WO2011002086A1 - 結晶シリコン系太陽電池およびその製造方法 - Google Patents
結晶シリコン系太陽電池およびその製造方法 Download PDFInfo
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- WO2011002086A1 WO2011002086A1 PCT/JP2010/061343 JP2010061343W WO2011002086A1 WO 2011002086 A1 WO2011002086 A1 WO 2011002086A1 JP 2010061343 W JP2010061343 W JP 2010061343W WO 2011002086 A1 WO2011002086 A1 WO 2011002086A1
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- zinc oxide
- layer
- transparent conductive
- crystalline silicon
- light incident
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a crystalline silicon solar cell having a heterojunction on the surface of a semiconductor substrate.
- Crystalline silicon solar cells using a crystalline silicon substrate have high photoelectric conversion efficiency and have already been widely put into practical use as photovoltaic power generation systems.
- a crystalline silicon solar cell in which an amorphous silicon thin film having a band gap different from that of single crystal silicon is formed on the surface of a crystalline silicon substrate to form a diffusion potential is called a heterojunction solar cell.
- a heterojunction solar cell in which a thin intrinsic (i-type) amorphous silicon layer is interposed between a conductive amorphous silicon thin film for forming a diffusion potential and crystalline silicon is a crystal with the highest conversion efficiency. This is known as one of the forms of silicon-based solar cells.
- the defects existing on the surface of the crystalline silicon substrate are passivated by the thin i-type amorphous silicon layer.
- the i-type amorphous silicon layer is provided, carrier introduction impurities are prevented from diffusing to the crystalline silicon surface when a conductive amorphous silicon thin film is formed (for example, patents). Reference 1).
- the current generated by photoelectric conversion is taken out of the solar cell through the electrode.
- a combination of a transparent conductive layer and a collecting electrode is used as the electrode.
- the transparent conductive layer a layer having an optical thickness (refractive index ⁇ thickness) of about 1 ⁇ 4 of a wavelength of 300 to 1200 nm that can be absorbed by single crystal silicon is preferably used.
- Indium oxide (ITO) is widely used. According to such a configuration, the transparent conductive layer functions as an antireflection layer due to the interference of the interface reflection light of the transparent conductive layer, so that the light capturing efficiency can be increased and the photoelectric conversion efficiency can be improved.
- the collecting electrode Ag paste or the like is used as a material. Since such a collector electrode is opaque, at least the collector electrode on the light incident side is patterned in a line shape by a screen printing method or the like from the viewpoint of expanding the light receiving area of the solar cell. The collector electrode is easily peeled off from the transparent conductive layer, and the peeling of the collector electrode becomes a fatal defect in the operation of the solar cell. For this reason, efforts to improve the adhesion strength between the transparent conductive layer and the collector electrode are currently most vigorously performed (see, for example, Patent Document 2).
- the heterojunction solar cell as described above has high photoelectric conversion efficiency, but has a problem in terms of cost because it uses a silicon single crystal substrate.
- the need to reduce the thickness of the crystalline silicon substrate is increasing because the supply of the crystalline silicon substrate tends to be insufficient.
- an object of the present invention is to provide a heterojunction solar cell in which the warpage of the substrate is suppressed and the photoelectric conversion efficiency is high even when the thickness of the silicon crystal substrate is small.
- the present invention provides a light incident side i-type silicon thin film layer 2, a reverse conductivity type silicon thin film layer 3, a light incident side transparent conductive layer 4, and a collector electrode on the light incident side main surface of the one conductivity type crystalline silicon substrate 1. 5 are formed in this order from the crystalline silicon substrate 1 side, and on the other main surface of the crystalline silicon substrate 1, a back side i-type silicon thin film layer 6, a one-conductivity type silicon thin film layer 7, a back side transparent conductive layer 8,
- the present invention also relates to a crystalline silicon solar cell in which the metal electrode layer 10 is formed in this order from the crystalline silicon substrate 1 side.
