JP2006144002A - Composite material and light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material from which a light emitting element being excellent in the heat resistance can be produced, to provide a composite material from which a light emitting element having such high durability that the element can be stably driven for a long period can be produced, to provide a composite material from which a light emitting element having both of the above-noted two properties can be produced, and to provide a composite material from which a light emitting element having both of the above-noted two properties and needing a consumed power which increases little during the use of the element can be produced. <P>SOLUTION: This composite material comprises an organic-inorganic hybrid material in which an organic group is bonded through a covalent bond to a silicon atom in a skeleton which is formed through siloxane linkages, and a substance which can perform the electron donating-accepting with the above-noted organic group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a material used for a light-emitting element. In addition, the present invention relates to an element (light emitting element) that emits light by sandwiching a light emitting material containing an organic substance between electrodes and passing an electric current between the electrodes, and particularly relates to a light emitting element that has excellent heat resistance and little deterioration in luminance due to accumulation of light emission time.

  In recent years, development of light-emitting devices and displays using light-emitting elements made of organic materials has been actively conducted. A light-emitting element is manufactured by sandwiching an organic compound between a pair of electrodes. Unlike a liquid crystal display device, the light-emitting element itself emits light, so a light source such as a backlight is not required, and the element itself is very thin, so a thin and light display This is very advantageous for manufacturing.

  The light emission mechanism of a light emitting device is that when electrons injected from the cathode and holes injected from the anode recombine at the emission center in the organic compound to form molecular excitons, and the molecular excitons return to the ground state. It is said that it emits energy by emitting light. Singlet excitation and triplet excitation are known as excited states, and light emission is considered to be possible through either excited state.

The organic compound layer sandwiched between the electrodes often has a laminated structure, and this laminated structure is typically a function-separated laminated structure of “hole transport layer / light emitting layer / electron transport layer”. is there. Efficiency is achieved by placing a layer made of a material with a high hole-transport property on the electrode side that functions as an anode and a layer made of a material with a high electron-transport property on the cathode side across a light-emitting layer where holes and electrons recombine Holes and electrons can be transported well, and the probability of recombination of holes and electrons can be increased. Since such a structure has very high luminous efficiency, almost all such light emitting display devices currently being researched and developed employ such a structure (see, for example, Non-Patent Document 1).
Chihaya Adachi, 3 others, Japanese Journal of Applied Physics, Vol. 27, no. 2, 1988, pp. L269-L271

As other structures, the hole injection layer, hole transport layer, light emitting layer, electron transport layer, or hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron from the electrode side functioning as the anode There is a structure in which injection layers are stacked in order, and each layer is made of a material specialized for each function. Note that a layer having two or more of these functions, such as a layer having both functions of the light emitting layer and the electron transport layer, may be used.

  The layer containing an organic compound has a typical laminated structure as described above, but may be a single layer structure or a mixed layer, and the light emitting layer may be doped with a fluorescent dye or the like. May be.

  By the way, such a light emitting element has a problem in durability and heat resistance. Since such a light emitting element is formed by laminating organic thin films using an organic compound as described above, the thinness of the organic compound thin film is considered to be the cause.

  On the other hand, an example in which a light-emitting element is manufactured by applying a layer in which an organic compound (a hole-transporting compound, an electron-transporting compound, or a light-emitting compound) is dispersed in a skeleton composed of siloxane bonds instead of an organic thin film Yes (see, for example, Patent Document 1 and Non-Patent Document 2). In Patent Document 1, it is also reported that the durability and heat resistance of the element are improved.

  Since the light emitting element generates heat during driving or may be used in a harsh environment such as a car in midsummer, the heat resistance of the material used for the light emitting element is an important factor.

  However, since the light-emitting elements disclosed in Patent Document 1 and Non-Patent Document 2 have organic compounds dispersed in a skeleton formed by insulating siloxane bonds, the current is smaller than that of conventional light-emitting elements. Becomes difficult to flow.

  Since these light-emitting elements have higher emission luminance in proportion to the current that flows, the fact that current does not flow easily increases the voltage (drive voltage) for obtaining a predetermined luminance. As a result of an increase in driving voltage, there is a problem that power consumption of a light emitting device manufactured using a light emitting element increases.

Further, in order to suppress a short circuit of the light emitting element due to dust or the like, it is effective to increase the film thickness of the light emitting element, but the configuration as shown in Patent Document 1 or Non-Patent Document 2 is effective. When the film thickness of the light emitting element is increased, the increase in driving voltage becomes more obvious.
JP 2000-306669 A Tony Dantas de Moreis, 3 others, Advanced Materials, Vol. 11, NO. 2, 107-112 (1999)

  Therefore, an object of the present invention is to provide a composite material capable of manufacturing a light-emitting element having excellent heat resistance. It is another object of the present invention to provide a composite material that can manufacture a highly durable light-emitting element that can be stably driven for a long time. It is another object of the present invention to provide a composite material capable of manufacturing a light-emitting element satisfying both of them. It is another object to provide a composite material that can manufacture a light-emitting element with little increase in power consumption while satisfying the above problems.

  It is another object of the present invention to provide a composite material that can easily prevent a short circuit between electrodes in a light-emitting element and can manufacture a light-emitting element with low power consumption.

  Another object of the present invention is to provide a light-emitting element with excellent heat resistance. It is another object of the present invention to provide a highly durable light-emitting element that can be stably driven for a long time. It is another object of the present invention to provide a light emitting element that satisfies both of them. It is another object of the present invention to provide a light-emitting element that satisfies the above-described problems and has little increase in power consumption.

  Another object is to provide a light-emitting element that can easily prevent a short circuit between electrodes in the light-emitting element and has low power consumption.

  The composite material of the present invention capable of solving the above problems is an organic-inorganic hybrid material in which an organic group is bonded to silicon in a skeleton bonded by a siloxane bond through a covalent bond, and exchange of electrons with the organic group. It is characterized by having a substance which can perform.

  The organic-inorganic hybrid material refers to a material formed by bonding an inorganic material and an organic material. In the present invention, an organic group is bonded to a part of silicon in a skeleton bonded mainly by a siloxane bond. This material is called an organic-inorganic hybrid material.

  The light-emitting element of the present invention that can solve the above problems includes a pair of electrodes and a skeleton that has a light-emitting layer that emits light by passing a current between the pair of electrodes, and is bonded to the pair of electrodes by a siloxane bond. An organic-inorganic hybrid material in which an organic group is bonded to the silicon therein via a covalent bond, and at least one layer made of a composite material having a substance that can exchange electrons with the organic group. Features.

  A light-emitting element using the composite material of the present invention having the above structure is a light-emitting element having excellent heat resistance. A light-emitting element using the composite material of the present invention having the above structure is a light-emitting element that can be driven stably for a long time. Further, a light-emitting element using the composite material of the present invention having the above structure is a light-emitting element that has excellent heat resistance and can be driven stably for a long time. In addition to the above effects, a light-emitting element using the composite material of the present invention becomes a light-emitting element with little increase in power consumption.

  The light-emitting element of the present invention having the above structure can be a light-emitting element with excellent heat resistance. The light-emitting element of the present invention having the above structure can be a light-emitting element that can be stably driven for a long time. The light-emitting element of the present invention having the above structure can be a light-emitting element that has excellent heat resistance and can be driven stably for a long time. In addition to the above effects, the light-emitting element having the structure of the present invention can be a light-emitting element with little increase in power consumption.

  In addition, a light-emitting element that can easily prevent a short circuit and consumes low power can be provided.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different modes, and those skilled in the art can easily understand that the modes and details can be variously changed without departing from the spirit and scope of the present invention. Is done. Therefore, the present invention is not construed as being limited to the description of this embodiment mode.

  Note that, in the present invention, when a voltage is applied so as to increase the potential of the pair of electrodes of the light-emitting element, the electrode that can emit light is called an electrode that functions as an anode, and the voltage is set so that the potential is decreased. When applied, the electrode that emits light is said to function as a cathode.

  Further, unless otherwise specified in the present invention, the hole injecting and transporting layer and the hole transporting layer are formed of a substance having a hole transporting property higher than the electron transporting property and are closer to the electrode side functioning as an anode than the light emitting layer. The electron injection transport layer and the electron transport layer are formed of a substance whose electron transportability is higher than the hole transportability, and is closer to the electrode side functioning as a cathode than the light emitting layer. Says the layer that is located. A layer having both of these functions may also be used. In some cases, the light emitting layer also functions as one of the functions.

(Embodiment 1)
The composite material of the present invention has an organic-inorganic hybrid material 103 in which an organic group 102 is bonded to silicon in a skeleton 101 bonded by a siloxane bond 100 through a covalent bond as shown in a schematic diagram in FIG. On the other hand, a substance 104 that can exchange electrons with the organic group is further added. Then, as shown in the schematic diagram of FIG. 2, electrons or holes are generated by exchanging electrons, and the electron or hole injection property and conductivity of the composite material are improved. In FIG. 2, by adding molybdenum oxide (MoOx) to a silica matrix having a triphenylamino group, the molybdenum oxide accepts unpaired electrons of the triphenylamino group and generates holes in the triphenylamino group. It is the schematic diagram which showed the mode.

  Since the composite material of the present invention has a skeleton composed of siloxane bonds, it is a material excellent in heat resistance and durability. In addition, since an organic group is covalently bonded to silicon in the skeleton, a material having a skeleton formed by a siloxane bond can have the hole or electron injection or transport property of the organic group. . In addition, the addition of a material that can exchange electrons with an organic group in the organic-inorganic hybrid material improves the injection or transport properties of holes or electrons, and further improves the conductivity. Can do.

First, a composite material that can be used for the hole injection layer or the hole transport layer will be described.

