JP5373045B2 - Photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion device having an improved photoelectric conversion efficiency. <P>SOLUTION: A photoelectric conversion device comprises a photoelectric conversion unit having a p-type layer 40 including a p-type dopant, an i-type layer 42 being a microcrystalline silicon layer functioning as a power generation layer, and an n-type layer 44 including an n-type dopant which are laminated. The p-type layer 40 comprises a laminated structure containing: a first p-type layer 40a being a microcrystalline silicon layer; and a second p-type layer 40b including at least one of an amorphous silicon p-type layer and an amorphous silicon carbide p-type layer disposed between the microcrystalline silicon p-type layer 40a and the i-type layer 42. The second p-type layer 40b comprises an oxide layer disposed on the i-type layer 42 side. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a photoelectric conversion device.

  Solar cells using polycrystalline, microcrystalline, or amorphous silicon are known. In particular, a photoelectric conversion device having a structure in which microcrystalline or amorphous silicon thin films are stacked has attracted attention from the viewpoint of resource consumption, cost reduction, and efficiency.

  In general, a photoelectric conversion device is formed by sequentially stacking a first electrode, one or more semiconductor thin film photoelectric conversion cells, and a second electrode on a substrate having an insulating surface. Each photoelectric conversion unit is configured by stacking a p-type layer, an i-type layer, and an n-type layer from the light incident side. As a method for improving the conversion efficiency of a photoelectric conversion device, it is known to stack two or more types of photoelectric conversion cells in the light incident direction. A first photoelectric conversion unit including a photoelectric conversion layer having a wide band gap is disposed on the light incident side of the photoelectric conversion device, and then a second photoelectric conversion layer including a photoelectric conversion layer having a narrower band gap than the first photoelectric conversion unit is disposed. A photoelectric conversion unit is arranged. Thereby, photoelectric conversion can be performed over a wide wavelength range of incident light, and the conversion efficiency of the entire apparatus can be improved. For example, a structure in which an amorphous silicon (a-Si) photoelectric conversion unit is a top cell and a microcrystalline (μc-Si) photoelectric conversion unit is a bottom cell is known. Among them, a structure in which amorphous silicon and microcrystalline silicon are stacked in this order on a light-transmitting substrate and light is incident from the surface of the substrate is attracting attention. The area of the region that does not contribute to photoelectric conversion in the substrate can be reduced.

  In addition, a technique for reducing the crystal grain boundaries and intragranular defects of the power generation layer and improving the photoelectric conversion efficiency by laminating the microcrystalline silicon thin film containing impurities and the amorphous silicon thin film containing impurities is disclosed. ing. In particular, a p-type microcrystalline silicon-based thin film and a p-type amorphous silicon-based thin film are stacked on the back electrode on the opposite side to the light incidence, and amorphous silicon or It is disclosed that amorphous silicon carbide can be used (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 10-294482

  In a photoelectric conversion device in which a power generation unit (top cell) using amorphous silicon as a power generation layer and a power generation unit (bottom cell) using microcrystalline silicon as a power generation layer are stacked in this order, and the amorphous silicon layer side is arranged on the light incident side Conventionally, the n-type layer of the top cell is a microcrystalline silicon layer, a p-type microcrystalline silicon layer (or p-type microcrystalline silicon carbide layer) is in contact therewith, and a microcrystalline silicon is further in contact with the p-type layer. A structure to install a power generation layer has been used. However, in this structure, changing the film quality (crystallization rate, doping rate) of the n-type microcrystalline silicon layer of the top cell and the p-type microcrystalline silicon layer of the bottom cell also changes the crystallinity of the microcrystalline silicon power generation layer. There has been a problem of deviating from the optimum film quality. Since the film quality could not be adjusted to be optimal for each layer alone, it was very difficult to derive the optimum formation conditions for a photoelectric conversion device in which two or more types of photoelectric conversion cells were stacked. In addition, since the formation conditions of each microcrystalline silicon layer in the bottom cell are very critical, it is necessary to readjust the formation conditions after maintenance of the manufacturing equipment or after processing a certain number of treatments. The same problem occurred with respect to, and there was a problem that the production volume in mass production was greatly reduced.

  When a structure in which a p-type microcrystalline silicon layer and a p-type amorphous silicon layer are stacked is arranged opposite to the light incident side, the crystallinity of the interface layer between the p-type microcrystalline silicon layer and the microcrystalline silicon power generation layer has junction characteristics. Is hardly affected. However, when the above laminated structure is disposed on the light incident side, the bonding characteristics are greatly affected by the crystallinity of the interface layer between the p-type microcrystalline silicon layer and the power generation layer, and the crystallization rate of the interface layer is low. And may prevent improvement of photoelectric conversion efficiency. Therefore, even when the p-type microcrystalline silicon layer and the p-type amorphous silicon layer are stacked on the p-type layer and this structure is disposed on the light incident side, the crystallization rate in the vicinity of the interface of the i-type layer is not lowered. Technology is needed.

