JP2013253317A - Substrate for semiconductor device, semiconductor device, dimming-type lighting device, self light-emitting display device, solar cell and reflective liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for a semiconductor device, which has high flexibility and constitutes a high performance flexible semiconductor device capable of being improved in productivity and yield, and which prevents the deterioration in properties caused by moisture and can prevent cracks in an anodic oxide film serving as an insulating layer, even in a semiconductor device using an organic semiconductor material in a photoelectric conversion layer; to provide a semiconductor device and a reflective liquid crystal display device using the substrate; and to provide a lighting device, display device and solar cell using the semiconductor device.SOLUTION: A substrate 10 comprises: a sheet-like aluminum base material 12; aluminum porous anodic oxide films 14 formed on both surfaces of the base material 12; and a protective layer 16 comprising a silicon-containing non-porous oxide, which is formed on at least one surface of the anodic oxide film. The anodic oxide films 14, formed on the both surfaces, each have a strain in the compression direction at room temperature.

Description

  The present invention relates to a substrate used in a semiconductor device, and a semiconductor device, a lighting device, a display device, and a solar cell. Specifically, the present invention relates to a semiconductor device substrate suitable for a semiconductor device, a semiconductor device and a reflective liquid crystal display device using the substrate, a dimming illumination device using the semiconductor device, a self-luminous display device, and a solar cell.

A semiconductor device such as a solar cell or an organic EL (electroluminescence) display may be required to have flexibility (flexibility) in order to cope with various applications.
A flexible semiconductor device (flexible electronics) is manufactured, for example, by forming a semiconductor element having an electrode, a photoelectric conversion layer, and the like on a flexible sheet-like (film-like) substrate. The

Attempts have been made to use a heat-resistant resin such as polyimide as a substrate for such a flexible semiconductor device.
However, in the manufacturing process of the semiconductor device, for example, a heat treatment exceeding 300 ° C. may be necessary, and a resin substrate often has insufficient heat resistance.

Resin substrates have low hydrophilicity (wetting properties). For this reason, in order to form each layer constituting the semiconductor element on the surface of the substrate by a coating method, surface treatment or the like may be necessary, which is disadvantageous in terms of productivity. In addition, the resin substrate has low chemical resistance, and when a coating method is used, it is necessary to select a solvent.
Resin substrates often degas such as moisture that inevitably remains inside. Therefore, when each layer constituting the element is formed on the surface of the substrate by a vapor deposition method (vapor deposition method) such as vacuum deposition, a degassing step is required before the formation. It is disadvantageous in terms. In particular, when an organic semiconductor material is used for a photoelectric conversion layer or the like, the influence of moisture on the characteristics of the element and the deterioration due to moisture are large. Therefore, it is important to suppress degassing (dehydration) in an element using an organic semiconductor material.

  In addition, the resin substrate has low adhesion to the upper layer (especially when the upper layer is an inorganic compound), triggered by stress such as bending, thermal stress accompanying temperature changes during use, etc. There is a risk of peeling.

On the other hand, in Patent Document 1, an insulating layer is provided on a metal foil, a lower power, a photoelectric conversion layer (electromotive force layer) and an upper electrode are formed thereon, and an organic thin film photoelectric conversion is used as the photoelectric conversion layer. Solar cells utilizing layers are described.
As the insulating layer, a metal oxide film formed by anodizing the surface of a metal foil is exemplified. Specifically, it is described that the surface of an aluminum foil is anodized to form an alumite film as an insulating layer.
In Patent Document 1, on a substrate formed with an insulating layer on the surface of a metal foil, by forming a semiconductor element that constitutes a solar cell, while ensuring sufficient heat resistance and flexibility of the element, A solar cell in which deterioration of an organic semiconductor material due to moisture is suppressed is obtained.

  Here, although not mentioned in Patent Document 1, it is known that the alumite film has a non-porous structure (barrier type) and a porous structure (porous type).

The barrier type alumite film is generally a dense metal oxide film. Therefore, the toughness is low, and a crack may occur due to a stress such as bending or a thermal stress accompanying a temperature change during use, and the insulating property may be lost.
Therefore, a substrate in which a barrier type alumite film is formed on an aluminum foil has disadvantages in terms of durability and the like as a substrate of a semiconductor device that requires flexibility.

  On the other hand, porous type anodized film has a porous structure, so stress is not concentrated, and it is compared with barrier type anodized film due to stress such as bending, or thermal stress accompanying temperature change during use. , Cracks hardly occur and insulation is high.

However, since the porous alumite film has a porous structure, components of a layer (such as a lower electrode) provided in the upper part of the insulating layer may enter the inside of the pores to form a conductive path. There is a problem that the insulating property is lowered.
Further, a substrate having a porous alumite film also has a problem of moisture adsorbed inside the pores. That is, when each layer for forming a semiconductor element is formed by a vapor deposition method, film formation at a sufficient degree of vacuum may be difficult due to evaporation (degassing) of moisture, and device characteristics may be deteriorated. . In addition, when an organic photoelectric conversion material is used, there is a problem of deterioration due to moisture that volatilizes over time.
In addition, the anodized film of aluminum, which is an amphoteric metal, has solubility in both acidic and basic solvents. Therefore, the porous type anodic oxide film having a porous structure has a problem that chemical resistance is inferior because of its high specific surface area. This is a problem particularly when providing each layer for forming a semiconductor element by a coating method.

As a substrate for a semiconductor device that can solve such problems, a substrate 12 with an insulating layer described in Patent Document 2 is known.
This substrate is formed by anodizing the surface of a metal substrate such as aluminum, providing an insulating oxide film, and providing a spin-on glass film on the insulating oxide film.

By forming a spin-on glass film on the anodized film, this substrate can compensate for unevenness and defects that occur during the formation of the anodized film and can be smoothed, so that sufficient insulation can be ensured. it can.
Also, by using this substrate for solar cells, etc., the unevenness of the microcrystalline grains at the junction of the photoelectric conversion layer (light absorption layer) can be smoothed, so that leakage current caused by non-uniformity of the junction is suppressed. Conversion efficiency can be further improved.

  Further, this substrate is covered with a porous anodic oxide film by a spin-on glass film. Therefore, even when the material of the semiconductor layer or the photoelectric conversion layer is formed by liquid phase coating of a precursor or coating of photoelectric conversion material fine particles such as semiconductor / CIGS, the precursor or compound fine particles are present inside the porous layer. Do not fit. Accordingly, a decrease in insulating properties is suppressed, and loss of materials can be reduced, so that semiconductor devices such as semiconductor elements and solar cells can be manufactured at low cost.

  In addition, since the pores of the anodized film are blocked, the apparent specific surface area is greatly reduced. As a result, current leakage due to moisture adsorbed inside the pores can be reduced, and insulation can be improved. Thus, even when a semiconductor element and a photoelectric conversion element are integrated, an element with low loss, low power consumption, and high conversion efficiency can be manufactured.

JP 2011-108883 A JP 2011-233874 A

However, according to the study by the present inventors, the semiconductor element characteristics that are expected stably can be obtained simply by using a substrate in which another layer is provided on the anodized film serving as an insulating layer. It is not possible to obtain a high-performance flexible semiconductor device.
In particular, a semiconductor device using an organic semiconductor material for a photoelectric conversion layer (a layer that expresses a target function such as photoelectric conversion), such as an organic thin-film solar cell, often does not have sufficient target characteristics.

  An object of the present invention is to solve the above-mentioned problems of the prior art, which can improve not only high flexibility but also productivity and yield, and also uses an organic semiconductor material for the photoelectric conversion layer. Even for semiconductor devices that use organic compounds, such as solar cells, it is possible to prevent deterioration of characteristics due to moisture, and also to prevent the occurrence of cracks in the anodic oxide film that becomes the insulating layer, resulting in excellent performance over a long period of time It is an object of the present invention to provide a substrate for a semiconductor device capable of obtaining a semiconductor device that exhibits the above and a semiconductor device using the substrate.

The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, the amount of dehydration from the substrate constituting the semiconductor device and the warpage generated on the substrate have a great influence on the performance of the semiconductor element formed on the substrate, and the anodic oxidation that becomes the insulating layer It was found that the internal stress of the film had a great influence on the occurrence of cracks.
The present invention achieves the above object by obtaining this finding.

  That is, in order to achieve the above object, a substrate for a semiconductor element of the present invention comprises a sheet-like aluminum base, an aluminum porous anodic oxide film formed by anodizing both sides of the aluminum base, and a double-sided anode. A protective layer made of a nonporous oxide containing silicon formed on at least one surface of the oxide film, and both the anodized films on both sides have a compressive strain at room temperature. A substrate for a semiconductor device is provided.

In such a substrate for a semiconductor device of the present invention, it is preferable that the thicknesses of the anodic oxide films on both sides are equal, the protective layer is formed on both sides, and the thicknesses are equal.
Moreover, it is preferable that both the distortions in the compression direction at room temperature of the anodized films on both sides are 0.005 to 0.25%.
Moreover, it is preferable that thickness is 300 micrometers or less.
Moreover, it is preferable that the amount of water to be released is 10 μg / cm ² or less.
Moreover, it is preferable that the surface roughness Ra of at least one of the protective layers is 20 nm or less.
Moreover, it is preferable that the contact angle with water with at least one surface of a protective layer is 80 degrees or less.
Moreover, it is preferable that the diameter of the pore which an anodized film has is 4-100 nm.
Moreover, it is preferable that the thickness of an anodized film is 0.5-20 micrometers.
Moreover, it is preferable that a protective layer does not contain an alkali metal.
The thickness of the protective layer is preferably not less than the diameter of the pores of the anodized film or not less than 20 nm and not more than 1 μm.
Moreover, it is preferable that an aluminum base material is formed with aluminum with a purity of 99% by mass or more.
The aluminum base material is preferably formed of aluminum containing at least one of magnesium and lithium and having an aluminum content of 95% by mass or more.
Moreover, it is preferable that the thickness of an aluminum base material is 5-260 micrometers.
Furthermore, it is preferable that the protective layer is formed by a coating method.

  Further, the semiconductor device of the present invention provides a semiconductor device in which a semiconductor element is formed on at least one of the protective layer using the substrate for a semiconductor device of the present invention.

In such a semiconductor device of the present invention, it is preferable that the semiconductor elements are integrated in series or in parallel.
The semiconductor element includes a photoelectric conversion layer, a lower electrode formed on at least a part below the photoelectric conversion layer, and a light transmissive upper electrode formed on at least a part on the photoelectric conversion layer. Is preferred.
Moreover, it is preferable that a photoelectric converting layer contains an organic compound.
Moreover, it is preferable to have a bus electrode which contacts an upper electrode.
Moreover, it is preferable to have an electron carrying layer containing a metal oxide between the photoelectric conversion layer and the upper electrode or the lower electrode.
It is preferable to have a switching circuit connected to the semiconductor element.

The dimming illumination device of the present invention provides a dimming illumination device using such a semiconductor device of the present invention.
The self-luminous display device of the present invention provides a self-luminous display device using such a semiconductor device of the present invention.
Moreover, the solar cell of this invention provides the solar cell using such a semiconductor device of this invention.
Furthermore, the reflective liquid crystal display device of the present invention provides a reflective liquid crystal display device using such a substrate for a semiconductor device of the present invention.

  As described above, the substrate for a semiconductor device of the present invention has an anodized film formed by anodizing both surfaces of the aluminum substrate on both surfaces of the sheet-like aluminum substrate, and anodized formed on both surfaces. A nonporous protective layer made of an oxide containing silicon is provided on at least one surface of the film. Moreover, the anodic oxide film used as an insulating layer has distortion of a compression direction at room temperature.

In the present invention, the anodized film functions as an insulating layer having flexibility. The warpage of the substrate can be suppressed by forming the anodized film on both sides. In addition, aluminum substrates with an anodized film formed on only one side are easily scratched because the back side is exposed to soft aluminum, and kinks are likely to enter, especially when the substrate is thin. For this reason, the manufacturing yield decreases and the reliability as an insulating substrate decreases. On the other hand, by using a substrate having an anodized film formed on both sides, these problems do not occur and the substrate 12 with an insulating layer is excellent. In roll-to-roll manufacturing, when the substrate is stacked and wound, if there is no anodized film on one side, the metal aluminum component adheres to the stacked lower anodized film and the insulating layer There is a problem that the function is deteriorated or metal contamination is caused. On the other hand, by forming an anodic oxide film on both sides of the substrate, there is an advantage that such a problem does not occur.
As described above, in an aluminum substrate with an insulating layer in which an anodized film is formed on both sides, productivity and yield can be improved, and further, deterioration of semiconductor characteristics of a semiconductor element formed on the substrate can be suppressed. .
Moreover, the nonporous protective layer made of an oxide containing silicon has an effect of suppressing dehydration from the porous anodic oxide film. Therefore, by having this protective layer on at least one surface, the problem that a semiconductor layer having high characteristics cannot be obtained by degassing during the process is solved. In addition, deterioration of the photoelectric conversion layer and the like due to moisture generated from the substrate over time can be suppressed. By suppressing this characteristic deterioration, high semiconductor performance can be maintained over a long period of time. In the substrate of the present invention, since the anodic oxide film is formed on both sides as described above, such a protective layer is preferably formed on both sides. In addition, the protective layer formed on the surface on which the semiconductor element is manufactured has functions such as flattening the surface on which the semiconductor element is formed and reducing the surface area due to pore blockage.
Furthermore, the anodic oxide coating on both sides has a compressive strain at room temperature. Therefore, cracks can be prevented from occurring in the anodic oxide film as the insulating layer even when subjected to bending strain or under conditions at high temperatures. Thereby, good insulation is demonstrated over a long period of time.

Preferably, as a substrate for a semiconductor device according to the present invention, a semiconductor element having high characteristics of flexibility can be obtained by using a material having an appropriate value for water content, surface roughness, and surface water contact angle. can get.
In particular, the use of a substrate having a low water content, that is, low dehydration, is extremely effective in improving initial characteristics and suppressing deterioration over time.

The semiconductor device (semiconductor device) and the reflective liquid crystal display device of the present invention using the substrate for a semiconductor device of the present invention, and the dimming illumination device, self-luminous display device and solar cell using the semiconductor device are good. In addition to the flexibility (flexibility), a device having durability and high characteristics can be obtained. In particular, when the semiconductor device of the present invention is used for an organic thin film solar cell, a solar cell that exhibits high photoelectric conversion efficiency and high flexibility can be manufactured.
Even when the module is formed by sealing, the dehydration with time from the substrate is extremely small, so that the semiconductor element hardly deteriorates.
Therefore, in particular, in an organic thin film solar cell, since the photoelectric conversion layer does not deteriorate with time, high conversion efficiency is maintained over a long period of time. Also, in other semiconductor devices, for example, zinc oxide used for the transparent electrode does not deteriorate with time, so that high characteristics are maintained over a long period of time.

It is a figure which shows notionally an example of the board | substrate for semiconductor devices of this invention. It is a figure which shows notionally an example of the solar cell of this invention. It is a figure which shows notionally another example of the solar cell of this invention. It is a figure which shows notionally an example of the light control type illuminating device of this invention. (A) and (B) are figures which show notionally an example of the reflection type liquid crystal display device of this invention, and (C) is a figure which each shows an example of a normal liquid crystal display device notionally.

  Hereinafter, a substrate for a semiconductor device, a semiconductor device, a dimming illumination device, a self-luminous display device, a solar cell, and a reflective liquid crystal display device according to the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings. To do.