  The organic group that is covalently bonded to silicon in a skeleton formed by a siloxane bond and has a hole injection property and / or a hole transport property in the skeleton desirably has an arylamine skeleton or a pyrrole skeleton. The organic-inorganic hybrid material in the composite material of the present invention can be obtained by polycondensing an alkoxysilane in which an organic group having the above-described skeleton is covalently bonded to silicon. Alternatively, it can also be obtained by polycondensation using both an alkoxysilane having an organic group having the above-described skeleton and a tetraalkoxysilane. Examples of the alkoxysilane having such an organic group include the following. The following structural formulas (1) to (3) as an alkoxysilane having an arylamine skeleton have the following structural formulas (4) to (6) as an alkoxysilane having a pyrrole skeleton, both having an arylamine skeleton and a pyrrole skeleton. As an alkoxysilane having such an organic group, the following structural formula (7) may be mentioned. In addition, only one kind of alkoxysilane having these organic groups may be used, or a plurality of kinds may be used. When an alkoxysilane having a plurality of types of organic groups is used, a composite material in which a plurality of types of organic groups are covalently bonded to silicon in the skeleton formed by siloxane bonds can be obtained.

  In addition, as a substance capable of accepting electrons from the organic group and improving the hole injection property and / or hole transport property of the composite material, an oxide or a hydroxide of a transition metal having electron acceptability Is mentioned. One or more of these are used. Specific examples include, but are not limited to, titanium, vanadium, molybdenum, tungsten, rhenium, ruthenium, niobium oxides or hydroxides.

  The organic-inorganic hybrid material in which the organic group in the alkoxysilane as shown in the above (1) to (7) is covalently bonded to silicon in the skeleton formed by the siloxane bond accepts electrons from the organic group. By adding one or more of the above substances that can be used, a composite material that can be used as a hole injection layer or a hole transport layer can be manufactured. Unlike the conventional organic-inorganic hybrid material, the composite material of the present invention has high hole injecting and transporting properties and high conductivity because hole carriers are generated.

  Subsequently, a composite material that can be used for the electron injection layer or the electron transport layer will be described.

  Organic groups that are covalently bonded to silicon in a skeleton composed of siloxane bonds and have electron injection property and / or electron transport property in the skeleton composed of siloxane bonds include pyridine skeleton, phenanthroline skeleton, quinoline skeleton, pyrazine It preferably has a skeleton, a triazine skeleton, an imidazole skeleton, a triazole skeleton, an oxadiazole skeleton, a thiadiazole skeleton, an oxazole skeleton, or a thiazole skeleton. The organic-inorganic hybrid material in the composite material of the present invention can be obtained by polycondensing an alkoxysilane in which an organic group having the above-described skeleton is covalently bonded to silicon. Alternatively, it can also be obtained by polycondensation using both an alkoxysilane having an organic group having the above-described skeleton and a tetraalkoxysilane. Examples of the alkoxysilane having such an organic group include the following. As the alkoxysilane having an organic group having a pyridine skeleton, the following structural formulas (8) to (14) (particularly, the following structural formulas (10) to (13) are phenanthroline skeletons and the following (14) is a quinoline skeleton) The following structural formula (15) is an alkoxysilane having an organic group having a pyrazine skeleton, and the following structural formula (16) is an alkoxysilane having an organic group having an imidazole skeleton as an alkoxysilane having an organic group having a triazole skeleton. The following structural formula (17) is the following structural formula (18) as an alkoxysilane having an organic group having an oxadiazole skeleton, and the following structural formula (19) is an oxazole as an alkoxysilane having an organic group having a thiadiazole skeleton. As an alkoxysilane having an organic group having a skeleton, the following structure is used. Equation (20), the following structural formula (21) can be mentioned as alkoxysilane having an organic group having a thiazole skeleton. In addition, only one kind of alkoxysilane having these organic groups may be used, or a plurality of kinds may be used. When an alkoxysilane having a plurality of types of organic groups is used, a composite material in which a plurality of types of organic groups are covalently bonded to silicon in the skeleton formed by siloxane bonds can be obtained.

  In addition, as a substance that can donate electrons to the organic group and improve the electron injecting property and / or the electron transporting property of the composite material, a substance exhibiting an electron donating property is desirable, and an alkali metal or alkaline earth metal is preferable. An oxide or a hydroxide is mentioned. One or more of these are used. Specific examples include lithium, barium oxides and hydroxides, but are not limited thereto.

  Electrons can be donated to organic-inorganic hybrid materials in which organic groups such as those shown in (8) to (21) above are covalently bonded to silicon in the skeleton formed by siloxane bonds. By adding one or more of the above substances, a composite material that can be used as an electron injection layer or an electron transport layer can be manufactured. Unlike the conventional organic-inorganic hybrid material, the composite material of the present invention has high electron injecting and transporting properties and high conductivity because electron carriers are generated.

  Note that this embodiment can be combined with any of the other embodiments as long as there is no contradiction.

(Embodiment 2)
In this embodiment mode, a method for manufacturing the composite material shown in Embodiment Mode 1 using a sol-gel method based on an alkoxide method will be described.

  First, an organic material capable of imparting hole injection or transport property or electron injection or transport property to the skeleton composed of tetraethoxysilane and / or methyltriethoxysilane and the siloxane bond shown in Embodiment Mode 1. An alkoxysilane having a group covalently bonded to silicon in the skeleton is dissolved in an acidic or alkaline solvent (for example, lower alcohol) to prepare a solution 1. By making it acidic or alkaline, tetraethoxysilane and / or methyltriethoxysilane and alkoxysilane having an organic group are polycondensed to form a sol. When the state after polycondensation is acidic, it is fibrous, and when it is alkaline, it is agglomerated. Therefore, the liquid property of the solution 1 is desirably acidic. The pH of the solution 1 is more preferably about pH 1 to pH 3.

  The solution 1 may be further subjected to a polycondensation reaction by performing either heating stirring or aging, or both. Heating and stirring may be performed at several tens of degrees for several hours, and in the case of aging, it may be performed at room temperature for about tens to 24 hours.

  Solution 1 does not use tetraethoxysilane and / or methyltriethoxysilane, and may be prepared only by alkoxysilane having an organic group, but preferably has tetraethoxysilane and / or methyltriethoxysilane and an organic group. Desirably, the molar ratio of alkoxysilane is between 10: 1 and 1:10. More preferably, the molar ratio of tetraethoxysilane and / or methyltriethoxysilane to alkoxysilane having an organic group is 5: 1 to 1: 5.

  Next, a sol of a metal metal alkoxide-organic solvent solution in a metal oxide that can exchange electrons with the organic group is prepared (solution 2). In addition, water or β-diketone as a stabilizer may be added to the solution 2. As the stabilizer, β-diketones represented by acetylacetone, ethyl acetoacetate and benzoylacetone can be used.

Examples of the organic solvent include lower alcohols, tetrahydrofuran, acetonitrile, chloroform, dichloroethane, chlorobenzene, acetone and the like, and these are used alone or in combination. As lower alcohols, methanol, ethanol, n-propanol, n-butanol, sec-butanol, tert-butanol and the like can be used.

Examples of the metal alkoxide include ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, tert-butoxide and the like. These alkoxides are preferably liquid or easily dissolved in an organic solvent.

  Finally, the solution 2 is added to the solution 1, stirred, applied, and baked (at 100 ° C. to 300 ° C. for several hours), whereby an organic group in which an organic group is covalently bonded to silicon in a skeleton composed of siloxane bonds A composite material in which a substance capable of exchanging electrons with an organic group is added to an inorganic hybrid material can be manufactured. Baking may be performed in the air, in an inert atmosphere such as nitrogen, or in a vacuum. At this time, the ratio of the number of moles of organic groups capable of imparting hole injection or transportability or electron injection or transportability to the skeleton composed of siloxane bonds and the number of moles of metal alkoxide in the solution 2 is 5 The ratio is preferably from 1: 1 to 1: 5, more preferably from 2: 1 to 1: 2.

  For the coating, a wet coating method, for example, a droplet coating method such as a dip coating method, a spin coating method, or an ink jet method can be used.

  By using the composite material of the present invention as a functional layer of a light emitting element, a light emitting element having excellent heat resistance can be obtained. Further, a light-emitting element that can be driven stably for a long time can be obtained.

  The solution 2 may be a metal alkoxide-organic solvent solution alone, but a weak chelating agent such as β-diketone is used as a stabilizer so that precipitation does not occur when mixed with the solution 1. It is desirable to add as. As the stabilizer, β-diketones represented by acetylacetone, ethyl acetoacetate and benzoylacetone can be used.

Water is added to hydrolyze and polycondense the metal alkoxide, but the hydrolysis of the metal alkoxide is not necessarily essential. In addition, it is desirable to add a weak chelating agent such as β-diketone as a stabilizer if precipitation occurs when water is added. Furthermore, it is desirable that the stabilizer is a material that can be removed from the metal by firing. As the stabilizer, β-diketones represented by acetylacetone, ethyl acetoacetate and benzoylacetone can be used.

  The amount of the stabilizer relative to the metal alkoxide is 2 equivalents or less and 0.1 equivalents or more, preferably 1 equivalent or less and 0.5 equivalents or more.

  In the composite material of the present invention manufactured by such a method, an organic group is bonded to a skeleton formed by a siloxane bond, and a metal oxide or / and a metal hydroxide are dispersed in the skeleton. It becomes a structure. In addition, a structure in which the metal oxide is incorporated in a skeleton partially formed of a siloxane bond (that is, a structure having a metal-oxygen-silicon bond) is obtained.

In addition, the composite material has improved conductivity, carrier injection, and transportability by adding a substance capable of transferring electrons to and from an organic group covalently bonded to silicon in a siloxane bond. . Thus, by using this composite material as a functional layer of the light-emitting element, a light-emitting element that has excellent heat resistance and can be driven stably for a long time without significantly increasing power consumption can be obtained.

  Note that since the composite material of the present invention is superior in conductivity compared to conventional organic-inorganic hybrid materials, a light-emitting element in which the composite material is formed as a functional layer is driven even if the functional layer is formed thick. Little increase in voltage. Therefore, among the pair of electrodes of the light-emitting element, the functional layer between the first electrode and the light-emitting layer can be formed thick, and the light-emitting element is short-circuited due to dust or the like. Can be reduced. If the film thickness is 100 nm or more, such defects can be effectively reduced.