  One embodiment of the present invention includes a photoelectric conversion unit including a p-type layer including a p-type dopant, an i-type layer that is a microcrystalline silicon layer serving as a power generation layer, and an n-type layer including an n-type dopant. In the conversion device, the p-type layer includes a first p-type layer that is a microcrystalline silicon layer, an amorphous silicon p-type layer disposed between the microcrystalline silicon p-type layer and the i-type layer, and amorphous carbonization. A photoelectric conversion device having a stacked structure of a second p-type layer including at least one of silicon p-type layers.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to improve the photoelectric conversion efficiency in a photoelectric conversion apparatus, the production efficiency of a photoelectric conversion apparatus can be improved.

It is a figure which shows the structure of the photoelectric conversion apparatus in embodiment of this invention. It is a figure which shows the structure of the (micro | micron | mu) c-Si unit of the photoelectric conversion apparatus in embodiment of this invention. It is a figure which shows the structure of the (micro | micron | mu) c-Si unit of the photoelectric conversion apparatus in embodiment of this invention. It is a figure which shows the relationship of the photoelectric conversion efficiency of the photoelectric conversion apparatus with respect to the film thickness of the 2nd p-type layer in Example 6 of this invention. It is a figure which shows the relationship of the photoelectric conversion efficiency of the photoelectric conversion apparatus with respect to the film thickness of the buffer layer in Example 7 of this invention. It is a figure which shows the relationship of the photoelectric conversion efficiency of the photoelectric conversion apparatus with respect to the hydrogen / silane dilution ratio at the time of film-forming of the buffer layer in Example 8 of this invention.

  FIG. 1 is a cross-sectional view showing the structure of a photoelectric conversion device 100 according to an embodiment of the present invention. In the photoelectric conversion device 100 according to the present embodiment, the transparent insulating substrate 10 is used as the light incident side, the transparent conductive film 12 and the amorphous silicon (a-Si) having a wide band gap as the top cell from the light incident side (photoelectric conversion). Unit 102, intermediate layer 14, microcrystalline silicon (μc-Si) (photoelectric conversion) unit 104 having a narrower band gap than a-Si unit 102 as a bottom cell, first back electrode layer 16, second back electrode layer 18, filler 20 and a protective film 22 are stacked.

  Hereinafter, the configuration and manufacturing method of the photoelectric conversion device 100 according to the embodiment of the present invention will be described.

For the transparent insulating substrate 10, for example, a material having transparency in at least a visible light wavelength region such as a glass substrate or a plastic substrate can be applied. A transparent conductive film 12 is formed on the transparent insulating substrate 10. The transparent conductive film 12 is doped with tin oxide (SnO ₂ ), zinc oxide (ZnO), indium tin oxide (ITO), etc. with tin (Sn), antimony (Sb), fluorine (F), aluminum (Al), etc. It is preferable to use at least one or a combination of a plurality of transparent conductive oxides (TCO). In particular, zinc oxide (ZnO) is preferable because it has high translucency, low resistivity, and excellent plasma resistance. The transparent conductive film 12 can be formed by, for example, sputtering. The film thickness of the transparent conductive film 12 is preferably in the range of 0.5 μm to 5 μm. Moreover, it is preferable to provide unevenness having a light confinement effect on the surface of the transparent conductive film 12.

A p-type layer, i-type layer, and n-type silicon thin film are sequentially laminated on the transparent conductive film 12 to form the a-Si unit 102. The a-Si unit 102 includes a silicon-containing gas such as silane (SiH ₄ ), disilane (Si ₂ H ₆ ), dichlorosilane (SiH ₂ Cl ₂ ), a carbon-containing gas such as methane (CH ₄ ), diborane (B ₂ H). ₆ ) formed by plasma CVD in which a mixed gas obtained by mixing a p-type dopant-containing gas such as phosphine (PH ₃ ) and a dilute gas such as phosphine (PH ₃ ) and a diluent gas such as hydrogen (H ₂ ) is formed into a plasma. be able to.

For plasma CVD, for example, 13.56 MHz RF plasma CVD is preferably applied. The RF plasma CVD can be a parallel plate type. It is good also as a structure which provided the gas shower hole for supplying the mixed gas of a raw material in the side which does not arrange | position the transparent insulating substrate 10 among parallel plate type electrodes. The input power density of plasma is preferably 5 mW / cm ² or more and 100 mW / cm ² or less.

  In general, the p-type layer, the i-type layer, and the n-type layer are formed in separate film formation chambers. The film forming chamber can be evacuated by a vacuum pump and has an electrode for RF plasma CVD. In addition, a transfer device for the transparent insulating substrate 10, a power source and matching device for RF plasma CVD, piping for gas supply, and the like are attached.

