JP2004335733A - Thin film solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon based thin film solar cell in which conversion efficiency is enhanced. <P>SOLUTION: The thin film solar cell has such a structure as one to ten layers of a laminate 10 consisting of a p-type microcrystal thin film 3 principally comprising silicon or germanium, an i-type microcrystal thin film 7 having a band gap larger than that of the p-type microcrystal thin film 3, and an i-type amorphous ultrathin film 8 are inserted at the junction interface of the p-type microcrystal thin film 3 and an i-type microcrystal thin film 4 of at least one pin junction. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a silicon-based thin-film solar cell, and more particularly to a solar cell including a non-single-crystal material.
[0002]
[Prior art]
Solar cells are attracting attention as an alternative energy source for fossil fuels such as petroleum, which is concerned about future supply and demand and has a problem of carbon dioxide emission that causes global warming. In this solar cell, a pn junction which is a semiconductor is used for a photoelectric conversion layer for converting light energy into electric power, and silicon is generally most often used as a semiconductor constituting the pn junction. As silicon, single crystal silicon is preferably used in terms of photoelectric conversion efficiency. However, single crystal silicon has problems such as a supply of a raw material, an increase in area, and a reduction in cost.
[0003]
On the other hand, a thin film solar cell using amorphous silicon or microcrystalline silicon as a photoelectric conversion layer as a material advantageous for realizing a large area and low cost has been put into practical use (for example, see Patent Document 1).
[0004]
[Patent Document 1]
JP-B-53-37718.
[0005]
[Problems to be solved by the invention]
However, in the above-mentioned thin film solar cell using amorphous silicon or microcrystalline silicon as a photoelectric conversion layer, low conversion efficiency from sunlight to electricity is the biggest problem for the spread of solar cells.
[0006]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thin-film solar cell in which the conversion efficiency of a silicon-based thin-film solar cell is increased.
[0007]
[Means for Solving the Problems]
The present invention solves such a problem, and the invention of claim 1 is a pin formed by stacking a p-type semiconductor layer containing silicon or germanium as a main component, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer. A thin-film solar cell having at least one junction, wherein the i-type semiconductor ultrathin film containing silicon or germanium as a main component and the i-type semiconductor layer at a junction interface between at least one pin junction p-type semiconductor layer and an i-type semiconductor layer. A thin-film solar cell characterized in that at least one layer and not more than 10 layers of an i-type semiconductor ultrathin film having a larger band gap than a type thin film are inserted.
[0008]
Therefore, according to the invention of claim 1, at the junction interface between at least one p-type semiconductor layer and the i-type semiconductor layer of the pin junction, the i-type semiconductor ultra-thin film containing silicon or germanium as a main component and the i-type thin film are used. Also, at least one layer and not more than ten layers of an i-type semiconductor ultrathin film having a large band gap are inserted. For this reason, when the laminated body is inserted into the pi interface of the thin-film Si-based solar cell, the leakage current is reduced, and accordingly, the fill factor and open circuit voltage of the solar cell element are increased, and high conversion efficiency can be obtained.
[0009]
According to a second aspect of the present invention, there is provided the thin-film solar cell, wherein the i-type semiconductor ultrathin film having a band gap larger than that of the substantially intrinsic i-type semiconductor layer has a thickness of 5 ° to 100 °.
[0010]
Therefore, according to the invention of claim 2, the thickness of the i-type semiconductor ultrathin film having a band gap larger than that of the substantially intrinsic i-type semiconductor layer is 5 ° to 100 °. For this reason, the effect of claim 1 can be further enhanced.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
FIG. 1 is a schematic sectional view showing a configuration of an embodiment of a solar cell according to the present invention. As a feature of this embodiment, in a thin-film silicon-based solar cell, at the interface between the p-type semiconductor layer and the i-type semiconductor layer, the i-type semiconductor layer and the ultrathin film having a larger band gap than the i-layer alternately. In which a plurality of stacked bodies are inserted.
[0012]
In addition, as a method for manufacturing a material containing silicon or germanium as a main component according to the embodiment of the present invention, a method in which any one of a plasma CVD method, a photo CVD method, a thermal CVD method, and a hot-wire CVD method is combined It is preferably produced by
[0013]
In the solar cell of the present invention, the base material may be either an insulating material or a conductive material, and may be either flexible or inflexible. In addition, the thin-film solar cell of the present embodiment may have any configuration of a pin-type (super-straight-type) solar cell and a nip-type (substrate-type) solar cell. May be laminated.