The functional layer to be thickened contains a substance that can exchange electrons with an organic group covalently bonded to silicon in a siloxane bond, thus improving conductivity, carrier injection, and transportability, and driving It is possible to reduce the occurrence of a short circuit of the light emitting element due to dust or the like without significantly increasing the voltage, that is, without significantly increasing the power consumption.

  Subsequently, an example in which a composite material that can be used specifically as a hole injecting and transporting layer of a light-emitting element will be described. In this embodiment mode, the triphenylamino group as an organic group covalently bonded to silicon in a siloxane bond and molybdenum oxide as an example of the substance that can exchange electrons with the triphenylamino group covalently bonded to silicon are used as examples of the present invention. A composite material is produced.

  Note that the basic principle is the same when other organic groups are used or when other metal oxides are used as substances capable of transferring electrons to and from the organic groups. The material may be selected from the combinations shown in Embodiment Mode 1 depending on the type of the functional layer manufactured using the composite material.

  First, a method for synthesizing an alkoxysilane (N- (4-triethoxysilylphenyl) -N, N-diphenylamine) with a triphenylamino group used as a material will be described. The reaction scheme is shown in Formula (22).

  By treating triphenylamine with NBS (N-bromosuccinimide) or reacting with bromine, N- (4-bromophenyl) -N, N-diphenylamine is obtained (A). The obtained N- (4-bromophenyl) -N, N-diphenylamine is reacted with butyllithium or magnesium to be metalized (B). N- (4-triethoxysilylphenyl) -N, N-diphenylamine is obtained by reaction of the resulting metallized product with chlorotriethoxysilane (C). The same method can be used when other organic groups are used in place of triphenylamine as the organic group capable of imparting hole injection, transportability, electron injection or transportability to the skeleton composed of siloxane bonds, or others. It may be synthesized by a known method.

Next, a method for producing a composite material film of the present invention using the obtained N- (4-triethoxysilylphenyl) -N, N-diphenylamine will be described. In addition, the preparation scheme is shown in Formulas (23) to (25).

  An alkoxysilane having a triphenylamino group (N- (4-triethoxysilylphenyl) -N, N-diphenylamine: compound A) and tetraethoxysilane (compound B) in an ethanol-hydrochloric acid solution at a molar ratio of 1: 1. Dissolve to make Solution 1. The amount of hydrochloric acid is adjusted so that the pH of the solution 1 is 2, and alkoxysilane (compound A) having an organic group and tetraethoxysilane (compound B) are polycondensed. The polycondensation may be further advanced by heating or aging. The degree of polymerization is set to such an extent that no precipitate is deposited (formula (23)).

  A sol solution, solution 2, is prepared by adding ethyl acetoacetate (compound D) as a stabilizer and water to an alcohol solution of pentaalkoxymolybdenum (for example, pentaethoxymolybdenum) (compound C). As the stabilizer, 1 equivalent of molybdenum alkoxide (compound C) is added (formula (24)). By adding a stabilizer, polymerization of molybdenum alkoxide can be suppressed, and the polymer can be prevented from being precipitated and deposited.

  Finally, the solution 1 is added to the solution 2, and after stirring, the solution is applied to the film formation surface by a spin coating method and baked at 150 ° C. for 2 hours to form a film of the composite material of the present invention (formula (25) ).

  By using the composite material of the present invention thus produced as a hole injection layer and / or a hole transport layer of a light emitting element, a light emitting element having excellent heat resistance can be obtained. Further, a light-emitting element that can be driven stably for a long time can be obtained.

(Embodiment 3)
In this embodiment, a method for manufacturing the material described in Embodiment 1 by a method using peptization will be described.

  First, a tetraethoxysilane and / or methyltriethoxysilane and an organic group capable of imparting hole injection, transportability, electron injection, or transportability are covalently bonded to silicon in a skeleton composed of siloxane bonds. A solution 1 obtained by dissolving the alkoxysilane in an alcohol / hydrochloric acid solution and stirring with heating is formed in the same manner as in the second embodiment.

  Subsequently, an aqueous ammonia solution is dropped into an aqueous metal chloride solution in the metal oxide that can exchange electrons with the organic group, thereby producing a multinuclear precipitate of the metal hydroxide. The polynuclear precipitation of hydroxide may be aged for about 10 to 24 hours at room temperature. This precipitate is added to a solution containing acetic acid and refluxed to obtain a sol (solution 3).

  The reflux may be performed for several hours at an appropriate temperature until the metal hydroxide in the solution containing acetic acid becomes a colloid of oxide and becomes a liquid (sol) having a transparent viscosity.

  In addition, when using this method using peptization, it is necessary to obtain a multinuclear precipitate of hydroxide, and this method cannot be used for a metal that does not produce a multinuclear precipitate of hydroxide. When this method is used, a sol of a metal oxide can be obtained without using a stabilizer, so that a transition metal oxide or a group 13 metal oxide can be preferably used. In addition, since acetic acid has a low boiling point of 118 ° C., there is little fear that it will be diffused by appropriately setting the firing temperature and affect the characteristics of the functional layer.

  Finally, the solution 3 is added to the solution 1, stirred, applied, and baked (at 100 ° C. to 300 ° C. for several hours), whereby an organic group in which an organic group is covalently bonded to silicon in a skeleton composed of siloxane bonds A composite material in which a substance that can exchange electrons with the organic group is added to the inorganic hybrid material can be manufactured. Baking may be performed in the air, in an inert atmosphere such as nitrogen, or in a vacuum. At this time, the ratio of the number of moles of organic groups capable of imparting hole injection or transportability or electron injection or transportability to the skeleton composed of siloxane bonds and the number of moles of metal contained in the solution 3 is The ratio is desirably 5: 1 to 1: 5, and more desirably 2: 1 to 1: 2.

  For the coating, a wet coating method, for example, a droplet coating method such as a dip coating method, a spin coating method, or an ink jet method can be used.

  By using the composite material of the present invention as a functional layer of a light emitting element, a light emitting element having excellent heat resistance can be obtained. Further, a light-emitting element that can be driven stably for a long time can be obtained.

  Note that a light-emitting element in which the composite material of the present invention is formed as a functional layer has little increase in driving voltage even when the functional layer is formed thick. Therefore, among the pair of electrodes of the light-emitting element, the functional layer between the first electrode and the light-emitting layer can be formed thick, and the light-emitting element is short-circuited due to dust or the like. Can be reduced. If the film thickness is 100 nm or more, such defects can be effectively reduced.

The functional layer to be thickened contains a substance that can exchange electrons with an organic group covalently bonded to silicon in a siloxane bond, thus improving conductivity, carrier injection, and transportability, and driving It is possible to reduce the occurrence of a short circuit of the light emitting element due to dust or the like without significantly increasing the voltage, that is, without significantly increasing the power consumption.

  Next, an example in which a composite material that can be specifically used as a hole injection layer and / or a hole transport layer of a light-emitting element is described. In this embodiment mode, a triphenylamino group as an organic group covalently bonded to silicon in a skeleton formed by a siloxane bond and aluminum oxide as an example of a substance that can exchange electrons with the triphenylamino group will be described. .

  Note that the basic principle is the same when other organic groups are used or when other metal oxides are used as substances capable of transferring electrons to and from the organic groups. The material may be selected from the combinations shown in Embodiment Mode 1 depending on the type of the functional layer manufactured using the composite material.

  The method for synthesizing the alkoxysilane (N- (4-triethoxysilylphenyl) -N, N-diphenylamine) with a triphenylamino group is the same as the method described in Embodiment 2, and therefore will be omitted.

  A method for producing a composite material film of the present invention using the obtained N- (4-triethoxysilylphenyl) -N, N-diphenylamine will be described. Note that a manufacturing method of the solution 1 is omitted because it can be manufactured by a method similar to the method described in Embodiment Mode 2.

  An aqueous ammonia solution is dropped into an aqueous solution of aluminum chloride to obtain a multinuclear precipitate of aluminum hydroxide (formula (26)). The resulting multinuclear precipitate of aluminum hydroxide is filtered, washed with pure water, then added to a solution containing acetic acid, and peptized by refluxing at 80 ° C. for 8 hours to produce a sol (formula (27)) .

  Finally, the solution 1 is added to the solution 3, and operations such as coating and baking after stirring are the same as in the method described in the second embodiment, and therefore will be omitted.

  By using the composite material of the present invention thus produced as a hole injection layer and / or a hole transport layer of a light emitting element, a light emitting element having excellent heat resistance can be obtained. Further, a light-emitting element that can be driven stably for a long time can be obtained.

(Embodiment 4)
Next, the light emitting device of the present invention will be described. In the light-emitting element of the present invention, at least one of the functional layers represented by the electron injection layer, the electron transport layer, the hole injection layer, and the hole transport layer is formed as described in Embodiments 1 to 3. It is formed of a composite material in which a substance capable of transferring electrons to and from the organic group is added to a hybrid material in which an organic group is bonded to silicon in the skeleton composed of siloxane bonds via a covalent bond. The light emitting element.

  In the light-emitting element of the present invention, a light-emitting layer containing at least a light-emitting substance is sandwiched between a pair of electrodes in addition to the layer formed of the composite material, and light can be emitted from the light-emitting layer by applying a voltage. .

  The light-emitting element of the present invention having such a structure has a skeleton in which at least one of the functional layers represented by the electron injection layer, the electron transport layer, the hole injection layer, and the hole transport layer is configured by a siloxane bond. A light emitting element with excellent heat resistance can be obtained by being formed of a material having the above. Further, a light-emitting element that can be driven stably for a long time can be obtained.

  In addition, the composite material is added with a substance capable of transferring electrons to and from an organic group covalently bonded to silicon in a skeleton composed of siloxane bonds, so that conductivity, carrier injection, and transportability are increased. Has improved. This makes it possible to form a functional layer having a skeleton composed of siloxane bonds without greatly increasing power consumption.