FIG. 1 conceptually shows an example of a semiconductor device substrate of the present invention.
A substrate 10 for a semiconductor device (hereinafter referred to as a substrate 10) shown in FIG. 1 basically includes a base 12 made of aluminum, an anodized film 14 formed on both surfaces of the base 12, and both anodized. And a protective layer 16 formed on the surface of the film 14. The protective layer 16 is made of a nonporous oxide containing silicon.
Such a substrate 10 of the present invention has high insulation and excellent flexibility (flexibility), and various semiconductor devices such as a dimming illumination device, a self-luminous display device, and a solar cell. The present invention is suitably used for such semiconductor devices and reflective liquid crystal display devices.

  Although there is no limitation in the thickness of the board | substrate 10 of this invention, 300 micrometers or less are preferable. By setting the thickness to 300 μm or less, the substrate 10 having suitable flexibility can be obtained.

Moreover, it is preferable that the board | substrate 10 has few curvature, and it is preferable that a curvature radius is 1 m or more especially at room temperature (25 degreeC).
By setting the radius of curvature of the substrate 10 at room temperature to 1 m or more, formation of each layer constituting the semiconductor element on the substrate 10 can be facilitated, that is, process suitability can be enhanced. In addition, by setting the radius of curvature of the substrate 10 to 1 m or more, a semiconductor element can be easily and properly manufactured on the substrate 10, so that the yield of the semiconductor device can be improved and the characteristics of the semiconductor device can also be improved.
In addition, the curvature of the board | substrate 10 is made small by forming the anodized film 14 and the protective layer 16 symmetrically (plane symmetry) in the possible range centering on the base material 12 (the center of the thickness direction). be able to.

The substrate 10 preferably releases a small amount of water, and particularly preferably 10 μg / cm ² or less. The moisture release amount of the substrate 10 is more preferably 5 μg / cm ² or less, and particularly preferably ² μg / cm ² or less.
Moisture contained in the substrate 10 is released over time even during the manufacture of the semiconductor element formed thereon and after the semiconductor device is completed. This moisture adversely affects each layer constituting the semiconductor element, such as a photoelectric conversion layer.
On the other hand, by setting the amount of moisture released from the substrate 10 to 10 μg / cm ² or less, the initial characteristics of the semiconductor element (semiconductor device) can be improved, and deterioration over time can be suppressed.

As described above, the substrate 10 has the anodized film 14 formed by anodic oxidation of aluminum on both surfaces of the aluminum base material 12, and the protective layer 16 thereon.
Such a substrate 10 is formed by anodizing both surfaces of a sheet-like (plate-like / film-like) aluminum material to be a base material 12 to form an anodized film 14. Alternatively, the protective layer 16 is formed by a vapor deposition method.

The substrate 12 is preferably a high-purity aluminum material, and particularly preferably has an aluminum content of 99% by mass or more.
By increasing the purity of the base material 12, the insulating property of the anodized film 14 can be increased. In particular, when the purity of aluminum is 99% by mass or more, the anodic oxide film 14 having sufficient insulation can be formed.

The substrate 12 is made of aluminum and inevitable impurities. Most of the inevitable impurities are contained in the aluminum ingot. If the inevitable impurities are contained in, for example, a metal having an aluminum purity of 99.7% to 99.99%, the effect of the present invention is not impaired.
As for the inevitable impurities, for example, the amount of impurities described in “Aluminum Alloys: Structure and properties” (1976) by LF Mondolfo may be contained. Examples of inevitable impurities contained in aluminum include, for example, zinc, titanium, boron, gallium, nickel, lithium, beryllium, scandium, molybdenum, silver, germanium, selenium, niobium, dysprosium, gold, potassium, rubidium, cesium, strontium, Yttrium, hafnium, tungsten, niobium, tantalum, technetium, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, indium, thallium, arsenic, selenium, tellurium, polonium, praseodymium, samarium, terbium, barium, cobalt, cadmium, Exemplified are one or more elements selected from the group consisting of bismuth, lanthanum, sodium, calcium, zirconium, chromium, vanadium, phosphorus, and sulfur. 00ppm may contain a.
Preferably, the inevitable impurities contained in the aluminum are at least one element of silicon, iron, copper, manganese, zinc, chromium, titanium, lead, nickel, gallium, zirconium, vanadium, scandium, boron, sodium, and the content thereof The amount is preferably 0 to 0.008% by mass, more preferably 0 to 0.006% by mass, and particularly preferably 0 to 0.005% by mass.

In addition, the base material 12 may contain manganese and / or lithium 1 mass% or more exceptionally besides aluminum.
In this case, the base material 12 preferably contains 95% by mass or more of aluminum. That is, the base material 12 may be an aluminum alloy containing 1 to 5% by mass of manganese and / or lithium, with the balance being aluminum or further unavoidable impurities.

When the base material 12 contains manganese, the anodic oxide film 14 can be formed with low energy.
The anodic oxide film 14 is generally produced by flowing a constant current for a certain period of time (constant current electrolysis) or applying a constant voltage for a certain period of time (constant voltage electrolysis) using aluminum immersed in an electrolytic solution as an anode. In the case of constant current electrolysis, the addition of manganese to aluminum lowers the anodic oxidation voltage. Therefore, less power is required and the anodized film 14 can be formed with low energy. On the other hand, in the case of constant voltage electrolysis, when manganese is added to aluminum, the anodic oxidation current increases, and an anodic oxide film having the same thickness can be obtained in a short time. Therefore, less electric power is required and manufacturing with low energy becomes possible.
Further, the addition of manganese increases the strength of the aluminum alloy, so that even in roll-to-roll manufacturing that transports while applying tension, distortion of the substrate is not easily generated, and the yield in manufacturing the substrate is increased. Therefore, the cost of the substrate 10 can be reduced.
Furthermore, the addition of manganese makes it difficult for the aluminum to soften during heating, makes it difficult for cracks to form in the anodized film, and improves the insulation reliability of the substrate 10.

In the base material 12, the content (addition amount) of manganese is preferably 1 to 5% by mass, and particularly preferably 2 to 5% by mass or less.
When the base material 12 contains 1% by mass or more of manganese, the effect of adding manganese is preferably obtained, and the anodic oxide film 14 can be formed with low energy. Further, by setting the manganese content of the base material 12 to 5% by mass or less, softening of the aluminum-manganese material portion when the substrate 10 is heated to high temperature for the formation of a semiconductor element or the like is suppressed, and the protective layer 16 Each layer constituting the semiconductor element formed thereon can be suitably held.

Moreover, when the base material 12 contains lithium, the anodic oxide film 14 can be formed with low energy as in the case of containing manganese.
In the base material 12, the lithium content (addition amount) is preferably 1 to 5% by mass, and particularly preferably 2 to 5% by mass or less.
When the substrate 12 contains 1% by mass or more of lithium, the effect of lithium addition is suitably obtained, and the anodic oxide film 14 can be formed with low energy. In addition, by making the lithium content of the base material 12 5% by mass or less, the softening of the aluminum-lithium material portion when the substrate 10 is heated to a high temperature (same as above) for forming a semiconductor element or the like is suppressed. Each layer constituting the semiconductor element formed on the protective layer 16 can be suitably held.
Note that manganese and lithium may be used in combination.

Although there is no limitation in the thickness (thickness of the aluminum part except the anodic oxide film 14 after anodizing sheet-like aluminum) of the base material 12, 5-260 micrometers is preferable.
By setting the thickness of the base material 12 to 5 μm or more, the influence on the base material 12 due to heating during the formation of a semiconductor element or the like can be suppressed, and the entire substrate 10 can be suitably prevented from being softened. In addition, by setting the thickness of the base material 12 to 260 μm or less, it is possible to stably ensure suitable flexibility.

An anodized film 14 is formed on both surfaces of the substrate 12. As described above, the anodized film 14 is formed by anodizing both surfaces of a sheet-like aluminum material to be the base 12.
This anodic oxide film 14 acts as an insulating layer for the semiconductor element formed on the substrate 10.

The types and thicknesses of the two anodic oxide films 14 may be the same or different.
From the viewpoint of suppressing the warpage of the substrate 10, the thicknesses of the two anodic oxide films 14 are preferably equal. Here, in the present invention, that the thickness of the two anodic oxide films 14 is equal means that the thickness of the other anodic oxide film 14 is within a range of ± 10% with respect to one thickness.

In the present invention, the two anodic oxide films 14 may be formed on one side or on both sides simultaneously.
When the anodic oxide film 14 is formed on both sides simultaneously, the types of the anodic oxide film 14 are the same, and generally the thicknesses are also equal.

The anodized film 14 usually has a porous structure having a large number of pores.
Since the anodized film 14 has a porous structure, the substrate 10 exhibits good flexibility. In addition, since the anodic oxide film 14 has a porous structure, damage such as cracking of the anodic oxide film 14 when the substrate 10 is bent can be prevented.

The pore diameter (diameter) of the anodized film 14 is preferably 4 to 100 nm.
By setting the pore diameter of the anodized film 14 to 4 nm or more, the specific surface area of the film can be prevented from becoming unnecessarily large, and an increase in moisture contained in the anodized film 14 can be suppressed. It is possible to sufficiently obtain a dehydration suppressing effect due to clogging of the pores, and to suitably prevent the performance of the semiconductor element from being deteriorated due to moisture.
In addition, a non-porous portion called a barrier layer is generated at the interface portion between the substrate 12 and the anodic oxide film 14. The thickness of the barrier layer is substantially proportional to the size of the pore diameter. Here, by setting the pore diameter of the anodized film 14 to 100 nm or less, it is possible to prevent the barrier layer from becoming unnecessarily thick and to increase the rigidity, and the substrate 10 having good flexibility can be obtained. Further, it is possible to prevent damage such as cracking of the anodic oxide film 14 when the substrate 10 is bent.

  The pore diameter of the anodized film 14 can be controlled by adjusting the anodizing conditions.

The thickness of the anodized film 14 is preferably 0.5 to 20 μm.
By setting the thickness of the anodic oxide film 14 to 0.5 μm or more, the substrate 10 can stably ensure sufficient insulation. Moreover, it can prevent that the influence of the base material 12 becomes large at the time of the heating in the case of formation of a semiconductor element, etc., and can prevent suitably the board | substrate 10 whole softening.
By setting the thickness of the anodic oxide film 14 to 20 μm or less, it is possible to suppress the increase in the overall rigidity and stably obtain the substrate 10 having excellent flexibility.

The anodized film 14 can be formed by known anodization of aluminum.
That is, the anodic oxide film 14 can form an anodic oxide film by immersing the aluminum material used as the base material 12 as an anode in an electrolytic solution together with a cathode, and applying a voltage between the anode and the cathode.
As the electrolytic solution, an acidic electrolytic solution containing one or more acids such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, malonic acid, tartaric acid, sulfamic acid, benzenesulfonic acid, and amidosulfonic acid is used. .

As described above, the pore diameter of the anodized film 14 is controlled by appropriately adjusting the anodizing conditions such as the type of the electrolyte, the concentration of the electrolyte, the temperature, the current density, the voltage, and the treatment time. can do.
Moreover, the anodic oxide film 14 may be simultaneously formed on both surfaces of the base material 14, or may be formed on each side using masking or the like.

Moreover, as for the board | substrate 10 of this invention, the anodized film 14 has a distortion of the compression direction c at room temperature (23 degreeC). Preferably, the anodized film 14 has a strain in the compression direction c of 0.005 to 0.25% (hereinafter also referred to as “compression strain”).
Since the anodic oxide film 14 has a compressive strain, it is possible to prevent the anodic oxide film 14 from being cracked even when exposed to a high temperature or when subjected to a bending force or the like. Therefore, the substrate 10 can maintain high insulation.
In particular, by having a compressive strain of 0.005% or more, the compressive force suitably acts on the anodized film 14, and a good crack resistance effect is obtained. On the other hand, if the compressive strain of the anodic oxide film 14 is too large, peeling of the anodic oxide film 14, generation of cracks due to too strong compressive strain, deterioration of flatness, etc. may occur, but the compressive strain is 0.25. By setting the ratio to not more than%, these inconveniences can be suitably prevented. Considering this point, the compressive strain of the anodized film 14 is particularly preferably 0.20% or less.

Conventionally, in a substrate for a semiconductor device in which an anodized film 14 is formed on a metal base material as an insulating layer, heat resistance at the time of manufacturing a semiconductor element, manufacturing at a roll-to-roll, and as a flexible substrate Bending resistance, long-term durability, and strength are issues.
The problem of heat resistance is due to the fact that the anodized film 14 cannot withstand the elongation of the metal base material when exposed to a high temperature, and the anodized film 14 breaks. This is because the difference in thermal expansion coefficient between the base material 12 and the anodized film 14 is large.

  Aluminum which is the base material 12 has a thermal expansion coefficient of 23 ppm / K, and the thermal expansion coefficient of the anodized film 14 is 4 to 5 ppm / K. For this reason, at a high temperature at which a difference in elongation occurs due to a difference in the thermal expansion coefficient, a tensile force is applied so that the anodized film 14 cannot withstand the elongation of the metal base material and the anodized film breaks. End up.

  The problem of bending resistance is caused by the fact that the anodized film 14 cannot withstand the tensile stress applied when the anodized film 14 is bent outward, and the anodized film 14 is broken.

  The problems of durability and strength are caused by the fact that the anodic oxide film 14 cannot withstand the stress change caused by the following disturbance and the anodic oxide film 14 is broken. Specific disturbances include thermal expansion / contraction of the substrate due to temperature increase / decrease associated with operation / stop for a long period of time on the anodic oxide film 14, anodic oxide film accompanying external stress, humidity / temperature / oxidation, etc.・ There are stresses associated with alteration and volume change of the semiconductor layer and sealing layer.

On the other hand, by giving a strain in the compression direction to the anodized film 14 at room temperature, heat resistance at the time of manufacturing a semiconductor element, manufacturing at a roll-to-roll, and bending resistance as a flexible substrate, An anodic oxide film 14 having long-term durability and strength can be realized.
The reason why crack resistance is improved by imparting strain in the compression direction to the anodized film 14 at room temperature can be explained as follows. Here, as an example, a mechanism for improving resistance to heat-resistant cracks will be schematically explained. It is estimated that a similar mechanism works throughout the improvement of sex.

The internal strain of the normal anodized film 14 is a tensile strain of about 0.005% to 0.06% at room temperature. Moreover, since the linear thermal expansion coefficient of the anodized film 14 is about 5 ppm / K, and the linear thermal expansion coefficient of aluminum is 23 ppm / K, in the case of the anodized film 14 on the aluminum substrate 12, As the temperature rises, tensile strain is applied to the anodized film 14 at a rate of 18 ppm / K. When a tensile strain of 0.16 to 0.23%, which is the breaking limit of the anodic oxide film 14, is applied, a crack is generated. This temperature is 120 ° C. to 150 ° C. for a normal anodic oxide film 14.
On the other hand, the anodized film 14 in the substrate 10 of the present invention has an internal strain of compressive strain at room temperature. Here, the linear thermal expansion coefficient of the anodized film 14 is about 5 ppm / K regardless of the type of film, and the anodized film 14 in the present invention is also about 5 ppm / K. Therefore, tensile strain is applied to the anodized film 14 at a rate of 18 ppm / K due to the temperature rise. The rupture limit of the anodized film 14 is estimated to be about 0.16 to 0.23% regardless of the type of film, and it is considered that cracking occurs when a tensile strain of this magnitude is applied.
In the case of an anodized film 14 having a compressive strain of 0.005% to 0.20% at room temperature, which is a preferred range, assuming that tensile strain is applied at a rate of 18 ppm / K, 0.16% to 0.00. A 23% tensile strain is applied at 170-340 ° C. Therefore, it is possible to prevent cracks from occurring even when exposed to high temperatures.