[0014]
Furthermore, the i-type semiconductor ultrathin film having a band gap larger than that of the substantially intrinsic i-type semiconductor layer according to claim 1 is amorphous silicon, amorphous silicon germanium, amorphous silicon carbide, amorphous silicon oxide, amorphous silicon nitride. , Microcrystalline silicon, microcrystalline silicon carbide, and the like, but are not limited thereto.
[0015]
Here, the thin-film solar cell according to the embodiment of the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to these drawings. 1 to 4 show schematic cross-sectional views of the thin-film solar cell of the present invention as an example.
[0016]
In the example of the configuration of the thin-film solar cell shown in FIG. 1, a transparent conductive film 2 and a p-type microcrystalline thin film 3 containing silicon or germanium as a main component are formed on a transparent substrate 1, and an i-type thin film of the present invention is formed thereon. A laminate 10 composed of an ultra-thin microcrystalline thin film 7 and an ultrathin i-type amorphous thin film 8 is formed, an i-type microcrystalline thin film 4 and an n-type thin film 5 are produced, and then a back metal electrode 6 is laminated. It is.
[0017]
In the example of the configuration of the thin-film solar cell shown in FIG. 2, the back metal electrode 6, the n-type thin film 5, and the i-type microcrystalline thin film 4 are formed on the transparent substrate 1, and the i-type amorphous of the present invention is further formed thereon. A laminate 10 composed of an ultra-thin crystalline ultrathin film 8 and an ultrathin i-type microcrystalline film 7 is formed, a p-type microcrystalline thin film 3 is produced, and finally a transparent conductive film 2 is laminated.
[0018]
In the example of the configuration of the thin-film solar cell shown in FIG. 3, a transparent conductive film 2 and a p-type microcrystalline thin film 3 containing silicon or germanium as a main component are formed on a transparent substrate 1, and the i-type thin film of the present invention is formed thereon. A laminated body 10 composed of an ultra-thin microcrystalline thin film 7 and an ultrathin i-type amorphous thin film 8 is formed, and an i-type microcrystalline thin film 4 and an n-type thin film 5 are formed. It was done.
[0019]
In the example of the configuration of the thin-film solar cell shown in FIG. 4, the back metal electrode 6, the n-type thin film 5, and the i-type microcrystalline thin film 4 are formed on the transparent substrate 1, and the i-type amorphous of the present invention is further formed thereon. The laminate 10 is formed by forming three layers of a laminated body 10 composed of a crystalline ultrathin film 8 and an i-type microcrystalline ultrathin film 7, further producing a p-type microcrystalline thin film 3, and finally laminating a transparent conductive film 2. The base material shown in FIGS. 2 and 4 may or may not transmit light.
[0020]
Further, the efficiency of the laminated body 10 according to the first aspect is maximized by inserting the laminated body 10 as one layer or more and ten layers or less. Preferably, the number of layers is one or more and three or less. Inserting more than ten layers greatly reduces the current and consequently the efficiency of the solar cell. Further, the thickness of the amorphous ultra-thin film in the laminate 10 needs to be 5 ° to 100 °, preferably 5 ° to 20 °. When the thickness is less than 5 °, no effect is obtained. When the thickness is more than 100 °, the current is greatly reduced and the efficiency of the solar cell is reduced.
[0021]
Hereinafter, an embodiment according to the present invention will be further described according to an actual preparation procedure.
[0022]
[Example 1]
As shown in FIG. 1, Ag (not shown) is formed on a glass substrate (not shown) by, for example, a sputtering method, for example, at a substrate temperature of 50 ° C. and a thickness of 300 nm, and a ZnO thin film doped with Al (back metal electrode 6) is formed thereon. ) Is formed, for example, at a substrate temperature of 140 ° C. and a thickness of 10 nm. A microcrystalline n-type doped silicon layer (n-type thin film 5) having a thickness of, for example, 40 nm is formed thereon by, for example, a plasma CVD method. The production conditions at this time are, for example, a flow rate of 3.5 SCCM for SiH _{4, a} flow rate of 28 SCCM for a PH ₃ / H ₂ mixed gas (PH ₃ concentration: 1000 ppm), a flow rate of H ₂ for 472 SCCM, an operating pressure of 1.5 Torr, and a power of 20 W is there.
