JP2008071924A - Method for producing photoelectric conversion device and photoelectric conversion device - Google Patents

Abstract

The present invention provides a method for manufacturing a photoelectric conversion device that can easily obtain a long photoelectric conversion device with high reliability at low cost, and a photoelectric conversion device that can easily obtain a high reliability even if the length is increased.
A data signal is generated based on a transparent substrate, a plurality of photoelectric conversion elements PE formed on the transparent substrate, and charges generated on each of the plurality of photoelectric conversion elements mounted on the transparent substrate. The signal generating means 30 to be generated, the plurality of first wirings 25 formed on the transparent substrate and connecting each of the plurality of photoelectric conversion elements to the signal generating means, and one at each end of the plurality of first wirings 25 Photoelectric conversion comprising a pad 27 connected between the one end and the signal generating means, and a plurality of second wirings 37 formed on the transparent substrate and connecting the signal generating means 30 and an external circuit. In manufacturing the device 1A, a pad and the second wiring 35 are formed by patterning at least one conductive layer.
[Selection] Figure 3

Description

  The present invention relates to a method for manufacturing a photoelectric conversion device that converts various information such as the shape of an object and an image into an electric signal, and the photoelectric conversion device.

  For example, linear image sensors used in facsimiles, image scanners, and the like can be broadly classified into optical reduction types and contact types. Among these linear image sensors, the contact type linear image sensor has an increasing demand because the original reading optical system can be made much smaller and thinner than the optical reduction type linear image sensor.

  The contact-type linear image sensor reads an original as it is by an equal-magnification optical system, and therefore, for example, a photoelectric conversion device having a length of about 300 mm is required to read an A3-size original. Today, as a photoelectric conversion device in a contact type linear image sensor, a CMOS (complementary metal-oxide-) which converts an image into an electric signal by a large number of inorganic photoelectric conversion elements (photodiodes) formed on a single crystal silicon substrate. A semiconductor type or CCD (Charge Coupled Device) type is used, and when a long length of about 300 mm is obtained, a long plate-like silicon chip on which an inorganic photoelectric conversion element is usually formed Are arranged on a straight line.

  In such photoelectric conversion devices, not only a large-scale semiconductor process is required for the production of silicon chips, but also a high-precision technique is required when arranging a plurality of silicon chips on a straight line, so the yield is high. Is low. In addition, since the inorganic photoelectric conversion element cannot be arranged at the joint between the silicon chips, information cannot be read at a position corresponding to the joint between the silicon chips, and sufficient reading quality cannot be obtained.

In recent years, organic photoelectric conversion elements have attracted attention as an alternative to inorganic photoelectric conversion elements. An organic photoelectric conversion element can form a photoelectric conversion part by applying a desired organic photoelectric conversion material on, for example, a glass substrate, and can exhibit the same function as an inorganic photoelectric conversion element. It is possible to obtain a conversion device at low cost. For example, in (Patent Document 1), three types of sensors (organic photoelectric conversion elements) are formed by three types of photoactive organic materials (organic photoelectric conversion materials) having different optical band gaps, and these sensors are used for full-color images. A sensing element for generating the electrical signal is described.
Special Table 2002-502120

  For example, even when a desired number of organic photoelectric conversion elements are formed on a glass substrate to obtain a photoelectric conversion device, signal generation means for detecting data generated in each of the plurality of photoelectric conversion elements and generating a data signal Is usually formed by forming a predetermined integrated circuit on a single crystal silicon substrate. A long photoelectric conversion device requires a plurality of signal generating means, and if these signal generating means are externally attached to the glass substrate, the apparatus becomes large. For this reason, when obtaining a photoelectric conversion device that is as small as possible, the signal generating means is mounted on the glass substrate via an anisotropic conductive film or the like.

  In mounting a plurality of signal generating means on a glass substrate, in many cases, signal generation is performed on wiring (hereinafter referred to as “first wiring”) connecting individual organic photoelectric conversion elements and predetermined signal generating means. A pad is connected to the end on the means side, and the pad is connected to the signal generating means via an anisotropic conductive film or the like.

  In order to ensure the connection between the pad and the signal generating means through the anisotropic conductive film or the like while suppressing conduction at an undesired location, it is desirable that the height of each pad is made uniform. Further, part of the wiring constituting the signal generating means and wiring for connecting the signal generating means to an external circuit (hereinafter, these wirings are collectively referred to as “second wiring”) are also formed on the glass substrate. However, for each of the second wirings, it is desirable to make the electrical resistance as small as possible in order to suppress a voltage drop in the signal propagation process. Furthermore, it is desirable to make the electrical resistance as small as possible for the second wiring used as the ground line for the signal generating means.

  Thus, in order to mount a plurality of signal generating means on a glass substrate with high reliability, it is possible to form pads and wirings with different shapes and electrical characteristics required on the glass substrate. Desirably, if these are formed separately, the number of processes increases and the manufacturing cost increases.

  The present invention has been made in view of the above circumstances, and a method for manufacturing a photoelectric conversion device that is easy to obtain a highly reliable long photoelectric conversion device at low cost, and is highly reliable even if the length is increased. An object is to provide a photoelectric conversion device that is easy to obtain.

  The manufacturing method of the photoelectric conversion device of the present invention that achieves the above object is produced in each of the transparent substrate, the plurality of photoelectric conversion elements formed on the transparent substrate, and the plurality of photoelectric conversion elements mounted on the transparent substrate. Signal generating means for generating a data signal based on the charged electric charge, a plurality of first wirings formed on a transparent substrate and connecting each of the plurality of photoelectric conversion elements and the signal generating means, and a plurality of first wirings, respectively Each of which is connected to one end of each of the electrodes and interposed between the one end and the signal generating means, and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and the external circuit. A method for manufacturing a conversion device, comprising a patterning step of patterning at least one conductive layer to form a pad and a second wiring.

  In addition, another method for manufacturing the photoelectric conversion device of the present invention that achieves the above object includes a transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and a plurality of photoelectric conversion elements mounted on the transparent substrate. A signal generation unit that generates a data signal based on the electric charges generated in each of the plurality of photoelectric conversion elements, a plurality of first wirings that are formed on the transparent substrate and connect each of the plurality of photoelectric conversion elements to the signal generation unit, A pad connected to one end of each first wiring and interposed between the one end and the signal generating means; a plurality of second wirings formed on the transparent substrate for connecting the signal generating means and the external circuit; A low-conductivity conductive layer forming step for forming a low-resistivity conductive layer comprising at least one layer and patterning the low-resistivity conductive layer by etching to form a pad To do A first etching step for forming a first conductive layer for pad and a first conductive layer for second wiring that will constitute a second wiring; a first conductive layer for pad and a first conductive layer for second wiring; A corrosion-resistant conductive layer forming step of forming at least one corrosion-resistant conductive layer so as to cover each outer surface, and a pad that covers the outer surface of the first conductive layer for pads by patterning the corrosion-resistant conductive layer by etching A second etching step of forming a second conductive layer for wiring and a second conductive layer for second wiring covering the outer surface of the first conductive layer for second wiring.

  On the other hand, the photoelectric conversion device of the present invention that achieves the above-described object is generated in each of the transparent substrate, the plurality of photoelectric conversion elements formed on the transparent substrate, and the plurality of photoelectric conversion elements mounted on the transparent substrate. Signal generating means for generating a data signal based on the electric charge, a plurality of first wirings formed on a transparent substrate and connecting each of the plurality of photoelectric conversion elements and the signal generating means, and a plurality of first wirings Photoelectric conversion comprising a pad connected to one end and interposed between one end and the signal generating means, and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and the external circuit A device that is manufactured by the above-described method for manufacturing a photoelectric conversion device of the present invention.

  In addition, another photoelectric conversion device of the present invention that achieves the above object includes a transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and each of the plurality of photoelectric conversion elements mounted on the transparent substrate. Signal generating means for generating a data signal based on the generated charge, a plurality of first wirings formed on a transparent substrate and connecting each of the plurality of photoelectric conversion elements to the signal generating means, and a plurality of first wirings One pad connected to each one end and interposed between the one end and the signal generating means, and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and the external circuit A photoelectric conversion device, wherein each of the pad and the second wiring includes a first conductive layer having a low resistivity and a second conductive layer formed on the first conductive layer by a corrosion-resistant material. It is.

  According to the method for manufacturing a photoelectric conversion device of the present invention, since the pads can be formed together with the same layer configuration and composition of the individual pads, it is easy to align the heights of these pads. For this reason, it is easy to reliably connect the pad and the signal generating means through the anisotropic conductive film while suppressing conduction at an undesired location. Moreover, since each pad and each 2nd wiring are formed in the same process, the number of processes decreases compared with the case where these are formed in a separate process. Furthermore, since the photoelectric conversion element is formed on the transparent substrate, it is easy to increase the length. Therefore, according to the present invention, it is easy to obtain a long and highly reliable photoelectric conversion device at low cost. Moreover, it becomes easy to obtain a highly reliable photoelectric conversion device even if the length is increased.

