This invention relates to a photoelectric conversion element structure and a solar cell including the photoelectric conversion element structure.
In hitherto proposed solar cells, there is a solar cell including a photoelectric conversion element structure formed by thin films. In this case, there may be employed a pin structure including a structure in which a one conductivity-type (e.g. p-type) semiconductor layer and an opposite conductivity-type (e.g. n-type) semiconductor layer are in contact with both surfaces of an i-type semiconductor layer, respectively. When such a pin structure is employed, it is possible to increase the carrier diffusion length by applying an electric field to the i-type semiconductor layer. It is proposed to form respective semiconductor layers in photoelectric conversion element structures of various semiconductors such as amorphous semiconductor, microcrystalline semiconductor, single-crystalline semiconductor, and polycrystalline semiconductor. Further, it is also proposed to use Si, SiC, Ge, SiGe, and so on as semiconductors forming respective semiconductor layers.
As described above, since it is necessary to form three kinds of semiconductor layers different from each other for the solar cell including the photoelectric conversion element structure of the three-layer structure including the i-layer, the situation is such that an increase in cost cannot be avoided.
Patent Documents 1 and 2 each disclose a thin-film solar cell including a pin-type photoelectric conversion element structure. Specifically, the thin-film solar cell described in Patent Document 1 has a pin-type amorphous photoelectric conversion element structure with a layer of amorphous silicon containing a microcrystalline phase (μc-Si). That is, the thin-film solar cell described in Patent Document 1 has pin layers forming a power generating layer in which the p-layer is formed by a semiconductor layer containing a microcrystalline phase (μc-Si), the i-layer is formed of amorphous silicon germanium (a-SiGe), and a p-type low impurity concentration interface layer with a band gap larger than that of the p-layer is provided between the p-layer and the i-layer. This photoelectric conversion element structure is capable of suppressing degradation of properties after light irradiation and improving the efficiency.
Patent Document 2 discloses the solar cell including a photoelectric conversion element structure with high conversion efficiency by suppressing degradation of interface properties due to thermal diffusion in a manufacturing process. Patent Document 2 proposes a photoelectric conversion element structure having pin layers forming a power generating layer in which the p-type and n-type semiconductor layers are respectively formed by amorphous silicon-based thin films each including a microcrystalline phase (μc-Si) and the i-type semiconductor layer is formed by an amorphous silicon-based film. Further, Patent Document 2 proposes a structure in which an interface semiconductor layer in the form of a plurality of layers is provided between the p-type or n-type semiconductor layer and the i-type semiconductor layer. Herein, the impurity addition amount in the interface semiconductor layer on the i-type semiconductor layer side is set smaller than that in the interface semiconductor layer on the amorphous semiconductor layer side, thereby causing a band gap at the junction interface, on the p-type semiconductor layer side, of the i-type semiconductor layer to be larger than that of the i-type semiconductor layer. The solar cell including the above-mentioned photoelectric conversion element structure can suppress degradation of interface properties.
Patent Document 1: JP-A-2001-168354
Patent Document 2: JP-A-2003-8038
As described above, Patent Documents 1 and 2 each aim to improve the conversion efficiency by changing the internal structure of the power generating layer, comprising the pin three layers, to suppress the degradation of interface properties.
That is, Patent Document 1 shows the structure in which the interface layer is provided between the p-layer and the i-layer and Patent Document 2 also shows the structure in which the interface semiconductor layer is provided between the i-type semiconductor layer and the p-type or n-type semiconductor layer. In other words, neither of Patent Documents 1 and 2 points out a problem caused by contact resistances due to electrode layers formed in contact with the pin layers.
It is an object of this invention to provide a photoelectric conversion element structure and a solar cell which can reduce the contact resistance between an electrode layer and a semiconductor layer.
It is another object of this invention to provide a photoelectric conversion element structure and a solar cell which are high in conversion efficiency and highly economical, by improving an electrode layer formed in contact with a power generating layer.
It is still another object of this invention to provide a photoelectric conversion element structure and a solar cell which are reduced in contact resistance by improving the structure of a power generating layer itself.
