JP4646724B2 - Chalcopyrite solar cell - Google Patents

Description

  The present invention relates to a solar cell having a light-absorbing layer of a chalcopyrite compound, and more particularly to a solar cell using a flexible mica or a material containing mica as a substrate material.

  Solar cells that receive light and convert it into electrical energy are classified into bulk and thin film systems depending on the thickness of the semiconductor. Among these, the thin film solar cell is a solar cell having a thickness of several tens of μm to several μm or less, and is classified into a Si thin film system and a compound thin film system. There are various types of compound thin film systems, such as II-VI group compound type and chalcopyrite type, and some have been commercialized so far. Among them, the chalcopyrite solar cell is also referred to as a CIGS (Cu (InGa) Se) -based thin film solar cell, CIGS solar cell, or I-III-VI group based on the material used.

  A chalcopyrite solar cell is a solar cell formed with a chalcopyrite compound as a light-absorbing layer. It has high efficiency, no light degradation (aging), excellent radiation resistance, a wide light absorption wavelength range, and light absorption. It has features such as a high coefficient, and is currently being studied for mass production.

  A cross-sectional structure of a general chalcopyrite solar cell is shown in FIG. As shown in FIG. 1, a chalcopyrite solar cell is formed on a lower electrode thin film formed on a glass substrate, a light absorbing layer thin film containing copper, indium, gallium, and selenium, and an upper side of the light absorbing layer thin film. And a buffer layer thin film and an upper electrode thin film. When this chalcopyrite solar cell is irradiated with light such as sunlight, a pair of electrons (-) and holes (+) is generated, and the electrons (-) and holes (+) are p-type semiconductor and n. At the junction surface with the n-type semiconductor, electrons (-) gather at the n-type semiconductor and holes (+) at the p-type semiconductor, and as a result, an electromotive force is generated between the n-type semiconductor and the p-type semiconductor. In this state, the current can be taken out by connecting the conductive wire to the electrode.

2 and 3 show a process for manufacturing a chalcopyrite solar cell. First, a Mo (molybdenum) electrode serving as a lower electrode is formed on a glass substrate such as soda lime glass by sputtering. Next, as shown in FIG. 3A, the Mo electrode is divided by laser irradiation or the like (first scribe). After the first scribe, the shavings are washed with water or the like, and copper (Cu), indium (In), and gallium (Ga) are attached by sputtering or the like to form a precursor. The precursor is put into a furnace and annealed in an atmosphere of H ₂ Se gas to form a chalcopyrite type light absorption layer thin film. This annealing step is usually referred to as vapor phase selenization or simply selenization.

  Next, an n-type buffer layer such as CdS, ZnO, or InS is stacked on the light absorption layer. The buffer layer is formed by a method such as sputtering or CBD (chemical bath deposition) as a general process. Next, as shown in FIG. 3B, the buffer layer and the precursor are divided by laser irradiation, a metal needle, or the like (second scribe).

Thereafter, as shown in FIG. 3C, a transparent electrode (TCO) such as ZnOAl to be an upper electrode is formed by sputtering or the like. Finally, as shown in FIG. 3D, the CIGS thin film solar cell is completed by dividing the TCO, the buffer layer, and the precursor by laser irradiation, a metal needle, or the like (third scribe).

  The solar cell obtained here is called a cell, but when actually used, a plurality of cells are packaged and processed as a module (panel). The cell is divided into solar cells forming a plurality of series stages by each scribing step, and the design of the cell voltage can be arbitrarily changed by changing the number of series stages.

  In such a conventional chalcopyrite solar cell, a glass substrate has been used as the substrate material. This is because the glass substrate is insulative, is easily available, is relatively inexpensive, has high adhesion to the Mo electrode layer (lower electrode thin film), and has a smooth surface. Is based on something. Furthermore, energy conversion efficiency becomes high because the sodium component contained in glass diffuses into a light absorption layer (p layer). On the other hand, glass has a low melting point and the annealing temperature cannot be set high in the selenization process. As a result, the energy conversion efficiency is kept low, and the manufacturing equipment becomes large because the substrate is thick and bulky. There are disadvantages such as inconvenience in subsequent handling and the inability to apply a mass production process such as a roll-toe-roll process because it hardly deforms.