  Specifically, the anodic oxide film 14 having a compressive strain at room temperature is obtained by a method as described below. Of course, it goes without saying that these methods are not the only ones.

  One method for imparting strain in the compression direction is a technique in which the base material 12 is anodized in a state where the base material 12 is stretched more than the use state at room temperature. For example, there is no particular limitation as long as a tensile force can be applied in a tensile direction within a range of elastic deformation or a curvature can be applied. For example, when the roll-to-roll method is used, a tensile force is applied to the substrate 12 by adjusting the tension during conveyance, or the curvature of the substrate 12 is imparted with the shape of the conveyance path in the anodizing tank as a curved surface. By performing anodizing treatment in such a state, an anodized film 14 having a compressive strain of 0.005% to 0.20% at room temperature (23 ° C.) can be obtained.

There are also the following methods. A state in which compressive strain is applied to the anodized film 14 when the base material 12 is anodized using an aqueous solution having a temperature of 50 ° C. to 98 ° C. in a state where the base material 12 is stretched more than the use state at room temperature. To change. In this method, since the upper limit of the temperature of the aqueous solution used for anodization is about 100 ° C., the elongation amount of the base material 12 is limited to 0.1%. For this reason, the amount of compressive strain of the anodized film 14 is also 0.1%. Therefore, when compressive strain is applied to the anodized film 14 using an aqueous solution having a temperature of 50 ° C. to 98 ° C., the upper limit value of the compressive strain is about 0.1%.
Thus, when anodic oxidation is performed in an aqueous solution at 50 ° C. to 98 ° C., it is preferable to use an aqueous solution made of an acid having a pKa (acid dissociation constant) at a temperature of 25 ° C. of 2.5 to 3.5. .

There are also the following methods. When the base material 12 on which the anodized film 14 is formed is heated to a temperature at which the anodized film 14 is not broken and subjected to a heat treatment (annealing process) to return to room temperature, the substrate 12 is compressed into the anodized film 14. It changes to a distorted state. This is because, when the anodic oxide film 14 is stretched at a high temperature, the structural change occurs to reduce the tensile strain, and the compressive strain occurs in the anodic oxide film 14 as the aluminum material contracts when the temperature decreases.
The heat treatment for imparting compressive strain to the anodized film 14 is preferably performed under the conditions of a heating temperature of 100 to 600 ° C. and a holding time of 1 second to 100 hours. In this case, the heating temperature of the heat treatment is not higher than the softening temperature of the substrate 12.
By setting the heat treatment to 100 ° C. or higher, a compression effect can be suitably obtained. On the other hand, if the heating temperature of the heat treatment is too high, the anodized film 14 may be cracked due to the difference in thermal expansion coefficient between the base material 12 and the anodized film 14, but if the temperature is 600 ° C. or lower, Inconvenience can be prevented. In the present invention, since aluminum is used as the substrate 12, the higher the temperature, the more soft the aluminum, and there is a risk of causing deformation of the substrate 12. Therefore, the temperature of the heat treatment is preferably 300 ° C. or less, more preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower.
In addition, since the heat treatment can be compressed even after a short time, compressive strain can be suitably imparted to the anodic oxide film 14 by performing heat treatment for 1 second or longer. On the other hand, since the compression effect is saturated even if the heat treatment holding time exceeds 100 hours, the upper limit is set to 100 hours.
The heat treatment for imparting compressive strain to the anodic oxide film 14 may also serve as the heat treatment of the protective layer 16 described in detail later.

The compression effect of the anodic oxide film 14 by this heat treatment can be obtained regardless of the anodic oxidation conditions. That is, as the electrolytic solution used for anodic oxidation, an aqueous electrolytic solution such as an inorganic acid, an organic acid, an alkali, a buffer solution, or a mixed solution thereof, and a nonaqueous electrolytic solution such as an organic solvent or a molten salt can be used. Furthermore, it is possible to control the structure of the anodic oxide film 14 by the concentration, voltage, temperature, etc. of the electrolyte solution. It is possible to change to compressive strain.
Furthermore, whether the atmosphere during the heat treatment is a vacuum or an air atmosphere, a compression effect can be obtained in which the strain of the anodic oxide film 14 is similarly changed to a compressive strain.

  In the present invention, the anodic oxide film 14 to which compressive strain is applied is described, but the strain and stress have a primary relationship as long as it is within the elastic range, with the Young's modulus of the material as a coefficient. The same is true for the anodic oxide film 14 subjected to compressive stress. The Young's modulus of the anodized film 14 is 50 GPa to 150 GPa. From this value and the above-mentioned preferable range of compressive strain, the preferable range of compressive stress is as follows.

In the substrate 10, stress in the compression direction (hereinafter referred to as compression stress) acts on the anodized film 14 at room temperature, and the magnitude of this compression stress is 2.5 to 300 MPa. Preferably, the magnitude of the compressive stress is 5 to 300 MPa, more preferably 5 to 150 MPa, and particularly preferably 5 to 75 MPa.
By setting the compressive stress to 2.5 MPa or more, the compressive stress suitably acts on the anodic oxide film 14, and good crack resistance is obtained. On the other hand, if the compressive stress is too high, peeling or cracking of the anodized film 14 may occur, but such inconvenience can be prevented by setting the compressive stress to 300 MPa or less.
In addition, as described above, when an aqueous solution having a temperature of 50 ° C. to 98 ° C. is used and the base material 12 is stretched more than the use state at room temperature, the compressive strain is applied to the anodized film 14. It is difficult to give distortion. For this reason, the upper limit is about 150 MPa.

Next, a method for measuring strain of the anodized film 14 will be described.
In the present invention, first, the length of the anodized film is measured in the state of the substrate 10.
Next, the base material 12 is dissolved, the base material 12 is removed, and the anodized film 14 is taken out from the substrate 10. Thereafter, the length of the anodized film 14 is measured.
The distortion is determined from the length before and after the removal of the substrate 12.
When the length of the anodized film 14 becomes longer after the substrate 12 is removed, a compressive force is applied to the anodized film 14. That is, the anodic oxide film 14 is strained in the compression direction. On the other hand, when the length of the anodized film 14 becomes shorter after the substrate 12 is removed, a tensile force is applied to the anodized film 14. That is, the anodized film 14 is strained in the tensile direction.

The length of the anodic oxide film 14 before and after the removal of the base material 12 may be the entire length of the anodic oxide film 14 or a part of the length of the anodic oxide film 14.
When the substrate 12 is dissolved, for example, a copper chloride hydrochloric acid aqueous solution, a mercury chloride hydrochloric acid aqueous solution, a tin chloride hydrochloric acid aqueous solution, an iodomethanol solution, or the like is used. In addition, according to the composition of the base material 12, a solution for dissolving is appropriately selected.

In the present invention, in addition to removing the base material 12, for example, the amount of warpage / deflection of the base material 12 with high flatness is measured, and then the anodized film 14 is formed only on one side of the base material 12. Then, the warp / deflection amount of the base material 12 after the formation of the anodized film 14 is measured. The amount of warpage and deflection before and after the formation of the anodic oxide film 14 is used to convert the amount of distortion.
The warpage / deflection amount of the substrate 12 is measured by, for example, a method of optically measuring accurately using a laser. Specifically, various measurement methods described in “Surface Technology” 58, 213 (2007) and “Toyota Central R & D Review” 34, 19 (1999) are used to determine the amount of warpage and deflection of the substrate 12. Can be used for measurement.

  Moreover, you may measure the distortion of the anodic oxide film 14 as follows. In this case, first, the length of the aluminum thin film used as the base material 12 is measured. Next, the anodic oxide film 14 is formed on the aluminum thin film, and the length of the aluminum thin film at this time is measured. The amount of shrinkage is obtained from the length of the aluminum thin film before and after the formation of the anodized film, and further converted into the amount of strain.

  In addition, since it is the method of measuring the distortion amount of the anodic oxide film 14 in the state which left the base material 12 except the method of removing the base material 12, the influence of the base material 12 has been completely excluded. It's hard to say. For this reason, if it is the method of removing the base material 12, the distortion amount of the anodic oxide film 14 itself can be directly measured without being influenced by the base material 12. For this reason, it is preferable to use the method of removing the base material 12 which can measure the distortion amount of the anodic oxide film 14 correctly for the measurement of the distortion amount in the present invention.

  The internal stress of the anodized film 14 can be calculated from the formula of material mechanics from the Young's modulus of the anodized film 14 and the amount of strain existing in the anodized film 14. In addition, what is necessary is just to obtain | require distortion amount as mentioned above.

On the other hand, the Young's modulus of the anodic oxide film 14 can be obtained by an indenter indentation test using an indentation tester, a nanoindenter, or the like with respect to the anodic oxide film 14 in the state of the substrate 10.
Further, the Young's modulus of the anodic oxide film 14 is determined by removing the base material 12 from the substrate 10 and taking out the anodic oxide film 14. It can also be determined by testing.

  Further, only a sample in which an anodized film is formed on a metal thin film such as aluminum or the substrate 10 is taken out, and a tensile test is performed on the extracted anodized film 14 or a dynamic viscosity is obtained. The Young's modulus of the anodized film 14 may be obtained by measuring elasticity or the like.

Note that when the Young's modulus of a thin film is measured by an indentation test, it may be affected by the substrate 12, and therefore it is generally necessary to suppress the indentation depth to within about one third of the thickness of the thin film. . Therefore, in order to accurately measure the Young's modulus of an anodized film with a thickness of about several tens of μm, the Young's modulus is measured using a nanoindenter that can measure the Young's modulus even when the indentation depth is about several hundred nm. It is preferable to do.
Needless to say, the Young's modulus may be measured using a method other than those described above.

In the semiconductor device substrate of the present invention, the protective layer 16 is formed on at least one surface of the anodic oxide film 14 formed on both surfaces. In the illustrated example, as a preferred embodiment, protective layers 16 are formed on the surfaces of both anodized films 14 formed on both surfaces of the substrate 12. The protective layer 16 is a layer made of a non-porous oxide containing Si (a non-porous layer mainly composed of an oxide containing Si).
Thus, the board | substrate 10 of this invention can suppress the curvature of the board | substrate 10 more suitably because the anodic oxide film 14 is formed in both surfaces of the base material 12. FIG. By suppressing the warpage of the substrate 10, productivity and yield can be improved, and further, deterioration of semiconductor characteristics of the semiconductor element formed on the substrate can be suppressed.
Further, the protective layer 16 has an effect of blocking the pores of the porous anodic oxide film 14 and suppressing dehydration from here. Therefore, according to the present invention, it is possible to suppress deterioration of a semiconductor element such as a photoelectric conversion layer caused by moisture generated from the substrate 10. By suppressing this characteristic deterioration, high semiconductor performance can be maintained over a long period of time. For the purpose of reducing the amount of moisture generated from the substrate 10, the protective layer 16 is preferably formed on both surfaces of the anodized film 14 formed on both surfaces. Here, regarding the protective layer 16 formed on the surface on which the semiconductor element is manufactured, a semiconductor element having excellent characteristics can be formed by flattening the surface where the semiconductor element is formed and reducing the surface area due to pore blockage. it can.

The protective layer 16 is a nonporous layer made of an oxide containing silicon. As a material for forming the protective layer 16, various glass compounds mainly composed of silicon oxide can be used. Here, the material used for the protective layer 16 has a moisture content of 10 μg / cm ² by a material having a moisture content of 10 μg / cm ² or less, or a heat treatment at a temperature lower than the heat resistance temperature of the substrate, even without heat treatment. ^A material of ² or less is preferably used.
This material is composed of silicon-oxygen bonds and has a network structure, so that it has few hydrophilic functional groups and a low water content. More specifically, tetraalkoxysilane, organoalkoxysilane, polysilazane, alkali silicate and the like are exemplified.

Here, the protective layer 16 does not contain an alkali metal in consideration of adverse effects on each layer constituting a semiconductor element to be described later, in particular, an organic semiconductor material used for an organic thin film solar cell, an organic EL lighting device, or the like. Is preferred.
Thus, alkali silicate is a low cost material, but is preferably not used. That is, the protective layer 16 is preferably formed of an alkali silicate having an alkali component as low as possible, or tetraalkoxysilane, organoalkoxysilane, polysilazane or the like not containing an alkali component.

  However, when forming a negative electrode of an organic thin film solar cell or a cathode of an organic EL lighting device, which will be described later, on the protective layer 16, the alkali metal salt reduces the contact resistance at the interface between the electrode and the functional layer described later. The effect is known, and the protective layer 16 may contain an alkali metal as necessary for the purpose of improving the characteristics by diffusion of the alkali metal to the electrode-functional layer interface.

Polysilazane reacts with moisture and changes to silicon oxide. Therefore, when the protective layer 16 made of polysilazane is formed on the anodized film 14, the protective layer 16 can be formed while consuming moisture contained in the anodized film 14, that is, included in the substrate 10. It also has the effect of reducing the amount of moisture.
Therefore, the use of polysilazane as the material for forming the protective layer 16 makes it possible to produce the substrate 10 having a water content of 10 μg / cm ² or less even without heat treatment or even at a relatively low heat treatment temperature, and thus is particularly preferably used. .

The protective layer 16 (at least one when it is present on both sides) preferably has a surface roughness Ra (arithmetic mean roughness Ra) of 20 nm or less at 10 μm square.
By forming a semiconductor element on a surface having a surface roughness Ra of 20 nm or less, a semiconductor element having good initial characteristics and little deterioration with time can be formed. That is, by increasing the flatness of the surface, it is possible to suppress a decrease in the uniformity of the interface due to the adverse effect of the roughness of the formation surface and to form a high-performance element.
Therefore, the semiconductor device using the substrate 10 of the present invention is preferably formed on the protective layer 16 having a surface roughness Ra of 20 nm or less.
In the case where the protective layer 16 is provided on both sides as a preferred embodiment as in the illustrated example, it is preferable that the surface roughness Ra of the protective layer 16 on which at least a semiconductor element is supposed to be formed is 20 nm or less. . In other words, when the substrate 10 has the protective layers 16 on both surfaces and only one of the protective layers 16 has a surface roughness Ra of 20 nm or less, the semiconductor device of the present invention described later has a surface roughness. It is preferable to form a semiconductor device by manufacturing a semiconductor element on the protective layer 16 having an Ra of 20 nm or less.

In the substrate 10 of the present invention, the protective layer 16 is preferably formed by a coating method in order to reduce the surface roughness Ra.
In the substrate 10 of the present invention, the anodized film 14 has a porous structure. Therefore, when an oxide containing silicon is formed by the vapor phase film formation method, the inside of the pores may occur while the film thickness is relatively thin, and it may be difficult to obtain a uniform protective layer 16. Therefore, it is preferable to form a relatively thick protective layer 16.
In contrast, when a silicon-containing oxide film is formed by a coating method, a smooth surface is easily obtained due to the surface tension of the coating solution, and the pores of the porous anodized film are blocked even with a relatively thin film thickness. Therefore, it is easy to reduce the surface roughness Ra. In addition, the thickness of the relatively thin protective layer 16 is sufficient to provide a function such as degassing suppression. In addition to reducing the material cost, there is a concern that the function is deteriorated (described later) when the protective layer 16 is too thick. Is also reduced. In general, the film formation by the coating method is lower in cost than the gas phase method, which is an advantage that the coating method is more suitably used.