  In addition, the light-emitting element of the present invention includes a composite material having a skeleton formed of siloxane bonds and added with a substance that can exchange electrons with an organic group covalently bonded to silicon in the skeleton. By using the light-emitting element, a light-emitting element with high heat resistance and / or stable driving for a long time can be obtained, and a light-emitting element with low power consumption can be manufactured.

  Note that in the light-emitting element of the present invention, a layer that is not formed using a composite material among the functional layers may be provided using another material. Also in this case, the heat resistance and durability can be improved by forming a layer having the most problematic heat resistance and durability with a composite material.

  Note that a light-emitting element in which the composite material of the present invention is formed as a functional layer has little increase in driving voltage even when the functional layer is formed thick. Therefore, among the pair of electrodes of the light-emitting element, the functional layer between the first electrode and the light-emitting layer can be formed thick, and the light-emitting element is short-circuited due to dust or the like. Can be reduced. If the film thickness is 100 nm or more, such defects can be effectively reduced.

Since the functional layer to be thickened contains a substance that can exchange electrons with an organic group covalently bonded to silicon in a siloxane bond, it has improved conductivity, carrier injection, and transportability. It is possible to reduce the occurrence of a short circuit of the light emitting element due to dust or the like without significantly increasing the power consumption, that is, without significantly increasing the power consumption.

  Note that in the light-emitting element of the present invention, any one of functional layers typified by an electron injection layer, an electron transport layer, a hole injection layer, and a hole transport layer may be formed of the composite material, or two or more A plurality of layers may be formed of the composite material. All of the functional layers may be formed of the composite material.

  In addition, when the light-emitting layer is also formed using an organic-inorganic hybrid material having a silica matrix, a light-emitting element that is more excellent in heat resistance and can be driven stably for a long time can be manufactured. At this time, a sol prepared by polycondensation of an alkoxysilane having an organic group that emits light when voltage is applied to tetraethoxysilane or methyltriethoxysilane is applied to the surface where the light emitting layer is to be formed and baked. Thus, a light-emitting layer having a structure in which an organic group that emits light by applying a voltage to silicon in a skeleton bonded by a siloxane bond is covalently bonded can be formed. In addition, when producing sol, the sol which polycondensed only the alkoxysilane which has an organic group may be sufficient. The sol production method is the same as the solution 1 production method in Embodiment 2 of the present invention, and the coating and baking methods are the same as the composite material coating and baking methods of the present invention. Thereby, a light emitting layer can be produced with an organic-inorganic hybrid material having a silica matrix.

  Subsequently, schematic views of examples of the light-emitting element of the present invention are shown in FIGS. In FIG. 11A, a first electrode 201 is formed on an insulating surface 200 such as a substrate, and a hole injecting and transporting layer 202, a light emitting layer 203, and a book formed of the composite material of the present invention are further formed thereon. An electron injecting and transporting layer 204 formed of the composite material of the invention is sequentially laminated. A second electrode 205 of the light-emitting element is provided thereover, and when the light-emitting element is driven, a voltage is applied so that the potential of the first electrode 201 is higher than that of the second electrode 205 ( That is, the first electrode 201 functions as an anode and the second electrode 205 functions as a cathode).

  The light emitting layer may be formed by an evaporation method, or may be formed of an organic-inorganic hybrid material having an organic group that has a silica matrix as described above and emits light when a voltage is applied.

  In this configuration, both the hole injecting and transporting layer 202 and the electron injecting and transporting layer 204 are formed of the composite material of the present invention, but only one of them may be formed of the composite material of the present invention.

  The layer that is not formed using the composite material of the present invention may be formed using a known material such as a vapor deposition method.

  A light-emitting element as illustrated in FIG. 11A has excellent heat resistance and can be a light-emitting element that can be driven stably over a long period of time.

  FIG. 11B is a schematic view of a light-emitting element having a hole injecting and transporting layer 206 formed by increasing the thickness of the hole injecting and transporting layer 202 in FIG. The other layers are the same as those in FIG. The light emitting element is formed by laminating an extremely thin thin film, but when the first electrode 201 formed in the lower portion has a convex portion with a small curvature and a high height (which is considered to be due to dust or unevenness in the lower portion), When the thin film cannot cover the convex portion and the film is interrupted, a defect such as a short circuit occurs. On the other hand, if a film is formed thick in order to prevent this, there is a disadvantage that the resistance increases and the drive voltage rises. However, since the composite material of the present invention includes both an organic group having carrier transportability bonded by an organic-inorganic hybrid material and a substance capable of transferring electrons to and from the organic group, the composite material has high conductivity. Even if the film thickness is increased, an increase in resistance can be suppressed. In addition, since the light-emitting element having the structure in FIG. 11B basically has the structure in FIG. 11A, the light-emitting element has excellent heat resistance and can be driven stably over a long period of time. is there. This shows that the light-emitting element of the present invention having the structure of FIG. 11B is excellent in heat resistance, can be driven stably over a long period of time, and is a light-emitting element with few defects.

  FIG. 12A shows an example in which a hole injecting and transporting layer 207 of the composite material of the present invention is formed between the electron injecting and transporting layer 204 and the second electrode 205 (electrode serving as a cathode) in FIG. It is. The hole injecting and transporting layer 207 uses a group having excellent hole injecting or transporting properties as an organic group of the organic-inorganic hybrid material in the composite material, and further includes a substance that can accept electrons from the organic group. It is made of a composite material, that is, a material used on the electrode side serving as an anode, that is, on the first electrode 201 side, with reference to the light emitting layer 203.

  However, when a voltage is applied by sequentially laminating the electron injecting and transporting layer 204 made of the composite material of the present invention and the hole injecting and transporting layer 207 made of the composite material of the present invention on the electrode side that acts as a cathode with respect to the light emitting layer 203. Electrons are generated from the electron injecting and transporting layer 204 made of the composite material of the present invention and injected into the light emitting layer, and holes are generated from the hole injecting and transporting layer 207 made of the composite material of the present invention and injected into the electrode serving as the cathode. Flows and light emission can be obtained.

  Similarly, a structure in which an electron injecting and transporting layer is provided on the electrode (first electrode 201) side serving as an anode with the light emitting layer 203 as a reference is also possible. That is, the electron injecting and transporting layer made of the composite material of the present invention, the hole injecting and transporting layer made of the composite material of the present invention, and the light emitting layer 203 are laminated in this order from the electrode side serving as the anode. Thus, when a voltage is applied, electrons are injected from the electron injecting and transporting layer into the electrode serving as the anode, and holes are injected from the hole injecting and transporting layer into the light emitting layer 203, whereby current flows and light emission can be obtained.

Note that such a structure in which the electron injecting and transporting layer and the hole injecting and transporting layer are stacked may be provided on either the electrode side serving as the cathode or the electrode side serving as the anode with the light emitting layer 203 as the center. May be.

  A light-emitting element having such a structure can select a material for the first electrode 201 and the second electrode 205 without considering the work function, and is more suitable for a structure such as a reflective electrode or a transparent electrode. It becomes possible to select an electrode.

  FIG. 12B illustrates an example of a light-emitting element capable of obtaining white light emission. A first light-emitting layer 208, a spacing layer 209, and a second light-emitting layer 210 are provided between the hole injecting and transporting layer 202 and the electron injecting and transporting layer 204 in FIG. The first light-emitting layer 208 and the second light-emitting layer 210 are made of a material that emits light having a complementary color relationship such as red and blue-green, whereby white light emission can be obtained.

  The spacing layer 209 can be formed using a material having a hole transporting property, a material having an electron transporting property, a material having a bipolar property, a material having a hole blocking property, a material that generates carriers, and the like, and has a light-transmitting property. Is a condition. The spacing layer 209 is provided for the purpose of preventing the light emission of the first light-emitting layer 208 and the light emission of the second light-emitting layer 210 from being strongly emitted due to energy transfer, and this phenomenon does not occur. If there is, there is no need to provide it.

  The light-emitting element having the structure illustrated in FIG. 12B can emit white light, has excellent heat resistance, and can be driven stably for a long time. Such an element can be suitably used for lighting applications.

  Note that this embodiment can be combined with any of the other embodiments as long as there is no contradiction.

(Embodiment 5)
In this embodiment mode, a light-emitting device of the present invention described in Embodiment Mode 1 or Embodiment Mode 2 will be described with reference to FIGS. Note that although an example of manufacturing an active matrix light-emitting device is described in this embodiment mode, it is needless to say that the light-emitting device of the present invention can be applied to a passive matrix light-emitting device.

  First, after the first base insulating layer 51a and the second base insulating layer 51b are formed over the substrate 50, a semiconductor layer is further formed over the second base insulating layer 51b. (Fig. 3 (A))

  As a material of the substrate 50, glass, quartz, plastic (polyimide, acrylic, polyethylene terephthalate, polycarbonate, polyacrylate, polyethersulfone, or the like) can be used. These substrates may be used after being polished by CMP or the like, if necessary. In this embodiment, a glass substrate is used.

  The first base insulating layer 51a and the second base insulating layer 51b prevent an element such as an alkali metal or an alkaline earth metal in the substrate 50 that adversely affects the characteristics of the semiconductor layer from diffusing into the semiconductor layer. Provided for this purpose. As a material, silicon oxide, silicon nitride, silicon oxide containing nitrogen, silicon nitride containing oxygen, or the like can be used. In this embodiment mode, the first base insulating layer 51a is formed using silicon nitride, and the second base insulating layer 51b is formed using silicon oxide. In this embodiment mode, the base insulating layer is formed of the first base insulating layer 51a and the second base insulating layer 51b. However, the base insulating layer may be formed of a single layer or a multilayer of two or more layers. It doesn't matter. Further, if the diffusion of impurities from the substrate does not become a problem, it is not necessary to provide a base insulating layer.

  A semiconductor layer formed subsequently is obtained by laser crystallization of an amorphous silicon film in this embodiment mode. An amorphous silicon film is formed to a thickness of 25 to 100 nm (preferably 30 to 60 nm) over the second base insulating layer 51b. As a manufacturing method, a known method such as a sputtering method, a low pressure CVD method or a plasma CVD method can be used. Then, hydrogen treatment is performed at 500 ° C. for 1 hour.