In order to solve these problems, a chalcopyrite solar cell using a polymer film substrate has been proposed (see, for example, Patent Document 1). In addition, a technique for forming a chalcopyrite solar cell structure on a base body on which a silicon oxide or hooker iron layer is formed on the upper and lower surfaces of a stainless steel substrate has been proposed (for example, Patent Document 2). reference). Furthermore, a technology that lists glass, alumina, mica, polyimide, molybdenum, tungsten, nickel, graphite, and stainless steel as chalcopyrite-based substrate materials is also disclosed (for example, see Patent Document 3).
JP-A-5-259494 JP 2001-339081 A JP 2000-58893 A

  Among those using materials other than glass as the substrate material of conventional chalcopyrite solar cells, those using the polymer film described in Patent Document 1, for example, in the case of polyimide, have a characteristic of 260 ° C. or higher It could not be processed at high temperature. Therefore, a high-temperature process exceeding 500 ° C. such as vapor phase selenization cannot be used, and as a result, a battery with high conversion efficiency cannot be manufactured.

Further, in the technique for forming silicon oxide or hooker iron layers (protective layers) above and below the stainless steel substrate described in Patent Document 2, the stainless steel substrate is protected from the aggressiveness of H ₂ Se gas in the gas phase selenization process. However, there was a problem that the Mo electrode layer (back electrode thin film) peeled off from the corroded stainless steel substrate. Moreover, since the protective layer is peeled off and the conductive stainless steel substrate is exposed, a scribing process using a metal needle cannot be introduced.

  Furthermore, in the technique described in Patent Document 3, various substrate materials are presented. However, all the techniques described as examples completed in the embodiment are those using a glass substrate. Each of the substrate materials is not disclosed in detail to the extent that one skilled in the art can implement it. For example, in each example, the substrate is annealed between 385 ° C. and 495 ° C., which is tailored to soda lime glass, and the same process using the other listed substrate materials. Whether it can be created with is unknown.

  As described above, in the conventional technology, high insulation, easy availability, relatively low cost, good adhesion with the Mo electrode layer (lower electrode thin film), and the surface The actual situation is that a substrate material that satisfies the requirements of being smooth, having a melting point of 600 ° C. or higher, being thin and lightweight, and being flexible is not used.

  Therefore, the present inventors have previously made a material containing mica or mica on a substrate as a solar cell having excellent flexibility, suitable for mass production of a roll-to-roll process, and having high conversion efficiency. In order to achieve flexibility, and to ensure flexibility, the intermediate layer made of a ceramic material is provided on the surface of the substrate in order to realize surface smoothness. A proposal was made to form a chalcopyrite-type light absorption layer on top of the substrate via a binder.

  As described above, by providing the intermediate layer made of a ceramic material on the surface of the substrate, it is possible to cover the unevenness of the surface, which is a defect inherent in the mica substrate. However, since the intermediate layer and the mica substrate have different compositions, if the intermediate layer is formed on the surface of the mica substrate, the intermediate layer has a large shrinkage rate, and warpage occurs so that the intermediate layer side is rounded inward. When warping occurs, handling in subsequent processes becomes difficult, and the range of application is limited even after the product has been manufactured.

  In order to solve the above problems, a chalcopyrite solar cell according to the present invention includes a substrate made of mica or a material containing mica, an intermediate layer containing a ceramic material formed on the surface side of the substrate, and the substrate A back surface layer containing a ceramic material formed for the purpose of preventing warpage, a nitride-based binder layer laminated on the intermediate layer, and a lower electrode layer formed on the binder layer, A p-type light absorption layer made of a chalcopyrite compound formed on the lower layer, an n-type buffer layer formed on the light absorption layer, and a transparent electrode layer formed on the buffer layer, Is provided.

  As described above, by providing the back layer on the back side of the mica substrate (mica or a substrate made of mica as a main component), it is possible to solve the problem of warpage newly generated by providing the intermediate layer. it can.