  According to a first aspect of the present invention, there is provided a method for producing a photoelectric conversion device, comprising: a transparent substrate; a plurality of photoelectric conversion elements formed on the transparent substrate; and a charge generated on each of the plurality of photoelectric conversion elements mounted on the transparent substrate. A signal generation means for generating a data signal, a plurality of first wirings formed on a transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generation means, and one end of each of the plurality of first wirings. Manufacture of a photoelectric conversion device comprising a pad that is connected to each other and interposed between one end and the signal generation means, and a plurality of second wirings that are formed on the transparent substrate and connect the signal generation means and the external circuit The method includes a patterning step of patterning at least one conductive layer to form a pad and a second wiring.

  In this manufacturing method, since the pad and the second wiring are formed by patterning at least one conductive layer, it is easy to align the height of each pad. For this reason, it is easy to reliably connect the pad and the signal generating means through the anisotropic conductive film while suppressing conduction at an undesired location. Moreover, since each pad and each 2nd wiring are formed in the same process, the number of processes decreases compared with the case where these are formed in a separate process. Furthermore, since the photoelectric conversion element is formed on the transparent substrate, it is easy to increase the length. Therefore, according to this manufacturing method, it is easy to obtain a long photoelectric conversion device with high reliability at low cost. Further, it is easy to obtain a highly reliable photoelectric conversion device even if the length is increased.

  In the method for manufacturing a photoelectric conversion device according to a second aspect of the invention, the conductive layer includes a first conductive layer having a low resistivity, and a second conductive layer formed on the first conductive layer with a corrosion-resistant material, The patterning step includes a first sub-step for forming the first conductive layer, a second sub-step for forming the second conductive layer, and a third sub-step for patterning the second conductive layer and the first conductive layer by etching, respectively. It is characterized by including.

  In this manufacturing method, since each pad and the second wiring are formed by the first conductive layer having a low resistivity and the second conductive layer made of a corrosion-resistant material, the pad and the second wiring having a low resistivity and a high corrosion resistance are formed. Can be formed. Even when, for example, a strong acid material is used in forming the photoelectric conversion element, it is possible to obtain a highly reliable photoelectric conversion device by suppressing corrosion of the pad and the second wiring by the strong acid material.

  The method for producing a photoelectric conversion device according to a third aspect is characterized in that at least the second conductive layer of the first conductive layer and the second conductive layer has acid resistance.

  In this manufacturing method, since at least the second conductive layer of the first conductive layer and the second conductive layer has acid resistance, even if a strong acidic material is used in forming the photoelectric conversion element, for example, the strong acidic material Thus, the highly reliable photoelectric conversion device can be obtained by suppressing the corrosion of the pad and the second wiring.

  In the method for manufacturing a photoelectric conversion device according to a fourth aspect of the invention, the first conductive layer is at least one of silver, copper, gold, aluminum, tungsten, molybdenum, cobalt, zinc, nickel, iron, platinum, and chromium. The second conductive layer is made of gold, chromium, indium, copper, titanium, molybdenum, nickel, iron, platinum, tin, silicon, palladium, iridium, manganese, vanadium, and tantalum. It consists of a metal simple substance, an alloy, or a metal oxide containing at least one of these.

  In the method for producing a photoelectric conversion device according to a fifth aspect of the invention, the photoelectric conversion element includes an organic compound as a photoelectric conversion material.

  In this manufacturing method, since a photoelectric conversion element containing an organic compound as a photoelectric conversion material, that is, an organic photoelectric conversion element is formed on a transparent substrate, the lengthening is easy.

  According to a sixth aspect of the present invention, there is provided a method for producing a photoelectric conversion device, comprising: a transparent substrate; a plurality of photoelectric conversion elements formed on the transparent substrate; and a charge generated on each of the plurality of photoelectric conversion elements mounted on the transparent substrate. A signal generation means for generating a data signal, a plurality of first wirings formed on a transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generation means, and one end of each of the plurality of first wirings. Manufacture of a photoelectric conversion device comprising a pad that is connected to each other and interposed between one end and the signal generation means, and a plurality of second wirings that are formed on the transparent substrate and connect the signal generation means and the external circuit A method of forming a low resistivity conductive layer comprising at least one low resistivity conductive layer; and a first pad for forming a pad by patterning the low resistivity conductive layer by etching. Conductive layer and second A first etching step for forming a first conductive layer for a second wiring that constitutes a line, and covering an outer surface of each of the first conductive layer for the pad and the first conductive layer for the second wiring, A corrosion-resistant conductive layer forming step for forming a corrosion-resistant conductive layer comprising at least one layer, and a second conductive layer for pads and a second wiring covering the outer surface of the first conductive layer for pads by patterning the corrosion-resistant conductive layer by etching And a second etching step of forming a second conductive layer for second wiring covering the outer surface of the first conductive layer.

  In this manufacturing method, the low resistivity conductive layer is patterned to form the first conductive layer for each pad, and then the corrosion-resistant conductive layer is patterned to form the second conductive layer for each pad. Easy to align. For this reason, it is easy to reliably connect the pad and the signal generating means through the anisotropic conductive film while suppressing conduction at an undesired location. Moreover, since each pad and each 2nd wiring are formed in the same process, the number of processes decreases compared with the case where these are formed in a separate process.

  Since the corrosion-resistant conductive layer is used as the uppermost layer of each pad and the second wiring, even when a strong acid material is used in forming the photoelectric conversion element, for example, the corrosion of the pad and the second wiring by the strong acid material is suppressed. And a highly reliable photoelectric conversion device can be obtained. Furthermore, since the photoelectric conversion element is formed on the transparent substrate, it is easy to increase the length.

  Therefore, according to this manufacturing method, it is easy to obtain a long photoelectric conversion device with high reliability at low cost. Further, it is easy to obtain a highly reliable photoelectric conversion device even if the length is increased.

  In the method for manufacturing a photoelectric conversion device according to a seventh aspect of the invention, the low resistivity conductive layer includes at least one of silver, copper, gold, aluminum, tungsten, molybdenum, cobalt, zinc, nickel, iron, platinum, and chromium. The corrosion-resistant conductive layer is composed of a single metal or an alloy including one of gold, chromium, indium, copper, titanium, molybdenum, nickel, iron, platinum, tin, silicon, palladium, iridium, manganese, vanadium, and tantalum. It consists of a metal simple substance, an alloy, or a metal oxide containing at least one of these.

  In the method for producing a photoelectric conversion device according to an eighth aspect, the photoelectric conversion element includes an organic compound as a photoelectric conversion material.

  In this manufacturing method, since a photoelectric conversion element containing an organic compound as a photoelectric conversion material, that is, an organic photoelectric conversion element is formed on a transparent substrate, the lengthening is easy.

  According to a ninth aspect of the present invention, there is provided a photoelectric conversion device comprising: a transparent substrate; a plurality of photoelectric conversion elements formed on the transparent substrate; and a data signal based on charges generated in each of the plurality of photoelectric conversion elements mounted on the transparent substrate. A signal generating means for generating a signal, a plurality of first wirings formed on a transparent substrate for connecting each of the plurality of photoelectric conversion elements to the signal generating means, and one connected to one end of each of the plurality of first wirings A photoelectric conversion device comprising a pad interposed between one end and the signal generation means, and a plurality of second wirings formed on the transparent substrate and connecting the signal generation means and the external circuit, It is manufactured by the method for manufacturing a photoelectric conversion device of the present invention.

  Since this photoelectric conversion device is manufactured by the above-described method for manufacturing a photoelectric conversion device of the present invention, it is easy to obtain a highly reliable device even if it is elongated.

  A photoelectric conversion device according to a tenth aspect of the present invention is a data signal based on a transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and charges generated in each of the plurality of photoelectric conversion elements mounted on the transparent substrate. A signal generating means for generating a signal, a plurality of first wirings formed on a transparent substrate for connecting each of the plurality of photoelectric conversion elements to the signal generating means, and one connected to one end of each of the plurality of first wirings A photoelectric conversion device comprising: a pad interposed between one end and the signal generation means; and a plurality of second wirings formed on the transparent substrate and connecting the signal generation means and the external circuit. Each of the second wiring includes a first conductive layer having a low resistivity and a second conductive layer formed on the first conductive layer with a corrosion-resistant material.

  In this photoelectric conversion device, since the photoelectric conversion element is formed on the transparent substrate, the lengthening is easy. In addition, since each pad and the second wiring are formed by the low resistivity conductive layer and the corrosion resistant conductive layer, it is possible to form the pad and the second wiring having low resistivity and high corrosion resistance. Even when, for example, a strong acid material is used in forming the photoelectric conversion element, it is possible to obtain a highly reliable photoelectric conversion device by suppressing corrosion of the pad and the second wiring by the strong acid material. Therefore, even if the length is increased, it is easy to obtain a highly reliable one.