  Subsequently, the amorphous silicon film is crystallized using a laser irradiation apparatus to form a crystalline silicon film. In the laser crystallization of the present embodiment, an excimer laser is used, and a laser beam oscillated is processed into a linear beam spot using an optical system and irradiated to an amorphous silicon film to form a crystalline silicon film. Used as a semiconductor layer.

  Other methods for crystallization of the amorphous silicon film include a method for crystallization only by heat treatment and a method for heat treatment using a catalyst element that promotes crystallization. Examples of elements that promote crystallization include nickel, iron, palladium, tin, lead, cobalt, platinum, copper, and gold. Compared to the case where crystallization is performed only by heat treatment by using such an element, Since crystallization is performed at a low temperature for a short time, there is little damage to the glass substrate. When crystallization is performed only by heat treatment, the substrate 50 may be a quartz substrate resistant to heat.

  Subsequently, in order to control the threshold value in the semiconductor layer as required, a small amount of impurity addition, so-called channel doping is performed. In order to obtain a required threshold value, N-type or P-type impurities (phosphorus, boron, etc.) are added by an ion doping method or the like.

  After that, as shown in FIG. 3A, the semiconductor layer is formed into a predetermined shape, and an island-shaped semiconductor layer 52 is obtained. Molding is performed by applying a photoresist to the semiconductor layer, exposing a predetermined mask shape, baking, forming a resist mask on the semiconductor layer, and etching using the mask.

Subsequently, a gate insulating layer 53 is formed so as to cover the semiconductor layer 52. The gate insulating layer 53 is formed of an insulating layer containing silicon with a thickness of 40 to 150 nm by plasma CVD or sputtering. In this embodiment mode, silicon oxide is used.

  Next, the gate electrode 54 is formed over the gate insulating layer 53. The gate electrode 54 may be formed of an element selected from tantalum, tungsten, titanium, molybdenum, aluminum, copper, chromium, and niobium, or an alloy material or a compound material containing the element as a main component. Alternatively, a semiconductor film typified by a polycrystalline silicon film doped with an impurity element such as phosphorus may be used. Further, an AgPdCu alloy may be used.

  Further, although the gate electrode 54 is formed as a single layer in this embodiment mode, a stacked structure of two or more layers such as tungsten in the lower layer and molybdenum in the upper layer may be used. Even in the case where the gate electrode is formed as a stacked structure, the materials described in the preceding stage may be used. Moreover, the combination may be selected as appropriate. The gate electrode 54 is processed by etching using a mask using a photoresist.

  Subsequently, a high concentration impurity is added to the semiconductor layer 52 using the gate electrode 54 as a mask. Thus, the thin film transistor 70 including the semiconductor layer 52, the gate insulating layer 53, and the gate electrode 54 is formed.

  Note that there is no particular limitation on the manufacturing process of the thin film transistor, and it may be changed as appropriate so that a transistor with a desired structure can be manufactured.

  In this embodiment mode, a top-gate thin film transistor using a crystalline silicon film crystallized by laser crystallization is used; however, a bottom-gate thin film transistor using an amorphous semiconductor film is used for a pixel portion. It is also possible. As the amorphous semiconductor, not only silicon but also silicon germanium can be used. When silicon germanium is used, the concentration of germanium is preferably about 0.01 to 4.5 atomic%.

  Alternatively, a microcrystalline semiconductor film (semi-amorphous semiconductor) in which crystals of 0.5 nm to 20 nm can be observed in an amorphous semiconductor may be used. Microcrystals capable of observing 0.5 nm to 20 nm crystals are also called so-called microcrystals (μc).

Semi-amorphous silicon (also referred to as SAS), which is a semi-amorphous semiconductor, can be obtained by glow discharge decomposition of a silicide gas. A typical silicide gas is SiH ₄ , and Si ₂ H ₆ , SiH ₂ Cl ₂ , SiHCl ₃ , SiCl ₄ , SiF _{4, and the} like can be used. The formation of the SAS can be facilitated by diluting the silicide gas with one or plural kinds of rare gas elements selected from hydrogen, hydrogen and helium, argon, krypton, and neon. It is preferable to dilute the silicide gas at a dilution ratio in the range of 10 times to 1000 times. The reaction generation of the film by glow discharge decomposition may be performed at a pressure in the range of 0.1 Pa to 133 Pa. The power for forming the glow discharge may be high frequency power of 1 MHz to 120 MHz, preferably 13 MHz to 60 MHz. The substrate heating temperature is preferably 300 ° C. or less, and a substrate heating temperature of 100 to 250 ° C. is suitable.

The SAS thus formed has a Raman spectrum shifted to a lower wavenumber than 520 cm ⁻¹ , and diffraction peaks of (111) and (220), which are considered to be derived from the Si crystal lattice in X-ray diffraction, are observed. Is done. In order to terminate dangling bonds (dangling bonds), hydrogen or halogen is contained at least 1 atomic% or more. As an impurity element in the film, impurities of atmospheric components such as oxygen, nitrogen, and carbon are desirably 1 × 10 ²⁰ cm −1 or less, and in particular, the oxygen concentration is 5 × 10 ¹⁹ / cm ³ or less, preferably 1 × 10 ¹⁹ / cm ³ or less. The mobility of a TFT manufactured using SAS is μ = 1 to 10 cm ² / Vsec.

  Further, this SAS may be further crystallized with a laser.

  Subsequently, an insulating film (hydrogenated film) 59 is formed of silicon nitride so as to cover the gate electrode 54 and the gate insulating layer 53. After the insulating film (hydrogenated film) 59 is formed, heating is performed at 480 ° C. for about 1 hour to activate the impurity element and hydrogenate the semiconductor layer 52.

  Subsequently, a first interlayer insulating layer 60 covering the insulating film (hydrogenated film) 59 is formed. As a material for forming the first interlayer insulating layer 60, silicon oxide, acrylic, polyimide, siloxane, a low-k material, or the like may be used. In this embodiment mode, the silicon oxide film is formed as the first interlayer insulating layer. (Fig. 3 (B))

  Next, a contact hole reaching the semiconductor layer 52 is opened. The contact hole can be formed by performing etching using a resist mask until the semiconductor layer 52 is exposed, and can be formed by either wet etching or dry etching. Note that etching may be performed once depending on conditions, or etching may be performed in a plurality of times. In addition, when etching is performed a plurality of times, both wet etching and dry etching may be used. (Figure 3 (C))

Then, a conductive layer covering the contact hole and the first interlayer insulating layer 60 is formed. The conductive layer is processed into a desired shape, and the connection portion 61a, the wiring 61b, and the like are formed. This wiring may be a single layer of aluminum, copper, an aluminum / carbon / nickel alloy, an aluminum / carbon / molybdenum alloy, etc., but in the order of formation, the laminated structure of molybdenum, aluminum, molybdenum, titanium, aluminum, titanium, titanium, nitriding A laminated structure such as titanium, aluminum, or titanium may be used. (Fig. 3 (D))

  Thereafter, a second interlayer insulating layer 63 is formed so as to cover the connection portion 61a, the wiring 61b, and the first interlayer insulating layer 60. As a material for the second interlayer insulating layer 63, a coating film of acrylic, polyimide, siloxane or the like having self-flatness can be suitably used. In this embodiment mode, siloxane is used as the second interlayer insulating layer 63. (Figure 3 (E))

  Subsequently, an insulating layer may be formed using silicon nitride or the like over the second interlayer insulating layer 63. This is formed to prevent the second interlayer insulating layer 63 from being etched more than necessary in the subsequent etching of the pixel electrode. Therefore, when the ratio of the etching rate between the pixel electrode and the second interlayer insulating layer is large, it may not be provided. Subsequently, a contact hole that penetrates through the second interlayer insulating layer 63 and reaches the connection portion 61a is formed.

  A light-transmitting conductive layer is formed so as to cover the contact hole and the second interlayer insulating layer 63 (or the insulating layer), and then the light-transmitting conductive layer is processed to form a thin film light-emitting element. 1 electrode 64 is formed. Here, the first electrode 64 is in electrical contact with the connecting portion 61a.

As the material of the first electrode 64, aluminum (Al), silver (Ag), gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), titanium (Ti), etc. Conductive metals or their alloys, or nitrides of metal materials (eg, TiN), indium tin oxide (ITO), silicon-containing ITO (ITSO), indium oxide mixed with zinc oxide (ZnO) It can be formed of a conductive film such as a metal oxide such as IZO.

Further, the electrode for extracting light may be formed of a conductive film having transparency, and an ultrathin film of a metal such as Al or Ag is used in addition to a metal oxide such as ITO, ITSO, or IZO. In the case where light emission is extracted from the second electrode, a material with high reflectivity (Al, Ag, or the like) can be used for the first electrode. In this embodiment mode, ITSO is used as the first electrode 64 (FIG. 4A).

  Next, an insulating layer made of an organic material or an inorganic material is formed so as to cover the second interlayer insulating layer 63 (or the insulating layer) and the first electrode 64. Subsequently, the insulating layer is processed so that a part of the first electrode 64 is exposed, and a partition wall 65 is formed. As the material of the partition wall 65, a photosensitive organic material (acrylic, polyimide, or the like) is preferably used, but it may be formed of an organic material or an inorganic material that does not have photosensitivity. Further, a black pigment or dye such as titanium black or carbon nitride may be dispersed in the material of the partition wall 65 by using a dispersing material or the like, and the partition wall 65 may be made black to be used like a black matrix. It is desirable that the end surface facing the opening of the partition wall 65 has a curvature and has a tapered shape in which the curvature continuously changes (FIG. 4B).