According to a first aspect of this invention, there is provided a photoelectric conversion element structure characterized by comprising a first electrode layer, a second electrode layer, and one or a plurality of power generating laminates provided between the first and second electrode layers, wherein the power generating laminate comprises a p-type semiconductor layer, an i-type semiconductor layer formed in contact with the p-type semiconductor layer, and an n-type semiconductor layer formed in contact with the i-type semiconductor layer, the p-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the first electrode layer and the n-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the second electrode layer, and at least a portion, being in contact with the n-type semiconductor layer, of the second electrode layer comprises a metal having a work function which is smaller in absolute value than an electron affinity of the contacting n-type semiconductor layer (4.09 eV in absolute value in the case of n-type silicon).
According to a second aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that the at least a portion, being in contact with the n-type semiconductor layer, of the second electrode layer is formed of at least one kind of elementary metal selected from the group comprising magnesium, hafnium, and yttrium, or an alloy thereof.
According to a third aspect of this invention, there is provided the photoelectric conversion element structure in any one of the above-mentioned aspects, characterized in that the i-type semiconductor layer in at least one of the power generating laminates is formed of any of crystalline silicon, microcrystalline amorphous silicon, and amorphous silicon.
According to a fourth aspect of this invention, there is provided the photoelectric conversion element structure in any one of the above-mentioned aspects, characterized in that the second electrode layer is formed of the metal having the work function which is smaller in absolute value than the electron affinity of the contacting n-type semiconductor layer.
According to a fifth aspect of this invention, there is provided the photoelectric conversion element in any one of the above-mentioned aspects, characterized in that a portion, other than the portion being in contact with the n-type semiconductor layer, of the second electrode layer is formed of a metal with a conductivity higher than that of the metal having the work function which is smaller in absolute value than the electron affinity of the contacting n-type semiconductor layer.
According to a sixth aspect of this invention, there is provided the photoelectric conversion element structure in any one of the above-mentioned aspects, characterized in that at least a portion, being in contact with the p-type semiconductor layer, of the first electrode layer comprises a metal having a work function which is larger in absolute value than an upper limit energy level of a valence band of the contacting p-type semiconductor layer (5.17 eV in absolute value in the case of p-type silicon).
According to a seventh aspect of this invention, there is provided a photoelectric conversion element structure characterized by comprising a first electrode layer, a second electrode layer, and one or a plurality of power generating laminates provided between the first and second electrode layers, wherein the power generating laminate comprises a p-type semiconductor layer, an i-type semiconductor layer formed in contact with the p-type semiconductor layer, and an n-type semiconductor layer formed in contact with the i-type semiconductor layer, the p-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the first electrode layer and the n-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the second electrode layer, and at least a portion, being in contact with the p-type semiconductor layer, of the first electrode layer comprises a metal having a work function which is larger in absolute value than an upper limit energy level of a valence band of the contacting p-type semiconductor layer.
According to an eighth aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that the at least a portion, being in contact with the p-type semiconductor layer, of the first electrode layer is formed of at least one kind of elementary metal selected from the group comprising nickel (Ni), iridium (Ir), palladium (Pd), and platinum (Pt), or an alloy thereof.
According to a ninth aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that the first electrode layer is formed of the metal having the work function which is larger in absolute value than the upper limit energy level of the valence band of the contacting p-type semiconductor layer.
According to a tenth aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that a portion, other than the portion being in contact with the p-type semiconductor layer, of the first electrode layer is formed of a metal with a conductivity higher than that of the metal having the work function which is larger in absolute value than the upper limit energy level of the valence band of the contacting p-type semiconductor layer.
According to an eleventh aspect of this invention, there is provided a photoelectric conversion element structure, characterized by comprising an i-type semiconductor layer, a one conductivity-type semiconductor layer formed in contact with one surface of the i-type semiconductor layer, and a metal layer comprising a predetermined metal and formed in direct contact with another surface of the i-type semiconductor layer.
According to a twelfth aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that the metal layer, along with the i-type semiconductor layer and the one conductivity-type semiconductor layer, forms a power generating region.