The protective layer 16 (at least one when it is present on both sides) has a surface contact angle with water of preferably 80 ° or less, more preferably 50 ° or less, and 20 ° or less. Is particularly preferred.
When the contact angle with water increases, the adhesion at the interface between the substrate 10 (protective layer 16) and the semiconductor element decreases, and peeling and the like are likely to occur, resulting in a decrease in element performance. On the other hand, by setting the contact angle of the surface of the protective layer 16 to 80 ° or less, the adhesion at the interface between the substrate 10 and the semiconductor element can be secured stably.
Therefore, the semiconductor device using the substrate 10 of the present invention is preferably formed on the protective layer 16 having a surface contact angle with water of 80 ° or less.
In addition, what is necessary is just to adjust the contact angle with the water of the protective layer 16 by a well-known method.
As in the above example, as in the illustrated example, when the protective layer 16 is provided on both sides as a preferred embodiment, at least the surface of the protective layer 16 on which the formation of the semiconductor element is supposed has a contact angle with water. It is preferably 80 ° or less. In other words, when the substrate 10 has the protective layers 16 on both surfaces and only one of the protective layers 16 has a contact angle with water of 80 ° or less, the semiconductor device of the present invention, which will be described later, It is preferable to form a semiconductor device by forming a semiconductor element on the protective layer 16 having a contact angle of 80 ° or less.

The thickness of the protective layer 16 is preferably not less than the pore diameter of the anodized film 14 or not less than 20 nm and not more than 1 μm.
By setting the thickness of the protective layer 16 to be equal to or larger than the pore diameter of the anodic oxide film 14 or 20 nm or more, the pores of the anodic oxide film 14 are sufficiently blocked and dehydration (degassing) from the pores. Can be suitably suppressed. As a result, when forming each layer constituting the semiconductor element on the substrate 10 (protective layer 16) by a vapor deposition method, a high-quality layer is formed in a state where the degree of vacuum is sufficiently lowered. Can do. Moreover, since it is possible to suppress the release of moisture from the substrate 10 during use of the semiconductor device, it is possible to prevent the occurrence of problems such as degradation of semiconductor element performance due to the influence of moisture.
Furthermore, by setting the thickness of the protective layer 16 to be equal to or larger than the pore diameter of the anodic oxide film 14 or 20 nm or more, the surface of the substrate 10 can be sufficiently flattened and the surface roughness Ra can be reduced. The layers constituting the semiconductor element to be formed can be made uniform uniformly, and the semiconductor element with good characteristics can be manufactured by reducing the resistance value at the electrode-semiconductor interface, suppressing the occurrence of pn junction defects in the semiconductor, and the like.
In addition, when the thickness of the protective layer 16 is not less than the pore diameter of the anodic oxide film 14 or not less than 20 nm, the inside of the pores is formed when each layer constituting the semiconductor element is formed on the substrate 10 by a coating method. Since it is possible to prevent the coating solution from entering the substrate, even if an acidic or alkaline coating solution is used, partial dissolution of the anodic oxide film 14, deterioration of insulation caused by this, and peeling can be prevented. .

By setting the thickness of the protective layer 16 to 1 μm or less, it is possible to prevent the rigidity of the protective layer 16 from becoming unnecessarily high, and the substrate 10 having excellent flexibility can be obtained.
Further, by setting the thickness of the protective layer 16 to 1 μm or less, it is possible to prevent the protective layer 16 from cracking or cracking when the substrate 10 is bent. Furthermore, when the protective layer 16 is formed by the liquid phase method, it is possible to prevent the protective layer 16 from being cracked or peeled off due to the shrinkage accompanying the drying of the solvent.

In addition, when it has the protective layer 16 on both surfaces like the example of illustration, the composition and thickness of the two protective layers 16 may be equal or different.
From the viewpoint of suppressing the warpage of the substrate 10, it is preferable that the thicknesses of both protective layers 16 are equal. That is, in the present invention, it is preferable that the thicknesses of the anodic oxide films 16 on both sides are equal, the protective layers 16 are provided on both sides, and the thicknesses of the protective layers 16 on both sides are equal.
Here, in the present invention, that the thicknesses of the two protective layers 10 are equal means that the thickness of the other protective layer 10 is within a range of ± 10% with respect to one thickness.

Such a protective layer 16 can be formed by a method for forming a layer (thin film / film) made of a known silicon compound.
As an example, a coating solution (coating material) whose main component is a compound that becomes the protective layer 16 such as tetraalkoxysilane is prepared, and this coating solution is applied to the surface of the anodized film 16 by a coating method or a sol-gel method. A method is illustrated.
Various known methods can be used for applying the coating solution. Among these, by using dip coating, it is generally possible to form the protective layer 16 simultaneously on both sides, which is preferable from the viewpoint of productivity. Further, by using dip coating, generally, the thicknesses of both protective layers 16 can be made equal.

You may heat-process as needed, after apply | coating a coating liquid.
The temperature of the heat treatment is preferably lower than the heat resistance temperature of the substrate 12, preferably 400 ° C. or less, more preferably 300 ° C. or less, and particularly preferably 200 ° C. or less.
Generally, dehydration from a material progresses and heat content is reduced as heat treatment is performed at a higher temperature, but the heat treatment temperature has an upper limit in relation to the heat-resistant temperature of the substrate.
The heat treatment time may be appropriately set according to the material for forming the protective layer 16 and the like, but is usually about 1 to 100 minutes.

  Alternatively, sputtering using the material of the protective layer 16 to be formed as a target, plasma CVD using a component that forms the protective layer 16 by reaction as a raw material gas, vacuum deposition using the material of the protective layer 16 to be formed as a film forming material, etc. The protective layer 16 may be formed by a vapor deposition method (vapor deposition method / vacuum deposition method).

  The protective layer 16 may be formed simultaneously on the surfaces of the anodic oxide films 14 on both sides, or may be formed on each surface of the anodic oxide film 14 using masking or the like.

The semiconductor device of the present invention is obtained by forming various semiconductor elements on the surface of the substrate 10 of the present invention. In the semiconductor device of the present invention, when the substrate 10 has the protective layers 16 on both surfaces, the semiconductor element is formed on the surface of at least one of the protective layers 16. On the other hand, when the substrate 10 has the protective layer 16 only on one side, the semiconductor device of the present invention forms a semiconductor element on the surface of the protective layer 14.
In the semiconductor device of the present invention, a plurality of semiconductor elements may be integrated on the surface of the substrate 10 in series and / or in parallel.

  Specific examples of the semiconductor device include a solar cell, a self-luminous display device, and a dimming illumination device.

As described above, the substrate 10 of the present invention has high flexibility, less warpage, and less moisture release (degassing amount).
Therefore, the semiconductor device of the present invention using the substrate 10 of the present invention can obtain a semiconductor device having high characteristics in addition to good flexibility. In particular, when the semiconductor device of the present invention is used for an organic thin film solar cell, a solar cell that exhibits high photoelectric conversion efficiency and high flexibility can be manufactured.
Even when the module is formed by sealing, the dehydration with time from the substrate is extremely small, so that the semiconductor element hardly deteriorates. Therefore, in particular, in an organic thin film solar cell, since the photoelectric conversion layer does not deteriorate with time, high conversion efficiency is maintained over a long period of time. Also, in other semiconductor devices, for example, zinc oxide used for the transparent electrode does not deteriorate with time, so that high characteristics are maintained over a long period of time.

FIG. 2 conceptually shows an example in which the semiconductor device of the present invention is used for an organic thin film solar cell.
An organic thin film solar cell 20 (organic thin film solar cell element 20) shown in FIG. 2 is obtained by forming a photoelectric conversion layer (light absorption layer) using an organic semiconductor material. The lower electrode 24, the photoelectric conversion layer 26, the upper electrode 28, the sealing layer 30 and the gas barrier film 32 are laminated in this order on one surface of the substrate 10 of the present invention composed of the protective layer 16. Moreover, the solar cell 20 of the example of illustration has the bus electrode 34 which contacts the upper electrode 28 and becomes auxiliary metal wiring as a preferable aspect.
This organic thin film solar cell 20 (hereinafter referred to as solar cell 20) is basically the same as a known organic thin film solar cell except that the substrate 10 of the present invention is used.
In addition, each layer forming the solar cell including a layer (not shown) such as an electron transport layer and a hole transport layer described later may be a single layer or a plurality of layers.

In addition, the solar cell 20 of the example of illustration has shown only one element which comprises a solar cell on the board | substrate 10 of this invention.
However, the present invention is not limited to this, and a plurality of elements may be integrated in series and / or in parallel. Alternatively, the semiconductor device of the present invention may be obtained by integrating a plurality of semiconductor devices in series and / or in parallel. In this case, a plurality of elements and semiconductor devices to be integrated may be the same or different.
In this regard, the same applies to a dimming illumination device and a self-luminous display device described later, and to the other semiconductor devices of the present invention.

In the solar cell 20, the lower electrode 24 is formed on the substrate 10.
The material for forming the lower electrode 24 can be appropriately selected from known electrode materials. When the lower electrode 24 functions as a negative electrode, metals such as magnesium, aluminum, calcium, titanium, chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, bismuth, and alloys thereof are preferably used. It is done.
On the other hand, when the lower electrode 24 functions as a positive electrode, metals such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, tantalum, tungsten, platinum, and gold, alloys thereof, and transparent conductive oxide (TCO) Conductive polymers such as polyaniline, polythiophene and polypyrrole are preferably used. Details of the conductive polymer layer suitable for the lower electrode 24 are disclosed in JP 2012-43835 A, polythiophene derivatives are preferable, and polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) is more preferable. These metals, TCO, and conductive polymers may be used alone or in combination or laminated.
In addition, when providing the below-mentioned electron carrying layer or hole transport layer on the lower electrode 24, the lower electrode 24 formation material is not limited to these.

The lower electrode 24 may be formed by a known method.
For example, from the wet film formation method by coating or printing, vacuum vapor deposition method, sputtering method, physical vapor deposition method such as ion plating method (PVD method), dry film formation method by various CVD methods, etc. It may be formed by a method appropriately selected in consideration of suitability with the formed material.
Patterning for forming the lower electrode 24 may also be performed by a known method. That is, it may be performed by chemical etching such as photolithography, may be performed by physical etching using a laser, etc., may be performed by vacuum deposition, sputtering, or the like by overlaying a shadow mask, or a lift-off method or a printing method. May be performed.
The thickness of the lower electrode 24 can be appropriately selected depending on its constituent materials and cannot be generally defined. However, from the viewpoint of conductivity, it is usually about 0.01 to 10 μm, and 0.05 to 1 μm is preferable.

A photoelectric conversion layer 26 is formed on the lower electrode 24.
After the photoelectric conversion layer 26 receives visible light such as sunlight and generates excitons (electron-hole pairs), the excitons dissociate into electrons and holes, and the electrons move to the negative electrode side. The material is selected from materials that exhibit a highly efficient photoelectric conversion process of being transported to the positive electrode side. In the case of an organic thin film solar cell, a photoelectric conversion layer including an electron donating region (donor) made of an organic material is formed, and from the viewpoint of conversion efficiency, a bulk heterojunction type photoelectric conversion layer 26 (hereinafter referred to as “to bulk”). The “terror layer” is also preferably applied.
The bulk hetero layer is an organic photoelectric conversion layer in which an electron donating material (donor) and an electron accepting material (acceptor) are mixed. The mixing ratio of the electron donating material and the electron accepting material is adjusted so that the conversion efficiency is the highest, but is usually selected from the range of 10:90 to 90:10 by mass ratio. As a method for forming such a mixed layer, for example, a co-evaporation method is used. Or it is also possible to produce by carrying out solvent application | coating using the solvent common to both organic materials.
The thickness of the bulk hetero layer is preferably 10 to 500 nm, particularly preferably 20 to 300 nm.

An electron-donating material (also referred to as a donor or a hole transporting material) is a π-electron conjugated compound having a highest occupied orbital (HOMO) level of 4.5 to 6.0 eV.
Specifically, conjugated polymers and phenylene vinylene polymers obtained by coupling various arenes (for example, thiophene, carbazole, fluorene, silafluorene, thienopyrazine, thienobenzothiophene, dithienosilole, quinoxaline, benzothiadiazole, thienothiophene). And porphyrins and phthalocyanines. In addition, a compound group described as Hole-Transporting Materials in Chemical Reviews vol. 107, pages 953 to 1010 (2007) and a porphyrin described in Journal of the American Chemical Society vol. 131, page 16048 (2009). Derivatives are also applicable.
Among these, a conjugated polymer obtained by coupling a structural unit selected from the group consisting of thiophene, carbazole, fluorene, silafluorene, thienopyrazine, thienobenzothiophene, dithienosilole, quinoxaline, benzothiadiazole, and thienothiophene is particularly preferable. Specific examples include poly-3-hexylthiophene (P3HT), poly-3-octylthiophene (P3OT), various polythiophene derivatives described in Journal of the American Chemical Society vol. 130, page 3020 (2008), Advanced Materials No. PCTBT described in Vol. 19, p. 2295 (2007), Journal of the American Chemical Society vol. 130, PCDTQx, PCDTPP, PCDTPT, PCDTBX, PCDTPX, Nature Photonics vol. 3, 649 described in p. 732 (2008) PBDTT-E, PBDTTTT-C, PBDTTTT-CF described in page (2009), PTB7 described in Advanced Materials Vol. 22, E135-E138 (2010), and the like.

An electron-accepting material (also referred to as an acceptor or an electron-transporting material) is a π-electron conjugated compound whose lowest unoccupied orbital (LUMO) level is 3.5 to 4.5 eV.
Specific examples include fullerene and derivatives thereof, phenylene vinylene polymers, naphthalene tetracarboxylic imide derivatives, and perylene tetracarboxylic imide derivatives. Of these, fullerene derivatives are preferred. Specific examples of fullerene derivatives include C ₆₀ , phenyl-C ₆₁ -butyric acid methyl ester (fullerene derivatives referred to as PCBM, [60] PCBM, or PC ₆₁ BM in the literature), C ₇₀ , phenyl-C ₇₁ -butyric acid. Methyl esters (fullerene derivatives referred to as PCBM, [70] PCBM, or PC ₇₁ BM in many literatures), and fullerene derivatives described in Advanced Functional Materials Vol. 19, pages 779-788 (2009), Journal Examples include fullerene derivatives SIMEF described in the American Chemical Society vol. 131, page 16048 (2009), fullerene derivatives ICBA described in Journal of the American Chemical Society vol. 132, page 1377 (2010), and the like.