  Next, a hole injection layer is formed using a composite material that covers the first electrode 64 exposed from the partition wall 65 and further includes molybdenum oxide in a silica matrix having a triphenylamino group. This hole injection layer may be manufactured by the method described in Embodiment Mode 2, and an inkjet method may be used for coating. Next, the light emitting layer is formed using the organic-inorganic hybrid material having the silica matrix described in Embodiment Mode 4. The application is similarly performed by an ink jet method. Subsequently, an electron injection layer is prepared from a composite material further including lithium oxide on a silica matrix having a pyridine group. This electron injection layer may also be formed by the method described in Embodiment Mode 2, and an ink jet method may be used for coating.

  Subsequently, a second electrode 67 that covers the light-emitting stacked body 66 is formed. Thus, a light-emitting element 93 in which a stacked body including a light-emitting layer is sandwiched between the first electrode 64 and the second electrode 67 can be manufactured, and a voltage higher than that of the second electrode is applied to the first electrode. Luminescence can be obtained by applying. As an electrode material used for forming the second electrode 67, the same material as that of the first electrode can be used. In this embodiment, aluminum is used as the second electrode.

  The light-emitting element having the above structure is a light-emitting element having excellent heat resistance and durability because a composite material having a skeleton formed of siloxane bonds is used for the light-emitting element. In addition, since a composite material is used in which a material that can exchange electrons with an organic group imparting electron or hole injection or transport properties to the skeleton is used, holes or electrons are used. Injecting or transporting can be improved, and further, a light emitting element with improved conductivity can be obtained.

  In addition, by using a composite material with improved hole or electron injection or transport properties and further improved conductivity, the thickness of the functional layer on the first electrode is increased to 100 nm or more, so that the driving voltage can be increased. The occurrence of defects due to dust on the first electrode can be reduced without causing a significant increase.

  Note that although the hole transport layer is formed over the first electrode in this embodiment mode, an electron transport layer may be provided over the first electrode and the stacking order may be reversed. In this case, light emission can be obtained by making the voltage applied to the first electrode lower than the voltage applied to the second electrode.

Thereafter, a silicon oxide film containing nitrogen is formed as a passivation film by a plasma CVD method. In the case of using a silicon oxide film containing nitrogen, a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, NH ₃ by a plasma CVD method, or a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, Alternatively, a silicon oxynitride film formed from a gas obtained by diluting SiH ₄ and N ₂ O with Ar may be formed.

Further, a silicon oxynitride silicon film formed from SiH ₄ , N ₂ O, and H ₂ may be applied as the passivation film. Of course, the passivation film is not limited to a single layer structure, and another insulating layer containing silicon may be used as a single layer structure or a laminated structure. Further, a multilayer film of a carbon nitride film and a silicon nitride film, a multilayer film of styrene polymer, a silicon nitride film, or a diamond-like carbon film may be formed instead of the silicon oxide film containing nitrogen.

  Subsequently, the display portion is sealed in order to protect the light emitting element from a substance that promotes deterioration such as water. In the case where the counter substrate is used for sealing, bonding is performed with an insulating sealing material so that the external connection portion is exposed. A space between the counter substrate and the element substrate may be filled with an inert gas such as dry nitrogen, or a sealing material may be applied to the entire surface of the pixel portion to bond the counter substrate. It is preferable to use an ultraviolet curable resin or the like for the sealing material. The sealing material may contain a desiccant or particles for keeping the gap between the substrates constant. Subsequently, a flexible wiring substrate is attached to the external connection portion, whereby the light emitting device is completed.

  An example of the structure of the light-emitting device manufactured as described above will be described with reference to FIG. In addition, even if the shapes are different, parts showing similar functions are denoted by the same reference numerals, and explanations thereof are omitted. In this embodiment mode, the thin film transistor 70 having an LDD structure is connected to the light emitting element 93 through the connection portion 61a.

  FIG. 5A illustrates a structure in which the first electrode 64 is formed using a light-transmitting conductive film, and light emitted from the light-emitting stacked body 66 is extracted to the substrate 50 side. Reference numeral 94 denotes a counter substrate, which is fixed to the substrate 50 by using a sealing material or the like after the light emitting element 93 is formed. Filling the counter substrate 94 with the light-transmitting resin 88 or the like between the elements and sealing them can prevent the light-emitting element 93 from being deteriorated by moisture. Further, it is desirable that the resin 88 has a hygroscopic property. Further, if a desiccant 89 having high translucency is dispersed in the resin 88, the influence of moisture can be further suppressed, which is a more desirable form.

  FIG. 5B illustrates a structure in which both the first electrode 64 and the second electrode 67 are formed using a light-transmitting conductive film, and light can be extracted to both the substrate 50 and the counter substrate 94. It has become. Further, in this configuration, by providing the polarizing plate 90 outside the substrate 50 and the counter substrate 94, it is possible to prevent the screen from being seen through, and visibility is improved. A protective film 91 may be provided outside the polarizing plate 90.

  Note that either an analog video signal or a digital video signal may be used for the light-emitting device of the present invention having a display function. When a digital video signal is used, the video signal is classified into one using a voltage and one using a current. When the light emitting element emits light, the video signal input to the pixel has a constant voltage and a constant current. When the video signal has a constant voltage, the voltage applied to the light emitting element is constant. And the current flowing through the light emitting element is constant. In addition, a video signal having a constant current includes a constant voltage applied to the light emitting element and a constant current flowing in the light emitting element. A constant voltage applied to the light emitting element is constant voltage driving, and a constant current flowing through the light emitting element is constant current driving. In constant current driving, a constant current flows regardless of the resistance change of the light emitting element. Any of the above driving methods may be used for the light emitting display device and the driving method thereof of the present invention.

  In the light emitting device of the present invention formed by the method of this embodiment mode, it is not necessary to consider the work function when selecting the material of the second electrode 67 of the light emitting element included in the light emitting device. In addition, when selecting a material for forming the second electrode 67, the range of material selection is widened. Accordingly, a material more suitable for the structure of the light emitting element can be used.

  This embodiment mode can be used in combination with any appropriate structure in Embodiment Modes 1 to 4.

(Embodiment 6)
In this embodiment, the appearance of a panel of a light-emitting device that corresponds to one embodiment of the present invention will be described with reference to FIGS. 6A is a top view of a panel in which a transistor and a light-emitting element formed over a substrate are sealed with a sealant formed between a counter substrate 4006 and FIG. 6B is a plan view of FIG. Corresponds to the cross-sectional view. The structure of the light-emitting element mounted on this panel is the structure shown in Embodiment Mode 4.

  A sealant 4005 is provided so as to surround the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 which are provided over the substrate 4001. A counter substrate 4006 is provided over the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. Therefore, the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 are sealed together with the filler 4007 by the substrate 4001, the sealant 4005, and the counter substrate 4006.

  The pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 provided over the substrate 4001 include a plurality of thin film transistors. In FIG. 6B, the thin film transistor 4008 included in the signal line driver circuit 4003 is provided. And a thin film transistor 4010 included in the pixel portion 4002.

  The light emitting element 4011 is electrically connected to the thin film transistor 4010.

  The lead wiring 4014 corresponds to a wiring for supplying a signal or a power supply voltage to the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. The lead wiring 4014 is connected to the connection terminal 4016 via the lead wiring 4015a and the lead wiring 4015b. The connection terminal 4016 is electrically connected to a terminal included in a flexible printed circuit (FPC) 4018 through an anisotropic conductive film 4019.

  Note that as the filler 4007, in addition to an inert gas such as nitrogen or argon, an ultraviolet curable resin or a thermosetting resin can be used, and polyvinyl chloride, acrylic, polyimide, epoxy resin, silicon resin, polyvinyl butyral, Alternatively, ethylene vinylene acetate can be used.

  Note that the light-emitting device of the present invention includes in its category a panel in which a pixel portion having a light-emitting element is formed and a module in which an IC is mounted on the panel.

  The panel and module having the structure as in this embodiment are a panel and module having excellent heat resistance and durability since a composite material having a skeleton formed of siloxane bonds is used for a light emitting element. In addition, since a composite material is used in which a material that can exchange electrons with an organic group imparting electron or hole injection or transport properties to the skeleton is used, holes or electrons are used. It is possible to obtain a panel and a module with improved injecting or transporting properties and further improved conductivity.

  In addition, by using a composite material with improved hole or electron injection or transport properties and further improved conductivity, the thickness of the functional layer on the first electrode is increased to 100 nm or more, so that the driving voltage can be increased. The occurrence of defects due to dust on the first electrode can be reduced without causing a significant increase.

  This embodiment mode can be combined with any suitable structure in Embodiment Modes 1 to 5.

(Embodiment 7)
As an electronic device of the present invention on which a module whose example is shown in Embodiment 6 is mounted, a video camera, a digital camera, a goggle-type display (head-mounted display), a navigation system, a sound reproduction device (car audio component, etc.) A recording medium such as a computer, a game machine, a portable information terminal (mobile computer, cellular phone, portable game machine, electronic book, etc.), an image reproducing device (specifically Digital Versatile Disc (DVD)) equipped with a recording medium And a device having a display capable of reproducing and displaying the image). Specific examples of these electronic devices are shown in FIGS.

  FIG. 7A illustrates a light-emitting display device, such as a television receiver or a personal computer monitor. A housing 2001, a display portion 2003, a speaker portion 2004, and the like are included. The light-emitting display device of the present invention is a highly reliable light-emitting display device because it has excellent heat resistance in the display portion 2003 and can be driven stably for a long time. In order to increase contrast, the pixel portion may be provided with a polarizing plate or a circular polarizing plate. For example, a film may be provided on the sealing substrate in the order of a 1 / 4λ plate, a 1 / 2λ plate, and a polarizing plate. Further, an antireflection film may be provided on the polarizing plate.

  FIG. 7B illustrates a mobile phone, which includes a main body 2101, a housing 2102, a display portion 2103, a voice input portion 2104, a voice output portion 2105, operation keys 2106, an antenna 2108, and the like. The mobile phone of the present invention is a highly reliable mobile phone because the display portion 2103 has excellent heat resistance and can be driven stably for a long time.

