JP2007273635A - Photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion device excellent in durability while maintaining high power generation efficiency. <P>SOLUTION: In the photoelectric conversion device 10 in which a first electrode layer 2, a power generation layer 5, and a second electrode layer 7 are laminated on the insulating substrate 1; the power generation layer 5 includes an optical reflection layer 4, and the second electrode layer 7 is formed of a silver alloy. As a first added element, the silver alloy includes at least one kind selected from among aluminum, indium, tin, bismuth, gallium, zinc and magnesium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion device provided with a reflective layer on a semiconductor film having a photoelectric conversion function.

  The use of solar cells is attracting attention because it can generate electricity using inexhaustible solar energy, is clean without emitting exhaust gas, and is safe without danger of releasing radioactivity. Collecting.

  The structure of this solar cell (photoelectric conversion device) will be described with reference to FIG. FIG. 4A is a conceptual diagram (hatching is omitted) of the solar cell 100 for briefly explaining the layer configuration of the solar cell 100. As shown in FIG. 4A, the solar cell 100 has a three-layer structure of a transparent conductive film (first electrode layer) 102 and a semiconductor film (semiconductor layer; p-layer, i-layer, and n-layer) on a glass substrate 101. .) 103 and a back electrode film (second electrode layer) 104 are sequentially laminated, and sunlight is incident from the transparent conductive film 102 side toward the back electrode film 104 side as indicated by an arrow.

The solar radiation of the power generation source that has passed (transmitted) through the semiconductor film 103 is reflected by the back electrode film 104 formed of silver (Ag) or aluminum (Al) having a high reflectivity, and returned to the semiconductor film 103 again. Thus, for example, Patent Literature 1 or 2 discloses a technique for improving the power generation amount.
JP 2004-336086 A WO2005 / 011002 Publication

  The solar cell module has a structure in which the glass substrate 101, the transparent electrode layer 102, the semiconductor film 103, and the back electrode film 104 are laminated as described above. In order to further improve the power generation efficiency, the present inventor Found the optimum configuration of the semiconductor film 103a through various trials and errors. The structure of the semiconductor film 103a is shown in FIG. FIG. 4B is a conceptual diagram (hatching is omitted) of the solar cell 110 that briefly explains the layer configuration of the solar cell 110 found by the present inventor. The configuration of the solar cell 110 is different from the configuration of the solar cell 100 in FIG. 4A only in that the semiconductor film 103a includes a reflective layer 105 (Cap-SiO layer). The reflective layer 105 exhibits a reflective action such that light incident from the glass substrate 101 side is confined in the semiconductor film 103a.

  As disclosed in Patent Document 1, in order to reflect a light beam, a conventional solar cell generally employs a highly reflective material such as silver (Ag) or aluminum (Al) for the back electrode film 104. Yes.

In many cases, the back electrode film 104 has a two-layer structure of a transparent reflective layer 104t and a back reflective layer 104m. In that case, a metal oxide such as ZnO or ITO is used for the transparent reflective layer 104t, and the back reflective film 104t is used. The aforementioned silver or aluminum is used for the layer 104m.
Moreover, in order to protect the back surface reflection layer 104m further outside the back surface reflection layer 104m, layers such as Ti and ZnO may be provided.

  However, the semiconductor film 103a including the above-described optimal reflective layer 105 and the back electrode film 104 have poor adhesion, and it may be difficult to maintain the two in close contact without being separated for a long time. It was. That is, it may be difficult to maintain good adhesion (durability) while maintaining high power generation efficiency.

  Then, this invention aims at providing the photoelectric conversion apparatus excellent in durability, maintaining high electric power generation efficiency.

  According to a first aspect of the present invention for solving the above-described problem, in the photoelectric conversion device in which the first electrode layer, the power generation layer, and the second electrode layer are laminated on the insulating substrate, the light generation layer contains light. A reflection layer is included, and the second electrode layer is formed of a silver (Ag) alloy.

  When the invention of claim 1 is carried out, since the power generation layer has a reflective layer and the second electrode layer is formed of a silver (Ag) alloy, it has excellent durability while maintaining high power generation efficiency. A photoelectric conversion device can be provided.

  According to a second aspect of the present invention, in a photoelectric conversion device in which a first electrode layer, a power generation layer, and a second electrode layer are stacked on an insulating substrate, a plurality of the power generation layers are disposed, and light is transmitted to the power generation layer. A photoelectric conversion device comprising a reflective layer, wherein the second electrode layer is made of a silver alloy.