The p-type layer is formed on the transparent conductive film 12. The p-type layer is a p-type amorphous silicon layer (p-type a-Si: H) or p-type amorphous silicon carbide (p-type a-SiC: H) having a thickness of 10 nm to 100 nm doped with a p-type dopant (boron or the like). ). The film quality of the p-type layer can be changed by adjusting the mixing ratio of the silicon-containing gas, the carbon-containing gas, the p-type dopant-containing gas and the dilution gas, the pressure, and the high frequency power for plasma generation. For example, the p-type layer includes a high absorption amorphous silicon carbide layer (p1 layer) doped with boron at a high concentration, and a low absorption amorphous silicon carbide layer (p2 layer) whose boron concentration is lower than that of the high absorption amorphous silicon carbide layer. It is preferable to have a laminated structure. At this time, it is preferable to form a film by RF plasma CVD in which power is supplied at a power density of 11 mW / cm ² with a substrate temperature of 180 ° C. and a reaction pressure of 80 Pa. At the time of film formation of the high absorption amorphous silicon carbide layer (p1 layer), the source gas is silane (SiH ₄ ), methane (CH ₄ ), hydrogen (H ₂ ), and diborane (B ₂ H ₆ ), respectively, at 40 sccm, 80 sccm, It is preferable to supply at 400 sccm and 12 sccm (1% dilution). At the time of forming the low absorption amorphous silicon carbide layer (p2 layer), the source gas is silane (SiH ₄ ), methane (CH ₄ ), hydrogen (H ₂ ), and diborane (B ₂ H ₆ ), respectively, at 40 sccm, 80 sccm, It is preferable to supply at 400 sccm and 1 sccm (1% dilution). The film thicknesses of the high absorption amorphous silicon carbide layer (p1 layer) and the low absorption amorphous silicon carbide layer (p2 layer) are preferably 7 nm and 3 nm, respectively. The i-type layer is an undoped amorphous silicon film of 50 nm to 500 nm formed on the p-type layer. The film quality of the i-type layer can be changed by adjusting the mixing ratio of the silicon-containing gas and the dilution gas, the pressure, and the high frequency power for plasma generation. The i-type layer is a power generation layer of the a-Si unit 102. For example, the i-type layer preferably has a structure in which a top cell buffer layer that is an amorphous silicon carbide layer and a normal i-type layer that is an amorphous silicon layer are stacked. At this time, the top cell buffer layer is preferably formed by RF plasma CVD in which power is supplied at a power density of 11 mW / cm ² under a source gas supply at a substrate temperature of 180 ° C. and a reaction pressure of 80 Pa. When forming the top cell buffer layer, it is preferable to supply silane (SiH ₄ ), methane (CH ₄ ), and hydrogen (H ₂ ) at 20 sccm, 10 sccm, and 2000 sccm, respectively. The film thickness of the top cell buffer layer is preferably 10 nm. A normal i-type layer that is an amorphous silicon layer is preferably formed by RF plasma CVD with power supplied at a power density of 11 mW / cm ² under a source gas supply of 180 ° C. and a reaction pressure of 100 Pa. is there. During normal i-type deposition, silane (SiH ₄ ) and hydrogen (H ₂ ) are preferably supplied at 300 and 1000 sccm, respectively. The film thickness of a normal i-type layer is preferably 300 nm. The n-type layer is an n-type amorphous silicon layer (n-type a-Si: H) or n-type microcrystalline silicon having a thickness of 10 nm or more and 100 nm or less doped with an n-type dopant (such as phosphorus) formed on the i-type layer. A layer (n-type μc-Si: H) is used. The film quality of the n-type layer can be changed by adjusting the mixing ratio of the silicon-containing gas, the carbon-containing gas, the n-type dopant-containing gas and the dilution gas, the pressure, and the high-frequency power for plasma generation. For example, the n-type layer is preferably formed by RF plasma CVD in which power is supplied at a power density of 110 mW / cm ² under the supply of a source gas having a substrate temperature of 180 ° C. and a reaction pressure of 200 Pa. At the time of forming the n-type layer, it is preferable to supply silane (SiH ₄ ), hydrogen (H ₂ ), and phosphine (PH 3) at 10 sccm, 2000 sccm, and 5 sccm (1% dilution), respectively. The film thickness of the n-type layer is preferably 20 nm.

  The intermediate layer 14 is formed on the a-Si unit 102. The intermediate layer 14 is preferably made of a transparent conductive oxide (TCO) such as zinc oxide (ZnO) or silicon oxide (SiOx). In particular, it is preferable to use zinc oxide (ZnO) or silicon oxide (SiOx) doped with magnesium Mg. The intermediate layer 14 can be formed by, for example, sputtering. The film thickness of the intermediate layer 14 is preferably in the range of 10 nm to 200 nm. The intermediate layer 14 need not be provided.

As shown in the enlarged sectional view of FIG. 2, the μc-Si unit 104 in which the p-type layer 40, the i-type layer 42, and the n-type layer 44 are sequentially laminated is formed on the intermediate layer 14. The μc-Si unit 104 includes a silicon-containing gas such as silane (SiH ₄ ), disilane (Si ₂ H ₆ ), dichlorosilane (SiH ₂ Cl ₂ ), a carbon-containing gas such as methane (CH ₄ ), diborane (B ₂ H ₆ ) formed by plasma CVD in which a mixed gas obtained by mixing a p-type dopant-containing gas such as phosphine (PH ₃ ) and a dilute gas such as phosphine (PH ₃ ) and a diluent gas such as hydrogen (H ₂ ) is formed into a plasma. be able to.