According to a thirteenth aspect of this invention, there is provided the photoelectric conversion element structure, characterized by comprising an electrode formed in contact with the one conductivity-type semiconductor layer directly or through another power generating region.
According to a fourteenth aspect of this invention, there is provided the photoelectric conversion element structure, characterized by comprising another electrode layer formed in contact with the metal layer.
According to a fifteenth aspect of this invention, there is provided the photoelectric conversion element structure, characterized in that the one conductivity-type semiconductor layer formed in contact with the one surface of the i-type semiconductor layer is a p-type semiconductor layer.
According to a sixteenth aspect of this invention, there is provided the photoelectric conversion element structure in any one of the eleventh to the fifteenth aspects, characterized in that when a semiconductor forming the i-type semiconductor layer is an n-type semiconductor, the metal of the metal layer formed in contact with the another surface of the i-type semiconductor layer is a metal having a work function which is smaller in absolute value than an electron affinity of the n-type semiconductor.
According to a seventeenth aspect of this invention, there is provided the photoelectric conversion element structure in any one of the eleventh to the fourteenth aspects, characterized in that the one conductivity-type semiconductor layer formed in contact with the one surface of the i-type semiconductor layer is an n-type semiconductor layer and, when a semiconductor forming the i-type semiconductor layer is a p-type semiconductor, the metal of the metal layer formed in contact with the another surface of the i-type semiconductor layer is a metal having a work function which is larger in absolute value than an upper limit energy level of a valence band of the p-type semiconductor.
According to an eighteenth aspect of this invention, there is provided a photoelectric conversion element structure characterized by comprising a first electrode layer, a second electrode layer, and one or a plurality of power generating laminates provided between the first and second electrode layers, wherein the power generating laminate comprises a p-type semiconductor layer, an i-type semiconductor layer formed in contact with the p-type semiconductor layer, and an n-type semiconductor layer formed in contact with the i-type semiconductor layer, the p-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the first electrode layer and the n-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the second electrode layer, and at least a portion, being in contact with the n-type semiconductor layer, of the second electrode layer comprises a metal having a work function which is smaller in absolute value than those of Al and Ag.
According to a nineteenth aspect of this invention, there is provided the photoelectric conversion element structure in the eighteenth aspect, characterized in that the at least a portion, being in contact with the n-type semiconductor layer, of the second electrode layer is formed of at least one kind of elementary metal selected from the group comprising manganese and zirconium, or an alloy thereof.
According to a twentieth aspect of this invention, there is provided a photoelectric conversion element structure characterized by comprising a first electrode layer, a second electrode layer, and one or a plurality of power generating laminates provided between the first and second electrode layers, wherein the power generating laminate comprises a p-type semiconductor layer, an i-type semiconductor layer formed in contact with the p-type semiconductor layer, and an n-type semiconductor layer formed in contact with the i-type semiconductor layer, the p-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the first electrode layer and the n-type semiconductor layer of the one power generating laminate or of the power generating laminate, on the first electrode side, of the plurality of power generating laminates is in contact with the second electrode layer, and at least a portion, being in contact with the p-type semiconductor layer, of the first electrode layer comprises a metal having a work function which is larger in absolute value than that of ZnO.
According to a twenty-first aspect of this invention, there is provided the photoelectric conversion element structure in the twentieth aspect, characterized in that the at least a portion, being in contact with the n-type semiconductor layer, of the second electrode layer is formed of at least one kind of elementary metal selected from the group comprising manganese and zirconium, or an alloy thereof.
According to a twenty-second aspect of this invention, there is provided the photoelectric conversion element structure in any one of the eleventh to the twenty-first aspects, characterized in that the i-type semiconductor layer is formed of silicon.
According to a twenty-third aspect of this invention, there is provided a solar cell characterized by comprising the photoelectric conversion element structure in any one of the eleventh to the twenty-second aspects.
According to this invention, a photoelectric conversion element structure with high conversion efficiency is obtained by reducing the contact resistance between an electrode layer and a semiconductor layer.