  In a photoelectric conversion device according to an eleventh aspect, the photoelectric conversion element includes an organic compound as a photoelectric conversion material.

  In the photoelectric conversion device of the present invention, a photoelectric conversion element containing an organic compound as a photoelectric conversion material, that is, an organic photoelectric conversion element is formed on a transparent substrate.

  Hereinafter, the manufacturing method of the photoelectric conversion device of this invention and embodiment of each photoelectric conversion device are described in detail using drawing. The present invention is not limited to the embodiments described below.

(Embodiment 1)
FIG. 1 is a plan view schematically showing an example of the photoelectric conversion device of the present invention. In the figure, 1 is a photoelectric conversion device, 5 is a transparent substrate, 20 is a photoelectric conversion region in which a large number of organic photoelectric conversion elements are arranged, 25 is a first wiring, 30 is a signal generating means, and 35 is a second wiring. is there. Moreover, Fig.2 (a) is a top view which shows roughly the planar arrangement | positioning of each of the organic photoelectric conversion element PE, the 1st wiring 25, and the 2nd wiring 35 in the photoelectric conversion device 1 shown in FIG. FIG. 2B is a plan view schematically showing the planar arrangement of each of the organic photoelectric conversion element PE, the first wiring 25, the second wiring 35, and the signal generating unit 30 in the photoelectric conversion device 1 shown in FIG. FIG. 2 (c) is a schematic view of a cross section taken along line II-II shown in FIG. 2 (b).

  In the photoelectric conversion device 1 shown in these drawings, a large number of organic photoelectric conversion elements PE are formed on a transparent substrate 5 under a predetermined pattern to form a photoelectric conversion region 20 and are generated in individual photoelectric conversion elements. A total of 11 signal generating means 30 for detecting the generated charges and generating data signals are mounted. Each signal generating unit 30 is made of, for example, a single crystal silicon substrate on which a predetermined integrated circuit is formed, and a predetermined number of bumps 30a (see FIG. 2C) are formed on one surface thereof.

  The individual signal generating means 30 and the organic photoelectric conversion element PE corresponding to the signal generating means 30 are connected via a first wiring 25 formed on the transparent substrate 5. Specifically, the first wiring 25 is a bump of the predetermined signal generating means 30 via the pad 27 disposed on one end of the first wiring 25 and the anisotropic conductive film 40 disposed on the pad 27. 30a, thereby connecting the individual signal generating means 30 and the organic photoelectric conversion element PE corresponding to the signal generating means 30. One first wiring 25 is disposed for each organic photoelectric conversion element PE. The region on the one end side of each first wiring 25 is wide, and a pad 27 is formed thereon.

  On the transparent substrate 5, a predetermined number of second wirings 35, which are part of the wirings constituting the individual signal generating means 30 and wirings for connecting the signal generating means 30 to an external circuit, are formed. The second wiring 35 is connected to a bump 30 a of a predetermined signal generating unit 30 through a pad 37 formed on one end thereof and an anisotropic conductive film 40 disposed on the pad 37. The region on the one end side of each second wiring 35 is wide, and a pad 37 is formed thereon. Each signal generating means 30 is connected to an external circuit via a predetermined second wiring 35. Therefore, the data signal generated by the signal generation unit 30 is sent to an external circuit via the predetermined second wiring 35. Further, the second wiring 25 includes control lines such as a power supply line and a ground line, and supply of power supply voltage to each signal generation means 30 and grounding are performed via the predetermined second wiring 25.

  The photoelectric conversion device 1 having such a configuration is characterized in that the layer configuration and composition of each pad 27 are the same, and the layer configuration and composition of these pads 27 and the layer configuration and composition of each second wiring 35. Are the same as each other, and each pad 37 includes a region having the same layer configuration and composition as the pad 27. Hereinafter, these characteristic portions will be described in detail with reference to FIG.

  FIG. 3 is a cross-sectional view schematically showing another example of the photoelectric conversion device of the present invention. In the figure, 1A is a photoelectric conversion device, 10R is a red color filter (hereinafter referred to as “red filter 10R”), 10G is a green color filter (hereinafter referred to as “green filter 10G”), and 10B is blue. A color filter (hereinafter referred to as “blue filter 10B”), 12 is a protective layer covering each filter 10R, 10G, 10B, 14a is a transparent electrode constituting the organic photoelectric conversion element PE, and 14b is an organic photoelectric conversion element PE. An organic photoelectric conversion unit 14c is a back electrode constituting the organic photoelectric conversion element PE, 16 is a sealing member for sealing each organic photoelectric conversion element PE, and 26 is an electrical insulating film covering the first wiring 25. 3 having the same functions as those shown in FIG. 1, FIG. 2 (a), FIG. 2 (b), or FIG. 2 (c) are shown in FIG. The same reference numerals as those used in a), FIG. 2B, or FIG.

  A photoelectric conversion device 1A shown in FIG. 3 can be used as a linear image sensor capable of obtaining full-color image data. A red filter 10R, a green filter 10G, and a blue filter 10B are provided on a transparent substrate 5. A large number of organic photoelectric conversion elements PE are arranged in a matrix over three rows and a plurality of columns on a protective layer 12 that is formed in a stripe shape and is provided so as to cover them. Each organic photoelectric conversion element PE has a structure in which an organic photoelectric conversion unit 14b and a back electrode 14c are stacked in this order on a transparent electrode 14a. The back electrode 14c in each organic photoelectric conversion element PE is: It consists of one mutually separate area | region in one electrode film. The sealing member 16 is disposed on the transparent substrate 5 to prevent intrusion of moisture or the like into the organic photoelectric conversion element PE, and forms a space for sealing each organic photoelectric conversion element PE together with the transparent substrate 5. is doing.

  The individual first wirings 25 are covered with an electric insulating film 26 and are electrically separated from each other by the electric insulating film 26. Each pad 27 interposed between the first wiring 25 and the signal generating means 30 protrudes from the electrical insulating film 26.

Each of the individual pads 27 and each of the second wirings 35 includes a first conductive layer CL ₁ having a low resistivity (low electrical resistivity) and a second conductive layer CL ₁ formed on the first conductive layer CL ₁ by a corrosion-resistant material. the two-layer structure of a conductive layer CL ₂ has. A first conductive layer CL ₁ at each pad 27 and the first conductive layer CL ₁ at each second wirings 35 have the same thickness and composition from each other. Similarly, the second conductive layer CL ₂ and the second conductive layer CL ₂ at each of the second wiring 35 at each pad 27 has the same thickness and composition from each other.

Further, each pad 37 interposed between the second wiring 35 and the signal generating means 30 is formed on the base layer L ₀ made of a conductive layer having the same thickness as the first wiring 25 and the first conductive layer CL ₁ and the second conductive layer CL ₁ . It has a three-layer structure in which the conductive layer CL ₂ is laminated in this order. A first conductive layer CL ₁ at each pad 37 and the first conductive layer CL ₁ at each pad 27 has the same thickness and composition from each other. Similarly, the second and the conductive layer CL ₂ of the second conductive layer CL ₂ and each pad 27 of each pad 37 has the same thickness and composition from each other.

In the photoelectric conversion device 1A having such a configuration, each pad 27 and each second wiring, and the first conductive layer CL ₁ and the second conductive layer CL ₂ in each pad 37 are formed together from one laminated film. Therefore, the heights of the pads 27 and 37 can be easily aligned. Therefore, it is easy to reliably connect the pads 27 and 37 and the signal generating unit 30 via the anisotropic conductive film 40 while suppressing conduction at an undesired location. Moreover, since each pad 27 and 37 and each 2nd wiring 35 can be formed by patterning one laminated film as mentioned above, compared with the case where these are formed in a separate process, the number of processes is large. Less. And since the organic photoelectric conversion element PE is provided as a photoelectric conversion element, it is also easy to arrange and lengthen many organic photoelectric conversion elements PE.

  Therefore, in the photoelectric conversion device 1A, it is easy to obtain a long and highly reliable device at low cost. Moreover, it is easy to obtain a highly reliable product even when the length is increased.

(Embodiment 2)
FIG. 4 is a cross-sectional view schematically showing still another example of the photoelectric conversion device of the present invention. In the figure, 1B is a photoelectric conversion device, and AL is an adhesion layer. Among the structural members shown in FIG. 4, those having the same functions as those of the structural members shown in FIG. 3 are denoted by the same reference numerals as those used in FIG.

In the photoelectric conversion device 1B shown in FIG. 4, each pad 27 and each second wiring 35 are each composed of three layers in which a first conductive layer CL ₁ and a second conductive layer CL ₂ are stacked in this order on the adhesion layer AL. It has a structure. Moreover, each pad 37 has a four-layer structure adhesion layer AL and the first conductive layer CL ₁ and the second conductive layer CL ₂ were laminated in this order on the base layer L _0. The thickness and composition of the adhesion layer AL are the same in each of the pads 27 and 37 and the second wirings 35. The configuration other than the adhesion layer AL in the photoelectric conversion device 1B is the same as the configuration in the photoelectric conversion device 1A shown in FIG.