- the crystalline silicon substrate 1 has a thickness of 50 ⁇ m to 200 ⁇ m, and the crystalline silicon substrate 1 has a concavo-convex structure at least on the light incident side main surface.
- the light incident side surface of the light incident side transparent conductive layer 4 has an uneven structure, and the height difference H2 of the uneven structure of the light incident side transparent conductive layer 4 is the difference in height of the uneven structure on the light incident surface side of the crystalline silicon substrate 1. Less than H1. Further, the interval L2 of the concavo-convex structure of the light incident side transparent conductive layer 4 is smaller than the interval L2 of the concavo-convex structure on the light incident surface side of the crystalline silicon substrate 1.
- the height difference H2 of the concavo-convex structure of the light incident side transparent conductive layer 4 is preferably 20 nm to 250 nm.
- the height difference H1 of the concavo-convex structure on the light incident surface side of the crystalline silicon substrate 1 is preferably 0.5 ⁇ m to 40 ⁇ m.
- the light incident side transparent conductive layer 4 has a zinc oxide layer having a thickness of 300 nm to 2500 nm.
- the zinc oxide layer contains hexagonal zinc oxide preferentially oriented in the (10-10) plane, (11-20) plane, or (10-11) plane direction, and the lattice constant of the a-axis of hexagonal zinc oxide is 0. It is preferably in the range of 3225 to 0.3246 nm.
- Stress strain parameter S (a ZnO -0.3249) ⁇ d ZnO zinc oxide layer is preferably 0.3nm 2 ⁇ 2.9nm 2.
- the warpage parameter W (a ZnO ⁇ 0.3249) ⁇ d ZnO 2 / d Si of the zinc oxide layer is preferably 0.3 ⁇ 10 ⁇ 5 nm to 2.9 ⁇ 10 ⁇ 5 nm.
- a ZnO is the a-axis lattice constant (unit: nm) of zinc oxide
- d ZnO is the thickness (unit: nm) of the zinc oxide layer
- d Si is the thickness (unit: nm) of the silicon substrate.
- the impurity concentration on the crystalline silicon substrate side of the zinc oxide layer is preferably lower than the impurity concentration on the opposite side of the zinc oxide layer to the crystalline silicon substrate.
- the carrier density of the zinc oxide layer is preferably 3 ⁇ 10 19 cm ⁇ 3 to 2.5 ⁇ 10 20 cm ⁇ 3 .
- this invention relates to the manufacturing method of a crystalline silicon type solar cell.
- the light incident side transparent conductive layer 4 is formed on the surface on the reverse conductivity type silicon-based thin film layer 3 side Forming a light incident side transparent conductive layer; forming a back side transparent conductive layer 8 on the surface on the one-conductivity-type silicon thin film layer 7 side; surface facing the light incident side transparent conductive layer 4 To the collector electrode 5
- a plurality of layers may be formed, but at least the surface of the light incident side transparent conductive layer 4 on the collector electrode 5 side has a zinc oxide layer having a thickness of 300 nm to 2500 nm by a thermal CVD method. Is preferably formed. Further, the temperature for forming the zinc oxide layer by thermal CVD preferably includes a range of 120 ° C. to 240 ° C., and more preferably includes a range of 130 ° C. to 180 ° C. Thus, by forming a zinc oxide layer by a thermal CVD method, a transparent conductive layer having the above-described crystal characteristics and having a fine concavo-convex structure formed on the surface is formed.
- the substrate on which the zinc oxide layer is further formed is 150 ° C. to 240 ° C. It is preferable to include a step of annealing the zinc oxide layer that is heated to a high temperature. From the viewpoint of setting the carrier density of the zinc oxide layer in the above range, the annealing treatment step is preferably performed under reduced pressure, more preferably under vacuum.