As with the a-Si unit 102, for example, 13.56 MHz RF plasma CVD is preferably applied to the plasma CVD. The RF plasma CVD can be a parallel plate type. It is good also as a structure which provided the gas shower hole for supplying the mixed gas of a raw material in the side which does not arrange | position the transparent insulating substrate 10 among parallel plate type electrodes. The input power density of plasma is preferably 5 mW / cm ² or more and 100 mW / cm ² or less.

  The p-type layer 40 is formed on the intermediate layer 14 or the n-type layer of the a-Si unit 102. In the present embodiment, at least two layers of a first p-type layer 40a that is a microcrystalline silicon layer and a second p-type layer 40b that is an amorphous layer are stacked. The amorphous layer is preferably an amorphous silicon layer (a-Si) or an amorphous silicon carbide layer (a-SiC).

  The first p-type layer 40a preferably has a thickness of 5 nm to 50 nm. In addition, when the second p-type layer 40b is an a-Si layer, it is preferable that the film thickness be 1 nm to 4.5 nm. When the second p-type layer 40b is an a-SiC layer, it is preferable that the film thickness be 1 nm to 4.5 nm.

  The film quality of the first p-type layer 40a and the second p-type layer 40b is adjusted by adjusting the mixing ratio of silicon-containing gas, carbon-containing gas, p-type dopant-containing gas and dilution gas, pressure, and high-frequency power for plasma generation. Can be changed.

Thereafter, a treatment for oxidizing the second p-type layer 40b is performed. For example, it is preferable that after forming the second p-type layer 40b, the transparent insulating substrate 10 is taken out from the vacuum layer of the film forming line and exposed to the atmosphere to be oxidized. The oxidation is preferably performed to such an extent that an oxygen atom concentration of 1 × 10 ²⁰ / cm ³ or more and 1 × 10 ²² / cm ³ or less is detected in secondary ion mass spectrometry (SIMS). Specifically, with a SIMA analyzer (IMF-4F) manufactured by Kameka, the primary ion species Cs ⁺ was irradiated with an acceleration voltage of 14.5 kV and a primary ion current of 15 nA at a vacuum degree of 1 × 10 ⁻⁷ Torr or less. When performed, it is preferable that an oxygen atom concentration of 1 × 10 ²⁰ / cm ³ or more and 1 × 10 ²² / cm ³ or less is detected.

  As described above, by oxidizing the second p-type layer 40b after forming the second p-type layer 40b, the surface layer of the second p-type layer 40b is oxidized, and the i-type layer formed on the second p-type layer 40b. The interface level (defect level) at the interface with 42 is reduced, and the output voltage of the photoelectric conversion device 100 is improved.

  Further, in the method of performing the oxidation treatment by exposing the p-type layer 40b to the atmosphere, the number of sheets that can be processed at one time per one forming apparatus of the a-Si unit 102 that is the top cell is large, and the μc-Si that is the bottom cell. This is particularly effective when the number of processed sheets per unit 104 is small. That is, after the a-Si unit and the p-type layer 40b are formed by the a-Si unit 102 forming apparatus, the a-Si unit 102 is once taken out from the a-Si unit 102 forming apparatus and exposed to the atmosphere. This is because the time until introduction into the forming apparatus can be used as the tact time adjustment time. In addition, by forming a large number of layers with the forming apparatus for the a-Si unit 102 that can be processed at a time, the operating efficiency of the forming apparatus can be improved without increasing the number of forming apparatuses for the μc-Si unit 104. it can.

  Also, if the thickness of the p-type layer 40b is less than 1 nm, the effect of providing the p-type layer 40b is not sufficiently obtained. If the thickness is greater than 4.5 nm, the series resistance of the p-type layer 40 increases, and the short-circuit current and There is a risk of lowering the fill factor.

  Furthermore, by applying an a-SiC layer as the p-type layer 40b, a wider band gap can be achieved than when an a-Si layer is applied. Thereby, the open circuit voltage of the photoelectric conversion device 100 can be further increased, and the loss of light absorption in the p-type layer 40 can be reduced, so that the short circuit current is also improved.

  An i-type layer 42 is formed on the p-type layer 40. The i-type layer 42 is a microcrystalline silicon film which is formed on the p-type layer 40 and has a thickness of 0.5 μm or more and 5 μm or less which is not mainly doped. The i-type layer 42 is a layer that becomes a power generation layer of the μc-Si unit 104.

  In the present embodiment, it is preferable that the i-type layer 42 has a configuration in which a buffer layer 42a is formed so as to be in contact with the p-type layer 40, and a main power generation layer 42b is formed on the buffer layer 42a. The buffer layer 42a is formed under a film formation condition that provides a higher crystallization rate than the film formation condition of the main power generation layer 42b. In other words, the buffer layer 42a is formed under film forming conditions such that the crystallization rate is higher than that of the main power generation layer 42b when it is formed as a single film on a glass substrate or the like. The buffer layer 42a may be a p-type layer to which a p-type dopant is added.