An upper electrode 28 is formed on the photoelectric conversion layer 26.
The upper electrode 28 is preferably formed of a transparent conductive film in order to allow light to enter the photoelectric conversion layer. Examples of the transparent conductive film include metals, metal oxides, conductive polymers, mixtures thereof, and laminated structures. Specific examples include TCO such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), metals and metals mentioned as the lower electrode 24 described above. Examples include ultrathin alloy films, conductive polymers such as polyaniline, polythiophene, and polypyrrole. Particularly preferred as TCO materials are ITO, IZO, tin oxide, antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), zinc oxide, antimony doped zinc oxide (AZO), gallium doped zinc oxide (GZO). Any of the materials.
The upper electrode 28 may be formed by a known method. For example, in consideration of suitability with the above-mentioned constituent materials from among PVD methods such as wet film formation methods by coating and printing, vacuum deposition methods, sputtering methods, ion plating methods, and dry film formation methods by CVD methods. What is necessary is just to form by the method selected suitably.
Patterning for forming the upper electrode may be performed by a known method. That is, it may be performed by chemical etching such as photolithography, may be performed by physical etching using a laser, etc., may be performed by vacuum deposition, sputtering, or the like by overlaying a shadow mask, or a lift-off method or a printing method. You may go by.
The thickness of the upper electrode 28 can be appropriately selected depending on the material of the upper electrode 28, and cannot be generally defined. In addition, from a viewpoint of electroconductivity, it is about 0.01-10 micrometers normally, and 0.05-1 micrometer is preferable.

  In the solar cell 20 of the present invention, either the lower electrode 26 or the upper electrode 28 may be a positive electrode and the other may be a negative electrode.

In the solar cell 20 of the present invention, an electron transport layer made of an electron transport material may be provided between the photoelectric conversion layer 26 and the negative electrode.
Examples of the electron transporting material that can be used for the electron transporting layer include the electron-accepting materials mentioned in the photoelectric conversion layer 26 described above, and Electron-Transporting and Hole- in Chemical Reviews Vol. 107, pages 953 to 1010 (2007). The thing described as Blocking Materials is mentioned. Various metal oxides are also preferably used as materials for highly stable electron transport layers, such as lithium oxide, magnesium oxide, aluminum oxide, calcium oxide, titanium oxide, zinc oxide, strontium oxide, niobium oxide, ruthenium oxide, and indium oxide. Zinc oxide and barium oxide. Of these, relatively stable aluminum oxide, titanium oxide, and zinc oxide are more preferable.
The film thickness of the electron transport layer is usually about 0.1 to 500 nm, preferably 0.5 to 300 nm.
The electron transport layer can be suitably formed by any of a wet film formation method such as coating, a dry film formation method such as vapor deposition and sputtering, a transfer method, and a printing method.

In the solar cell 20 of the present invention, a hole transport layer made of a hole transport material may be provided between the photoelectric conversion layer 26 and the positive electrode.
Examples of the hole transporting material that can be used for the hole transporting layer include the electron donating materials exemplified for the photoelectric conversion layer 26 described above. The conductive polymer mentioned for the lower electrode 24 is also preferable as a stable hole transport material. Various metal oxides are also used as a material for the hole transport layer having high stability. For example, vanadium oxide, molybdenum oxide, and tungsten oxide are preferable.
The film thickness of a positive hole transport layer is about 0.1-500 nm normally, Preferably it is 0.5-300 nm.
The hole transport layer can be suitably formed by any of a wet film formation method such as coating, a dry film formation method such as vapor deposition and sputtering, a transfer method, and a printing method.

Further, in the solar cell 20 of the present invention, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide is formed between the photoelectric conversion layer 26 and the negative electrode in a thickness of 0.1 to 5 nm. It may be inserted. This dielectric layer can also be regarded as a kind of electron injection layer.
The dielectric layer can be formed by, for example, a wet film formation method by coating or the like, or a dry film formation method by PVD method such as vapor deposition.

In addition to these layers, the solar cell 20 of the present invention includes auxiliary layers such as a hole injection layer, an electron blocking layer, an electron injection layer, a hole blocking layer, and an exciton diffusion preventing layer as necessary. You may have.
In the present invention, the photoelectric conversion layer 26 (bulk hetero layer), hole injection layer, hole transport layer, electron blocking layer, electron injection layer, electron transport layer formed between the lower electrode 24 and the upper electrode 28 are formed. The term “functional layer” is used as a general term for layers that transport electrons and holes, such as a hole blocking layer and an exciton diffusion preventing layer.
When the film thickness of the functional layer such as the photoelectric conversion layer 26 between the lower electrode 24 and the upper electrode 28 is small and / or the film thickness of the lower electrode 24 is large, the step on the outer edge of the lower electrode 24 is defined as the functional layer. May not be completely covered, and defects (cracks, pinholes, etc.) may occur, which may cause a contact between the upper electrode 28 and the lower electrode 24, and thus a short circuit. . For the planarization layer and the partition wall, a material constituting the gas barrier layer described later is preferably used, and in particular, an inorganic material such as silicon nitride, silicon oxide, silicon nitride oxide, or a polymer such as (meth) acrylate is used. it can.

A sealing layer 30 (sealant) is formed on the upper electrode 28 as necessary.
The sealing layer 30 is a layer for preventing a substance that degrades the photoelectric conversion layer 26 (photoelectric conversion material) such as water or oxygen from entering the photoelectric conversion layer 26. The sealing layer 30 may be a single layer or a multilayer structure.
As a material for forming the sealing layer 30, magnesium oxide, aluminum oxide, silicon oxide (SiO _x ), titanium oxide, germanium oxide, yttrium oxide, zirconium oxide, hafnium metal oxide, silicon nitride (SiN _x ), and the like Metal nitride, metal nitride oxide (metal oxynitride) such as silicon nitride oxide (SiO _x N _y ), metal fluoride such as lithium fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, diamond-like Inorganic materials such as carbon (DLC) can be given.
An organic material can also be used as a material for forming the sealing layer 30. Examples of the organic material include polymers such as polyimide, polyethylene, polyparaxylylene, polyvinyl alcohol, and polypropylene, acrylic resins, silicone resins, urea resins, and fluorine resins. Of these, metal oxides, nitrides, nitride oxides and DLC are preferred, and silicon, aluminum oxides, nitrides and nitride oxides are particularly preferred.

  There are no limitations on the method for forming the sealing layer, and various methods including, for example, PVD methods such as vacuum deposition, sputtering, ion plating, and plasma polymerization, and atomic layer deposition (ALD and ALE methods). A CVD method, a coating method, a printing method, and a transfer method can be applied.

A gas barrier film 32 is provided on the upper electrode 28 or the sealing layer 30.
As with the sealing layer 30, the gas barrier film 32 is provided to prevent a substance that degrades the photoelectric conversion layer 26 (photoelectric conversion material) such as water or oxygen from entering the photoelectric conversion layer 26.

Examples of the gas barrier film include a configuration in which the material exemplified above as the sealing layer 30 is formed as a gas barrier layer on a PET (polyethylene terephthalate) film or a PEN (polyethylene naphthalate) film. These may be pure substances, or may be a mixture of multiple compositions or a gradient composition. Of these, oxides, nitrides, and nitride oxides of silicon and aluminum are preferable.
The gas barrier layer may be a single layer or a plurality of layers. An organic material layer and an inorganic material layer may be laminated, or a plurality of inorganic material layers and a plurality of organic material layers may be alternately laminated. The organic material layer is not particularly limited as long as it has smoothness, but a layer made of a polymer of (meth) acrylate is preferably used. The above-mentioned protective layer material is preferable for the inorganic material layer, and silicon, aluminum oxide, nitride, and nitride oxide are particularly preferable.
Although there is no limitation in the thickness of an inorganic material layer, it is attached to 1 layer, and is usually 5-500 nm, Preferably it is 10-200 nm. The inorganic material layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as disclosed in US Patent Application Publication No. 2004/0046497, the interface with the organic material layer made of a polymer is not clear, and the layer may be a layer whose composition continuously changes in the film thickness direction. .

The gas barrier film 32 may be provided by a known method such as adhesion using a transparent adhesive, heat fusion to the sealing layer 30 via various sealant materials, vacuum heating lamination, or the like.
The gas barrier film 32 is preferably provided on the sealing layer 30 such that a support such as a PET film is on the outer side (the side opposite to the sealing layer 30, that is, the gas barrier layer is on the inner side).
A surface functional layer may be provided outside the gas barrier film 32 (on the side opposite to the sealing layer 30) as necessary. Examples of the surface functional layer include a matting agent layer, an antireflection layer, a hard coat layer, an antifogging layer, an antifouling layer, and an easy adhesion layer. In addition, the surface functional layer is described in detail in JP-A-2006-289627.

In the illustrated solar cell 20, as a preferred embodiment, the bus electrode 34 is formed on the upper electrode 28.
In order to improve the photoelectric conversion efficiency of the solar cell 20, it is preferable to make the upper electrode 28 thinner to increase the light transmittance. On the other hand, if the upper electrode 28 is made thin, sufficient conductivity may not be obtained.
The bus electrode 34 is an auxiliary metal wiring for avoiding such an inconvenience. The bus electrode 34 is for thinning the upper electrode 28 to obtain good photoelectric conversion efficiency and to ensure sufficient conductivity.

Examples of the metal material forming the bus electrode 34 include aluminum, chromium, iron, cobalt, nickel, copper, zinc, molybdenum, indium, tin, tungsten, silver, platinum, and gold. Of these, low resistance metals such as aluminum, nickel, copper, zinc, silver, and gold are preferably used.
The pattern shape of the bus electrode 34 is not limited, but a mesh shape (mesh pattern electrode) is preferable from the viewpoint of light transmittance and conductivity. There is no particular limitation on the mesh pattern, and a lattice shape such as a square, a rectangle, or a rhombus, a stripe shape (stripe shape), a honeycomb, or a combination of curves may be used.
These mesh designs are adjusted so that the aperture ratio (light transmittance) and the surface resistance (conductivity) have desired values. When a bus electrode having such a mesh pattern is used, the mesh opening ratio is usually 70% or more, preferably 80% or more, and more preferably 85% or more. The larger the aperture ratio, the better. However, in practice, it becomes 95% or less.
Although there is no restriction | limiting in particular in the thickness of the bus electrode 34, Usually 0.02-20 micrometers is preferable and 0.1-10 micrometers is more preferable.
The line width in the mesh pattern of the bus electrode 34 is preferably 0.001 to 1 mm, more preferably 0.005 to 0.5 mm in plan view, from the viewpoint of light transmittance and conductivity.
A smaller pitch in the mesh pattern of the bus electrode 34 (fine mesh) is advantageous in terms of solar cell characteristics. However, if the pitch is small, the light transmittance decreases, so a compromise is chosen. Although a pitch changes according to the line | wire width of a metal fine wire, it is preferable that the pitch by planar view is 0.05-30 mm, 0.1-20 mm is more preferable, 0.2-10 mm is further more preferable.
There is no restriction | limiting in particular as a formation method of the bus electrode 34, A well-known formation method can be used suitably. For example, a method in which a mesh pattern metal prepared in advance is bonded to the support surface, a method in which a conductive material is applied to the mesh pattern, a conductive film is formed on the entire surface using a PVD method such as vapor deposition or sputtering, and then the mesh pattern is etched. A method of forming a conductive film, a method of applying a conductive material of a mesh pattern by various printing methods such as screen printing, ink jet printing, and the like. Examples thereof include a forming method, a method using a silver halide photosensitive material described in JP-A-2006-352073, JP-A-2009-231194, and the like.

In the present invention, the bus electrode is not limited to be provided corresponding to only the upper electrode 28.
That is, the solar cell of the present invention is a bus electrode for securing the conductivity of the lower electrode 24 in addition to the bus electrode 34 for securing the conductivity of the upper electrode 28 as in the solar cell 36 shown in FIG. 38 may be included.

FIG. 4 conceptually shows an example in which the semiconductor device of the present invention is used in a dimming illumination device.
A dimming illumination device 40 (hereinafter referred to as illumination device 40) shown in FIG. 4 is an illumination device that uses a so-called organic EL material (organic electroluminescence material) as a light emitting layer. The anode 42, the hole injection layer 46, the hole transport layer 48, the light emitting layer 50, the electron transport layer 52, the electron injection layer 54, and the cathode 56 are formed on one surface of the substrate 10 of the present invention composed of 14 and the protective layer 16. They are laminated in order. Alternatively, the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be laminated on one surface of the substrate 10 in the reverse order.

The illumination device 40 is basically the same as the illumination device using a known organic EL material except that the substrate 10 of the present invention is used.
Therefore, the illuminating device (self-luminous display device) of the present invention may have various layers used in known illuminating devices using organic EL in addition to these layers.

The anode 42 is an electrode that supplies holes to the light emitting layer 50.
As long as the anode 42 has the above function, the anode 42 functions as a positive electrode in the above-mentioned (organic thin film) solar cell 20 and various types used in a lighting device (display) using an organic EL material. The materials are available. Moreover, copper iodide, copper sulfide, etc. can also be used.

The method for forming the anode 42 is not limited, and may be formed by a known method such as a coating method, a vapor deposition method such as sputtering or vacuum deposition, depending on the forming material and the like.
Further, when the anode 42 is patterned as necessary, a known method such as a method using a mask, a method using photolithography, or a processing using a laser or the like may be used.

The hole injection layer 46 and the hole transport layer 48 are layers having a function of receiving holes from the anode 42 or the anode 42 side and transporting them to the cathode 56 side.
As long as the hole injection layer 46 and the hole transport layer 48 have the above-described functions, various types used for an illumination device (display) using an organic EL material can be used. Examples include pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, and the like.
The method for forming the hole injection layer 46 and the hole transport layer 48 is not limited, and depending on the forming material, depending on the forming material, etc., a coating method, a vapor deposition method such as sputtering or vacuum deposition, etc. What is necessary is just to form by a well-known method.

The light emitting layer 50 is a light emitting layer using an organic EL material, and includes at least a host material and a phosphorescent light emitting material.
The host material includes at least a first host material and a second host material.

As the first host material and the second host material, various materials used in organic EL materials can be used. Examples thereof include an electron transporting host material and a hole transporting host material.
Examples of the electron transporting host material include pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide. , Fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, azole derivatives, azine derivatives, metal complexes and the like.
Further, as the hole transporting host material, indole derivatives, carbazole derivatives, azaindole derivatives, azacarbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives are preferable, and indole skeleton, carbazole skeleton, azaindole skeleton in the molecule And those having an azacarbazole skeleton or an aromatic tertiary amine skeleton.

Examples of phosphorescent materials include complexes containing transition metal atoms and lanthanoid atoms.
Examples of the transition metal atom include ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, platinum and the like. Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
Specific ligands include, for example, halogen ligands, aromatic carbocyclic ligands, nitrogen-containing heterocyclic ligands, diketone ligands, carboxylic acid ligands, alcoholate ligands, and monoxide Examples include carbon ligands, isonitrile ligands, cyano ligands and the like.

The method for forming the light emitting layer 50 is not limited, and may be formed by a known method such as a coating method, a vapor deposition method such as sputtering or vacuum deposition, depending on the forming material, the forming material, and the like. .
Further, if necessary, after the light emitting layer 50 is formed, the light emitting layer 50 may be subjected to heat treatment (annealing) for the purpose of modifying the first host material.

The electron transport layer 52 and the electron injection layer 54 are layers having a function of receiving electrons from the cathode 56 or the cathode 56 side and transporting them to the anode 42 side.
As long as the electron transport layer 52 and the electron injection layer 54 have the above-described functions, various types that are used in a lighting device using an organic EL material can be used. Examples include quinoline derivatives, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, perylene derivatives, pyridine derivatives, pyrimidine derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorene derivatives, and the like.
The formation method of the electron transport layer 52 and the electron injection layer 54 is not limited, and a known method such as a coating method, a vapor deposition method such as sputtering or vacuum deposition, or the like may be used depending on the forming material or the like. It may be formed by a method.