- the zinc oxide layer is used for the light incident side transparent conductive layer, stress in the shrinking direction can be applied to the light incident side of the silicon substrate. Therefore, cell warpage can be suppressed by balancing the stress in the shrinkage direction due to the metal electrode layer on the back side of the silicon substrate and the stress in the shrinkage direction due to the zinc oxide layer, despite the small thickness of the silicon substrate. .
- the optical path length of incident light in the crystalline silicon substrate is increased by light scattering, and the fine concavo-convex structure is multiplexed.
- the effect of preventing reflection is obtained by reflection. Therefore, the light utilization efficiency can be improved and high photoelectric conversion characteristics can be realized.
- the surface area of the light incident surface side transparent conductive layer is increased due to the fine concavo-convex structure, the adhesion strength between the transparent conductive layer and the collector electrode is increased, and the collector electrode is unlikely to peel off and has high reliability. A battery is obtained.
- the solar cell of the present invention has the advantage that the cost can be reduced and high mass productivity can be realized because the thickness of the silicon substrate is small. Further, a silicon substrate having a predetermined crystal structure and having a fine concavo-convex structure formed on the surface is used as the transparent conductive layer on the light incident side even though the thickness of the silicon substrate is small. Can achieve photoelectric conversion characteristics equivalent to or better than those of conventional heterojunction solar cells having a thickness of about 300 ⁇ m.
- FIG. 2 is a schematic cross-sectional view in which a light incident side in FIG. 1 is enlarged. It is a figure which shows the measurement result of XRD of a zinc oxide layer. It is a graph which shows the relationship between the lattice constant of the a axis
- the crystalline silicon solar cell of the present invention is i-type on each of the principal surface on the light incident side of the one-conductivity-type crystalline silicon substrate and the principal surface on the opposite non-light incident side (hereinafter also referred to as “back side”).
- a silicon-based thin film layer, a conductive silicon-based thin film layer, a transparent conductive layer, and an electrode are formed.
- FIG. 1 shows an embodiment of the crystalline silicon solar cell 11 of the present invention.
- an n-type crystalline silicon substrate 1 is used as the one-conductivity-type crystalline silicon substrate 1
- the light incident side transparent conductive layer 4 / collector electrode 5 are laminated in this order from the silicon substrate 1 side.
- the light incident side i-type silicon thin film layer 2 / n-type silicon thin film is formed on the light incident side surface of the p-type crystalline silicon substrate 1.
- Layer 3 / light incident side transparent conductive layer 4 / collector electrode 5 are laminated in this order from the silicon substrate 1 side.
- the crystalline silicon substrate 1 will be described.
- the one-conductivity type crystalline silicon substrate 1 any of those showing p-type or n-type conductivity may be used.
- electrons with smaller effective mass and scattering cross section generally have higher mobility, so that it is easy to obtain solar cells with high conversion efficiency.
- the substrate 1 is preferably an n-type single crystal silicon semiconductor substrate.
- the thickness of the crystalline silicon substrate 1 is 200 ⁇ m or less, preferably 170 ⁇ m or less, more preferably 150 ⁇ m or less.
- the thickness of the crystalline silicon substrate 1 is preferably 50 ⁇ m or more, and more preferably 70 ⁇ m or more.
- the thickness of the crystalline silicon substrate is as shown by H0 in FIG. It is calculated by the distance from the straight line connecting the convex side vertices of the concavo-convex structure.
- a concavo-convex structure is formed on at least one main surface (light incident side main surface) of the silicon substrate 1, more preferably on the surfaces of both main surfaces. If the surface is uneven, light incident on the crystalline silicon substrate is scattered, so that the optical path length in the crystalline silicon substrate can be increased.
- a quadrangular pyramid shape is suitable. The quadrangular pyramidal uneven structure can be easily formed on the surface of the crystalline silicon substrate by using, for example, an anisotropic etching technique.
- the anisotropic etching technique uses a characteristic that different etching rates are realized on the (100) plane and the (111) plane of silicon crystal by selecting an etchant (for example, an aqueous potassium hydroxide solution). is there.