In the photoelectric conversion device 1B having such a configuration, it is easy to obtain a long and highly reliable device at low cost for the same reason as in the above-described photoelectric conversion device 1A. Moreover, even if the length is increased, it is easy to obtain a highly reliable one. Furthermore, since the adhesion of the first conductive layer CL ₁ can be enhanced by the adhesion layer AL, it is easy to prevent the pads 27 and 37 or the second wiring 35 from being lost.

(Embodiment 3)
FIG. 5 is a cross-sectional view schematically showing still another example of the photoelectric conversion device of the present invention. In the figure, 1C is a photoelectric conversion device. Among the structural members shown in FIG. 5, those having the same functions as the structural members shown in FIG. 3 are denoted by the same reference numerals as those used in FIG.

In the photoelectric conversion device 1 </ b> C shown in FIG. 5, each second conductive layer CL ₂ covers the outer surface (upper surface and side surface) of the first conductive layer CL ₁ therebelow. Other configurations in the photoelectric conversion device 1C are the same as the configurations in the photoelectric conversion device 1A shown in FIG.

  In the photoelectric conversion device 1C having such a configuration, it is easy to obtain a long and highly reliable device at low cost for the same reason as in the above-described photoelectric conversion device 1A. Moreover, it is easy to obtain a highly reliable product even when the length is increased.

Furthermore, since the second conductive layer CL ₂ covers the outer surface of the first conductive layer CL ₁ , by appropriately selecting the material of the second conductive layer CL ₂ , for example, the pads 27 and 37 and the second wiring Even if the strong acid material is applied to the entire surface when forming the organic photoelectric conversion element PE using a strongly acidic material such as polyethylenedioxythiophene (PEDOT) after the formation of 35, each pad 27, 37 or each second It becomes easy to prevent the wiring 35 from being corroded by the strong acid material. Also from this point, it is easy to obtain a highly reliable photoelectric conversion device.

(Embodiment 4)
The photoelectric conversion device of the present invention described in Embodiment 1 or 2 can be manufactured, for example, by the method for manufacturing a photoelectric conversion device of the present invention. The manufacturing method of the photoelectric conversion device of the present invention includes a patterning step of patterning at least one conductive layer to form the aforementioned pad and the second wiring, and the first wiring before the patterning step. After the patterning process, an element forming process for forming the organic photoelectric conversion element and a mounting process for mounting the signal generating means are performed. Hereinafter, it explains in full detail for every process.

(First wiring formation process)
In the first wiring formation step, a predetermined number of first wirings are formed on the transparent substrate. When manufacturing a photoelectric conversion device having a color filter like the photoelectric conversion devices 1A to 1C described in the first to third embodiments, the color filter is formed on the transparent substrate prior to the formation of the first wiring. The first sub-step and the second sub-step for forming the protective layer are performed in this order.

  At this time, as the transparent substrate, a transparent or translucent substrate having mechanical and thermal strength is used. The transparent substrate is preferably an electrical insulator, but has a conductivity or a conductive region within a range that does not hinder the operation of each organic photoelectric conversion element or according to the use of the photoelectric conversion device. May be included.

Examples of such transparent substrates include (1) soda quartz glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz glass, alkali-free glass, fluoride glass, and the like. (2) Organic polymer compounds such as (2) polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyether sulfone, polyvinyl fluoride, polypropylene, polyethylene, polyacrylate, amorphous polyolefin, fluorine-based resin, (3) As ₂ Chalcogenide glass such as S ₃ , As ₄₀ S ₁₀ , S ₄₀ Ge ₁₀ , (4) Metal oxide such as zinc oxide, niobium oxide, tantalum oxide, silicon oxide, hafnium oxide, titanium oxide, and metal nitride such as silicon nitride Products, (5) depending on pigments, etc. Color is transparent substrate material, and (6) a metal material subjected to an insulating treatment on the surface, it is possible to use one made of, or the like. Further, a material made of a material that transmits only light of a specific wavelength, a material that converts incident light into light of a specific wavelength by a light-light conversion function, or the like can also be used. In addition to a single-layer structure, the transparent substrate can also have a stacked structure in which a plurality of substrate materials are stacked.

  In the case where the first sub-process for forming the color filter is performed, the color filter is formed in the first sub-process using, for example, an organic composition (for example, a color resin) colored with a color material such as a desired dye or pigment. This is done by patterning the formed layer into a predetermined shape by photolithography. The color filter can also be formed by applying a desired organic composition colored with a coloring material in a predetermined pattern by a printing method, an ink-jet method, a vapor deposition method or the like, or depositing it on a predetermined location by an electrodeposition method. Can be formed. As the color filter, a primary color system or a complementary color system may be formed.

  When the color filter is formed, a second sub-process is performed thereafter to form a protective layer that covers each color filter. In addition to being excellent in heat resistance and solvent resistance, this protective layer is preferably excellent in flatness, adhesion, transparency, light resistance, heat discoloration resistance, storage stability, etc. As a raw material for such a protective layer, for example, an acrylic, epoxy, polyimide, siloxane, or alkyl photocurable or thermosetting resin composition or the like is used. When forming a protective layer using a photocurable or thermosetting resin composition, the resin composition is applied by a method such as spin coating to form a coating film, and then applied to the coating film. It is irradiated with light in a predetermined wavelength range and semi-cured and then patterned into a predetermined shape, or heat-treated to be semi-cured and then patterned into a predetermined shape, and then completely cured by light irradiation or heat treatment.

  The 1st wiring can also be formed separately from the transparent electrode which constitutes an organic photoelectric conversion element, and can also be formed together. When the first wiring and the transparent electrode are formed separately, the transparent electrode is formed before the first wiring is formed or after the first wiring is formed.

  When the first electrode and the transparent electrode are formed together, these materials include (1) indium tin oxide (ITO; including coated ITO), tin oxide, zinc oxide, indium zinc oxide. Transparent conductive oxides such as antimony-doped tin oxide and aluminum-doped zinc oxide; (2) metal thin films such as thin films of metals such as aluminum, copper, titanium and silver, mixed thin films of these metals, and laminated thin films; (3) Polypyrrole, polyethylenedioxythiophene (hereinafter abbreviated as “PEDOT”), polyphenylene vinylene (hereinafter abbreviated as “PPV”), conductive polymer compounds such as polyfluorene, and the like can be used.

  The formation of the first wiring and the transparent electrode is performed by, for example, forming a physical vapor phase such as a vacuum vapor deposition method (resistance heating vapor deposition method, electron beam vapor deposition method) or a sputtering method according to the material of these films. After forming by a vapor deposition method (PVD method) or various polymerization methods (electric field polymerization method, etc.), the film is formed into a predetermined shape using a lithography method (a photolithography method, an electron beam lithography method, etc.) and an etching method. This is done by patterning. It is also possible to directly form the first wiring and the transparent electrode having a desired shape by a PVD method or a polymerization method using a mask having a predetermined shape.

  The first wiring and the transparent electrode may have a single layer structure or a stacked structure. In order to provide sufficient conductivity, or in order to prevent uneven light incidence on the organic photoelectric conversion element due to the unevenness of the surface of the transparent substrate, the film thickness is desirably 1 nm or more. Further, it is desirable that the transparent electrode has a film thickness of 500 nm or less in order to provide sufficient transparency.

Note that, like the photoelectric conversion devices 1A and 1B described in the first and second embodiments, the pad 37 interposed between the second wiring 35 and the signal generating means 30 is the base layer L ₀ (see FIGS. 3 and 4). When the first wiring is formed by patterning the film that is the source of the first wiring, the base layer L ₀ is preferably formed together.

(Patterning process)
In the patterning step, at least one conductive layer is patterned to form a pad and a second wiring that are interposed between the first wiring and the signal generating means. At this time, as in the photoelectric conversion devices 1A and 1B described in the first and second embodiments, the base layer L ₀ in the pad 37 interposed between the second wiring 35 and the signal generating means 30 (see FIGS. 3 and 4). The layers other than) are preferably formed together from the conductive layer.

  When the conductive layer has a single-layer structure, the conductive layer may be a low-resistivity conductive layer or a conductive layer made of a corrosion-resistant material. From the viewpoint of formation, a conductive layer having a low resistivity is preferable. In the case where the conductive layer has a multi-layer structure, the conductive layer may have a two-layer structure as in the photoelectric conversion device 1A described in Embodiment 1, or the photoelectric layer described in Embodiment 2. A three-layer structure as in the conversion device 1B may be used, or a laminated structure of four or more layers may be used. When the conductive layer has a laminated structure of two or more layers, the first conductive layer having a low resistivity and the second conductive layer made of a corrosion-resistant material are combined, and the second conductive layer is the uppermost layer. Is preferred. First, a first sub-process for forming a first conductive layer with a low resistivity is performed, and then a second sub-process for forming a second conductive layer made of a corrosion-resistant material on the first conductive layer.