The cathode 56 is an electrode that injects electrons into the light emitting layer 50.
As long as the cathode 56 has the above function, various types of materials used in lighting devices that use organic EL materials and the material of the lower electrode 24 that functions as a negative electrode in the above-described solar cell 20 can be used. . Examples thereof include alkali metals such as lithium and sodium, alkaline earth metals such as manganese and calcium, rare earths such as indium and ytterbium, and other metals such as gold, silver and aluminum.
These may be used alone, but from the viewpoint of achieving both stability and electron injection properties, it is preferable to use two or more in combination.

The formation method of the cathode 56 is not particularly limited, and may be formed by a known method such as a coating method, a vapor deposition method such as sputtering or vacuum deposition, depending on the forming material.
Further, when patterning the cathode 56 as necessary, a known method such as a method using a mask, a method using photolithography, or a processing using a laser or the like may be used.

In addition to the illustrated layers, the display device 40 of the present invention may include various layers included in a lighting device that uses organic EL.
As an example, an electron blocking layer that prevents electrons transported from the cathode 56 side to the light emitting layer 50 from passing through to the anode 42 side may be provided. Such an electron blocking layer is usually provided as an organic compound layer adjacent to the light emitting layer on the anode side.

The display device 40 may be entirely protected by a sealing layer as necessary.
There are no particular limitations on the material for forming the sealing layer, and various materials can be used as long as they have a function of preventing elements that promote element deterioration such as moisture and oxygen from entering the element. For example, the forming material of the sealing layer 30 exemplified in the above-described solar cell 20 is preferably used.

Furthermore, the entire display device 40 may be sealed using the gas barrier film 32 or the sealing container as described above. Further, a moisture absorbent or an inert liquid may be sealed in the space between the sealing container and the display device 40.
Examples of the moisture absorbent include barium oxide, sodium oxide, potassium oxide, calcium oxide and the like. Examples of the inert liquid include paraffins, liquid paraffins, fluorinated solvents, chlorinated solvents, silicone oils, and the like.

When the semiconductor device of the present invention is used for a self-luminous display device (organic EL display), for example, the anode 42 or the cathode 56 is patterned in accordance with individual pixels in the illumination device 40. A switching circuit may be provided by connecting to each pixel electrode as a pixel electrode.
As the switching circuit, various known thin film transistors (TFTs) can be used. As an example, thin film transistors such as amorphous silicon (a-Si), low-temperature polysilicon (p-Si), microcrystalline silicon (μc-Si), oxide semiconductors such as IGZO, and organic semiconductors are preferably used.

The board | substrate for semiconductor devices of this invention, such as the board | substrate 10 of this invention, can be utilized suitably for various uses besides semiconductor devices, such as a solar cell, a light control type illuminating device, and a self-light-emitting display apparatus.
As a suitable example, in addition to the above-described characteristics of high flexibility, low warpage, and low moisture release (degassing amount), high light reflection makes it possible to flexibly use the semiconductor device substrate of the present invention. A reflective liquid crystal display device is exemplified.

FIG. 5A conceptually shows an example of the reflective liquid crystal display device of the present invention using the substrate for a semiconductor device of the present invention.
A reflective liquid crystal display device 60 (hereinafter, also referred to as a liquid crystal display device 60) shown in FIG. The lower transparent electrode 62, the liquid crystal layer 64, the upper transparent electrode 68, the polarizing plate 70, and the color filter 72 are laminated in this order.
In the substrate 10 of the present invention, the protective layer 16 is basically the same as glass. Therefore, although the substrate 10 of the present invention has flexibility, it can be handled in the same manner as a glass substrate used in a normal reflective liquid crystal display device.

As shown in FIG. 5C, a normal (reflection type) liquid crystal display device 100 includes a reflective layer 104, a first polarizing plate 106, a lower transparent electrode 108, a liquid crystal layer 110, and an upper transparent electrode 112 on a glass substrate 102. The second polarizing plate 114 and the color filter 116 are laminated in this order.
Here, in the substrate 10 of the present invention, the interface between the base material 12 (aluminum) and the anodized film 14 has very high light reflectivity, and this interface can be used as a reflective layer. Therefore, the liquid crystal display device 60 using the substrate 10 of the present invention has an advantage that the reflective layer 104 necessary for the normal liquid crystal display device 100 shown in FIG.

Further, as disclosed in Japanese Patent Application Laid-Open No. 8-201802 and the like, in a reflection type liquid crystal display device, by making a reflection layer a specular reflection plate (regular reflection plate), light is incident from the polarizing plate side. Since the light is reflected by the reflector and passes through the polarizing plate twice, the polarizing plate disposed between the liquid crystal layer and the reflective layer (reflection interface) can be eliminated.
In the substrate 10 of the present invention, the interface between the base material 12 serving as a light reflecting surface and the anodized film 14 is a smooth metal / oxide interface, and the reflected light has few irregular reflection components and most of the regular reflection components. Become. Therefore, the liquid crystal display device 60 using the substrate 10 of the present invention eliminates the polarizing plate 106 between the reflective layer 104 and the liquid crystal layer 110, which is necessary for the normal liquid crystal display device 100 shown in FIG. There is also an advantage of being able to.

As described above, the liquid crystal display device 60 using the substrate 10 of the present invention is excellent in flexibility.
Here, in the liquid crystal display device 60, the thickness between the liquid crystal layer 64 and the reflective layer is basically the sum of the thicknesses of the anodized film 14, the protective layer 16, and the lower transparent electrode 62. These layers are all solid. Therefore, in the liquid crystal display device 60 using the substrate 10 of the present invention, even if it is bent using flexibility, there is no change in the thickness between the layers, so that the generation of false colors during bending can be suppressed. There is also.

In the liquid crystal display device 60, the lower transparent electrode 62 is a so-called common electrode, which is a known transparent electrode used in a reflective liquid crystal display device.
As an example, various transparent conductive films such as ITO, IZO, IWO, etc., exemplified as the upper electrode 28, can be used. In addition, when the lower transparent electrode 62 is patterned as necessary, a known method such as a method using a mask, a method using photolithography, or a processing using a laser or the like may be used.

The liquid crystal layer 64 is a known liquid crystal layer (liquid crystal cell) used in a liquid crystal display device (LCD), which is filled with aligned liquid crystals.
Therefore, various known liquid crystal materials used in LCDs can be used as the liquid crystal. The display modes are TN (Twisted Nematic), STN (Super Twisted Nematic), HAN (Hybrid Alignment Nematic), GH (Guest Host), PCGH (Phase Changed Guest Host), PDLC (Polymer Dispersed Liquid Crystal), ECB ( Various display modes that can be used for reflective liquid crystal display devices, such as Electrically Controlled Birefringence (CSH), CSH (Color Super Homeotropic), and vent alignment, can be used.

The upper transparent electrode 68 is a drive electrode for driving the liquid crystal layer 64, and similarly, a simple matrix type having a pixel electrode for each pixel (for each subpixel) used in a reflective liquid crystal display device. Various known transparent drive electrodes such as an active matrix type using a thin film transistor can be used. Moreover, it is preferable that the upper transparent electrode 68 is a thing using various TOC similar to the lower transparent electrode 62. In the reflective liquid crystal display device of the present invention, the lower transparent electrode may be a drive electrode and the upper transparent electrode may be a common electrode.
The polarizing plate 70 is also a known polarizing plate (polarizer) used in an LCD or the like. The polarizing plate 70 has a crossed nicols (or parallel nicols) polarization transmission axis with respect to the liquid crystal filled in the liquid crystal layer 64 (or its orientation direction) when the liquid crystal layer 64 is energized or not energized. It is arranged to become.

In the liquid crystal display device 60, light that is linearly polarized by the polarizing plate 70 passes through the liquid crystal layer 64 when the liquid crystal layer 68 and the polarizing plate 70 are in a parallel Nicol state under the energization action of the upper transparent electrode 68. The light is reflected by the substrate 10 (interface between the base material 12 and the anodic oxide film 14), passes through the liquid crystal layer 64 and the polarizing plate 70 again, and is displayed as a visible image.
Conversely, when the liquid crystal layer 68 and the polarizing plate 70 are in a crossed Nicol state, the light that has been linearly polarized by the polarizing plate 70 cannot pass through the liquid crystal layer 64, so that this light is a component that is displayed as a visible image. Must not.

  The color filter 72 is a well-known color filter used in an LCD in which three color filters of R filter, G filter, and B filter corresponding to the pixel electrode of the upper transparent electrode 68 are arranged in a predetermined repeating pattern. . The color filter 72 may be provided between the upper transparent electrode 68 and the polarizing plate 70.

Here, the substrate 10 of the present invention is formed of aluminum whose base 12 is a good conductor.
Therefore, in the reflection type liquid crystal display device using the substrate 10 of the present invention, the lower transparent electrode is omitted as shown in FIG. be able to. For energization between the liquid crystal layer 64 and the substrate 12, various methods such as a method using wiring and a method of partially removing the protective layer 16 and the anodized film 14 can be used.

  Furthermore, in the liquid crystal display device of the present invention, a birefringent film for improving viewing angle characteristics may be provided between the polarizing plate 70 and the liquid crystal layer 64 as necessary. Similarly, a forward scattering film may be provided above the liquid crystal layer 64 in order to improve viewing angle characteristics.

Note that the anodized film used in the liquid crystal display device preferably has high transmittance and low light absorption in the visible light region. As a result, a substrate having very high light reflectivity with little absorption of light reaching the interface between the base material 12 (aluminum) and the anodized film 14 and reflected light can be obtained.
The anodized film 14 having a high transmittance can be suitably produced by anodizing aluminum containing a small amount of impurities. Moreover, the anodized film 14 having low light absorption in the visible light region can be suitably produced by anodizing aluminum in an inorganic acid such as sulfuric acid or phosphoric acid solution. Furthermore, even when using organic acids such as oxalic acid, malonic acid, tartaric acid, etc., anodization at a low voltage suppresses the mixing of organic components into the anodized film, and light in the visible light region An anodized film 14 having low absorption can be suitably produced.

  As described above, the semiconductor device substrate, the semiconductor device, the dimming illumination device, the self-luminous display device, the solar cell, and the reflective liquid crystal display device have been described in detail. However, the present invention is not limited to the above-described examples. Of course, various improvements and changes may be made without departing from the scope of the invention.

[Example 1]
An aluminum plate (purity 4N) having a thickness of 40 μm was prepared as a material for the base 12.
This aluminum plate is anodized with a thickness of 10 μm on both surfaces of the substrate 12 by performing anodizing treatment on both surfaces with an anodizing voltage of 40 V using an oxalic acid aqueous solution having a temperature of 50 ° C. and a concentration of 0.5 M. A film 14 was formed (that is, the thickness of the substrate 12 was about 20 μm).
Subsequently, a coating liquid (hereinafter referred to as coating liquid B) mixed in a ratio of 3.92 parts by mass of pure water, 0.05 part by mass of 35% hydrochloric acid, 12.53 parts by mass of ethanol, and 4.17 parts by mass of tetraethoxysilane. Was applied to the surface of the anodized film 14 on both sides and dried. Application was performed by dip coating.
Thereafter, the base material 12 coated with the coating liquid B was placed in a 300 ° C. thermostat and subjected to heat treatment for 10 minutes to form a protective layer 16 having a thickness of 300 nm, and the substrate 10 shown in FIG. 1 was produced.

After forming the anodic oxide film 14, a part is cut out, and as described above, the length of the anodic oxide film 14 is measured. Thereafter, the base material 12 is dissolved and removed, and the anode after the base material 12 is removed. The length of the oxide film 14 was measured, and the strain of the anodized film 14 at room temperature was measured based on the length of the anodized film before and after removing the substrate 12.
The fabricated substrate 10 is cut out to an appropriate size and bent so that a fracture surface of the anodized film 14 is obtained. The pore size was calculated. In the SEM photograph, the magnification was adjusted in the range of 1 to 150,000 times according to the pore diameter of the anodized film 14.
The average pore diameter of the anodized film 14 was measured by the following method. That is, from the SEM photograph, 30 center intervals between adjacent pores of the anodic oxide film 14 were measured, and the average value was taken as the average pore period. Moreover, the thickness of 30 adjacent wall parts of the anodic oxide film 14 was measured, and the average value was made into average wall thickness. A value obtained by subtracting the average wall pressure from the average pore period was defined as the average pore diameter.
As a result, the average pore diameter of the anodized film 14 was 25 nm.

Titanium (thickness 5 nm) and silver (thickness 100 nm) were continuously vacuum-deposited on one surface of the substrate 10 thus produced, thereby forming the lower electrode 24. At this time, a shadow mask was used so that the element area was 16 cm ² .
A PEDOT-PSS aqueous solution (manufactured by Heraeus Precious Metals, Clevios P VP.AI 4083) was spin-coated on the lower electrode 24 and heat-treated at 140 ° C. for 15 minutes. This formed a positive hole transport layer (film thickness 0.04 micrometer).
A composition in which P3HT (manufactured by Merck, lisicon SP001) as an electron donating material and ICBA (manufactured by Sigma-Aldrich) as an electron accepting material are dissolved in dichlorobenzene at a weight ratio of 1: 1 on the hole transport layer, It spin-coated on the positive hole transport layer in the dry nitrogen atmosphere, and heat-processed at 140 degreeC for 15 minute (s). As a result, a bulk heterojunction photoelectric conversion layer 26 was formed. The film thickness of the photoelectric conversion layer 26 was 0.2 μm.
Aluminum (film thickness 2 nm) and silver (film thickness 10 nm) were continuously vacuum-deposited on the photoelectric conversion layer 26. At this time, a shadow mask was used so that the element area was 16 cm ² . Subsequently, silver (film thickness: 0.4 μm) was vacuum deposited on the upper electrode 28 as the bus electrode 34. At this time, a striped bus electrode 34 having a line width of 0.3 mm and a pitch of 20 mm was formed using a shadow mask having a stripe pattern. Further, ITO (film thickness: 0.1 μm) is formed through a shadow mask with an opening of 16 cm ² by high-frequency magnetron sputtering while heating the substrate to 160 ° C. in an atmosphere of 1 Pa vacuum introduced with Ar gas and O ₂ gas. An optically transparent upper electrode 28 having a three-layer structure of aluminum / silver / ITO having a bus electrode 34 between the aluminum layer and the ITO layer was formed.
In the above steps, an organic EL element manufacturing apparatus in which a vacuum deposition apparatus for forming aluminum and silver and a sputtering apparatus for forming ITO are directly connected to a cluster type vacuum transfer system having a degree of vacuum of 1 × 10 ⁻⁴ Pa or less. Was done using.
Furthermore, a PEN film in which a silicon nitride film and an acrylate polymer were laminated was prepared as the gas barrier film 32. This gas barrier film 32 was vacuum-heated laminated at 140 ° C. across an ethylene-vinyl acetate copolymer (EVA) film as a sealant, and the gas barrier film 32 was laminated. The gas barrier film 32 was vacuum-heated laminated so that the outermost silicon nitride film faces the upper electrode 28.
The solar cell having the same configuration as that shown in FIG. 2 except that the hole transport layer is provided between the lower electrode 24 and the photoelectric conversion layer 26 and the bus electrode 34 is incorporated in the upper electrode 28 by the above steps ( An organic photoelectric conversion element) was produced. In the solar cell having this configuration, the lower electrode 24 functions as a positive electrode and the upper electrode 28 functions as a negative electrode.