- an etchant for example, an aqueous potassium hydroxide solution.
- the size (depth) of the uneven structure of the crystalline silicon substrate generally tends to increase as etching progresses.
- the etching time may be increased.
- the reaction rate may be increased by increasing the etchant concentration or the liquid temperature.
- the size of the concavo-convex structure can be controlled by performing a process such as rubbing to change the surface state.
- the concavo-convex structure of the crystalline silicon substrate 1 is continuous as schematically shown in FIG. This is because the light scattering characteristics tend to be reduced unless the concavo-convex structure has a continuous shape.
- the term “continuous” means that the structure has a substantially flat portion and the convex portions are adjacent to each other.
- the size of the concavo-convex structure on the surface of the crystalline silicon substrate can be characterized by the height difference between the apex and valley of the convex portion.
- the height difference H1 is defined by the distance between the line connecting the vertices T1 and T2 of the convex portions of the adjacent concavo-convex structure and the concave valley V1 between the two vertices.
- the difference in level of the concavo-convex structure on the surface of the crystalline silicon substrate can be determined by, for example, a method of observing the cross-sectional shape of the substrate using a scanning electron microscope (SEM), or the surface shape of the substrate using an atomic force microscope or a laser microscope. It can be specified by measuring.
- the height difference can be determined more easily by specifying the surface shape than the cross-sectional shape. It is important to determine the top of the concavo-convex structure when determining the level difference of the concavo-convex structure of the crystalline silicon substrate, and it is easier and more accurate to find the top of the concavo-convex structure by observing the surface shape. Because it can.
- the height difference H1 is obtained by measuring the surface shape by scanning the surface of the crystalline silicon substrate with an area of about 40 ⁇ 40 ⁇ m 2 with an atomic force microscope (AFM).
- a vertex T1 of the convex portion of the concavo-convex structure is selected at random from the measured planar shape (AFM image), the vertex of the convex portion of one concavo-convex structure adjacent to the vertex T1 is T2, and the concave portion between T1 and T2
- the height difference H1 may be calculated from the distance between the straight line T1-T2 and V1 with the valley of V1 being V1.
- the surface shape at an arbitrary position of the crystalline silicon substrate is measured, and calculating the height difference by the above method is repeated 20 times to obtain the average value of the height of the concavo-convex structure.
- the average value is obtained as the height H1 of the concavo-convex structure.
- the height difference H1 of the concavo-convex structure is preferably in the range of 0.5 ⁇ m to 40 ⁇ m, and more preferably in the range of 1 ⁇ m to 20 ⁇ m. If the height difference on the surface of the crystalline silicon substrate is less than 0.5 ⁇ m, the formation of unevenness may be insufficient, and a flat portion with no unevenness may remain on the surface of the crystalline silicon substrate. On the other hand, if the height difference exceeds 40 ⁇ m, the mechanical strength of the crystalline silicon substrate tends to decrease.
- the optical path length is increased in the wavelength region of 300 to 1200 nm that can be absorbed by the single crystalline silicon due to light scattering on the surface of the crystalline silicon substrate.
- an effect of reducing interface reflection due to effective scattering of light by the concavo-convex structure can be obtained efficiently.
- the interval L1 of the concavo-convex structure of the crystalline silicon substrate can be obtained from the distance between T1 and T2. If there is a distribution in the uneven structure spacing, measure the surface shape of the crystalline silicon substrate at any position and calculate the uneven structure spacing using the above method, as in calculating the height difference of the uneven structure. Is repeated 20 times to obtain an average value of the interval between the concavo-convex structures, and this average value may be set as the interval between the concavo-convex structures.
- i-type silicon thin film layers 2 and 6 and conductive silicon thin film layers 3 and 7 are formed on both main surfaces of the crystalline silicon substrate 1.
