substrate for transfer according to claim 7 or 8, wherein a layer is further formed, and convex portions of the support are formed by etching, and a roughening treatment is performed between the convex portions of the support. A step of making the donor substrate for transfer described in any one of claims 1 to 6 or the donor substrate for transfer manufactured by the method described in any one of claims 7 to 9 face a device substrate, and the photothermal conversion A device manufacturing method comprising a step of transferring a transfer layer formed between convex portions of the transfer substrate to the device substrate by irradiating the layer with light.

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