In the present invention, a substrate made of mica or a material mainly containing mica is used as the substrate. Mica has a high insulating property of 10 ¹² to 10 ¹⁶ Ω, a high heat resistant temperature of 800 to 1000 ° C., and a high resistance to acids, alkalis, and H ₂ Se gas. Therefore, since vapor phase selenization can be performed at an optimum temperature, high conversion efficiency can be obtained. That is, in the manufacturing process of the CIGS solar cell, when the selenization treatment is performed at a relatively low processing temperature of about 500 ° C. used for the soda lime glass substrate, Ga is not crystallized on the lower electrode thin film side of the light absorption layer. Therefore, the band gap is small and the current density is lowered. In contrast, when heat treatment for vapor phase selenization is performed at a temperature of 600 ° C. or more and 700 ° C. or less, Ga diffuses uniformly in the light absorption layer, and the non-crystalline state is eliminated, so that the band gap is expanded. As a result, the open circuit voltage (Voc) is improved. Therefore, by using mica or a material mainly composed of mica as the substrate material, a solar cell with high conversion efficiency can be realized. Furthermore, since mica and laminated mica have high flexibility, they can be produced by a roll-to-roll manufacturing process, and therefore can meet the demand for mass productivity.

  However, it has been found that the surface of the mica or the laminated mica substrate which is a material mainly composed of mica is not smooth and has a maximum surface roughness of 5 to 6 μm in the range of several tens of μm. When a substrate having such a large surface roughness is used, the surface coverage is incomplete, leakage is likely to occur, and the open-circuit voltage (Voc) of the solar cell tends to decrease, so that sufficient conversion efficiency is achieved. This causes a problem that cannot be obtained. In order to solve this problem, in the present invention, a thick intermediate layer for flattening or smoothing the substrate surface is formed between the mica or laminated mica substrate and the metal electrode. By forming this intermediate layer, it is possible to ensure the consistency between the various layers constituting the solar cell formed on the substrate, and to solve the problem that the conversion efficiency is lowered.

  The thickness of the intermediate layer is preferably 2 μm or more from the viewpoint of flattening the surface of mica or laminated mica, and is set to 20 μm or less from the viewpoint of ensuring the flexibility of the substrate. On the other hand, when forming a thick intermediate layer, the oxide film or nitride film formed by vacuum processing such as sputtering does not only take a long time to form the film, but also when the solar cell is bent or curved In addition to cracking in the nitride film, there is a problem that flexibility is also lowered. Therefore, in the present invention, the thick intermediate layer is formed by non-vacuum processing such as application with a brush, spray application, silk printing, spin coating, and the like. By utilizing these non-vacuum film forming techniques, an intermediate layer having a desired thickness can be easily formed.

  The back layer may be made of a material different from the intermediate layer, or the same material may be used. In order to prevent warpage, it is preferable that the thickness of the back surface layer is the same as or thicker than that of the intermediate layer. For example, when the same material is used, the thickness of the back surface layer is 1.0 to 1.5 times the thickness of the intermediate layer.

  For example, the thickness of the intermediate layer is 2 μm or more and 20 μm or less, and the thickness of the back layer is 3 μm or more and 30 μm or less.

  Moreover, it is preferable to provide a binder layer of a nitride compound such as TiN and TaN between an intermediate layer formed on a mica or laminated mica substrate and a molybdenum electrode formed on the intermediate layer. This binder layer has a barrier effect that suppresses the diffusion of impurities and also has high adhesion with molybdenum and the like. The thickness of the binder layer is, for example, not less than 3000 mm and not more than 8000 mm.

A SiN or SiO ₂ silicon-based smooth layer may be provided on the surface of the intermediate layer (between the intermediate layer and the binder layer). This makes it possible to smooth the surface of the intermediate layer made of a ceramic material and improve the degree of adhesion with the binder layer.