  The first conductive layer (low resistivity conductive layer) is, for example, silver (Ag), copper (Cu), gold (Au), aluminum (Al), tungsten (W), molybdenum (Mo), cobalt ( It can be formed of a single metal or an alloy containing at least one of Co), zinc (Zn), nickel (Ni), iron (Fe), platinum (Pt), and chromium (Cr). The second conductive layer (conductive layer made of a corrosion-resistant material) is, for example, gold (Au), chromium (Cr), indium (In), copper (Cu), titanium (Ti), molybdenum (Mo), Nickel (Ni), Iron (Fe), Platinum (Pt), Tin (Sn), Silicon (Si), Palladium (Pd), Iridium (Ir), Manganese (Mn), Vanadium (V), and Tantalum (Ta) It can form with the metal simple substance, alloy, or metal oxide containing at least 1 of these.

  In forming the conductive layer, for example, a PVD method is used. After forming a conductive layer having a desired layer structure, a third sub-step of patterning the conductive layer is performed to obtain each pad and second wiring. The patterning of the conductive layer is performed using, for example, a lithography method (a photolithography method, an electron beam lithography method, etc.) and an etching method.

(Element formation process)
In the element formation step, the organic photoelectric conversion portion and the back electrode are formed on the above-described transparent electrode formed before or after the first wiring formation step, thereby obtaining a desired number of organic photoelectric conversion elements. When each of the first wirings 25 is covered with the electrical insulating film 26 (see FIGS. 3 and 4) as in the photoelectric conversion devices 1A and 1B described in the first and second embodiments, prior to the formation of the organic photoelectric conversion portion. It is preferable to form the electrical insulating film 26.

  In the case of forming the electrical insulating film 26, the electrical insulating film 26 is formed of, for example, an organic material such as a photocurable resin or an inorganic material such as silicon nitride. In the case where the electrical insulating film is formed using an organic material, a light-shielding property may be imparted by adding a desired color material to the organic material. The method for forming the electrical insulating film 26 is appropriately selected according to the material, such as coating, spin coating, printing, physical vapor deposition, and chemical vapor deposition.

  For example, in the case of forming an electrical insulating film from a photo-curable resin, the resin composition as a base is applied by a coating method, a spin coating method, a printing method, etc., and then cured by irradiation with light in a predetermined wavelength range. Let At this time, it may be patterned into a predetermined shape by a photolithography method. When an electrical insulating film is formed of an inorganic material, the original film is formed by a PVD method or a chemical vapor deposition method (CVD method), and thereafter, a lithography method and an etching method are used. Pattern into a predetermined shape. It is also possible to directly form an electric insulating film having a desired shape by a PVD method or a CVD method using a vapor deposition mask having a predetermined shape.

  The organic photoelectric conversion part constituting the organic photoelectric conversion element is formed using, for example, an electron donating material and an electron accepting material. These electron donating material and electron accepting material may form a mixture with each other or may be separated from each other.

  Here, the above-mentioned “mixture” refers to a liquid phase or solid phase material placed in a container, added with a solvent as necessary, and mixed by stirring or the like, and this is a spin coating method. And those formed by an inkjet method or the like. In addition, the mixed state of the electron donating material and the electron accepting material does not need to be uniform, and may be mixed nonuniformly or only a part may form a mixture. On the other hand, when the electron donating material and the electron accepting material are separated from each other, the layers may not be completely separated from each other, and the layer including the electron donating material and the layer including the electron accepting material These layers may form a mixed state at the interface. For example, by forming the layer containing an electron donating material and the layer containing an electron accepting material by different methods, an organic photoelectric conversion part in which these layers are completely separated from each other can be obtained. Specific examples of the electron donating material and the electron accepting material will be described later.

  The organic photoelectric conversion units in the individual organic photoelectric conversion elements may be separated from each other, or may be separate areas from one organic photoelectric conversion film. Such an organic photoelectric conversion part can be formed by a vacuum process such as a vacuum deposition method or a sputtering method, or a wet process such as a spin coating method, a dipping method, or an ink jet method, depending on the material used. When the organic photoelectric conversion part is formed by a wet process, it becomes easy to obtain a photoelectric conversion device with low cost and high productivity. For example, when the organic photoelectric conversion film is formed by spin coating, the organic photoelectric conversion film is formed outside the region designed as the organic photoelectric conversion element. Pattern by the method.

  It is preferable to form the back electrode which comprises an organic photoelectric conversion element with the material which can take out the electron produced in the organic photoelectric conversion part efficiently. Examples of such materials include aluminum (Al), indium (In), magnesium (Mg), titanium (Ti), silver (Ag), calcium (Ca), strontium (Sr), tungsten (W), and chromium. Metals such as (Cr), barium (Ba), nickel (Ni), alloys containing these metals, or conductive oxides or fluorides containing the above metals are used. In order to increase the photoelectric conversion efficiency in the organic photoelectric conversion unit, the light that has reached the back electrode without contributing to the photoelectric conversion can be supplied to the organic photoelectric conversion unit again to contribute to the photoelectric conversion. The back electrode is preferably formed of a conductive material having a high reflectance.

  The back electrode can have a single layer structure or a laminated structure. The back electrode can be formed by a PVD method such as resistance heating vapor deposition, electron beam vapor deposition, or sputtering. The back electrodes in each organic photoelectric conversion element may be separated from each other, or may be separate areas in one electrode film.

  By forming up to the back electrode in this way, a desired number of organic photoelectric conversion elements can be obtained. When each organic photoelectric conversion element PE is sealed with the sealing member 16 (see FIGS. 3 and 4) as in the photoelectric conversion devices 1A and 1B described in the first and second embodiments, the material of the sealing member 16 is For this, glass, resin, or the like having a desired water vapor transmission rate and oxygen transmission rate is used. For example, the sealing member 16 can be obtained by forming a recess in a flat plate made of a desired inorganic material or organic material and forming the flat plate into an extremely shallow box shape. Such a sealing member 16 is made of, for example, an inorganic adhesive such as soft wax having a desired water vapor transmission rate and oxygen transmission rate, a photo-curing adhesive, a thermosetting adhesive, a two-component adhesive, or the like. It is fixed on the transparent substrate by an organic adhesive. In addition, an inorganic film made of silicon oxide, silicon oxynitride, aluminum oxide, silicon nitride, lithium fluoride or the like so as to cover the back electrode and the organic photoelectric conversion portion, a glass film by a sol-gel method, or a thermosetting resin It is also possible to use an organic film made of a photocurable resin, a silane polymer material having a sealing effect, or the like as a sealing member.

  The above-mentioned electron donating materials constituting the organic photoelectric conversion part include (1) phenylene vinylene and derivatives thereof, fluorene and derivatives thereof (fluorene copolymers having a quinoline group or a pyridine group in the skeleton (P0F66, P1F66, PFPV). Fluorene-containing arylamine polymer, carbazole and derivatives thereof, indole and derivatives thereof, pyrene and derivatives thereof, pyrrole and derivatives thereof, picoline and derivatives thereof, thiophene and derivatives thereof, acetylene and derivatives thereof, diacetylene and derivatives thereof Polymers such as derivatives and derivatives thereof, (2) a group of polymer materials collectively referred to as dendrimers, (3) porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide (4) 1,1-bis (4- (di-p-tolylamino) phenyl) cyclohexane, 4,4 ′, 4 ″ -trimethyltriphenylamine, N, N, N ′, N′-tetrakis (P-tolyl) -p-phenylenediamine, 1- (N, N-di-p-tolylamino) naphthalene, 4,4′-bis (dimethylamino) -2,2′-dimethyltriphenylmethane, N, N , N ′, N′-tetraphenyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di-m-tolyl-4,4′-diaminobiphenyl, N-phenylcarbazole, etc. Stilbes such as aromatic tertiary amines, (5) 4-di-p-tolylaminostilbene, 4- (di-p-tolylamino) -4 ′-(4- (di-p-tolylamino) styryl) stilbene Compound, or the like can be used.

  Furthermore, triazole and its derivatives, oxadiazole and its derivatives, imidazole and its derivatives, polyarylalkane and its derivatives, pyrazoline and its derivatives, pyrazolone and its derivatives, phenylenediamine and its derivatives, arylamine and its derivatives, amino Substituted chalcone and derivatives thereof, oxazole and derivatives thereof, styryl anthracene and derivatives thereof, fluorenone and derivatives thereof, hydrazone and derivatives thereof, silazane and derivatives thereof, polysilane aniline copolymers, styrylamine compounds, aromatic dimethylidin compounds Poly-3-methylthiophene can also be used. The electron donating material can be chemically modified to adjust the absorption wavelength characteristic.