- plasma CVD Chemical Vapor Deposition
- conditions for forming the silicon-based thin film generally, a substrate temperature of 100 to 300 ° C., a pressure of 20 to 2600 Pa, and a high frequency power density of 0.003 to 0.5 W / cm 2 are preferably used.
- a source gas used for forming a silicon-based thin film for example, a silicon-containing gas such as SiH 4 or Si 2 H 6 or a mixture of these gases and H 2 is used.
- the i-type silicon thin film layers 2 and 6 which are substantially intrinsic semiconductors are made of, for example, i-type hydrogenated amorphous silicon (a-Si: H) composed of silicon and hydrogen, silicon, hydrogen and oxygen. Consists of i-type hydrogenated amorphous silicon oxide (a-SiO x : H) or i-type hydrogenated amorphous silicon carbide (a-SiC x : H) composed of silicon, hydrogen and carbon can do.
- the i-type silicon thin film layer is preferably i-type hydrogenated amorphous silicon.
- the energy gap can have an effective profile for carrier recovery.
- a p-type silicon thin film layer 3 and an n-type silicon thin film layer 7 are formed on the i-type silicon thin film layers 2 and 6, respectively.
- a dopant gas for forming the p-type layer or the n-type layer for example, B 2 H 6 or PH 3 is preferably used. Since the addition amount of impurities such as P and B may be small, it is preferable to use a mixed gas in which B 2 H 6 or PH 3 is diluted with SiH 4 or H 2 in advance. Further, by adding a gas containing a different element such as CH 4 , CO 2 , NH 3 , GeH 4, etc., silicon can be alloyed and the energy gap of the conductive silicon thin film layer can be changed.
- the p-type silicon-based thin film layer 3 is, for example, p-type hydrogenated amorphous silicon composed of silicon and hydrogen, p-type hydrogenated amorphous silicon oxide composed of silicon, hydrogen, and oxygen, or silicon and hydrogen. And p-type hydrogenated amorphous silicon carbide composed of carbon.
- the p-type silicon thin film layer 3 is preferably a p-type hydrogenated amorphous silicon layer or a p-type oxidized amorphous silicon layer. From the viewpoint of suppressing impurity diffusion and reducing the series resistance component of the solar battery cell, a p-type hydrogenated amorphous silicon layer is preferably used.
- a p-type oxide amorphous silicon layer is preferably used from the viewpoint of reducing optical loss.
- the n-type silicon thin film layer 7 may be composed of a single layer of an n-type amorphous silicon thin film layer or may be composed of a plurality of layers.
- the n-type silicon thin film layer 7 is preferably composed of two layers of an n-type amorphous silicon thin film layer 7a and an n-type microcrystalline silicon thin film layer 7b. That is, when the n-type silicon-based thin film layer 7 is an n-type microcrystalline silicon-based thin film, there is an advantage that a good ohmic junction is formed at the interface with the back-side transparent conductive layer 8.
- an n-type amorphous silicon layer 7a is thinly formed on an i-type hydrogenated amorphous silicon layer 6, and this is used as a base to form an n-type microcrystalline silicon system.
- the thin film layer 7b the power required for film formation can be reduced. Therefore, when the n-type silicon-based thin film layer 7 is composed of two layers, impurity diffusion into the i-type silicon-based thin film layer 6 and film formation damage are reduced.
- n-type amorphous silicon thin film layer 7a an n-type hydrogenated amorphous silicon layer or an n-type amorphous silicon nitride layer is preferably used because good bonding characteristics with an adjacent layer are easily obtained.
- the n-type microcrystalline silicon thin film layer 7b include an n-type microcrystalline silicon layer, an n-type microcrystalline silicon carbide layer, and an n-type microcrystalline silicon oxide layer. From the viewpoint of suppressing generation of defects inside the n-type layer, an n-type microcrystalline silicon layer to which impurities other than the dopant are not positively added is preferably used.
- the effective optical gap can be widened and the refractive index is also reduced. Therefore, optical merit can be obtained.