Specifically, the buffer layer 42a is formed by introducing a mixed gas having a hydrogen (H ₂ ) / silane (SiH ₄ ) dilution ratio of 130 or more and 800 or less at a pressure of 200 Pa by an RF plasma deposition method of 13.56 MHz. Is preferred. The substrate temperature during film formation was set to 80 ° C. or higher 250 ° C. or less, introducing power to the plasma is preferably set to 30 mW / cm ² or more 1000 mW / cm ² or less. The main power generation layer 42b is preferably formed by introducing a mixed gas having a hydrogen (H ₂ ) / silane (SiH ₄ ) dilution ratio of 30 or more and 200 or less at a pressure of 600 Pa by an RF plasma film forming method of 13.56 MHz. is there. The substrate temperature during film formation was set to 80 ° C. or higher 250 ° C. or less, introducing power to the plasma is preferably set to 30 mW / cm ² or more 3000 mW / cm ² or less. Note that the film may be formed using VHF plasma of 27 MHz or the like.

  By providing the buffer layer 42a, the crystallization rate in the vicinity of the interface of the p-type layer 40 in the i-type layer 42 is increased, and the crystallization rate of the entire i-type layer 42 serving as the power generation layer of the μc-Si unit 104 is increased. The photoelectric conversion efficiency of the photoelectric conversion device 100 can be improved.

  The thickness of the buffer layer 42a is preferably 8 nm or more and 100 nm or less. If the film thickness is less than 8 nm, the effect of inserting the buffer layer 42a is not sufficient, and if it is more than 100 nm, the photoelectric conversion characteristics such as the fill factor FF may be deteriorated.

Further, as shown in the enlarged sectional view of FIG. 3, in addition to the buffer layer 42a which is a microcrystalline silicon layer, a buffer layer 42c which is an amorphous silicon layer may be provided between the p-type layer 40 and the buffer layer 42a. Is preferred. The buffer layer 42c may be formed under the general conditions for forming an amorphous silicon layer. For example, a mixed gas having a hydrogen (H ₂ ) / silane (SiH ₄ ) dilution ratio of 10 or less is introduced at a pressure of 100 Pa. It is preferable to form the film by an RF plasma deposition method of .56 MHz. Further, it is preferable that the substrate temperature during film formation is 80 ° C. or higher and 250 ° C. or lower, and the power introduced into the plasma is 5 mW / cm ² or higher and 100 mW / cm ² or lower. The film thickness of the buffer layer 42c is preferably 1 nm or more and 5 nm or less.

  By providing the buffer layer 42c, which is an amorphous silicon layer, between the p-type layer 40 and the buffer layer 42a as a base, the crystallization rate of the buffer layer 42a can be increased without being affected by the p-type layer 40. Thereby, the series resistance of the μc-Si unit 104 can be reduced and the short-circuit current can be improved.

  However, at least one of the configuration in which the p-type layer 40 is formed in two layers and the configuration in which the buffer layers 42 a and 42 c are provided in the i-type layer 42 may be applied. Of course, both actions and effects can be obtained by applying both configurations simultaneously.

  The n-type layer 44 is formed on the i-type layer 42. The n-type layer 44 is an n-type microcrystalline silicon layer (n-type μc-Si: H) having a thickness of 5 nm to 50 nm doped with an n-type dopant (phosphorus or the like). However, the μc-Si unit 104 is not limited to this, and any i-type microcrystalline silicon layer (i-type μc-Si: H) described below may be used as the power generation layer.

A stacked structure of a reflective metal and a transparent conductive oxide (TCO) is formed on the μc-Si unit 104 as the first back electrode layer 16 and the second back electrode layer 18. As the first back electrode layer 16, a transparent conductive oxide (TCO) such as tin oxide (SnO ₂ ), zinc oxide (ZnO), indium tin oxide (ITO), or the like is used. The TCO can be formed by, for example, sputtering. Moreover, as the 2nd back surface electrode layer 18, metals, such as silver (Ag) and aluminum (Al), can be used. The first back electrode layer 16 and the second back electrode layer 18 are preferably about 1 μm in total. It is preferable that at least one of the first back electrode layer 16 and the second back electrode layer 18 is provided with unevenness for enhancing the light confinement effect.

  Further, the surface of the second back electrode layer 18 is covered with the protective film 22 with the filler 20. The filler 20 and the protective film 22 can be made of a resin material such as EVA or polyimide. This can prevent moisture from entering the power generation layer of the photoelectric conversion device 100.

  The transparent conductive film 12, the a-Si unit 102, the intermediate layer 14, the μc-Si unit 104, the first back electrode layer 16, the second back electrode using a YAG laser (fundamental wave 1064nm, double wave 532nm). A configuration may be adopted in which a plurality of cells are connected in series by separating the layer 18.

<Example>
Examples of the present invention and comparative examples are shown below.

(Comparative Example 1)
As the transparent insulating substrate 10, a glass substrate having a size of 33 cm × 43 cm square and 4 mm was used. On the transparent insulating substrate 10, 600 nm thick SnO ₂ having a concavo-convex shape on the surface was formed as a transparent conductive film 12 by thermal CVD. Thereafter, the transparent conductive film 12 was patterned into strips with a YAG laser. A YAG laser having a wavelength of 1064 nm, an energy density of 13 J / cm ² and a pulse frequency of 3 kHz was used.