[Example 2]
The same procedure as in Example 1 was carried out except that AQUAMICA NP140 (hereinafter referred to as coating solution C) manufactured by AZ Electronic Materials was used instead of coating solution B, and the protective layer 16 was formed at a heat treatment temperature of 200 ° C. Thus, the substrate 10 was manufactured, and further, a solar cell was manufactured.
In addition, it was 25 nm when the average pore diameter of the anodic oxide film 14 of the board | substrate 10 was measured like Example 1. FIG.

[Example 3]
A substrate 10 was produced in the same manner as in Example 1 except that the heat treatment temperature was 150 ° C. and the protective layer 16 having a thickness of 800 nm was formed. Further, a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 4]
A substrate 10 was produced in the same manner as in Example 1 except that the protective layer 16 was formed at a heat treatment temperature of 150 ° C. Further, a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 5]
A substrate 10 was produced in the same manner as in Example 1 except that the coating liquid C was used instead of the coating liquid B, and the protective layer 16 was formed without performing heat treatment, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 6]
Anodization is performed using sulfuric acid having a temperature of 20 ° C. and a concentration of 1.5 M at an anodic oxidation voltage of 13 V, and using the coating solution C instead of the coating solution B, the heat treatment temperature is set to 200 ° C. and the thickness is increased. A substrate 10 was produced in the same manner as in Example 1 except that the protective layer 16 having a thickness of 50 nm was formed, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 9 nm.

[Example 7]
Anodic oxidation is performed using a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M at an anodic oxidation voltage of 80 V, and using the coating solution C instead of the coating solution B, the heat treatment temperature is set to 200 ° C., and the protective layer Except that 16 was formed, a substrate 10 was produced in the same manner as in Example 1, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 60 nm.

[Example 8]
Anodization is performed using a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1M at an anodic oxidation voltage of 120 V, and using the coating solution C instead of the coating solution B, the heat treatment temperature is set to 200 ° C. and the thickness is increased. The substrate 10 was produced in the same manner as in Example 1 except that the protective layer 16 having a thickness of 150 nm was formed. Further, a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 95 nm.

[Example 9]
Anodization was performed in the same manner as in Example 1 except that sulfuric acid having a temperature of 20 ° C. and a concentration of 1.5 M was used, an anodizing voltage of 13 V, and the thickness of the protective layer 16 was changed to 25 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 9 nm.

[Example 10]
Anodization was performed in the same manner as in Example 1 except that the malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M was used, an anodization voltage of 80 V, and the thickness of the protective layer 16 was changed to 80 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 60 nm.

[Example 11]
Anodization was performed in the same manner as in Example 1 except that a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M was used, an anodization voltage of 120 V, and the thickness of the protective layer 16 was changed to 100 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 95 nm.

[Example 12]
Instead of coating solution B, 5 parts by mass of methyltrimethoxysilane, 2.87 parts by mass of aminopropyltrimethoxysilane, 0.2 parts by mass of aluminum acetylacetonate, 2 parts by mass of 35% hydrochloric acid, and 5 parts by mass of pure water The substrate 10 was prepared in the same manner as in Example 1 except that the protective layer 16 was formed by using a coating solution (hereinafter referred to as coating solution D) mixed at a ratio of Furthermore, a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 13]
Except having changed the thickness of the protective layer 16 into 30 nm, it carried out similarly to Example 1, the substrate 10 was produced, and also the solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 14]
Except for changing the thickness of the aluminum plate to 300 μm, the thickness of the anodized film to 30 μm (that is, the thickness of the substrate 12 is about 240 μm), and the thickness of the protective layer to 500 nm. In the same manner as in Example 1, a substrate 10 was produced, and further a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 15]
A substrate 10 was produced in the same manner as in Example 1 except that the protective layer 16 was formed at a heat treatment temperature of 100 ° C., and a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 16]
A substrate 10 was produced in the same manner as in Example 1 except that an anodization was performed using a tartaric acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M at an anodization voltage of 160 V, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 142 nm.

[Example 17]
Anodization is performed using a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M at an anodization voltage of 80 V, and the coating solution C is used instead of the coating solution B, and the heat treatment temperature is 200 ° C. to increase the thickness. A substrate 10 was produced in the same manner as in Example 1 except that the 50 nm protective layer 16 was formed, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 60 nm.

[Example 18]
Anodization was performed using a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M at an anodic oxidation voltage of 80 V, and using the coating liquid C instead of the coating liquid B, forming a protective layer 16 having a thickness of 1200 nm. In the same manner as in Example 1, a substrate 10 was produced, and further a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 60 nm.

[Example 19]
A substrate 10 was produced in the same manner as in Example 1 except that the coating liquid C was used instead of the coating liquid B, and a protective layer having a thickness of 15 nm was formed without performing heat treatment, and a solar cell was further produced. .
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 20]
Anodization was performed in the same manner as in Example 1 except that sulfuric acid having a temperature of 20 ° C. and a concentration of 1.5 M was used, an anodization voltage of 13 V, and the thickness of the protective layer 16 was changed to 15 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 9 nm.

[Example 21]
Anodization was performed in the same manner as in Example 1 except that the malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M was used, an anodization voltage of 80 V, and the thickness of the protective layer 16 was changed to 50 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 60 nm.

[Example 22]
Anodization was carried out in the same manner as in Example 1 except that a malonic acid aqueous solution having a temperature of 80 ° C. and a concentration of 1 M was used, an anodization voltage of 120 V, and the thickness of the protective layer 16 was changed to 60 nm. The board | substrate 10 was produced and the solar cell was produced further.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 95 nm.

[Example 23]
In place of the coating solution B, a protective layer 16 having a thickness of 500 nm is formed using a coating solution (hereinafter referred to as coating solution A) mixed at a ratio of 2 parts by mass of No. 3 sodium silicate and 2 parts by mass of lithium silicate. Except for the formation, a substrate 10 was produced in the same manner as in Example 1, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 24]
A substrate 10 was produced in the same manner as in Example 1 except that a 2 wt% magnesium-aluminum plate was used instead of the 4N purity aluminum plate, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Example 25]
A substrate 10 was produced in the same manner as in Example 1 except that a 0.3 wt% lithium-aluminum plate was used instead of the 4N purity aluminum plate, and a solar cell was further produced.
When the average pore diameter of the anodic oxide film 14 of the substrate 10 was measured in the same manner as in Example 1, it was 25 nm.

[Comparative Example 1]
Similar to Example 1, except that the anodic oxidation was performed only on one surface, and the coating solution A was used instead of the coating solution B, and the protective layer 16 having a thickness of 500 nm was formed only on the surface on which the anodic oxide film 14 was formed. Thus, a substrate was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate was measured in the same manner as in Example 1, it was 25 nm.
In this example, the warpage of the substrate was large, and an appropriate solar cell could not be produced.

[Comparative Example 2]
Anodization was performed in the same manner as in Example 1 except that sulfuric acid having a temperature of 20 ° C. and a concentration of 1.5 M was used, an anodizing voltage of 13 V, and the protective layer 16 was not formed. Furthermore, a solar cell was produced.
When the average pore diameter of the anodic oxide film 14 of the substrate was measured in the same manner as in Example 1, it was 9 nm.

[Comparative Example 3]
A substrate was produced and a solar cell was produced in the same manner as in Example 1 except that the temperature of anodization was 16 ° C. and the protective layer 16 having a thickness of 300 nm was formed without performing heat treatment.
When the average pore diameter of the anodic oxide film 14 of the substrate was measured in the same manner as in Example 1, it was 25 nm.

[Evaluation test]
About the produced board | substrate 10 of Examples 1-25 and the board | substrate of Comparative Examples 1-3, the curvature angle, the moisture content, the contact angle of water of the surface (surface of the protective layer 16), and surface roughness Ra were measured.
The curvature radius was measured by cutting the substrate 10 into 30 mm square and using an optical non-contact three-dimensional surface shape measuring device (Wyko NT1100 manufactured by Veeco) at room temperature.
The moisture content was determined by measuring the amount of dehydration up to 500 ° C. using a Karl Fischer moisture meter (MCT-610-DT manufactured by Kyoto Electronics Co., Ltd.) using an amount equivalent to 100 cm ^{2 of} the substrate 10.
The contact angle of water on the surface was measured using an automatic contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.).
Furthermore, the surface roughness was measured by using an atomic force microscope (Atomic Force Microscope: manufactured by Seiko Instruments Inc., probe: SI-DF20, measurement frequency: 1 Hz) and measuring the average surface roughness Ra in a measuring area of 10 μm square.

Moreover, about the produced solar cell of Examples 1-26 and Comparative Examples 1-3, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured.
The conversion efficiency was measured by irradiating the solar cell with a pseudo sun with Air Mass (AM) = 1.5 and 100 mW / cm ² . The bending test was performed by bending the solar cell ten times with a curvature radius of 1 cm.
Table 1 shows the specifications of each substrate, and Table 2 shows the results of each evaluation test.

As shown in Tables 1 and 2, each of the solar cells produced using the substrate 10 of the present invention has a good initial conversion efficiency, and is good after a bending test and after 100 hours. Maintaining high conversion efficiency.
On the other hand, in Comparative Example 2 in which the heat treatment is not performed without the protective layer 16, the strain of the anodized film 14 is strain in the tensile direction, the initial conversion efficiency is very low, and after the bending test and The conversion efficiency after 100 hours has become 0%. Furthermore, in Comparative Example 3 having the protective layer 16 but not subjected to heat treatment, the strain of the anodized film 14 is strain in the tensile direction at room temperature, and the conversion efficiency after the bending test is 0%. In Comparative Example 2 and Comparative Example 3, it is estimated that the conversion efficiency after the bending test was 0% because a crack was generated by the bending test and current was leaked.
In Comparative Example 1 in which the anodic oxide film 14 and the protective layer 16 were formed only on one surface of the base material 12, the warpage of the substrate was large (the radius of curvature was 5 cm), and an appropriate solar cell could not be produced. It is as follows.

[Example 27]
Chromium (film thickness 5 nm) and silver (film thickness 10 nm) were continuously vacuum-deposited on one surface of the substrate 10 produced in Example 2. At this time, a shadow mask was used so that the element area was 4 cm ² . Subsequently, ITO (thickness 0.1 μm) was applied through a shadow mask with an opening of 4 cm ² by high-frequency magnetron sputtering while heating the substrate to 200 ° C. in an atmosphere of 1 Pa vacuum introduced Ar gas and O ₂ gas. A lower electrode 24 having a three-layer structure of chromium / silver / ITO was formed.
On the lower electrode 24, molybdenum (VI) (film thickness 10 nm) was formed by vacuum deposition as a hole transport layer.
Subsequently, after zinc phthalocyanine (ZnPc: film thickness 40 nm) was vacuum-deposited on the hole transport layer, ZnPc and fullerene C ₆₀ were co-deposited at a volume ratio of 1: 1 (film thickness 20 nm), and C ₆₀ ( The photoelectric conversion layer 26 having a total film thickness of 100 nm was formed by vapor deposition. The photoelectric conversion layer 26, ZnPc is an electron donor material, C ₆₀ is an electron accepting material. These vacuum deposition processes were performed while heating the substrate 10 to 80 ° C. with a degree of vacuum of 1 × 10 ⁻⁴ Pa or less.
On the photoelectric conversion layer 26, 2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline (NBphen, film thickness 10 nm) was vacuum deposited as a hole blocking layer.
Silver (film thickness: 10 nm) was vacuum deposited on the hole blocking layer. At this time, a shadow mask was used so that the element area was 4 cm ² . Further, ITO (film thickness: 0.1 μm) was formed through a shadow mask with an opening of 4 cm ² by high-frequency magnetron sputtering in an atmosphere with a vacuum degree of 1 Pa into which Ar gas and O ₂ gas were introduced. A light transmissive upper electrode 28 having a two-layer structure was formed.
Aluminum (thickness 0.6 μm) was vacuum deposited on the upper electrode 28 as the bus electrode 34. At this time, a striped bus electrode having a width of 0.2 mm and an interval of 10 mm was formed using a shadow mask having a stripe pattern.
Further, silicon nitride oxide (film thickness) is formed on the upper electrode 28 and the bus electrode 34 by plasma CVD in an atmosphere of a vacuum degree of 10 Pa in which N ₂ gas, O ₂ gas, and SiH ₄ gas are introduced as the sealing layer 30. 1 μm) was formed.
The above steps include a vacuum deposition apparatus for forming aluminum, chromium and silver, a vacuum deposition apparatus for forming ZnPc, C ₆₀ , NBphen, and molybdenum oxide, a sputtering apparatus for forming ITO, and a plasma for forming silicon nitride oxide. The CVD apparatus was performed using an organic EL element manufacturing apparatus directly connected to a cluster type vacuum transfer system having a degree of vacuum of 1 × 10 ⁻⁴ Pa or less.
As the gas barrier film 32, a PEN film in which an aluminum oxide film and an acrylate polymer were laminated was prepared. This gas barrier film 32 is laminated by vacuum heating at 120 ° C. with an outermost aluminum oxide film facing the sealing layer 30 with an ionomer film (High Milan made by Mitsui DuPont Polychemical) sandwiched between them. did.
2 except that a hole transport layer is provided between the lower electrode 24 and the photoelectric conversion layer 26 and a hole blocking layer is provided between the photoelectric conversion layer 26 and the upper electrode 28 by the above steps. A solar cell having the same configuration was produced. In the solar cell having this configuration, the lower electrode 24 functions as a positive electrode and the upper electrode 28 functions as a negative electrode.

About the produced solar cell, similarly to the previous Example 1, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured.
As a result, the initial conversion efficiency was 1.2%, the conversion efficiency after the bending test was 1.0%, and the conversion efficiency after 100 hours was 1.1%, confirming excellent characteristics and performance maintenance performance against bending and aging. It was done.

[Example 28]
A lower electrode 24 having a three-layer structure (chrome / silver / ITO) is formed on one surface of the substrate 10 produced in Example 1 through a shadow mask so as to have an element area of 1 cm ² in the same manner as in Example 27. did.
On the lower electrode 24, a 2-ethoxyethanol solution of cesium carbonate was spin-coated and heat-treated at 160 ° C. for 20 minutes. Thereby, a hole blocking layer (film thickness: 1 nm) was formed.
A bulk heterojunction photoelectric conversion layer 26 made of P3HT and ICBA was formed on the hole blocking layer in the same manner as in Example 1.
On the photoelectric conversion layer 26, molybdenum oxide (VI) (film thickness: 10 nm) was formed by vacuum deposition as a hole transport layer.
Subsequently, silver (film thickness 0.4 μm) was vacuum-deposited as a bus electrode 34 on the hole transport layer. At this time, a striped bus electrode having a width of 0.3 mm and an interval of 5 mm was formed using a shadow mask having a stripe pattern.
On the hole transport layer and the bus electrode 34, a shadow mask having an opening of 1 cm ² is formed as a light transmissive upper electrode 28 by high-frequency magnetron sputtering in an atmosphere of 0.1 Pa in which Ar gas and O ₂ gas are introduced. ITO (thickness 0.1 μm) was formed through the film.
Further, in the same manner as in Example 27, an ionomer film was sandwiched as a sealant, and the gas barrier film 32 was laminated by vacuum heating (120 ° C.).
Through the above steps, a hole blocking layer is provided between the lower electrode 24 and the photoelectric conversion layer 26, a hole transport layer is provided between the photoelectric conversion layer 26 and the upper electrode 28, and the bus electrode 34 is provided. 2 was prepared between the upper electrode 28 and the hole transport layer, and a solar cell having the same configuration as in FIG. 2 was produced. In the solar cell having this configuration, the lower electrode 24 functions as a negative electrode and the upper electrode 28 functions as a positive electrode.