- oxygen or carbon is added to the n-type microcrystalline silicon-based thin film layer 7b, it is preferable to add it within a range of flow rate ratios (CO 2 / SiH 4 ⁇ 10, CH 4 / SiH 4 ⁇ 3) that do not hinder crystallization. .
- the thicknesses of the i-type silicon thin film layers 2 and 6 and the conductive silicon thin film layers 3 and 7 are each preferably in the range of 3 to 20 nm. Within this range, the thickness of each layer is much smaller than the dimension ( ⁇ m order) of the concavo-convex structure of the crystalline silicon substrate 1, and therefore the p-type silicon thin film layer 3 and the n-type silicon thin film layer 7.
- the surface shape of is substantially the same as the surface shape of the crystalline silicon substrate as schematically shown in FIGS.
- a light incident side transparent conductive layer 4 is formed on the p-type silicon thin film layer 3, and a back side transparent conductive layer 8 is formed on the n-type silicon thin film layer 7.
- the configuration of these transparent conductive layers, the film forming method, etc. will be described in detail later.
- a collecting electrode 5 as an electrode on the light incident side is formed. Since an opaque material such as an Ag paste is generally used for the collector electrode, if the area of the collector electrode is large, the light receiving area of the photoelectric conversion device is reduced, resulting in a disadvantage that the output current is reduced. Therefore, the collector electrode 5 is preferably patterned. Examples of the patterning method include a method of forming a collecting electrode by an inkjet method, a screen printing method, a conductive wire bonding method, a spray method, or the like. From the viewpoint of productivity, a screen printing method is preferably employed.
- a process for forming a patterned collector electrode by applying a conductive paste composed of metal particles (Ag particles, etc.), a resin binder, and a solvent to a desired pattern using a printing screen and drying.
- a conductive paste composed of metal particles (Ag particles, etc.), a resin binder, and a solvent to a desired pattern using a printing screen and drying.
- the area of the collecting electrode 5 is small.
- the shape and line width of the collector electrode may be determined in consideration of the balance between the two.
- a metal electrode layer 10 is formed on the back side transparent conductive layer 8.
- a highly reflective material such as Ag or Al for the metal electrode layer 10
- the metal electrode layer 10 can be formed by the same method as that of the collector electrode 5 except that the metal electrode layer 10 is formed on almost the entire surface of the transparent conductive layer 8.
- a reflective layer (not shown) may be formed between the back side transparent conductive layer 8 and the metal electrode layer 10.
- a metal layer such as Ag or Al is preferably used as the reflective layer.
- a silicon substrate 101 having a thickness of about 300 ⁇ m is used, and i-type silicon-based thin film layers 102 and 106, conductive silicon-based thin films are formed on both main surfaces, respectively.
- the reflective metal electrode layer 10 on the back surface, reflect the light that has not been absorbed by the silicon substrate 1, and enter the silicon substrate 1 again.
- the collector 5 on the light incident side is patterned, whereas in the configuration having the metal electrode layer 10 on the back surface formed on almost the entire surface of the cell, the light incident side of the silicon substrate 1 and Since the laminated structure is different between the back side and the back side, there is a problem that the cell is warped.
- solar cell manufacturing processes such as formation of collector electrodes and measurement of conversion efficiency are performed with the solar cells fixed on a processing table.
- a method in which the solar battery cell is adsorbed to the processing table by exhausting from a hole formed in the processing table is widely used.
- adsorption method in which the solar battery cell is adsorbed to the processing table by exhausting from a hole formed in the processing table is widely used.
- the present inventors produced a cell in which a silicon substrate 1 having a thickness of about 150 ⁇ m was used, an ITO layer having a thickness of about 100 nm was sputtered as a light incident side transparent conductive layer, and a collector electrode was formed thereon.
- the warp with the light incident surface side convex was generated.