  According to the present invention, a chalcopyrite light absorption layer is formed by coating a mica substrate or a laminated mica substrate with a ceramic material (intermediate layer) having a predetermined thickness, and a nitride-based binder layer having a predetermined thickness on the intermediate layer. Since it is provided, it is possible to obtain a chalcopyrite solar cell that is lightweight, flexible, and has high conversion efficiency without diffusing impurities (particularly potassium) from the substrate into the light absorption layer.

  Nitride-based binders are relatively expensive, but the thickness of the binder layer can be reduced by using an inexpensive ceramic-based material as an intermediate layer, and a chalcopyrite solar cell using a conventional glass substrate Can be manufactured at a lower cost.

  Furthermore, according to the present invention, since the back surface layer is provided on the back surface side (the side opposite to the side where the intermediate layer is provided) of the substrate, the warp caused by providing the intermediate layer is prevented, and the handling property is greatly improved. .

  Prior to the description of the examples, the surface shape of the laminated mica substrate will be described. 4 (A) and 4 (B) show the measurement results of the surface shape at any two locations on the laminated mica substrate. In FIG. 4, the horizontal axis indicates the horizontal position of the laminated mica substrate, and the vertical axis indicates the height position. As a feature of the integrated mica substrate, the maximum height difference changes very steeply (the aspect ratio is large). As is clear from FIG. 4, there is a maximum height difference of 5 to 6 μm in the range of several tens of μm in the lateral direction. This cause is understood to be due to the manufacturing method of the laminated mica, and since the pulverized mica is mixed in the resin, the pulverized mica pieces are present on the surface, and the aspect ratio is greatly increased. It is understood that it is. The surface roughness of the laminated mica substrate was Ra = 1.6 μm and Ra = 0.8 μm at the two measured locations, respectively. In the case of such a surface state, even if an electrode such as Mo is directly formed on the substrate and a light absorption layer is formed thereon, the surface coating is incomplete, leading to leakage and causing a solar cell Function is significantly reduced. Specifically, the open circuit voltage (Voc) of the solar cell is lowered, and the conversion efficiency is lowered.

  Next, the measurement results of the surface shape after coating the surface of the laminated mica substrate with a ceramic paint as an intermediate layer material to a thickness of 8 μm are shown in FIGS. FIG. 5 shows measurement results at two arbitrary locations. As is clear from FIG. 5, the large undulation inherent to the substrate was measured, but the maximum height difference of 5 to 6 μm occurring in the range of several μm observed in the surface shape measurement of the laminated mica substrate is It has disappeared. Therefore, from the measurement results shown in FIGS. 4 and 5, the thickness of the intermediate layer may be 2 μm or more, preferably 5 μm.

  FIG. 6 is a cross-sectional view showing a configuration of an example of a solar cell according to the present invention. In this example, the laminated mica substrate 1 is used as the substrate, the intermediate layer 2 is formed on the front side of the laminated mica substrate 1, and the back layer 3 is formed on the back side of the laminated mica substrate 1.

  The intermediate layer 2 flattens or smoothes the surface of the laminated mica substrate 1 and is formed to a thickness of 2 to 20 μm. As described above, the thickness of the intermediate layer needs to be 2 μm or more in order to flatten the surface of the laminated mica, and 20 μm or less in order to ensure flexibility when a solar cell is formed. And

  The intermediate layer 2 is made of a ceramic material containing silicon (Si) and aluminum (Al). As an example, titanium is 39 wt%, oxygen is 28.8 wt%, silicon is 25.7 wt%, carbon is 2.7 wt%, aluminum is 1.6 wt%, nitrogen is 1.1 wt%, phosphorus Is 0.1% by weight, iron is 0.2% by weight, and zirconium is 0.6% by weight.

  On the other hand, the back surface layer 3 prevents warpage of the laminated mica substrate 1 due to the provision of the intermediate layer 2, and considering that a light absorption layer or the like is further formed on the intermediate layer 2, The thickness is preferably 1.0 to 1.5 times that of the intermediate layer 2. Moreover, if the same material as that of the intermediate layer 2 is used as the material of the back layer 3, the design is easy and the process can be simplified.