Next, the p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were laminated in order. The p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were formed under the film formation conditions shown in Table 1. Thereafter, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the n-type layer of the a-Si unit 102 was exposed to the atmosphere and oxidized. In the following description, diborane (B ₂ H ₆ ) and phosphine (PH ₃ ) are represented by a gas flow rate of 1% concentration on a hydrogen basis.

  Next, the μc-Si unit 104 was formed on the n-type layer of the a-Si unit 102. The p-type layer 40, i-type layer 42, and n-type layer 44 of the μc-Si unit 104 were formed under the film formation conditions shown in Table 2.

Thereafter, a YAG laser was irradiated to a position 50 μm lateral from the patterning position of the transparent conductive film 12, and the a-Si unit 102 and the μc-Si unit 104 were patterned into strips. A YAG laser having an energy density of 0.7 J / cm ² and a pulse frequency of 3 kHz was used.

Next, a ZnO film was formed as the first back electrode layer 16 by sputtering, and an Ag electrode was formed as the second back electrode layer 18 by sputtering. Thereafter, a YAG laser was irradiated to a position 50 μm lateral from the patterning positions of the a-Si unit 102 and the μc-Si unit 104, and the first back electrode layer 16 and the second back electrode layer 18 were patterned into strips. A YAG laser having an energy density of 0.7 J / cm ² and a pulse frequency of 4 kHz was used.

(Comparative Example 2)
A transparent conductive film 12 was formed on the transparent insulating substrate 10 in the same manner as in Comparative Example 1, and patterned into strips with a YAG laser. Next, the p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were laminated in order. The p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were formed under the film formation conditions shown in Table 3. Thereafter, the p-type layer 40 of the μc-Si unit 104 was formed as a single layer under the conditions shown in Table 3 without taking the transparent insulating substrate 10 from the film formation chamber into the atmosphere.

  Next, the transparent insulating substrate 10 was taken out from the film formation chamber into the atmosphere, and the p-type layer 40 of the μc-Si unit 104 formed as a single layer was exposed to the atmosphere and oxidized. Subsequently, the μc-Si unit 104 was formed on the p-type layer 40 of the oxidized μc-Si unit 104. The i-type layer 42 and the n-type layer 44 of the μc-Si unit 104 were formed under the film formation conditions shown in Table 4.

  Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

Example 1
A transparent conductive film 12 was formed on the transparent insulating substrate 10 in the same manner as in Comparative Example 1, and patterned into strips with a YAG laser. Next, the p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were laminated in order. The p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were formed under the film forming conditions shown in Table 5. Thereafter, the first p-type layer 40a and the second p-type layer 40b of the μc-Si unit 104 were formed under the conditions shown in Table 5 without taking the transparent insulating substrate 10 from the film formation chamber into the atmosphere.

  Next, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the second p-type layer 40b of the μc-Si unit 104 was exposed to the atmosphere and oxidized. Subsequently, the μc-Si unit 104 was formed on the oxidized second p-type layer 40b. The i-type layer 42 and the n-type layer 44 of the μc-Si unit 104 were formed under the film formation conditions shown in Table 4 as in Comparative Example 2. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

(Example 2)
Similar to the first embodiment, the transparent conductive film 12, the p-type layer of the a-Si unit 102, the i-type layer and the n-type layer, and the first p-type layer 40a and the first p-type layer 40a of the μc-Si unit 104 are formed on the transparent insulating substrate 10. Two p-type layers 40b were formed. Next, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the second p-type layer 40b of the μc-Si unit 104 was exposed to the atmosphere and oxidized.

  Subsequently, the μc-Si unit 104 was formed on the oxidized second p-type layer 40b. The i-type layer 42 was formed by laminating the buffer layer 42 a and the main power generation layer 42 b of the μc-Si unit 104, and the n-type layer 44 was formed on the i-type layer 42. The i-type layer 42 and the n-type layer 44 were formed under the film formation conditions shown in Table 6. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

(Example 3)
The transparent conductive film 12 and the p-type layer, i-type layer, and n-type layer of the a-Si unit 102 were formed on the transparent insulating substrate 10 in the same manner as in Example 1. Furthermore, as shown in Table 7, the first p-type layer 40a and the second p-type layer 40b of the μc-Si unit 104 were formed. Here, the second p-type layer 40b is an amorphous silicon carbide layer. Next, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the second p-type layer 40b of the μc-Si unit 104 was exposed to the atmosphere and oxidized.

  Subsequently, the μc-Si unit 104 was formed on the oxidized second p-type layer 40b. In the μc-Si unit 104, the i-type layer 42 and the n-type layer 44 were formed under the film formation conditions shown in Table 6 as in Example 2. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

Example 4
The transparent conductive film 12, the p-type layer, the i-type layer and the n-type layer of the a-Si unit 102, and the first p-type layer 40a and the first p-type layer 40a of the μc-Si unit 104 are formed on the transparent insulating substrate 10 as in the third embodiment. Two p-type layers 40b were formed. Next, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the second p-type layer 40b of the μc-Si unit 104 was exposed to the atmosphere and oxidized.