  FIG. 7C illustrates a computer, which includes a main body 2201, a housing 2202, a display portion 2203, a keyboard 2204, an external connection port 2205, a pointing mouse 2206, and the like. The computer of the present invention is a reliable computer because the display portion 2203 has excellent heat resistance and can be driven stably for a long time. Although FIG. 7C illustrates a notebook computer, the present invention can also be applied to a desktop computer or the like.

  FIG. 7D illustrates a mobile computer, which includes a main body 2301, a display portion 2302, a switch 2303, operation keys 2304, an infrared port 2305, and the like. The mobile computer of the present invention is a highly reliable mobile computer because the display portion 2302 has excellent heat resistance and can be driven stably for a long time.

  FIG. 7E illustrates a portable game machine which includes a housing 2401, a display portion 2402, speaker portions 2403, operation keys 2404, a recording medium insertion portion 2405, and the like. The portable game machine of the present invention is a highly reliable portable game machine because the light-emitting element included in the display portion 2402 has excellent heat resistance and can be driven stably for a long time.

  As described above, the applicable range of the present invention is so wide that it can be used for electronic devices in various fields.

Embodiment Mode 8 FIG. 8 shows an example of bottom emission, double-side emission, and top emission. A structure in which a manufacturing process is described in Embodiment 2 corresponds to the structure in FIG. 8A and 8B, the first interlayer insulating layer 63 in FIG. 8C is formed of a material having self-planarity, and a wiring connected to the thin film transistor 70 and the first electrode 64 of the light-emitting element are provided. This is a configuration when formed on the same interlayer insulating layer. FIG. 8A illustrates a bottom emission structure in which only the first electrode 64 of the light-emitting element is formed using a light-transmitting material and light is emitted toward the lower portion of the light-emitting device, and FIG. By forming a light-transmitting material such as ITSO or IZO as the second electrode 67, a light-emitting display device that emits light from both sides as shown in FIG. 8B can be obtained. . Note that although the film is non-light-transmitting when formed of a thick film such as aluminum or silver, the light-transmitting property is obtained when the film is thinned. Therefore, the second electrode 67 is formed of a thin film having light-transmitting properties of aluminum or silver. Even if formed, double-sided light emission can be achieved.

Embodiment Mode 9 In this embodiment mode, pixel circuits and protection circuits included in the panel and module described in Embodiment Mode 6 and operations thereof will be described. Note that the cross-sectional views shown in FIGS. 3 and 4 are cross-sectional views of the driving TFT 1403 and the light emitting element 1405.

  In the pixel shown in FIG. 9A, a signal line 1410 and power supply lines 1411 and 1412 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. The pixel further includes a switching TFT 1401, a driving TFT 1403, a current control TFT 1404, a capacitor element 1402, and a light emitting element 1405.

  The pixel shown in FIG. 9C is different from the pixel shown in FIG. 9A except that the gate electrode of the driving TFT 1403 is connected to the power supply line 1412 arranged in the row direction. It is a configuration. That is, both pixels shown in FIGS. 9A and 9C show the same equivalent circuit diagram. However, in the case where the power supply line 1412 is arranged in the column direction (FIG. 9A) and in the case where the power supply line 1412 is arranged in the row direction (FIG. 9C), each power supply line has a different layer. It is formed of a conductive film. Here, attention is paid to the wiring to which the gate electrode of the driving TFT 1403 is connected, and FIGS. 9A and 9C are shown separately to show that the layers for manufacturing these are different.

  9A and 9C, a driving TFT 1403 and a current control TFT 1404 are connected in series in the pixel, and the channel length L (1403) and channel width W (1403) of the driving TFT 1403 are connected. ), The channel length L (1404) and the channel width W (1404) of the current control TFT 1404 satisfy L (1403) / W (1403): L (1404) / W (1404) = 5 to 6000: 1. It is good to set to.

  Note that the driving TFT 1403 operates in a saturation region and has a role of controlling a current value flowing through the light emitting element 1405, and the current control TFT 1404 operates in a linear region and has a role of controlling supply of current to the light emitting element 1405. . Both TFTs preferably have the same conductivity type in terms of manufacturing process, and in this embodiment mode, they are formed as n-channel TFTs. The driving TFT 1403 may be a depletion type TFT as well as an enhancement type. In the present invention having the above configuration, since the current control TFT 1404 operates in a linear region, a slight change in Vgs of the current control TFT 1404 does not affect the current value of the light emitting element 1405. That is, the current value of the light emitting element 1405 can be determined by the driving TFT 1403 operating in the saturation region. With the above structure, it is possible to provide a light-emitting device in which luminance unevenness of a light-emitting element due to variation in TFT characteristics is improved and image quality is improved.

  In the pixel shown in FIGS. 9A to 9D, the switching TFT 1401 controls input of a video signal to the pixel. When the switching TFT 1401 is turned on, the video signal is input into the pixel. Then, the voltage of the video signal is held in the capacitor element 1402. Note that FIGS. 9A and 9C illustrate a structure in which the capacitor 1402 is provided; however, the present invention is not limited to this, and the capacity for holding a video signal can be covered by a gate capacity or the like. In this case, the capacitor 1402 is not necessarily provided.

  The pixel shown in FIG. 9B has the same pixel structure as that shown in FIG. 9A except that a TFT 1406 and a scanning line 1415 are added. Similarly, the pixel illustrated in FIG. 9D has the same pixel structure as that illustrated in FIG. 9C except that a TFT 1406 and a scanning line 1415 are added.

  The TFT 1406 is controlled to be turned on or off by a newly arranged scanning line 1415. When the TFT 1406 is turned on, the charge held in the capacitor element 1402 is discharged, and the current control TFT 1404 is turned off. That is, the arrangement of the TFT 1406 can forcibly create a state where no current flows through the light-emitting element 1405. Therefore, the TFT 1406 can be called an erasing TFT. 9B and 9D can improve the duty ratio because the lighting period can be started simultaneously with or immediately after the start of the writing period without waiting for signal writing to all pixels. It becomes possible.

  In the pixel shown in FIG. 9E, a signal line 1410, a power supply line 1411 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. Further, the pixel includes a switching TFT 1401, a driving TFT 1403, a capacitor element 1402, and a light emitting element 1405. The pixel shown in FIG. 9F has the same pixel structure as that shown in FIG. 7E except that a TFT 1406 and a scanning line 1415 are added. Note that the duty ratio of the structure in FIG. 9F can also be improved by the arrangement of the TFT 1406.

  As described above, various pixel circuits can be employed. In particular, in the case where a thin film transistor is formed using an amorphous semiconductor film, it is preferable to increase the semiconductor film of the driving TFT 1403. Therefore, it is preferable that the pixel circuit be a top emission type in which light from the electroluminescent layer is emitted from the sealing substrate side.

  Such an active matrix light-emitting device is considered to be advantageous because it can be driven at a low voltage because a TFT is provided in each pixel when the pixel density is increased.

  In this embodiment mode, an active matrix light-emitting device in which each pixel is provided with each TFT has been described; however, a passive matrix light-emitting device in which a TFT is provided for each column can also be formed. A passive matrix light-emitting device has a high aperture ratio because a TFT is not provided for each pixel. In the case of a light-emitting device in which light emission is emitted to both sides of the electroluminescent layer, the transmittance increases when a passive matrix light-emitting device is used.

  The light-emitting device of the present invention further including such a pixel circuit has high heat resistance and can be driven stably for a long time, so that it has high reliability and can be a display device having the characteristics of each circuit described above.

  Next, the case where a diode is provided as a protective circuit in the scan line and the signal line will be described using the equivalent circuit illustrated in FIG.

  In FIG. 10, a switching TFT 1401, a driving TFT 1403, a capacitor element 1402, and a light emitting element 1405 are provided in the pixel portion 1500. The signal line 1410 is provided with diodes 1561 and 1562. Similarly to the switching TFT 1401 or 1403, the diodes 1561 and 1562 are manufactured based on the above embodiment mode, and include a gate electrode, a semiconductor layer, a source electrode, a drain electrode, and the like. The diodes 1561 and 1562 operate as diodes by connecting a gate electrode and a drain electrode or a source electrode.

  Common potential lines 1554 and 1555 connected to the diode are formed in the same layer as the gate electrode. Therefore, in order to connect to the source electrode or the drain electrode of the diode, it is necessary to form a contact hole in the gate insulating layer.

  A diode provided in the scan line 1414 has a similar structure.

  Thus, according to the present invention, the protection diode provided in the input stage can be formed simultaneously. Note that the position where the protective diode is formed is not limited to this, and the protective diode can be provided between the driver circuit and the pixel.

The light-emitting device of the present invention having such a protection circuit is highly reliable because the light-emitting device has excellent heat resistance and can be driven stably for a long time, and the above structure further increases the reliability of the light-emitting device. It becomes possible to raise.

  In this example, a production example of the composite material of the present invention is specifically illustrated.

<< Preparation of Example Sample >>
[1. Synthesis of alkoxysilane represented by structural formula (1)]
A 300 ml three-necked flask was charged with 4.86 g (15 mmol) of 4-bromotriphenylamine and 50 ml of tetrahydrofuran (THF) and 11.39 ml of n-butyllithium (15% hexane solution) with stirring at −78 ° C. in a nitrogen atmosphere. (18 mmol) was added dropwise. After stirring for 30 minutes, 3.67 g (18 mmol) of triethoxychlorosilane was added dropwise. After warming to room temperature and stirring overnight, THF was removed under reduced pressure. Thereafter, hexane was added to precipitate LiBr and removed by filtration. Further, hexane was removed under reduced pressure, whereby N- (4-triethoxysilylphenyl) -N, N represented by the structural formula (1) was obtained. -5.9g of diphenylamine (abbreviation; TPA-Si) was obtained (yield 96.5%).

[2. Preparation of sol]
Next, 0.421 g (1.0 mmol) of TPA-Si synthesized as described above and 0.139 g of methyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) in a glove box in which the moisture concentration is kept at several ppm. 1.0 mmol) and a solution 1 dispersed in 7.43 g (100 mmol) of THF was prepared.