- Such cell warpage is presumed to be caused by the difference in the laminated structure between the light incident side and the back side of the silicon substrate. That is, the stress generated in each layer constituting the solar cell varies mainly depending on the material constant such as Young's modulus, the internal strain of the material, and the film thickness of the layer, but is laminated on the light incident side and the back side of the silicon substrate 1.
- the configurations are different, there is a difference in stress between the front and back surfaces of the silicon substrate, and it is considered that warpage is caused by the stress difference.
- the thickness of the silicon substrate 1 is as small as 200 ⁇ m or less, the bending rigidity of the silicon substrate is small, and thus warp tends to occur.
- the Jsc is remarkably lowered in addition to the warpage.
- the silicon single crystal has a small extinction coefficient with respect to light having a wavelength longer than 850 nm (infrared light). Therefore, when the thickness of the crystalline silicon substrate of the silicon single crystal is 200 ⁇ m or less, particularly 150 ⁇ m or less, silicon It is presumed that light on the long wavelength side cannot be completely absorbed in the substrate, and reflected light from the metal electrode layer on the back surface is emitted again from the light incident side of the cell.
- the light incident side transparent conductive layer disposed on the light incident side has a predetermined configuration, so that it is possible to prevent the cell from warping.
- the possibility of suppressing the warpage of the cell by the configuration of the light incident side transparent conductive layer first, an explanation will be given of the estimation principle that the cell warps when the thickness of the silicon crystal substrate is small.
- the stress caused by these layers examines the warpage of the solar cell. In many cases, it is not necessary to take this into consideration.
- the collector electrode and the back surface metal electrode are formed by applying a paste material, drying and solidifying the paste material, so that stress in the shrinking direction is applied to the silicon substrate.
- these layers are formed to a thickness of about 10 to 80 ⁇ m, which is much larger than that of a silicon-based thin film. Therefore, when they are formed on a substrate, they tend to warp in the direction of lifting the cell periphery. .
- the shrinking direction on the back side of the silicon substrate is reduced. It is considered that the stress becomes relatively larger than the stress in the contraction direction on the light incident surface side, and the cell tends to bend convexly on the light incident surface side.
- metal oxides such as tin oxide, zinc oxide, indium tin oxide (ITO), indium-titanium oxide, CVD, sputtering
- ITO indium tin oxide
- CVD indium-titanium oxide
- sputtering A film formed by a method such as vapor deposition is used.
- an ITO layer having a thickness of about 100 nm formed by sputtering is widely used. in use. In such a configuration, since the difference in stress in the contraction direction between the front and back sides of the silicon substrate is not relaxed, the cell is likely to warp when a silicon substrate having a small thickness is used.
- the light incident side transparent conductive layer 4 which is a light incident side transparent conductive layer contains hexagonal zinc oxide having a predetermined orientation characteristic, and has an uneven structure on the surface.
- a zinc layer is used.
- the light incident side transparent conductive layer has a zinc oxide layer.
- the zinc oxide layer in the transparent conductive layer 4 contains hexagonal zinc oxide preferentially oriented in the (10-10) plane, (11-20) plane, or (10-11) plane direction. Furthermore, by setting the lattice constant of zinc oxide in the a-axis direction ((11-20) plane direction) within a predetermined range, it is possible to reduce cell warpage.
- FIG. 3 is an X-ray diffraction (XRD) pattern of a zinc oxide film having a hexagonal crystal structure formed by a CVD method.
- XRD X-ray diffraction
- the peaks near 2 ⁇ 31.5 °, 34.5 °, 36.5 °, and 57.0 ° are respectively from the (10-10), (0002), (10-11), and (11-20) planes. It is a diffraction peak.
- the diffraction intensity from the (11-20) plane is higher than the diffraction intensity from other diffraction planes, it is preferentially oriented in the (11-20) plane direction.
- the diffraction intensity from the (10-11) plane is higher than the diffraction intensity from the other diffraction planes
- the diffraction intensity from the (10-10) plane is higher than the diffraction intensity from the other diffraction planes.