  Subsequently, the μc-Si unit 104 was formed on the oxidized second p-type layer 40b. The buffer layer 42 a, the buffer layer 42 c and the main power generation layer 42 b of the μc-Si unit 104 were stacked to form the i-type layer 42, and the n-type layer 44 was formed on the i-type layer 42. The i-type layer 42 and the n-type layer 44 were formed under the film formation conditions shown in Table 8. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

(Example 5)
The transparent conductive film 12, the p-type layer, the i-type layer and the n-type layer of the a-Si unit 102, and the first p-type layer 40a and the first p-type layer 40a of the μc-Si unit 104 are formed on the transparent insulating substrate 10 as in the third embodiment. Two p-type layers 40b were formed. Next, the transparent insulating substrate 10 was taken out from the film formation chamber to the atmosphere, and the second p-type layer 40b of the μc-Si unit 104 was exposed to the atmosphere and oxidized.

  Subsequently, the μc-Si unit 104 was formed on the oxidized second p-type layer 40b. The μc-Si unit 104 forms the i-type layer 42 by stacking the buffer layer 42a and the main power generation layer 42b on the second p-type layer 40b under the film formation conditions shown in Table 9. An n-type layer 44 was formed. Here, boron, which is a p-type dopant, is added to the buffer layer 42a to form a p-type layer. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

(Example 6)
In Example 3, the film thickness dependency of the second p-type layer 40b was examined and determined as Example 6. In addition to the case where the second p-type layer 40b was not provided, the photoelectric conversion efficiency was measured when the thickness of the second p-type layer 40b was changed from 1 nm to 10 nm.

(Example 7)
In Example 3, the film thickness dependency of the buffer layer 42a was examined and determined as Example 6. In addition to the case where the buffer layer 42a was not provided, the photoelectric conversion efficiency was measured when the thickness of the buffer layer 42a was changed to 300 nm.

(Example 8)
In Example 3, the dependency of the hydrogen (H ₂ ) / silane (SiH ₄ ) dilution ratio upon formation of the buffer layer 42 a was examined and determined as Example 8. The dilution ratio of hydrogen (H ₂ ) / silane (SiH ₄ ) was varied in the range of 50 to 400.

(Comparative Example 3)
A transparent conductive film 12 was formed on the transparent insulating substrate 10 in the same manner as in Comparative Example 1, and patterned into strips with a YAG laser. Next, the p-type layer 40, the i-type layer 42, and the n-type layer 44 of the μc-Si unit 104 were formed under the film forming conditions shown in Table 2 without forming the a-Si unit 102. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

Example 9
A transparent conductive film 12 was formed on the transparent insulating substrate 10 in the same manner as in Comparative Example 1, and patterned into strips with a YAG laser. Next, without forming the a-Si unit 102, the first p-type layer 40a and the second p-type layer 40b are formed under the film-forming conditions shown in Table 7, and the second p-type layer 40b is placed in the atmosphere. After exposure and oxidation, the i-type layer 42 and the n-type layer 44 of the μc-Si unit 104 were formed under the film formation conditions shown in Table 6. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

(Example 10)
A transparent conductive film 12 was formed on the transparent insulating substrate 10 in the same manner as in Comparative Example 1, and patterned into strips with a YAG laser. Next, an a-Si unit 102 was formed as in Comparative Example 1. Then, after taking out once to air | atmosphere, as shown in Table 10, the p-type semiconductor layer of the μc-Si unit 104 was formed. For the p-type layer, a p-type amorphous silicon carbide semiconductor layer was formed after forming a p-type crystalline silicon semiconductor layer. Subsequently, an i-type microcrystalline silicon layer (buffer layer), an i-type microcrystalline silicon layer, and an n-type crystalline silicon layer were formed. Thereafter, similarly to Comparative Example 1, formation and patterning of the first back electrode layer 16 and the second back electrode layer 18 were performed.

  Table 11 shows the results of measuring the open-circuit voltage Voc, the short-circuit current density Jsc, the fill factor FF, and the photoelectric conversion efficiency η for the photoelectric conversion devices of Comparative Examples 1 and 2 and Examples 1 to 5. In Table 11, the measurement result of the comparative example 1 is set to 1, and the measurement result of the comparative example 2 and Examples 1-5 is normalized and shown.

  In Example 1, although the short circuit current density Jsc and the fill factor FF are lower than those of Comparative Examples 1 and 2, the open circuit voltage Voc is increased by 1%, and the effect of inserting the second p-type layer 40b is obtained. It has been. Further, in Example 2, by inserting the buffer layer 42a into the i-type layer 42 of the μc-Si unit 104, in addition to the improvement of the open circuit voltage Voc, the decrease of the fill factor FF is suppressed, and the photoelectric conversion efficiency η is Compared to Comparative Example 1, it was improved by 5%. Further, in Example 3, the open circuit voltage Voc and the short circuit current density Jsc increased compared to Example 2, and the photoelectric conversion efficiency η was improved by 7% compared to Comparative Example 1. Moreover, in Example 4, the short circuit current density Jsc increased compared with Example 3, and the photoelectric conversion efficiency (eta) improved 10% with respect to the comparative example 1. FIG. Moreover, in Example 5, the open circuit voltage Voc and the short circuit current density Jsc increased compared with the comparative example 1, and the photoelectric conversion efficiency (eta) improved 5% with respect to the comparative example 1. FIG.