  On the other hand, as the above-described electron-accepting material constituting the organic photoelectric conversion part, in addition to the low-molecular and high-molecular materials similar to the electron-donating material described above, the following compounds (i) to (vi), (I) 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene and other oxadiazoles and derivatives thereof, (ii) fluorenes and derivatives thereof, (iii) anthraquinodimethane and Its derivatives, (iv) diphenylquinone and its derivatives, (v) fullerene and its derivatives ([5,6] -phenyl C61 butyric acid methyl ester, [6,6] -phenyl C61 butyric acid methyl ester, etc.), (vi) carbon Polymers having nanotubes and their derivatives as repeating units, and copolymers of compounds (i) to (vi) above with other monomers It is used. Furthermore, a group of polymer materials collectively referred to as dendrimers can be used. The electron-accepting material can be chemically modified to adjust the absorption wavelength characteristic.

(Mounting process)
In the mounting process, a predetermined number of signal generating means are mounted on the transparent substrate. As the signal generation means, for example, a semiconductor bare chip in which a predetermined integrated circuit is formed on a single crystal silicon substrate can be used. Of course, it is also possible to use a packaged semiconductor chip as signal generating means.

  In mounting the signal generating means on the transparent substrate, it is preferable to use the anisotropic conductive film 40 (see FIGS. 3 and 4) as in the photoelectric conversion devices 1A and 1B described in the first and second embodiments. By using the anisotropic conductive film 40, each signal generating means can be mounted in a small mounting area, so that the photoelectric conversion device can be easily downsized. Of course, each signal generating means can be mounted on the transparent substrate with an anisotropic conductive adhesive, and if the mounting area can be increased, each signal can be formed by wire bonding, for example, without using an anisotropic conductive film. It is also possible to configure the photoelectric conversion device so that the generation means is mounted on the transparent substrate. By carrying out up to this mounting process, the intended photoelectric conversion device is obtained.

  When the photoelectric conversion device is manufactured in this manner, the pads can be formed together with the same layer configuration and composition of the pads interposed between the first wiring and the signal generating means. It is easy to align the height. Similarly, it is easy to align the heights of the pads interposed between the second wiring and the signal generating means. For this reason, it is easy to reliably connect the pad and the signal generating means through the anisotropic conductive film while suppressing conduction at an undesired location. Moreover, since each pad and each 2nd wiring are formed in the same process, the number of processes reduces compared with the case where these are formed in a separate process. And since a photoelectric conversion device is comprised using an organic photoelectric conversion element as a photoelectric conversion element, lengthening is easy.

  Therefore, according to the manufacturing method described above, it is easy to obtain a long photoelectric conversion device with high reliability at low cost. Further, it is easy to obtain a highly reliable photoelectric conversion device even if the length is increased.

(Embodiment 5)
The photoelectric conversion device of the present invention described in Embodiment 3 can be manufactured by, for example, another manufacturing method of the photoelectric conversion device of the present invention.

  This manufacturing method includes a low-resistivity conductive layer forming step for forming a low-resistivity conductive layer comprising at least one layer, and a first pad for pad that forms a pad by patterning the low-resistivity conductive layer by etching. A first etching step for forming a conductive layer and a first conductive layer for second wiring that constitutes the second wiring; and an outer surface of each of the first conductive layer for pad and the first conductive layer for second wiring. A corrosion-resistant conductive layer forming step for forming a corrosion-resistant conductive layer comprising at least one layer so as to cover, and a second conductive layer for pad covering the outer surface of the first conductive layer for pad by patterning the corrosion-resistant conductive layer by etching And a second etching step of forming a second conductive layer for second wiring covering the outer surface of the first conductive layer for second wiring.

  Each of the above steps is positioned as a sub-step in the patterning step in the manufacturing method described in the fourth embodiment, and each of the low resistivity conductive layer and the corrosion resistant conductive layer is formed by, for example, the PVD method. The patterning of the conductive layer is performed using, for example, a lithography method (a photolithography method, an electron beam lithography method, etc.) and an etching method. Examples of the material of the low resistivity conductive layer are the same as the materials of the first conductive layer (low resistivity conductive layer) described in Embodiment 4, and the material of the corrosion resistant conductive layer is The same material as that of the second conductive layer (conductive layer made of a corrosion-resistant material) described in the fourth embodiment is exemplified.

  By performing the above-described steps, each of the pads interposed between the first wiring and the signal generating means and each of the second wiring are formed. In addition, it is preferable that a layer other than the base layer at the pad interposed between the second wiring and the signal generating means is also formed in each of the above steps. Of the constituent members of the photoelectric conversion device, the remaining constituent members excluding the pad and the second wiring are formed in the same manner as in the manufacturing method described in the fourth embodiment.

  When a photoelectric conversion device is manufactured in this manner, a long and highly reliable photoelectric conversion device can be easily obtained at low cost for the same reason as in the manufacturing method described in Embodiment 4. Moreover, it becomes easy to obtain a highly reliable photoelectric conversion device even if the length is increased. Furthermore, since the outermost layer in each pad and each second wiring is formed of a corrosion-resistant conductive layer, the strong acid is used in forming an organic photoelectric conversion element using a strongly acidic material such as polyethylenedioxythiophene (PEDOT). Even if the material is applied to the entire surface, it is easy to prevent the pads and the second wirings from being corroded by the strong acid material.

  As mentioned above, although the manufacturing method of the photoelectric conversion device of this invention and embodiment of each photoelectric conversion device were explained in full detail, as mentioned above, this invention is not limited to these forms.

  For example, the arrangement form of the photoelectric conversion elements is not limited to 3 rows and many columns, and may be one row and many rows, two rows and many columns, or may be four or more rows and many rows. . The form in which the photoelectric conversion elements are arranged can be appropriately selected according to the use of the photoelectric conversion device.

  When each of the photoelectric conversion elements is an organic photoelectric conversion element, these organic photoelectric conversion elements may be configured such that one separate region in one organic photoelectric conversion film is an organic photoelectric conversion unit. Moreover, you may have a back electrode isolate | separated mutually for every organic photoelectric conversion element. If necessary, a positive electrode buffer layer can be interposed between the electrode used as the positive electrode and the organic photoelectric conversion unit. This positive electrode buffer layer has a work function higher than that of the electron-accepting material constituting the organic photoelectric conversion portion and has a work function lower than that of the positive electrode, for example, an oxide of inorganic metal such as molybdenum oxide, It is made of an inorganic metal fluoride, an inorganic metal nitride, or an organic semiconductor such as polyethylenedioxythiophene (PEDOT) or bathocuproine. Similarly, a negative electrode buffer layer can be interposed between the electrode used as the negative electrode and the organic photoelectric conversion unit. This negative electrode buffer layer is a substance having a work function lower than that of the electron donating material constituting the organic photoelectric conversion portion and higher than that of the negative electrode, such as metal fluorides and metal oxides including lithium fluoride. Etc. are formed.

When the outer surface of the first conductive layer CL ₁ is covered with the second conductive layer CL ₂ (see FIG. 5) as in the photoelectric conversion device 1C described in the third embodiment, the second conductive layer CL ₂ is the first conductive layer. It may be formed directly on the layer CL ₁ , or another conductive layer may be interposed between the first conductive layer CL ₁ and the second conductive layer CL ₂ as necessary. The photoelectric conversion device manufacturing method and photoelectric conversion device of the present invention can be variously modified, modified, combined, and the like in addition to those described above. Hereinafter, specific examples of the present invention will be described with reference to examples.

(Example 1)
(First wiring formation process)
First, an alkali-free glass substrate was prepared as a transparent substrate. A color resin of the desired color is applied onto this alkali-free glass substrate to form a coating film, which is then calcined at 100 ° C., then exposed through a photomask, developed, and patterned into stripes. A colored resin layer is obtained. This process is performed for each of the red, green, and blue color resins to form a total of 3 layers of pre-fired color resin layers having a film thickness of 2 μm in parallel, and then these are fired to produce a red filter and a green color. The filter and the blue filter were formed on a transparent substrate (non-alkali glass substrate).

  Next, the thermosetting resin composition was applied by a spin coat method so as to cover each of the above filters to form a coating film, and after drying, a photomask having a predetermined shape was formed on the coating film. Using this photomask, the coated film after drying is selectively exposed and developed, and baked at 200 ° C. to form a protective layer having a thickness of about 1.8 μm covering the upper and side surfaces of the color filter portion. Obtained.

  An ITO film having a thickness of 150 nm is formed on the protective layer and the surface (exposed surface) of the transparent substrate by sputtering, and then a resist material (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is formed on the ITO film by spin coating. (Product Name) was applied to form a resist film having a thickness of 1 μm, and this resist film was selectively exposed and developed to obtain a resist pattern having a predetermined shape. Then, the transparent substrate (non-alkali glass substrate) formed up to the resist pattern was dipped in a 50% hydrochloric acid aqueous solution at a liquid temperature of 60 ° C., and the ITO film in the portion where the resist pattern was not formed was etched.

  Thereafter, the resist pattern is removed, a large number of ITO electrodes arranged in a matrix over 3 rows and 7500 columns, a first wiring connected to each of the ITO electrodes, and a later-described first wiring. A predetermined number of ITO layers used as a base layer in a pad connected to two wirings were obtained.