  As a method for forming the thick intermediate layer 2 and the back surface layer 3, for example, a coating film is formed by coating with a brush, spray coating, silk printing, spin coating, dipping, etc., followed by drying and baking processes.

  The ceramic material-based paint used to form the intermediate layer 2 and the back layer 3 is based on an inorganic resin produced by a sol-gel process, and silicon and oxygen are strongly bonded by ionic bonds, and have a heat resistance temperature of about 1200 ° C. Have. Therefore, it has sufficient heat resistance even at an ideal processing temperature of vapor phase selenium processing for forming a chalcopyrite type light absorption layer described later.

  By coating the surface of the substrate with the intermediate layer 2 made of a ceramic material, the open circuit voltage (Voc) can be increased and the fill factor (FF) value can be improved, resulting in higher conversion efficiency. The reason for this is that, conventionally, the surface smoothing layer and the binder layer cannot follow the sudden height difference on the surface of the laminated mica substrate, that is, the oxide film or nitride film cannot enter the deep valley portion, so that the surface smoothness This is because sex cannot be improved.

  Note that it is possible to form a thick oxide film (nitride film) and smooth the surface by repeating sputtering many times. In this case, however, the oxide film (nitride film) is bent when the solar cell is bent. May crack and damage the lower electrode layer and the light absorption layer, so that the flexibility which is an advantage of the laminated mica substrate is spoiled. Furthermore, since sputtering costs itself, it is not suitable for mass production.

Next, the surface smoothing layer 4 is formed on the intermediate layer 2. As the surface smooth layer 4, SiN or SiO ₂ can be used, and is formed by a dry process such as sputtering. The reason for using the Si-based material is that the surface of the intermediate layer 2 can be made smoother, and the adhesion between the intermediate layer of the underlying ceramic-based material and a binder layer described later can be increased. It is done. The surface smoothing layer 4 can be formed as necessary and can be omitted.

  Next, a binder layer 5 is formed on the surface smooth layer 4. The binder layer 5 prevents diffusion of impurities or compositions from the underlying mica substrate and intermediate layer, and a metal electrode 6 such as molybdenum or tungsten formed thereon and a mica substrate structure (mica substrate 1 and In order to improve adhesion between the intermediate layer 2 and the intermediate layer 2). As a material for the binder layer 5, a nitride compound such as TiN or TaN is suitable. The thickness of the binder layer 5 is preferably 3000 mm or more and 8000 mm or less.

  Each layer is formed on the binder layer 5 similarly to the conventional chalcopyrite solar cell. That is, first, a molybdenum (Mo) electrode 6 to be a lower electrode is formed by sputtering, and the Mo electrode 6 is divided by laser irradiation (first scribe).

Next, after forming a precursor by depositing copper (Cu), indium (In), and gallium (Ga) by sputtering or the like, the precursor is placed in a furnace and annealed in an atmosphere of H ₂ Se gas. The chalcopyrite light absorption layer 6 is formed by the phase selenization treatment. If necessary, a step of adding sodium (Na), which is an alkali metal, can be performed prior to the vapor phase selenization treatment. This is because, by diffusing Na in the light absorption layer, the grains of the light absorption layer grow, thereby increasing the energy conversion efficiency.

  The light absorption layer 7 is a p-type semiconductor layer. On the light absorption layer 7, an n-type buffer layer 8 that functions as an n-type semiconductor layer such as CdS, ZnO, or InS is formed by sputtering or CBD (chemical bath device). For example, a thickness of several hundreds of inches. On the n-type buffer layer 7, a high resistance layer 9 can be formed to a thickness of several hundreds of inches as required. Thereafter, the light absorption layer and the buffer layer are divided by laser irradiation or a metal needle (second scribe).

  Thereafter, a transparent electrode (TCO) 10 such as ZnOAl to be an upper electrode is formed by sputtering, CBD or the like, and an antireflection film 11 is formed thereon. Further, the antireflection film, the transparent electrode, the binder layer, and the light absorption layer are divided by laser-irradiated light absorption layer irradiation or a metal needle (third scribe). Finally, lead electrodes 12 and 13 are formed on the lower electrode layer 6 and the upper electrode layer 10 to complete a chalcopyrite thin film solar cell.