  In addition, as shown in FIG. 4, the film thickness dependence of the second p-type layer 40b in Example 6 is that the photoelectric conversion efficiency η is 90% or more of the maximum value when the film thickness is in the range of 1 nm to 4.5 nm. Thus, the photoelectric conversion efficiency showed a high value. When the film thickness was larger than 4.5 nm, the series resistance value of the photoelectric conversion device increased and the characteristics deteriorated.

  Further, as shown in FIG. 5, the film thickness dependence of the buffer layer 42a in Example 7 has a maximum photoelectric conversion efficiency η when the film thickness is 30 nm, and a high value in the range of the film thickness from 10 nm to 50 nm. showed that. In addition, in the range where the film thickness is 8 nm or more and 100 nm or less, the photoelectric conversion efficiency η was maintained at 90% or more of the maximum value, and a sufficient characteristic improvement was obtained.

In addition, the dependency of the hydrogen (H ₂ ) / silane (SiH ₄ ) dilution ratio upon formation of the buffer layer 42a in Example 8 is that the photoelectric conversion efficiency η is maximum when the dilution ratio is around 250 times as shown in FIG. It became. Further, when the dilution ratio was 130 times or more, the photoelectric conversion efficiency η was maintained at about 90% or more of the maximum value, and a sufficient characteristic improvement was obtained. On the other hand, if the dilution ratio is greater than 800 times, a sufficient film formation speed cannot be obtained from the relationship between the film thickness of the buffer layer 42a and the production tact time, so the dilution ratio is preferably 800 times or less.

  Table 12 shows the measurement results of the open-circuit voltage Voc, the short-circuit current density Jsc, the fill factor FF, and the photoelectric conversion efficiency η for the photoelectric conversion devices of Comparative Example 3 and Example 9. In Table 11, the measurement result of Comparative Example 3 is set to 1, and the measurement result of Example 9 is normalized and shown.

  In Example 9, the open circuit voltage Voc and the short-circuit current density Jsc increased compared to Comparative Example 3, and the photoelectric conversion efficiency η improved by 6% compared to Comparative Example 3. As described above, the present invention is effective not only in a tandem photoelectric conversion device including the a-Si unit 102 and the μc-Si unit 104 but also in a single photoelectric conversion device including only the μc-Si unit 104. is there.

  In Example 10, the open circuit voltage Voc and the short circuit current density Jsc increased compared to Comparative Example 1, and the photoelectric conversion efficiency η was improved by 3% compared to Comparative Example 1. As described above, after the a-Si unit 102 is formed and exposed to the atmosphere, a p-type crystalline silicon semiconductor layer is formed as a p-type layer of the μc-Si unit 104, and then a p-type amorphous silicon carbide semiconductor layer is formed. Subsequently, the present invention is effective even when an i-type microcrystalline silicon layer (buffer layer) is formed.

  DESCRIPTION OF SYMBOLS 10 Transparent insulating substrate, 12 Transparent electrically conductive film, 14 Intermediate layer, 16 1st back surface electrode layer, 18 2nd back surface electrode layer, 20 Filler, 22 Protective film, 40 p-type layer, 40a 1st p-type layer, 40b Second p-type layer, 42 i-type layer, 42a buffer layer, 42b main power generation layer, 44 n-type layer, 100 photoelectric conversion device, 102 amorphous silicon photoelectric conversion unit (a-Si unit), 104 microcrystalline silicon photoelectric conversion Unit (μc-Si unit).

Claims (5)

A photoelectric conversion device including a photoelectric conversion unit in which a p-type layer containing a p-type dopant, an i-type layer which is a microcrystalline silicon layer serving as a power generation layer, and an n-type layer containing an n-type dopant are stacked.
The p-type layer includes a first p-type layer which is a microcrystalline silicon layer, an amorphous silicon p-type layer and an amorphous silicon carbide p-type disposed between the microcrystalline silicon p-type layer and the i-type layer. A laminated structure of a second p-type layer including at least one of the layers ,
A photoelectric conversion device comprising a buffer layer including a microcrystalline silicon layer having higher crystallinity than the i-type layer between the second p-type layer and the i-type layer . The photoelectric conversion device according to claim 1 ,
The buffer layer includes a stacked structure of an amorphous silicon layer and the microcrystalline silicon layer . The photoelectric conversion device according to claim 1 or 2 ,
A film thickness of the second p-type layer is 1 nm to 4.5 nm. It is a photoelectric conversion device according to any one of claims 1 to 3 ,
The photoelectric conversion device, wherein the microcrystalline silicon layer included in the buffer layer has a thickness of 8 nm to 100 nm. It is a photoelectric conversion device according to any one of claims 1 to 4 ,
A photoelectric conversion device, wherein an amorphous silicon layer serving as a power generation layer is laminated on a light incident side of the i-type layer.

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