About the produced solar cell, similarly to the previous Example 1, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured.
As a result, the initial conversion efficiency was 2.4%, the conversion efficiency after the bending test was 2.0%, and the conversion efficiency after 100 hours was 2.2%. It was done.

[Example 29]
On one surface of the substrate 10 prepared in Example 1, through a shadow mask so the device area is 1 cm ^2, was vacuum deposited continuously chromium (thickness 5 nm) and silver (film thickness 100 nm), 2 A lower electrode 24 having a layer structure (chrome / silver) was formed.
A composition obtained by dissolving zinc acetate and 2-aminoethanol in 2-methoxyethanol in a mass ratio of 1: 1 on the lower electrode 24 was spin-coated on the lower electrode and heat-treated at 300 ° C. for 20 minutes. Thereby, an electron transport layer having a thickness of 0.1 μm was formed.
On the electron transport layer, a bulk heterojunction photoelectric conversion layer 26 made of P3HT and ICBA was formed in the same manner as in Example 1.
On the photoelectric conversion layer 26, poly (thiophene-3- [2 [(2-methoxyethoxy) ethoxy] -2,5-diyl] 2-butoxyethanol mixed aqueous solution (Plextronics, Plexcore OC RG-1200) is added. This was spin-coated and heat-treated at 140 ° C. for 10 minutes, thereby forming a hole transport layer (film thickness 0.05 μm).
On the hole transport layer, a composition in which dimethyl sulfoxide was added to a PEDOT-PSS aqueous solution of another composition (manufactured by Heraeus Precious Metals, Clevios PH 500) was spin-coated. Heat treatment was performed at 140 ° C. for 15 minutes. As a result, a light transmissive upper electrode 28 (thickness: 0.1 μm) was formed.
On the upper electrode 28, silver (film thickness 0.4 μm) was vacuum deposited as the bus electrode 34. At this time, a stripe-shaped auxiliary bus electrode having a width of 0.3 mm and an interval of 3 mm was formed using a shadow mask having a stripe pattern.
Further, in the same manner as in Example 1, an EVA film was sandwiched as a sealant, and the gas barrier film 32 was laminated by vacuum heating at 140 ° C.
Except for having the electron transport layer between the lower electrode 24 and the photoelectric conversion layer 26 and the hole transport layer between the photoelectric conversion layer 26 and the upper electrode 28 by the above steps, FIG. A solar cell having the same configuration was produced. In the solar cell having this configuration, the lower electrode 24 functions as a negative electrode and the upper electrode functions as a positive electrode.

About the produced solar cell, similarly to the previous Example 1, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured.
As a result, the initial conversion efficiency was 2.2%, the conversion efficiency after the bending test was 2.1%, and the conversion efficiency after 100 hours was 2.1%. It was done.

[Example 30]
A silver fine particle dispersion (NPS-JL manufactured by Harima Chemicals Co., Ltd.) was printed on one surface of the substrate 10 produced in Example 5 by inkjet so that the element area was 1 cm ² . Next, heat treatment was performed at 160 ° C. for 1 hour to form the lower electrode 24 (film thickness 1 μm).
A 2-acetoxy-1-methoxypropane (PGMEA) solution of trimethylolpropane triacrylate added with a photopolymerization initiator (Lamberti, Esacure KTO 46) was printed on the outer edge of the lower electrode 24 by inkjet. Next, an insulating partition (width 1 mm, height 1.1 μm) was formed by irradiation with ultraviolet rays (wavelength 365 nm).
A titanium oxide fine particle dispersion (Solaronix Ti-Nanoxide HT-L / SC) was spin-coated on the lower electrode 24 and heat-treated at 160 ° C. for 20 minutes. Thereby, an electron transport layer (thickness: 0.1 μm) was formed.
On the electron transport layer, a bulk heterojunction photoelectric conversion layer 26 made of P3HT and ICBA was formed in the same manner as in Example 1.
A composition obtained by adding diethylene glycol and a surfactant (Zonyl FS-300 manufactured by DuPont) to a PEDOT-PSS aqueous solution having a different composition (Clevios PH 1000 manufactured by Heraeus Precious Metals) on the photoelectric conversion layer 26 is spin-coated, Heat treatment was performed at 140 ° C. for 15 minutes. As a result, a light transmissive upper electrode 28 (thickness: 0.1 μm) was formed.
On the upper electrode 28, the silver fine particle dispersion was printed by ink jet so as to have a stripe shape with a width of 0.3 mm and an interval of 1 mm. Next, heat treatment was performed at 160 ° C. for 1 hour to form a bus electrode 34 (film thickness 1 μm).
Further, in the same manner as in Example 1, an EVA film was sandwiched as a sealant, and the gas barrier film 32 was laminated by vacuum heating at 140 ° C.
The solar cell having the same structure as that shown in FIG. 2 except that the electron transport layer is provided between the lower electrode 24 and the photoelectric conversion layer 26 and the insulating partition is provided on the outer edge of the lower electrode through the above steps. Was made. In the solar cell having this configuration, the lower electrode 24 functions as a negative electrode and the upper electrode 28 functions as a positive electrode.

About the produced solar cell, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured similarly to Example 1 etc. above.
As a result, the initial conversion efficiency was 2.0%, the conversion efficiency after the bending test was 1.9%, and the conversion efficiency after 100 hours was 1.9%. It was done.

[Example 31]
Copper (film thickness: 0.1 μm) was vacuum-deposited as a bus electrode 38 on one surface of the substrate 10 produced in Example 5. At this time, a striped bus electrode 38 having a width of 0.3 mm and a pitch of 1 mm was formed using a shadow mask having a stripe pattern.
Subsequently, an aqueous PEDOT-PSS solution (Orgacon IJ-1005 manufactured by Agfa-Gevaert) having a different composition was printed on the bus electrode 38 and the substrate 10 by inkjet so that the element area would be 1 cm ² . Next, heat treatment was performed at 130 ° C. for 10 minutes to form a light transmissive lower electrode 24 (film thickness: 0.1 μm).
A hole transport layer made of PEDOT-PSS was formed on the lower electrode 24 in the same manner as in Example 1.
A bulk heterojunction photoelectric conversion layer 26 made of P3HT and ICBA was formed on the hole transport layer in the same manner as in Example 1.
On the photoelectric conversion layer 26, an ethanol solution of titanium (IV) isopropoxide was spin-coated and heat-treated at 160 ° C. for 20 minutes. This formed the electron carrying layer (thickness 0.01 micrometer).
On the electron transport layer, similarly to the lower electrode 24, an aqueous PEDOT-PSS solution is printed by ink jet so that the element area becomes 1 cm ² , and then heat treatment is performed, so that the light transmissive upper electrode 28 (film thickness) 0.1 μm) was formed.
On the upper electrode 28, in the same manner as in Example 31, a silver fine particle dispersion was printed by inkjet, and then heat-treated to form a striped bus electrode 34 (thickness 1 μm) having a width of 0.3 mm and a pitch of 1 mm. .
Further, in the same manner as in Example 1, an EVA film was sandwiched as a sealant, and the gas barrier film 32 was laminated by vacuum heating at 140 ° C.
Except for having the hole transport layer between the lower electrode 24 and the photoelectric conversion layer 26 and the electron transport layer between the photoelectric conversion layer 26 and the upper electrode, the same configuration as in FIG. The solar cell which has was produced. In the solar cell having this configuration, the lower electrode 24 functions as a positive electrode and the upper electrode 28 functions as a negative electrode.

About the produced solar cell, similarly to the previous Example 1, the initial conversion efficiency, the conversion efficiency after a bending test, and the conversion efficiency after 100 hours were measured.
As a result, the initial conversion efficiency was 1.6%, the conversion efficiency after the bending test was 1.5%, and the conversion efficiency after 100 hours was 1.6%. It was done.

[Example 32]
A 100 nm-thick ITO film was formed on one surface of the substrate 10 produced in Example 1 by high-frequency magnetron sputtering in an atmosphere of 0.1 Pa in which Ar gas and O ₂ gas were introduced to form an anode 42. did.

On the anode 42, 2-TNATA (4,4 ′, 4 ″ -tris (N, N- (2-naphthyl) -phenylamino) triphenylamine was added to F4-TCNQ (2,3,5) by vacuum deposition. , 6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) was doped with 0.3% by mass to form a hole injection layer 46 having a thickness of 120 nm.
The following vacuum deposition including the hole injection layer 46 was performed at a substrate temperature of 20 ° C. and a vacuum degree of 1 × 10 ⁻⁴ Pa.

  An NPD (N, N′-dinaphthyl-N, N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine) film having a thickness of 10 nm is formed on the hole injection layer 46 by vacuum deposition. Then, the hole transport layer 48 was formed.

  On the hole transport layer 48, 44.9% by mass of the compound A represented by the following structural formula, which is the first host material, is formed by vacuum deposition, and the compound B represented by the following structural formula, which is the second host material. 40% by mass, 15% by mass of phosphorescent light-emitting material A represented by the following structural formula with respect to Compound A and Compound B, and 0.1% by mass of phosphorescent light-emitting material B represented by the following structural formula Thus, the light emitting layer 50 having a thickness of 30 nm was formed.

On the light-emitting layer 50, BAlq (bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolato) -aluminum (III)) was formed to a thickness of 29 nm by vacuum deposition.
On this BAlq, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) was formed to a thickness of 1 nm by vacuum deposition, and an electron transport layer 52 composed of a BAlq layer and a BCP layer was formed. .

On the surface of the electron transport layer 52, 1 nm of lithium fluoride was deposited by vacuum deposition to form the electron injection layer 54.
Further, aluminum (film thickness 2 nm) and silver (film thickness 10 nm) were continuously vacuum-deposited on the electron injection layer 54. Furthermore, ITO (film thickness: 0.1 μm) is formed by high frequency magnetron sputtering in an atmosphere with a vacuum degree of 0.1 Pa into which Ar gas and O ₂ gas are introduced, and the light has a three-layer laminated structure of aluminum / silver / ITO. A transparent cathode 56 was formed. At this time, a shadow mask was installed so that the light emitting area was 2 mm square.
The illumination device 40 as shown in FIG. 4 was produced through the above steps.

This lighting device 40 was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV manufactured by Nagase ChemteX).
The above steps include a vacuum deposition apparatus for forming aluminum and silver, a vacuum deposition apparatus for forming a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and a sputtering apparatus for forming ITO. And an organic EL element manufacturing apparatus in which the glove box is directly connected to a cluster type vacuum transfer system having a degree of vacuum of 1 × 10 ⁻⁴ Pa or less.

A spectroradiometer (SR-3 manufactured by Topcon Technohouse Co., Ltd.) is installed at the same height in the vertical direction with respect to the center of the manufactured lighting device 40 and 1 m away, and 2.5 mA / cm. ^The luminance was measured by energizing at ² and turning on one point of light emission (near the center of the panel).
As a result of the measurement, the luminance was 1140 cd / m ² .

DESCRIPTION OF SYMBOLS 10 (For semiconductor devices) Board | substrate 12 Base material 14 Anodized film 16 Protective layer 20, 36 Solar cell 24 Lower electrode 26 Photoelectric conversion layer 28 Upper electrode 30 Sealing layer 32 Gas barrier film 34, 38 Bus electrode 40 (Dimming type) Illuminating device 42 Anode 46 Hole injection layer 48 Hole transport layer 50 Light emitting layer 52 Electron transport layer 54 Electron injection layer 56 Cathode 60,100 (reflection type) liquid crystal display device 62,108 Lower transparent electrode 64,110 Liquid crystal layer 68, 112 Upper transparent electrode 70 Polarizing plate 72, 116 Color filter 102 Glass substrate 104 Reflective layer 106 First polarizing plate 114 Upper transparent electrode

Claims (26)

  Sheet-like aluminum base material, aluminum porous anodic oxide film formed by anodizing both surfaces of the aluminum base material, and nonporous material containing silicon formed on at least one surface of the anodic oxide film on both surfaces And a protective layer made of an oxide, and both the anodic oxide films on both sides have a compressive strain at room temperature.   The substrate for a semiconductor device according to claim 1, wherein the thicknesses of the anodized films on both sides are equal, the protective layer is formed on both sides, and the thicknesses are equal.   The substrate for a semiconductor device according to claim 1, wherein both of the anodic oxide films on both sides have a strain in the compression direction at room temperature of 0.005 to 0.25%.   The substrate for a semiconductor device according to claim 1, wherein the thickness is 300 μm or less. The substrate for a semiconductor device according to any one of claims 1 to 4, wherein the amount of water to be released is 10 µg / cm ² or less.   The semiconductor device substrate according to claim 1, wherein the surface roughness Ra of at least one of the protective layers is 20 nm or less.   The substrate for a semiconductor device according to claim 1, wherein a contact angle between at least one surface of the protective layer and water is 80 ° or less.   The substrate for a semiconductor device according to any one of claims 1 to 7, wherein a diameter of pores of the anodized film is 4 to 100 nm.   The substrate for a semiconductor device according to claim 1, wherein the anodic oxide film has a thickness of 0.5 to 20 μm.   The substrate for a semiconductor device according to claim 1, wherein the protective layer does not contain an alkali metal.   11. The substrate for a semiconductor device according to claim 1, wherein a thickness of the protective layer is not less than a diameter of pores of the anodized film or not less than 20 nm and not more than 1 μm.   The substrate for a semiconductor device according to claim 1, wherein the aluminum base material is formed of aluminum having a purity of 99% by mass or more.   The substrate for a semiconductor device according to any one of claims 1 to 12, wherein the aluminum base material is formed of aluminum containing at least one of magnesium and lithium and having an aluminum content of 95% by mass or more.   The substrate for a semiconductor device according to claim 1, wherein the aluminum base has a thickness of 5 to 260 μm.   The substrate for a semiconductor device according to claim 1, wherein the protective layer is formed by a coating method.   A semiconductor device comprising the semiconductor device substrate according to claim 1 and a semiconductor element formed on at least one of the protective layers.   The semiconductor device according to claim 16, wherein the semiconductor elements are integrated in series or in parallel.   The semiconductor element includes a photoelectric conversion layer, a lower electrode formed on at least a part below the photoelectric conversion layer, and a light transmissive upper electrode formed on at least a part on the photoelectric conversion layer. The semiconductor device according to claim 16 or 17.   The semiconductor device according to claim 18, wherein the photoelectric conversion layer contains an organic compound.   The semiconductor device according to claim 18, further comprising a bus electrode in contact with the upper electrode.   21. The semiconductor device according to claim 18, further comprising an electron transport layer including a metal oxide between the photoelectric conversion layer and the upper electrode or the lower electrode.   The semiconductor device according to claim 16, further comprising a switching circuit connected to the semiconductor element.   A dimming illumination device using the semiconductor device according to any one of claims 16 to 22.   A self-luminous display device using the semiconductor device according to any one of claims 16 to 22.   The solar cell using the semiconductor device of any one of Claims 16-22.   A reflective liquid crystal display device using the semiconductor device substrate according to claim 1.