[0023]
An i-type microcrystalline layer (i-type microcrystalline thin film 4) is formed thereon at 1 μm. The preparation conditions at this time are, for example, SiH ₄ flow rate 10 SCCM, H ₂ flow rate 400 SCCM, operating pressure 1.5 Torr, and input power 20 W. Thereafter, an i-type amorphous silicon layer (i-type ultra-thin amorphous film 8) is formed by 20 °. The production conditions at this time are, for example, an SiH ₄ flow rate of 20 SCCM, an H ₂ flow rate of 100 SCCM, an operating pressure of 1.0 Torr, and an input power of 10 W. Further, an i-type microcrystalline silicon layer (i-type microcrystalline ultrathin film 7) is formed to a thickness of 20 nm. At this time, for example, the production conditions are as follows: SiH ₄ flow rate is 10 SCCM, H ₂ flow rate is 400 SCCM, operating pressure is 1.5 Torr, and input power is 20 W. These i-type microcrystalline ultrathin film 7 and i-type amorphous ultrathin film 8 are referred to as a laminate 10.
[0024]
Further, a p-type microcrystalline silicon layer (p-type microcrystalline thin film 3) is formed to a thickness of 35 nm. The creation condition at this time, for example, SiH ₄ flow rate _{3.5SCCM, B 2 H 6 / H} 2 gas mixture _(B 2 _{H 6} concentration 5000 ppm) flow rate 1 SCCM, _{H 2} flow rate 630SCCM, the operating pressure 1.5 Torr. Finally, as a front electrode (transparent conductive film 2), ITO (Indium Tin Oxide) is formed to a thickness of 200 nm by, for example, a sputtering method, and a comb electrode of Ag is formed by, for example, a sputtering method.
[0025]
[Example 2]
Next, as Example 2, as shown in FIG. 3, Ag (not shown) is formed on a glass substrate (not shown) by, for example, a sputtering method at a substrate temperature of 50 ° C. and a thickness of 300 nm, for example, and Al is doped thereon. The formed ZnO thin film (back metal electrode 6) is formed, for example, at a substrate temperature of 140 ° C. and a thickness of 10 nm. A microcrystalline n-type doped silicon layer (n-type thin film 5) having a thickness of, for example, 40 nm is formed thereon by, for example, a plasma CVD method. The manufacturing conditions at this time are, for example, a SiH ₄ flow rate of 3.5 SCCM, a PH ₃ / H ₂ mixed gas (PH ₃ concentration of 1000 ppm) flow rate of 28 SCCM, an H ₂ flow rate of 472 SCCM, an operating pressure of 1.5 Torr, and an input power of 20 W. And An i-type microcrystalline layer (i-type microcrystalline thin film 4) having a thickness of 1 μm is formed thereon. The production conditions at this time are, for example, SiH ₄ flow rate 10 SCCM, H ₂ flow rate 400 SCCM, operating pressure 1.5 Torr, and input power 20 W.
[0026]
Thereafter, the i-type amorphous silicon layer (i-type amorphous ultra-thin film 8) [production conditions: SiH ₄ flow rate 20 SCCM, H ₂ flow rate 100 SCCM, operating pressure 1.0 Torr, input power 10 W] 20%; Crystalline silicon layer (i-type microcrystalline ultrathin film 7) [Preparation conditions: 3 layers of 10 nm of SiH ₄ flow rate, 400 SCCM H ₂ flow rate, operating pressure of 1.5 Torr, input power of 20 W], and three layers of 20 nm are formed. I do.
[0027]
Further, a p-type microcrystalline silicon layer (p-type microcrystalline thin film 3) is formed to a thickness of 35 nm. The preparation conditions at this time are, for example, a SiH ₄ flow rate of 3.5 SCCM, a B ₂ H ₆ / H ₂ mixed gas (B ₂ H ₆ concentration 5000 ppm) flow rate of 1 SCCM, an H ₂ flow rate of 630 SCCM, and an operating pressure of 1.5 Torr.
[0028]
Finally, ITO (Indium Tin Oxide) is formed to a thickness of 200 nm as a front electrode (transparent conductive film 2) by, for example, a sputtering method, and an Ag comb electrode is formed by, for example, a sputtering method.
[0029]
Hereinafter, for comparison of data with [Example 1] and [Example 2], a thin-film solar cell without using the laminate 10 of the present invention is prepared. The forming method is the same as that of [Example 2] except for the step of forming the laminate 10 of [Example 2].