  The ITO electrode is used as a transparent electrode in an organic photoelectric conversion element, the pitch between ITO electrodes adjacent in the row direction is 0.042 mm, and the distance between the ITO electrodes adjacent in the row direction is 0. 0.005 mm. Similarly, the pitch between the ITO electrodes adjacent in the column direction is 0.042 mm, and the distance between the ITO electrodes adjacent in the column direction is 0.005 mm. Each first wiring is connected to the corresponding ITO electrode and extends in the column direction, and one end thereof (the end opposite to the ITO electrode) is wide.

(Patterning process)
A copper (Cu) layer having a thickness of 2 μm is formed as a first conductive layer by the PVD method on the entire transparent substrate formed up to the ITO electrode as described above, and a 0.15 μm thickness is formed as a second conductive layer thereon. The ITO layer was formed by the PVD method.

  A resist material (OFPR-800 (trade name) manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto the ITO layer by spin coating to form a resist film having a thickness of 1.8 μm. After developing to obtain a resist pattern of a predetermined shape, the ITO layer where the resist pattern is not formed is selectively dry etched, and the copper layer exposed by the dry etching is selectively wet etched. did.

  As a result, a pad (hereinafter referred to as “first pad”) that is interposed between the first wiring and a signal generation means described later is formed on one wide end of each first wiring. On the ITO layer as the base layer described above, a pad (hereinafter referred to as “second pad”) to be interposed between the second wiring described later and the signal generating means described later was formed. A plurality of second wirings were formed at predetermined locations on the transparent substrate.

  Each of the first pads has a two-layer structure of a copper layer as a first conductive layer and an ITO layer as a second conductive layer, and each of the second pads includes an ITO layer as a base layer, It has a three-layer structure of a copper layer as the first conductive layer and an ITO layer as the second conductive layer. Each of the second wirings has a two-layer structure of a copper layer as the first conductive layer and an ITO layer as the second conductive layer. When the transparent substrate is used as a reference, the heights of the first pads and the second pads are substantially the same.

  Of the second wirings, those used as ground lines for the signal generation means described later are set to a line width of about 3 mm so that the length is, for example, 300 mm (corresponding to the length of the short side in the A3 size). However, since the electrical resistance at both ends is 1Ω or less, it is easy to operate the signal generating means normally.

(Element formation process)
First, a polyimide photosensitive resin composition (Photo Nice (trade name) manufactured by Toray Industries, Inc.) is spin-coated on a transparent substrate formed up to each of the first pad, the second pad, and the second wiring. A resin composition layer having a thickness of about 1 μm is formed. After pre-baking the resin composition layer, the layer is selectively exposed, developed, and post-baked to obtain an electrical insulating film that covers each first wiring. It was. The electrical insulating layer is for electrically separating adjacent first wirings, and electrically connecting each of the first wirings from an organic photoelectric conversion element other than the organic photoelectric conversion element corresponding to the first wiring. It is also for separation. A gap of about 1 μm was formed between the electrical insulating film and each first pad.

  Since the height of each of the first pad and the second pad is about 2.3 μm with respect to the transparent substrate, these pads protrude from the above-described electrical insulating film. For this reason, when the signal generation means described later is mounted on the transparent substrate via the anisotropic conductive film, it is easy to achieve conduction between each pad and the signal generation means.

  Next, a mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate was dropped on a transparent substrate through a filter having an aperture of 0.45 μm, and uniformly applied by a spin coat method. This was heated in a clean oven at 200 ° C. for 30 minutes to form a positive electrode buffer layer covering each of the above-mentioned ITO electrodes. Since the ITO layer as the second conductive layer has acid resistance, the positive buffer layer is formed using poly (3,4-ethylenedioxythiophene), which is a strongly acidic material. Corrosion of the pad and the second wiring was suppressed.

  Next, a chlorobenzene solution containing poly (2-methoxy-5- (2′-ethylhexyloxy) -1,4-phenylenevinylene) and [5,6] -phenyl C61 butyric acid methyl ester in a weight ratio of 1: 4 Was applied on the positive electrode buffer layer by spin coating, and was heat-treated in a clean oven at 100 ° C. for 30 minutes to form an organic photoelectric conversion film having a thickness of about 100 nm covering each ITO electrode in plan view. .

Subsequently, a 2 nm-thick lithium fluoride film as a negative electrode buffer layer and a back electrode in a resistance heating vapor deposition apparatus depressurized to a vacuum of 0.27 mPa (2 × 10 ⁻⁶ Torr) or less An aluminum film having a thickness of about 100 nm as a film was formed on the organic photoelectric conversion film in this order. By forming up to this electrode film, a predetermined number of organic photoelectric conversion elements including a transparent electrode (ITO electrode), a positive electrode buffer layer, an organic photoelectric conversion unit, a negative electrode buffer layer, and a back electrode were formed. . Each organic photoelectric conversion unit is composed of a single region which is separate from the organic photoelectric conversion film described above.

  Thereafter, an extremely shallow box-shaped object made of glass is prepared as a sealing member, and the box-shaped object is fixed on a transparent substrate with an epoxy-based photocurable adhesive so as to cover each organic photoelectric conversion element. Each organic photoelectric conversion element was sealed.

(Mounting process)
A predetermined number of semiconductor chips each having a predetermined integrated circuit formed on a single crystal silicon substrate were used as signal generating means, and these signal generating means were mounted on a transparent substrate via an anisotropic conductive film. Thus, the target photoelectric conversion device was obtained by carrying out to the mounting of the signal generation means. This photoelectric conversion device has the same structure as the photoelectric conversion device 1A shown in FIG.

(Example 2)
After performing the first wiring formation step under the same conditions as the first wiring formation step in Example 1, a chromium (Cr) layer having a thickness of 1.8 μm as an adhesion layer is formed on the entire transparent substrate formed up to the ITO electrode. Is formed by a PVD method, an aluminum (Al) layer having a thickness of 1.8 μm is formed thereon by a PVD method as a first conductive layer, and further a chromium having a thickness of 0.15 μm is formed thereon as a second conductive layer. The (Cr) layer was formed by the PVD method.

  A resist material (OFPR-800 (trade name) manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto the chromium layer as the second conductive layer by spin coating to form a resist film having a thickness of 2 μm. Exposure and development were performed to obtain a resist pattern having a predetermined shape. Thereafter, a portion of the chromium layer where the resist pattern is not formed (second conductive layer) is selectively wet etched, and the exposed aluminum layer (first conductive layer) is selectively wet etched. The chromium layer (adhesion layer) exposed by selective wet etching of the aluminum layer was selectively wet etched.

  As a result, a first pad which is interposed between the first wiring and a signal generating means described later is formed on one wide end of each first wiring. On the ITO layer as the base layer described above The second pad to be interposed between the second wiring and the signal generating means is formed. A plurality of second wirings were formed at predetermined locations on the transparent substrate.

  Each of the first pads has a three-layer structure of a chromium layer as an adhesion layer, an aluminum layer as a first conductive layer, and a chromium layer as a second conductive layer. The four-layer structure includes an ITO layer as a base layer, a chromium layer as an adhesion layer, an aluminum layer as a first conductive layer, and a chromium layer as a second conductive layer. Each of the second wirings has a three-layer structure including a chromium layer as an adhesion layer, an aluminum layer as a first conductive layer, and a chromium layer as a second conductive layer. When the transparent substrate is used as a reference, the heights of the first pads and the second pads are substantially the same.

  By setting the line width of the second wiring used as the ground line of the signal generating means to about 3 mm, the length can be set to, for example, 300 mm (corresponding to the length of the short side in the A3 size). Since the electrical resistance at both ends is 1.5Ω or less, it is easy to operate the signal generating means normally.

  Then, the element formation process and the mounting process were performed under the same conditions as in Example 1, and the target photoelectric conversion device was obtained. This photoelectric conversion device has the same structure as the photoelectric conversion device 1B shown in FIG. Since the above-mentioned chromium layer has acid resistance, the pad or second due to the formation of the positive electrode buffer layer using strongly acidic poly (3,4-ethylenedioxythiophene) in the element forming step. Corrosion of the wiring was suppressed.

(Example 3)
After performing the first wiring formation process under the same conditions as the first wiring formation process in Example 1, a 2 μm thick copper (Cu) layer as a low resistivity conductive layer is formed on the entire transparent substrate formed up to the ITO electrode. Is formed by a PVD method, and a resist material (OFPR-800 (trade name) manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied thereon by a spin coating method to form a resist film having a thickness of 1.8 μm. Were subjected to selective exposure and development to obtain a resist pattern having a predetermined shape.

  A portion of the copper layer where the resist pattern was not formed was selectively wet etched. As a result, a first conductive layer for the first pad, which is interposed between the first wiring and the signal generating means, is formed on one wide end of each first wiring. On the ITO layer, a first conductive layer for a second pad, which is interposed between the second wiring and the signal generating means, was formed. Moreover, the 1st conductive layer for 2nd wiring was formed in the predetermined location on a transparent substrate.