Referring to an equivalent circuit diagram of a photoelectric conversion element shown in
The principle of this invention is to improve the conversion efficiency of the photoelectric conversion element structure by reducing the contact resistances of the resistances Rs in the equivalent circuit shown in
Referring to
On the other hand, the electron affinity of n-Si is −4.09 eV and a metal having a work function smaller in absolute value than that is used as the second electrode 22. Alternatively, a metal or its alloy having a work function smaller in absolute value than those of Al and Ag is used as the second electrode 22.
In the first embodiment of this invention, attention has been paid to the work function of the back electrode, i.e. the second electrode 22, thus reducing the contact resistance between the second electrode 22 and the n-type semiconductor layer 252. In general, aluminum (Al) having a work function of −4.28 eV or silver (Ag) having a work function of −4.26 eV is used as the second electrode 22.
Herein, the second electrode 22 is formed of a metal material having a work function smaller in absolute value than the electron affinity −4.09 eV of the semiconductor (n-Si) and preferably having a high reflectance. Specifically, by forming the second electrode 22 of the metal material adapted to form an ohmic contact with the semiconductor made of n-Si, the contact resistance can be reduced as compared with Al or Ag.
Alternatively, even by using a metal material adapted to form a Schottky barrier with the semiconductor made of n-Si, the contact resistance can be reduced as compared with Al or Ag.
The above-mentioned metal material capable of reducing the contact resistance can be determined taking into account the work function thereof with respect to n-Si. Hereinafter, the work function of a metal material will be given by φm and the electron affinity of a semiconductor (herein n-Si) will be given by φs.
Now, referring to
On the other hand, even by using a metal having a work function smaller in absolute value than those of Al and Ag, it is possible to reduce the contact resistance as compared with the case where Al or Ag is brought into contact with n-Si.
For example, Mn or Zr having a work function of −4.1 eV is, like Al with −4.28 eV and Ag with −4.26 eV, slightly smaller in work function than n-Si having the work function of −4.09 eV and thus the work functions thereof are in a relationship of φs<φm. In this case, a state before such a metal material is brought into contact with n-Si is as shown in
Since the work function of Mn or Zr is closer than those of Al and Ag to the work function φs of n-Si and is smaller in absolute value than those of Al and Ag, even if the second electrode 22 is formed of Mn or Zr, it is possible to reduce the contact resistance as compared with the case of using Al or Ag.
In fact, the contact resistance between Al and n-Si is about 5×10-6 Ω·cm2 while, in the case of Mn or Zr where the difference between the work function φm of the metal and the work function φs of n-Si is 0.05 eV, it is possible to achieve a contact resistance of about 5×10-12 Ω·cm2. Further, also in the case of another metal such as Mg, Hf, or Y, it is possible to reduce the contact resistance to about 10-8 Ω·cm2.
In the above-mentioned example, consideration has been given to the contact resistance between the second electrode 22 and n-Si shown in
Referring to
In order to reduce the contact resistance between p-Si 251 having a work function of −5.15 eV and a first electrode 21, an additional metal layer may be provided between p-Si 251 and the first electrode 21. When ZnO having a work function of −4.25 eV is used as the electrode on the p-Si side, the contact resistance can be reduced by using, as the additional metal layer, a metal material having a work function larger in absolute value than that of ZnO, such as Co with −5.0 eV or Ni with −5.2 eV.
Referring to
In the above-mentioned embodiments, the description has been given only of the case where crystalline silicon is used. However, this invention is by no means limited thereto and is also similarly applicable to the case where use is made of amorphous silicon or microcrystal-containing amorphous silicon (μc-Si). In this case, it is needless to say that a metal is selected taking into account the work function of amorphous silicon or μc-Si.
Further, this invention is applicable not only to the case where silicon is used, but also to the case where another semiconductor is used, thereby reducing the contact resistance to improve the conversion efficiency.
A photoelectric conversion element according to this invention is applicable not only to a solar cell, but also to a photoelectric conversion element for another electronic device.
Number | Date | Country | Kind |
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2008-057314 | Mar 2008 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP2009/053814 | 3/2/2009 | WO | 00 | 9/3/2010 |