  In the invention of claim 2, since the light reflection layer is disposed between the plurality of power generation layers, the light reflected by the reflection layer is easily returned into each power generation layer, and the power generation efficiency can be improved. .

  According to a third aspect of the present invention, in the photoelectric conversion device in which the first electrode layer, the power generation layer, and the second electrode layer are laminated on the insulating substrate, a plurality of the power generation layers are arranged, and each of the power generation layers The photoelectric conversion device is characterized in that a light reflection layer is disposed in at least one of the spaces, and the second electrode layer is made of a silver alloy.

  In the invention of claim 3, since a plurality of power generation layers are arranged and the light reflection layer is arranged at least in one place between the power generation layers, the light is reflected by the arranged reflection layers, and the power generation efficiency is reduced. Can be improved.

  The invention of claim 4 is characterized in that the silver (Ag) alloy uses a silver alloy containing at least one kind of aluminum, indium, tin, bismuth, gallium, zinc, and magnesium as the first additive element. It is a photoelectric conversion apparatus in any one of Claims 1 thru | or 3.

  The first element described in claim 4 is mainly composed of silver and limits additive elements that contribute to adhesion improvement, and the additive elements are aluminum, indium, which are metal elements having a melting point lower than that of silver, Adhesion can be improved by adopting tin, bismuth, gallium, zinc, calcium, and magnesium.

  The invention according to claim 5 is the photoelectric conversion device according to claim 4, wherein the first additive element is gallium.

  According to the study by the present inventors, among the low melting point metal elements mentioned as the first additive element, in the silver alloy added with gallium, various properties required for the reflective film can be maintained at a particularly high level. It has been confirmed.

  The invention according to claim 6 provides platinum, gold, rhodium, iridium, ruthenium, palladium, copper, manganese, silicon, nickel, chromium, cobalt, yttrium, iron, scandium as the second additive element or as the first additive element. Silver added with at least one of zirconium, titanium, niobium, molybdenum, tantalum, tungsten, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, thulium, ytterbium, boron, erbium The photoelectric conversion device according to claim 4 or 5, wherein an alloy is used.

  The first or second additive element defined in claim 6 is obtained as a result of conducting an adhesion improvement study, as a result of platinum, gold, rhodium, iridium, ruthenium, palladium, copper, manganese, silicon, nickel, chromium, cobalt, At least one of yttrium, iron, scandium, zirconium, titanium, niobium, molybdenum, tantalum, tungsten, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, thulium, ytterbium, boron, erbium This is because it has been found that a seed added is preferable. These elements act in combination with the first additive element to improve adhesion.

  The invention according to claim 7 is the photoelectric conversion device according to claim 6, wherein the first or second additive element is at least one of platinum, palladium, dysprosium, copper, and erbium.

  In particular, when a silver alloy to which platinum, palladium, dysprosium, copper, or erbium is added as the first or second additive element is employed, an agglomeration phenomenon that may occur in the back side electrode layer evaluation sample material in a humidified environment. It can be effectively suppressed.

  The invention according to claim 8 is the photoelectric conversion device according to any one of claims 4 to 7, wherein the total concentration of the additive elements is 0.01 to 5.0% by weight.

  The invention according to claim 9 is the photoelectric conversion device according to claim 8, wherein the total concentration of the additive elements is 0.01 to 3.0% by weight.

  Here, the concentration of the additive element is preferably 0.01 to 5.0% by weight. When the additive amount is less than 0.01% by weight, there is no effect of improving the environmental resistance. When the additive element concentration exceeds 5.0% by weight, the specific resistance of the alloy increases, which is relative to silver. This is because the reflectance decreases. A particularly preferred concentration is 0.01 to 3.0% by weight. In this range, the specific resistance can be maintained at a higher dimension regardless of the use environment.

  The invention according to claim 10 is the photoelectric conversion device according to claim 9, wherein the additive elements are two kinds of gallium and copper, and the addition amount is 0.01 to 3.0% by weight.

  The additive elements are two kinds of gallium and copper, and the total amount of addition is 0.01 to 3.0% by weight. The photoelectric conversion device according to claim 9 has the most excellent durability and characteristics as a photoelectric conversion device. Is big.