  Next, an ITO layer having a thickness of 0.15 μm is formed as a corrosion-resistant conductive layer on the entire transparent substrate on which each of the first conductive layers is formed, and a resist material (Tokyo Ohka Kogyo Co., Ltd.) is formed thereon by spin coating. A resist film having a thickness of 1.8 μm was formed by applying OFPR-800 (trade name) manufactured by the company, and the resist film was selectively exposed and developed to obtain a resist pattern having a predetermined shape.

  A portion of the ITO layer where the resist pattern was not formed was selectively dry etched. Thus, the first conductive layer for the first pad, the first conductive layer for the second pad, and the first conductive layer for the second wiring are respectively covered with the outer surface of the first conductive layer. Thus, a second conductive layer made of an ITO layer was formed.

  By forming up to the second conductive layer in this way, a first pad that is interposed between the first wiring and the signal generating means is formed on the wide end of each first wiring, On the above-described ITO layer as the base layer, a second pad to be interposed between the second wiring and the signal generating means was formed. A plurality of second wirings were formed at predetermined locations on the transparent substrate.

  Each of the first pads is a first pad first conductive layer made of a copper layer and a first pad second conductive layer (ITO layer) covering the outer surface of the first pad first conductive layer. Each of the second pads has an ITO layer as a base layer, a first conductive layer for a second pad made of a copper layer, and an outer surface of the first conductive layer for the second pad. It has a three-layer structure with a second conductive layer (ITO layer) for covering the second pad. Each of the second wirings includes a first conductive layer for the second wiring made of a copper layer, a second conductive layer for the second wiring (ITO layer) covering the outer surface of the first conductive layer for the second wiring, It has a two-layer structure. When the transparent substrate is used as a reference, the heights of the first pads and the second pads are substantially the same.

  Among the second wirings used as the ground line of the signal generating means, the thickness of the copper layer which is the first conductive layer is 2 μm as in the photoelectric conversion device in the first embodiment. The electric resistance value is sufficiently low, and it is easy to operate the signal generating means normally.

  Then, the element formation process and the mounting process were performed under the same conditions as in Example 1, and the target photoelectric conversion device was obtained. This photoelectric conversion device has the same structure as the photoelectric conversion device 1C shown in FIG. Since the above-mentioned ITO layer has acid resistance, the pad or second due to the formation of the positive electrode buffer layer using strongly acidic poly (3,4-ethylenedioxythiophene) in the element forming step. Corrosion of the wiring was suppressed.

  The photoelectric conversion device of the present invention can be manufactured by a simple process, and can be used as an image sensor in a scanner, a facsimile, or the like that extracts various information such as an object shape and an image as an electrical signal. .

The top view which shows roughly an example of the photoelectric conversion device of this invention (A) The top view which shows roughly the planar arrangement | positioning of each of the organic photoelectric conversion element, 1st wiring, and 2nd wiring in the photoelectric conversion device shown in FIG. 1, (b) With the photoelectric conversion device shown in FIG. The top view which shows roughly each plane arrangement | positioning of an organic photoelectric conversion element of this, 1st wiring, 2nd wiring, and a signal generation means, (c) The schematic diagram of the II-II line cross section shown in FIG.2 (b) Sectional drawing which shows schematically another example of the photoelectric conversion device of this invention Sectional drawing which shows schematically the further another example of the photoelectric conversion device of this invention Sectional drawing which shows schematically the further another example of the photoelectric conversion device of this invention

Explanation of symbols

1, 1A, 1B, 1C Photoelectric conversion device 5 Transparent substrate 10R Red filter 10G Green filter 10B Blue filter 12 Protective layer 14a Transparent electrode of organic photoelectric conversion element 14b Organic photoelectric conversion part 14c Back electrode of organic photoelectric conversion element 16 Sealing member 25 First wiring 27 Pad 30 Signal generating means 35 Second wiring 37 Pad 40 Anisotropic conductive film PE Organic photoelectric conversion element CL ₁ First conductive layer CL ₂ Second conductive layer AL Adhesion layer

Claims (11)

A transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and a signal generating unit that is mounted on the transparent substrate and generates a data signal based on charges generated in each of the plurality of photoelectric conversion elements; A plurality of first wirings formed on the transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generating means, and one connected to one end of each of the plurality of first wirings. A method of manufacturing a photoelectric conversion device comprising: a pad interposed between one end and the signal generating means; and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and an external circuit. There,
A method of manufacturing a photoelectric conversion device, comprising a patterning step of patterning at least one conductive layer to form the pad and the second wiring. The conductive layer includes a first conductive layer having a low resistivity and a second conductive layer formed on the first conductive layer with a corrosion-resistant material,
The patterning step includes a first sub-step for forming the first conductive layer, a second sub-step for forming the second conductive layer, and a third pattern for patterning the second conductive layer and the first conductive layer, respectively. Including sub-steps,
The manufacturing method of the photoelectric conversion device of Claim 1 or 2 characterized by the above-mentioned. 3. The method of manufacturing a photoelectric conversion device according to claim 2, wherein at least a second conductive layer of the first conductive layer and the second conductive layer has acid resistance. The first conductive layer is made of a single metal or an alloy containing at least one of silver, copper, gold, aluminum, tungsten, molybdenum, cobalt, zinc, nickel, iron, platinum, and chromium,
The second conductive layer is a simple metal including at least one of gold, chromium, indium, copper, titanium, molybdenum, nickel, iron, platinum, tin, silicon, palladium, iridium, manganese, vanadium, and tantalum, Made of alloy or metal oxide,
The method of manufacturing a photoelectric conversion device according to claim 2 or 3, The said photoelectric conversion element contains an organic compound as a photoelectric conversion material, The manufacturing method of the photoelectric conversion device as described in any one of Claims 1-4 characterized by the above-mentioned. A transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and a signal generating unit that is mounted on the transparent substrate and generates a data signal based on charges generated in each of the plurality of photoelectric conversion elements; A plurality of first wirings formed on the transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generating means, and one connected to one end of each of the plurality of first wirings. A method of manufacturing a photoelectric conversion device comprising: a pad interposed between one end and the signal generating means; and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and an external circuit. There,
A low resistivity conductive layer forming step of forming a low resistivity conductive layer comprising at least one layer;
The low resistivity conductive layer is patterned by etching to form a first conductive layer for pads that constitutes the pad and a first conductive layer for second wiring that constitutes the second wiring. A first etching step;
A corrosion-resistant conductive layer forming step of forming at least one corrosion-resistant conductive layer so as to cover the outer surfaces of the first conductive layer for pads and the first conductive layer for second wiring,
The second conductive layer for the second wiring covering the outer surface of the first conductive layer for the second wiring and the second conductive layer for the pad and the second conductive layer for the second wiring by patterning the corrosion-resistant conductive layer by etching. A second etching step for forming a conductive layer;
A process for producing a photoelectric conversion device comprising: The low resistivity conductive layer is made of a single metal or an alloy containing at least one of silver, copper, gold, aluminum, tungsten, molybdenum, cobalt, zinc, nickel, iron, platinum, and chromium,
The corrosion-resistant conductive layer is a simple metal or alloy containing at least one of gold, chromium, indium, copper, titanium, molybdenum, nickel, iron, platinum, tin, silicon, palladium, iridium, manganese, vanadium, and tantalum. Or consisting of a metal oxide,
The manufacturing method of the photoelectric conversion device of Claim 6 characterized by the above-mentioned. The said photoelectric conversion element contains an organic compound as a photoelectric conversion material, The manufacturing method of the photoelectric conversion device of Claim 6 or 7 characterized by the above-mentioned. A transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and a signal generating unit that is mounted on the transparent substrate and generates a data signal based on charges generated in each of the plurality of photoelectric conversion elements; A plurality of first wirings formed on the transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generating means, and one connected to one end of each of the plurality of first wirings. A photoelectric conversion device comprising: a pad interposed between one end and the signal generating means; and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and an external circuit,
A photoelectric conversion device manufactured by the method according to claim 1. A transparent substrate, a plurality of photoelectric conversion elements formed on the transparent substrate, and a signal generating unit that is mounted on the transparent substrate and generates a data signal based on charges generated in each of the plurality of photoelectric conversion elements; A plurality of first wirings formed on the transparent substrate for connecting each of the plurality of photoelectric conversion elements and the signal generating means, and one connected to one end of each of the plurality of first wirings. A photoelectric conversion device comprising: a pad interposed between one end and the signal generating means; and a plurality of second wirings formed on the transparent substrate and connecting the signal generating means and an external circuit,
Each of the pad and the second wiring includes a first conductive layer having a low resistivity and a second conductive layer formed on the first conductive layer with a corrosion-resistant material. The photoelectric conversion device according to claim 10, wherein the photoelectric conversion element contains an organic compound as a photoelectric conversion material.

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