  Introducing the “roll-to-roll process” that forms the solar cell by supplying the assembled mica substrate from the roll by replacing the wet process such as CBD with the dry process for the processes after the molybdenum electrode 6 formation process. It becomes possible to do. When introducing the roll-to-roll process, the step of forming the intermediate layer of the ceramic material may be performed on the laminated mica substrate in advance, or during the roll-to-roll process It can also be incorporated.

  FIG. 7 is a graph showing the performance (IV characteristics) of a chalcopyrite solar cell in which only the intermediate layer is formed and a chalcopyrite solar cell in which both the intermediate layer and the back layer are formed, as shown in this graph. In a chalcopyrite solar cell in which only the intermediate layer is formed, the conversion efficiency η = 7.4%, Voc = 0.52V, series resistance = 32Ω, and parallel resistance = 310Ω, whereas the intermediate layer and the back surface In a chalcopyrite solar cell in which both layers are formed, the conversion efficiency η = 11.6%, Voc = 0.58V, series resistance = 4.5Ω, parallel resistance = 710Ω, and series resistance (Rs) As a result, the parallel resistance (Rsh) is increased and the conversion efficiency is increased as a result.

This prevents the substrate from becoming a scroll, so upper and lower electrode layers,
This is because cracks do not occur in a chalcopyrite type light absorption layer, buffer layer, or the like. In addition, when the transparent electrode as the upper electrode is formed in a state where the light absorption layer or the buffer layer is cracked, the occurrence of a leak also causes a decrease in conversion efficiency.
Specifically, for example, since the resistance value is reduced when cracks do not occur in the lower electrode, the series resistance (Rs) is lowered. Further, the parallel resistance (Rsh) increases by suppressing the occurrence of leakage.

Sectional view showing the structure of a conventional chalcopyrite solar cell The figure which shows a series of manufacturing processes of the conventional chalcopyrite type solar cell Diagram explaining the main part of the manufacturing process Graph showing surface shape of laminated mica substrate (A) And (B) is a diagram which shows the surface shape after forming the intermediate | middle layer of a thick film on the surface of a laminated mica substrate Sectional drawing which shows the structure of an example of the solar cell by this invention The graph which shows the performance (IV characteristic) of the chalcopyrite solar cell which formed only the intermediate | middle layer, and the chalcopyrite solar cell which formed both the intermediate | middle layer and the back surface layer

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Glue mica board | substrate 2 ... Intermediate | middle layer 3 ... Back surface layer 4 ... Surface smooth layer 5 ... Binder layer 6 ... Metal lower electrode layer 7 ... Light absorption layer 8 ... N-type buffer layer 9 ... High resistance layer 10 ... Transparent electrode layer 11 ... Antireflection film 12, 13 ... Extraction electrode

Claims (4)

A substrate made of mica or a material containing mica;
An intermediate layer made of a ceramic material formed on the surface side of the substrate in order to flatten or smooth the surface of the substrate;
A back layer made of the same material as the intermediate layer formed for the purpose of preventing warpage on the back side of the substrate;
A binder layer made of a the nitride laminated on the intermediate layer in order to improve the adhesion between the electrode and thereby suppress the diffusion of impurities from the substrate,
A lower electrode layer formed on the binder layer;
A p-type light absorption layer made of a chalcopyrite compound formed on the lower layer;
An n-type buffer layer formed on the light absorption layer;
A chalcopyrite solar cell comprising a transparent electrode layer formed on the buffer layer. The chalcopyrite solar cell according to claim 1, wherein the ceramic material constituting the intermediate layer contains silicon (Si) and aluminum (Al) . The chalcopyrite solar cell according to claim 1 or 2, wherein the thickness of the back layer is 1.0 to 1.5 times the thickness of the intermediate layer. Type solar cell. 4. The chalcopyrite solar cell according to claim 3, wherein the intermediate layer has a thickness of 2 μm or more and 20 μm or less, and the back layer has a thickness of 3 μm or more and 30 μm or less. .