  In the present invention, since the power generation layer has a reflective layer and the second electrode layer is formed of a silver (Ag) alloy, photoelectric conversion with excellent adhesion and durability is maintained while maintaining high power generation efficiency. An apparatus can be provided.

  Fig.1 (a)-(f) is sectional drawing of the board | substrate which shows each process of manufacture of the solar cell 10 (photoelectric conversion apparatus) which implements this invention. FIG. 2 is an enlarged view of a portion II in FIG. FIG. 3 is a cross-sectional view of a solar cell 11 having a configuration different from that of FIG.

As shown in FIG. 1A, the solar cell 10 forms a transparent conductive film (first electrode layer) 2 on a substrate 1 (insulating substrate) having translucency such as glass as shown in FIG. To do. For the transparent conductive film 2, indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like is used. The transparent conductive film 2 is formed on the substrate 1 by a method such as vacuum deposition, thermal CVD or sputtering.

  Subsequently, a first laser scribe process is performed, and the first groove 3 is formed on the transparent conductive film 2 by a well-known laser scribe as shown in FIG. The substrate 1 is placed on an XY table (not shown) with the transparent conductive film 2 side down. By moving the XY table, the first groove 3 (the second groove 6 and the common groove 8 described later are also formed). The substrate 1 can be moved in the direction necessary to form the same).

  Next, the substrate 1 is put into an isolation formation type plasma CVD apparatus (not shown), and a p-type silicon layer, an i-type silicon layer, a Cap-SiO layer 4 (reflection layer) and an n-type silicon layer are sequentially deposited. Then, a semiconductor film 5 (power generation layer) as shown in FIG. 1C is formed. Then, a second laser scribing process is performed on the substrate 1 taken out from the CVD apparatus to form a second groove 6 in the semiconductor film 5 as shown in FIG.

  Subsequently, by a known apparatus such as a magnetron sputtering apparatus, 0.01 to 5.0 wt% (more preferably 0.01 to 3.0 wt%) is formed on the semiconductor film 5 as shown in FIG. %) Aluminum, indium, tin, bismuth, gallium, zinc, magnesium, and a back electrode layer (second electrode layer) 7 made of a silver (Ag) alloy including at least one kind.

Here, as shown in FIG. 2, the rear surface side electrode layer (second electrode layer) 7 is indium tin oxide (ITO), tin oxide (SnO ₂₎ made of such as zinc oxide (ZnO) transparent reflective layer 7t and 0. Back reflection made of a silver (Ag) alloy containing at least one kind of aluminum, indium, tin, bismuth, gallium, zinc, and magnesium of 01 to 5.0% by weight (more preferably 0.01 to 3.0% by weight). It may be a two-layer structure with the layer 7m.
First, Table 1 shows the evaluation results of the reflectance before and after the durability test. Each measured value is a value at wavelengths of 405 nm, 520 nm, and 670 nm. Moreover, the test result about the back side electrode layer evaluation sample using the pure silver which is a prior art is also shown in the table | surface for the comparison.

  Subsequently, a third laser scribing step is performed to form a common groove 8 in both the back-side electrode layer 7 and the semiconductor film 5 as shown in FIG. The apparatus and procedure used when performing the third laser scribing process are the same as those of the previous second laser scribing process.

  Then, a solar cell 10 is completed by covering a film film (not shown) from the back side electrode layer 7. By providing the film film, exposure of the back-side electrode layer 7 is prevented, and damage and wear of the solar cell 10 are prevented. Note that the film film is not directly related to the present invention, and therefore the depiction is omitted for the sake of clarifying the configuration.

  The solar cell 10 is manufactured through the above steps. This manufacturing process is well known, and the characteristic part of the present invention will be described below.

  The present invention is characterized by a combination of the configuration in the semiconductor film 5 and the configuration of the back surface side electrode layer 7. Details of the semiconductor film 5 and the back electrode layer 7 will be described with reference to FIG. The semiconductor film 5 has a four-layer structure of a p layer, an i layer, a Cap-SiO layer 4 (reflection layer), and an n layer in order from the side closer to the substrate 1. The total thickness of the semiconductor film 5 is, for example, 0.1 to 3.0 μm. On the other hand, the thickness of the Cap-SiO layer 4 can be set to, for example, 50 to 800 angstroms.