  Separately from this, 0.244 g (1.0 mmol) of vanadium triisopropoxide oxide (manufactured by Kojundo Chemical Co., Ltd.), and ethyl acetate acetoacetate (manufactured by Kishida Chemical Co., Ltd.) as stabilizers were added in the same glove box. 136 g (1.0 mmol) was collected, and a solution 2 dispersed in 6.89 g (96 mmol) of THF was prepared.

  Then, in the glove box, the solution 2 was added dropwise to the solution 1 while stirring, and then stirred for 2 hours to obtain a sol for producing the composite material of the present invention. In this sol, TPA-Si: methyltrimethoxysilane: vanadium triisopropoxide oxide: ethyl acetoacetate: THF = 1.0: 1.0: 1.0: 1.0: 196 (unit; [ mmol]).

[3. Production of composite material of the present invention]
Further, the obtained sol was dropped on a glass substrate while passing through a 0.45 μm filter, and spin-coated under the conditions of 2000 rpm and 60 seconds. A spin-coated substrate and a beaker containing pure water were placed in an electric furnace and heated at 70 ° C. for 8 hours to be hydrolyzed with water vapor. Further, the beaker containing pure water was taken out from the furnace and fired at 150 ° C. for 16 hours to obtain the composite material of the present invention. In the composite material of this example, the organic group bonded to the silicon in the skeleton bonded by the siloxane bond through a covalent bond is a 4-triphenylamino group, and exchanges electrons with this organic group. A possible material is vanadium oxide.

<< Preparation of Comparative Sample 1 >>
For comparison, a sol excluding vanadium triisopropoxide oxide was prepared from the above example, and Comparative Sample 1 was prepared. That is, a sol in which 0.217 g (0.53 mmol) of TPA-Si and 0.072 g (0.53 mmol) of methyltrimethoxysilane were dispersed in 7.40 g (100 mmol) of THF was treated in the same manner as in the above example. A sample was prepared, coated and fired on a glass substrate under the same conditions. This comparative sample 1 is a conventional organic-inorganic hybrid material that does not contain vanadium oxide, which is a substance that can exchange electrons with an organic group (4-triphenylamino group).

<< Preparation of Comparative Sample 2 >>
For comparison, a sol in which TPA-Si was removed from the above example was prepared, and comparative sample 2 was produced. That is, 7.21 g (0.072 g (0.53 mmol) of methyltrimethoxysilane, 0.122 g (0.50 mmol) of vanadium triisopropoxide oxide, and 0.067 g (0.51 mmol) of ethyl acetoacetate) A sol dispersed in 100 mmol) of THF was prepared in the same manner as in the above example, and a sample was prepared by applying and baking on a glass substrate under the same conditions. This comparative sample 2 is an organic-inorganic hybrid material that has vanadium oxide but does not have an organic group (4-triphenylamino group) that can exchange electrons with vanadium oxide and has only a methyl group.

"Experimental result"
Using a spectrophotometer (manufactured by Hitachi, U-4000), the ultraviolet-visible-infrared absorption spectra of the sample of this example, comparative sample 1 and comparative sample 2 prepared as described above were measured. The results are shown in FIG. Moreover, the figure which expanded the spectrum from the visible region of 400 nm-1200 nm to the near infrared region is shown in FIG.13 (b).

  As shown in FIG. 13, the spectrum of the sample of this example has a broad absorption spectrum near the visible / infrared boundary region of 600 nm to 800 nm as compared with Comparative Samples 1 and 2. This broad absorption is not observed in Comparative Samples 1 and 2, suggesting that charge transfer occurs between the 4-triphenylamino group and vanadium oxide. Since an arylamino group generally has a high electron donating property, it is considered that 4-triphenylamino group is an electron donor and vanadium oxide is an electron acceptor.

In the sol-gel method, it is known that an oxide skeleton (metal-oxygen-metal bond) is formed by hydrolysis and firing. That is, a siloxane bond is formed by TPA-Si and methyltrimethoxysilane, and vanadium triisopropoxide oxide forms a vanadium oxide skeleton. Therefore, from the above-described embodiment, an organic-inorganic hybrid material in which an organic group (4-triphenylamino group) is bonded to silicon in a skeleton bonded by a siloxane bond through a covalent bond, and the organic group and the electron It was possible to produce a composite material having a substance (vanadium oxide) capable of receiving and delivering the above.

Schematic diagram of the composite material of the present invention Schematic diagram showing the state of electron transfer in the composite material of the present invention 4A and 4B illustrate a manufacturing process of a thin film light-emitting element of the present invention. 4A and 4B illustrate a manufacturing process of a thin film light-emitting element of the present invention. The figure which illustrated the structure of the display apparatus. 2A and 2B are a top view and a cross-sectional view of a light-emitting device of the present invention. FIG. 10 illustrates an electronic device to which the present invention is applicable. The figure which illustrated the structure of the display apparatus. FIG. 14 illustrates an example of a pixel circuit of a display device. FIG. 11 illustrates an example of a protection circuit of a display device. 1 shows an example of a structure of a light-emitting element of the present invention. 1 shows an example of a structure of a light-emitting element of the present invention. Absorption spectra of the composite material of the present invention and a comparative sample.

Explanation of symbols

50 Substrate 52 Semiconductor layer 53 Gate insulating layer 54 Gate electrode 59 Insulating film (hydrogenated film)
60 Interlayer insulating layer 63 Interlayer insulating layer 64 Electrode 65 Partition 66 Light emitting laminate 67 Electrode 70 Thin film transistor 88 Resin 89 Desiccant 90 Polarizing plate 91 Protective film 93 Light emitting element 94 Opposite substrate 100 Siloxane bond 101 Skeleton 102 Organic group 103 Organic inorganic hybrid material 104 Material 200 Insulating surface 201 Electrode 202 Hole injection transport layer 203 Light emitting layer 204 Electron injection transport layer 205 Electrode 206 Hole injection transport layer 207 Hole injection transport layer 208 Light emitting layer 209 Spacing layer 210 Light emitting layer 51a Base insulating layer 51b Base Insulating layer 61a Connection portion 61b Wiring 1401 Switching TFT
1402 Capacitor element 1403 Driving TFT
1404 Current control TFT
1405 Light Emitting Element 1406 TFT
1410 Signal line 1411 Power supply line 1412 Power supply line 1414 Scanning line 1415 Scanning line 1500 Pixel part 1554 Common potential line 1561 Diode 2001 Case 2003 Display part 2004 Speaker part 2101 Main body 2102 Case 2103 Display part 2104 Audio input part 2105 Audio output part 2106 Operation key 2108 Antenna 2201 Main body 2202 Case 2203 Display unit 2204 Keyboard 2205 External connection port 2206 Pointing mouse 2301 Main body 2302 Display unit 2303 Switch 2304 Operation key 2305 Infrared port 2401 Case 2402 Display unit 2403 Speaker unit 2404 Operation key 2405 Recording medium insertion Portion 4001 Substrate 4001 Substrate 4002 Pixel portion 4003 Signal line driver circuit 4004 Scan line driver circuit 4005 Sealing material 4 006 Counter substrate 4007 Filler 4008 Thin film transistor 4010 Thin film transistor 4011 Light emitting element 4014 Wiring 4016 Connection terminal 4018 Flexible printed circuit (FPC)
4019 Anisotropic conductive film 4015a Wiring 4015b Wiring

Claims (14)

An organic-inorganic hybrid material in which an organic group is bonded to silicon in a skeleton bonded by a siloxane bond via a covalent bond;
A composite material comprising the organic group and a substance capable of transferring electrons. In claim 1,
The organic group is an organic group having a hole transport property higher than an electron transport property,
The composite material characterized in that the substance that can exchange electrons with the organic group is a substance that can accept electrons from the organic group. In claim 1,
The organic group is an organic group having an electron transport property higher than a hole transport property,
The composite material characterized in that the substance capable of transferring electrons to and from the organic group is a substance capable of donating electrons to the organic group.   3. The composite material according to claim 2, wherein the organic group has an arylamine skeleton, a pyrrole skeleton, or both.   In Claim 2, one or more types of organic groups having an arylamine skeleton, a pyrrole skeleton, or both of them are covalently bonded to at least one or more of silicon in the skeleton bonded by the siloxane bond. A composite material characterized by   4. The organic group according to claim 3, wherein the organic group is one or more of a pyridine skeleton, a phenanthroline skeleton, a quinoline skeleton, a pyrazine skeleton, a triazine skeleton, an imidazole skeleton, a triazole skeleton, an oxadiazole skeleton, a thiadiazole skeleton, an oxazole skeleton, and a thiazole skeleton. A composite material comprising:   The pyridine skeleton, the phenanthroline skeleton, the quinoline skeleton, the pyrazine skeleton, the triazine skeleton, the imidazole skeleton, the triazole skeleton, the oxadiazole skeleton, and the thiadiazole are added to at least one or more of silicon in the skeleton bonded by the siloxane bond. A composite material in which one or more organic groups having one or more skeletons, oxazole skeletons, and thiazole skeletons are covalently bonded.   6. The substance according to claim 2, wherein the substance that can accept electrons from the organic group is an oxide of a transition metal, a hydroxide, or both. And composite materials.   9. The composite material according to claim 8, wherein the transition metal is any one of Group 4 to Group 8.   9. The composite material according to claim 8, wherein the transition metal is any one of titanium, vanadium, molybdenum, tungsten, rhenium, ruthenium, and niobium.   The substance capable of donating an electron to the organic group according to any one of claims 3, 6, and 7 is an alkali metal or alkaline earth metal oxide or hydroxide or both. A composite material characterized by 12. The composite material according to claim 11, wherein the alkali metal or alkaline earth metal is lithium or barium. A pair of electrodes;
A light emitting layer that emits light by passing a current between the pair of electrodes;
A light emitting element comprising at least one layer made of the composite material according to any one of claims 1 to 12 between the pair of electrodes. In claim 13,
The light-emitting element is a layer including a substance in which an organic group that emits light when a voltage is applied to silicon in a skeleton bonded by a siloxane bond.