[0030]
[Comparative example]
Ag is formed on a glass substrate by sputtering, for example, at a substrate temperature of 50 ° C. and a thickness of 300 nm, and a ZnO thin film doped with Al is formed thereon at a substrate temperature of 140 ° C. and a thickness of 10 nm. A microcrystalline n-type doped silicon layer having a thickness of 40 nm is formed thereon by a plasma CVD method. The fabrication conditions were as follows: SiH ₄ flow rate was 3.5 SCCM, PH ₃ / H ₂ mixed gas (PH ₃ concentration: 1000 ppm) flow rate was 28 SCCM, H ₂ flow rate was 472 SCCM, operating pressure was 1.5 Torr, and input power was 20 W. Its on the i-type microcrystalline layer Create Conditions: SiH ₄ flow rate 10 SCCM, _{H 2} flow rate 400 SCCM, operating pressure 1.5 Torr, applied power is 20W] to 1μm form. Further, a p-type microcrystalline silicon layer [preparation conditions: SiH ₄ flow rate 3.5 SCCM, B ₂ H ₆ / H ₂ mixed gas (B ₂ H ₆ concentration 5000 ppm) flow rate 1 SCCM, H ₂ flow rate 630 SCCM, operating pressure 1.5 Torr] Is formed to a thickness of 35 nm. Finally, ITO (Indium Tin Oxide) is formed to a thickness of 200 nm by a sputtering method as a front electrode, and an Ag comb electrode is formed by a sputtering method.
[0031]
[Test and results]
Next, FIG. 5 shows the thin-film solar cell characteristics of [Example 1], [Example 2], and [Comparative Example]. As shown in the figure, by inserting a laminated body 10 composed of an ultra-thin amorphous silicon film and an ultra-thin microcrystalline silicon film of the present invention into a junction interface between a p-type semiconductor layer and an i-type semiconductor layer of a microcrystalline silicon solar cell, The open circuit voltage and fill factor (FF value) are greatly improved, and the conversion efficiency of the solar cell is greatly increased.
[0032]
Note that the present invention is not limited to the above-described embodiments as they are, and can be embodied by modifying the components without departing from the scope of the invention at the stage of implementation. Various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the above embodiments. For example, some components may be deleted from all the components shown in the embodiment. Further, components of different embodiments may be appropriately combined.
[0033]
【The invention's effect】
As described in detail above, according to the present invention, a laminate comprising the ultra-thin amorphous silicon film and the ultra-thin microcrystalline silicon film of the present invention is inserted into the junction interface between the p-type semiconductor layer and the i-type semiconductor layer of the microcrystalline silicon solar cell. As a result, the open-circuit voltage and the fill factor are greatly improved, and the conversion efficiency of the solar cell is greatly increased.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing one embodiment of a configuration of a thin-film solar cell according to the present invention.
FIG. 2 is a schematic sectional view showing an embodiment of the configuration of the thin-film solar cell according to the present invention.
FIG. 3 is a schematic sectional view showing an embodiment of the configuration of the thin-film solar cell according to the present invention.
FIG. 4 is a schematic sectional view showing an embodiment of the configuration of the thin-film solar cell according to the present invention.
FIG. 5 is a diagram showing thin-film solar cell characteristics of [Example 1], [Example 2], and [Comparative Example].
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Transparent base material, 2 ... Transparent conductive film, 3 ... P-type microcrystalline thin film, 4 ... I-type microcrystalline thin film, 5 ... N-type thin film, 6 ... Backside metal electrode, 7 ... I-type microcrystalline ultrathin film, 8 ... i-type amorphous ultra-thin film, 10 ... laminate

Claims (2)

A thin-film solar cell having at least one pin junction in which a p-type semiconductor layer containing silicon or germanium as a main component, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer are stacked,
An i-type semiconductor ultrathin film containing silicon or germanium as a main component and an i-type semiconductor ultrathin film having a larger band gap than the i-type thin film at a junction interface between the p-type semiconductor layer and the i-type semiconductor layer of at least one pin junction; Characterized in that at least one layer and not more than 10 layers of the laminate are inserted. The thin-film solar cell according to claim 1,
A thin-film solar cell, wherein the i-type semiconductor ultrathin film having a band gap larger than that of the substantially intrinsic i-type semiconductor layer has a thickness of 5 ° to 100 °.

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