  As the Cap-SiO layer 4 (reflection layer), silicon oxide is typically used. The Cap-SiO layer 4 (reflective layer) may or may not contain a crystalline silicon component.

The refractive index at a wavelength of 600 nm of the Cap-SiO layer 4 (reflection layer) is preferably 2.5 or less. As the ratio of the most constituent elements excluding silicon in the cap-SiO layer 4 (reflection layer), 25% by weight or more is preferably used. If the silicon oxide was used as the Cap-SiO layer 4 (the reflective layer), the proportion of oxygen occupied in the layer or, in order to realize the refractive _index, as the gas ratio of CO 2 / SiH _4, about 2 to 10 Is used.

  The Cap-SiO layer 4 (reflection layer) may have a constant refractive index in the film thickness direction, or the refractive index may change in the middle. Furthermore, the refractive index may be increased or decreased periodically.

  Note that FIG. 2 shows a structure in which the Cap-SiO layer 4 (reflective layer) is disposed on the upper side of the i layer in contact with the i layer, but between the i layer and the Cap-SiO layer 4 (reflective layer). Another layer such as an n layer may be sandwiched between the two layers.

  As the reflective layer, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, or the like, in which silicon contains one or more elements of nitrogen, carbon, and oxygen instead of silicon oxide. There may be.

  In the example of FIG. 2, an example in which one semiconductor film 5 (power generation layer) is provided in the solar cell 10 is shown. However, a solar cell including a plurality of semiconductor films called a hybrid substrate may be used. Can be implemented. An example is shown in FIG.

  In the example of FIG. 3, the solar cell 11 provided with a-Si (amorphous silicon) and p-Si (polysilicon) is shown. When there are two semiconductor films (a-Si and p-Si) as in the example of FIG. 3, an intermediate layer-SiO (reflection layer) is disposed between a-Si and p-Si, and the back surface A Cap-SiO layer (reflection layer) is provided between an i layer and an n layer in p-Si, which is a semiconductor film close to the side electrode layer 7.

  However, the intermediate layer SiO (reflection layer) may be omitted.

  Light entering from the insulating substrate side is mainly reflected by the intermediate layer -SiO and the Cap-SiO layer, and the light reciprocates in the a-Si i layer and the p-Si i layer. This improves power generation efficiency.

  Hereinafter, preferred embodiments of the back-side electrode layer 7 of the present invention will be described together with comparative examples. Here, the back surface side electrode layer 7 has a two-layer structure of a transparent reflection layer 7t and a back surface reflection layer 7m. ZnO is used for the transparent reflecting layer 7t, and the back reflecting layer 7m is a silver alloy having various binary and ternary compositions containing silver as a main component, and is formed by a sputtering method. Form. Durability tests were performed on the solar cell 10 under various environments, and changes in characteristics of the solar cell 10 after the test were examined.

The back side electrode layer evaluation sample was manufactured by placing a solar cell substrate without the back side electrode layer 7 and a target in a sputtering apparatus, and evacuating the inside of the apparatus to 5.0 × 10 ⁻³ Pa. Up to 5.0 × 10 ⁻¹ Pa was introduced. As sputtering conditions, the film was formed at a direct current of 0.4 kW, and the film thickness was 2000 mm. The film thickness distribution was within ± 10%.

  The manufactured back side electrode layer 7 was examined by conducting a durability test in which the back side electrode layer evaluation sample was exposed to various environments, and evaluating the characteristics of the back side electrode layer evaluation sample before and after the test. As a durability test of the back side electrode layer evaluation sample, the evaluation sample was placed on a hot plate, heated in the atmosphere at 250 ° C. for 1 hour, and the characteristics after the heating were evaluated (heating test). In addition, as a humidification test for examining the moisture resistance of the backside electrode layer evaluation sample, the backside electrode layer evaluation sample was exposed to an atmosphere at a temperature of 85 ° C. and a humidity of 85%, and the characteristics after humidification were evaluated. In the humidification test, the exposure time was 24 hours.

  The characteristics evaluated before and after the durability test are reflectance and specific resistance. The reflectance was measured with a spectrophotometer, and the reflectance of each back-side electrode layer sample was relatively evaluated with pure silver as 100.

  First, Table 1 shows the evaluation results of the reflectance before and after the durability test. Each measured value is a value at wavelengths of 405 nm, 520 nm, and 670 nm. Table 1 also shows the test results for the back-side electrode layer evaluation sample using pure silver, which is the prior art, for comparison.

  In this evaluation of the reflectance, when comparing the rate of change immediately after film formation and after the durability test for the backside electrode layer evaluation sample made of the silver alloy according to the present invention, the rate of change is more than that in the case of pure silver. It was confirmed that the silver alloy was superior to pure silver at each wavelength. In general, the difference between wavelengths is small compared to silver. Such a low difference in reflectivity reduction due to wavelength is a great advantage for the photoelectric conversion device.

  Next, Table 2 shows the evaluation results of the specific resistance of each silver alloy coating before and after the durability test.

  In the evaluation of specific resistance, the specific resistance of pure silver of the prior art before the durability test is the lowest, but increases of about 30% after the heating test and about 20% after the humidification test. On the other hand, in the case of the silver alloy according to the present invention, the rate of increase in specific resistance is approximately 10% or less in both cases after the heating test and after the humidification test, indicating that it is electrically stable. Yes.

  Next, the test which evaluates the adhesiveness of the back surface side electrode layer evaluation sample with respect to a board | substrate was done. In the adhesion evaluation test, the back side electrode layer evaluation samples before and after the above durability test were used as samples. Apply a commercially available cellophane tape (3M mending tape, tape width 12mm) to the back side electrode layer evaluation sample on the substrate with a length of about 30mm, and press it sufficiently to make it adhere to the surface. I peeled it off. After peeling off the tape, it was evaluated in three stages from the degree of film peeling. In the three-level evaluation, “No” indicates that there is no peeling, “Δ” indicates that there is only a small amount of peeling, and “X” indicates that most of the peeling has occurred. Table 3 shows the results.

  In the case of pure silver (Ag), after the durability test (heating test, humidification test), the back side electrode layer evaluation sample was peeled off from the substrate. On the other hand, in the silver alloy according to the present invention, the adhesion is greatly improved, and in particular, it is possible to maintain a strong adhesion that does not peel at all after the environmental test as well as immediately after the film formation. This is a great advantage for a photoelectric conversion device that is often used outdoors.

Next, the high temperature and high humidity of the substrate in which a silver alloy containing 0.8% by weight of gallium and 1.0% by weight of copper is used as the back electrode layer 7 in the solar cell 10 (photoelectric conversion device) having the layer structure shown in FIG. The test was conducted.
For the back electrode layer 7, zinc oxide (ZnO) was used as the transparent reflective layer 7t, and a silver alloy containing 0.8% by weight of gallium and 1.0% by weight of copper was used as the back reflective layer 7m.

In the high-temperature and high-humidity test, a sample in which only the back-side electrode layer 7 is not formed is placed in a constant temperature and humidity chamber at 22 ° C. and 70%, and left for a set period between 0 days (no holding) and 12 days. Immediately after the end of the period, the back-side electrode layer 7 is formed by sputtering.
Thereafter, a peel test was performed over time to examine when peeling occurred. In addition, the amount of power generation as a photoelectric conversion device was investigated immediately before the peel test was performed, and compared with before the test.
In the peeling test, a commercially available cellophane tape (3M mending tape, tape width: 12 mm) was applied with a length of about 30 mm, and after pressing it sufficiently, it was peeled in a direction perpendicular to the surface at once. After peeling off the tape, it was evaluated in two stages from the degree of film peeling. In the two-stage evaluation, “no peeling” was evaluated as “◯”, and “with peeling” was set as “X”.
The results are shown in Table 4 as examples. As a comparative example, Table 5 shows the results of using pure silver (Ag) for the back reflective layer 7m.

  From the results of Table 4 and Table 5, it can be seen that the silver alloy containing 0.8 wt% Ga and 1.0 wt% Ga has higher durability against the high temperature and high humidity test than pure silver (Ag). Moreover, as a result of performing the test by changing the contents of Ga (gallium) and Cu (copper), the content ratio with relatively good adhesion between the back-side electrode layer and the Cap-SiO layer is 0.01 to It was between 5.0% by weight, of which 0.01 to 3.0% by weight was particularly good. By the way, when a similar test is performed without providing a Cap-SiO layer, even if the back side electrode layer is silver (Ag) that does not contain Ga (gallium) and Cu (copper), good adhesion is confirmed. I was able to.

  That is, it can be seen that if the Cap-SiO layer is not provided on the semiconductor film, there is no problem in the adhesion between the two even if the back electrode layer is silver (Ag) containing no mixture. However, in order to improve power generation efficiency, it is preferable to provide a Cap-SiO layer in the semiconductor film. Therefore, when the present invention is carried out and an element such as Ga (gallium) is mixed in the silver (Ag) of the back electrode layer 7 at a content of 0.01 to 5.0% by weight, the back electrode layer and the semiconductor film The power generation efficiency can be improved while maintaining good adhesion to the power.

  In addition, in the conventional solar cell 100 shown in FIG. 4, the poor adhesion between the back-side electrode film 104 and the semiconductor film 103a (reflective layer 105) is due to moisture entering between the two. it is conceivable that. When the present invention is implemented and the back electrode layer 7 is made of a silver (Ag) alloy mixed with an element such as Ga (gallium), the adhesion between the two can be improved.

In addition, the amount of power generation when the peeling of the back side electrode layer occurs is reduced to 80 or less, assuming that the amount of power generation before the high temperature and high humidity test is 100. When the separation does not occur, the power generation amount is maintained at 95 or more, and there is a correlation between the separation and the power generation amount.
Therefore, when a silver alloy is used for the back electrode layer, peeling can be suppressed even under high-temperature and high-humidity conditions, which is a great advantage for the photoelectric conversion device.

(A)-(f) is sectional drawing of the board | substrate which shows each process of the manufacturing method of the solar cell (photoelectric conversion apparatus) of embodiment of this invention. It is an enlarged view of the II section of Drawing 1 (f). It is sectional drawing of the solar cell of a structure different from FIG. (A) is a conceptual diagram of the conventional solar cell. (B) is a conceptual diagram of a conventional solar cell different from (a).

Explanation of symbols

1 Substrate (insulating substrate)
2 Transparent conductive film (first electrode layer)
4 Cap-SiO layer (reflection layer)
5 Semiconductor film 7 Back side electrode layer (second electrode layer)
7t transparent reflective layer 7m back reflective layer 10 solar cell (photoelectric conversion device)
11 Solar cell (photoelectric conversion device)

Claims (10)

  In the photoelectric conversion device in which a first electrode layer, a power generation layer, and a second electrode layer are stacked on an insulating substrate, a light reflection layer is included in the power generation layer, and the second electrode layer is A photoelectric conversion device formed of a silver alloy.   In a photoelectric conversion device in which a first electrode layer, a power generation layer, and a second electrode layer are stacked on an insulating substrate, a plurality of the power generation layers are disposed, a light reflection layer is disposed on the power generation layer, and A photoelectric conversion device, wherein the second electrode layer is formed of a silver alloy.   In a photoelectric conversion device in which a first electrode layer, a power generation layer, and a second electrode layer are stacked on an insulating substrate, a plurality of the power generation layers are arranged, and at least one place among the power generation layers A photoelectric conversion device, wherein a light reflection layer is disposed on the second electrode layer, and the second electrode layer is made of a silver alloy.   The silver alloy contains at least one of aluminum, indium, tin, bismuth, gallium, zinc, and magnesium as the first additive element, according to any one of claims 1 to 3. Photoelectric conversion device.   The photoelectric conversion device according to claim 4, wherein the first additive element of the silver alloy is gallium.   As the second additive element or as the first additive element, platinum, gold, rhodium, iridium, ruthenium, palladium, copper, manganese, silicon, nickel, chromium, cobalt, yttrium, iron, scandium, zirconium, titanium, niobium, Using a silver alloy containing at least one of molybdenum, tantalum, tungsten, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, thulium, ytterbium, boron, erbium The photoelectric conversion device according to claim 4 or 5, wherein the photoelectric conversion device is characterized.   The photoelectric conversion device according to claim 6, wherein the second additive element or the first additive element is at least one of platinum, palladium, dysprosium, copper, and erbium.   The photoelectric conversion device according to claim 4, wherein the total concentration of the additive elements is 0.01 to 5.0% by weight.   The photoelectric conversion device according to claim 8, wherein the total concentration of the additive elements is 0.01 to 3.0% by weight.   The photoelectric conversion device according to claim 9, wherein the additive elements are two kinds of gallium and copper, and the total addition amount is 0.01 to 3.0% by weight.

Images