- the orientation is preferentially oriented in the (10-11) ridge direction and (10-11) ridge direction, respectively.
- crystal orientation of zinc oxide When evaluating the crystal orientation of zinc oxide, if a zinc oxide layer formed on a silicon substrate having a concavo-convex structure is used, the diffraction peak of Si and the diffraction peak of zinc oxide may overlap, It is preferable to measure by adjusting the tilt angle of the substrate so that the diffraction peaks do not overlap. Further, as a simple method, crystal orientation may be evaluated by forming zinc oxide on a glass substrate under the same conditions as those for forming a film on a silicon substrate and measuring an X-ray diffraction pattern.
- Equation 1 ⁇ / sin ( ⁇ a ) (Formula 1)
- the a-axis lattice constant of the zinc oxide single crystal is 0.3249 nm, it can be said that shrinkage strain is generated in the zinc oxide layer when the a-axis lattice constant is smaller than 0.3249 nm.
- the present inventors apply stress in the shrinking direction to the light incident side transparent conductive layer 4 disposed on the light incident side of the silicon substrate 1, thereby causing the metal electrode layer 10 disposed on the back surface side of the silicon substrate 1. The idea of canceling the stress in the shrinking direction and suppressing the warpage of the cell was obtained.
- the film thickness is varied under various film formation conditions by a thermal CVD method on a silicon substrate having a thickness of 150 ⁇ m and a 125 mm square with concavo-convex structures formed on both main surfaces.
- a 1300 nm zinc oxide layer was formed, and the relationship between the lattice constant of the a axis and the amount of warpage of the substrate was evaluated. The result is shown in FIG. In FIG. 4, when the side on which the zinc oxide layer is formed warps in a concave shape, the sign of the amount of warpage is positive (+).
- the lattice constant of the a-axis of zinc oxide is set to less than 0.3249 nm, a contraction stress is generated in the light incident side transparent conductive layer, and this contraction stress is balanced with the contraction stress by the metal electrode layer 10, thereby It can be seen that warpage can be suppressed.
- the shrinkage stress due to the zinc oxide layer is preferably adjusted to balance with the shrinkage stress due to the metal electrode layer. Although it is difficult to directly evaluate the shrinkage stress due to the metal electrode layer itself, for example, the warpage when a metal electrode layer is formed on a silicon substrate and the amount of warpage is evaluated, and a zinc oxide layer is formed on the silicon substrate. The amount and the amount of warpage when the metal electrode layer is formed may be approximately the same.
- the amount of warpage may vary depending on the thickness and size of the silicon substrate. Regardless of the thickness and size of the silicon substrate, the amount of warpage when the zinc oxide layer is formed on the silicon substrate is about 0.1 mm to 1 mm. Thus, it is preferable to adjust the a-axis lattice constant of zinc oxide. If the amount of warpage when the zinc oxide layer is formed is excessively small, the shrinkage stress due to the zinc oxide layer is not sufficient to cancel the shrinkage stress due to the metal electrode layer 10, and the cell is warped on the light incident surface side convexity. There is a tendency to.
- the lattice constant of the a-axis of the zinc oxide layer is preferably in the range of 0.3225 nm to 0.3246 nm, and in the range of 0.3230 nm to 0.3240 nm. More preferably.
- the solar cell can be prevented from warping if the lattice constant of the a-axis of zinc oxide is in the above range. From the viewpoint of suppressing warpage more strictly, it is preferable to control the a-axis lattice constant in consideration of the thickness of the zinc oxide layer. That is, as will be described later, the thickness of the zinc oxide layer is preferably 300 to 2500 nm. If the thickness is within this range, the shrinkage stress caused by the zinc oxide layer is caused by distortion of the crystal structure, and zinc oxide. It is approximately proportional to the layer thickness d ZnO .
- the stress strain parameter S is preferably 0.3 nm 2 ⁇ 2.9 nm 2, more preferably from 0.5nm 2 ⁇ 2.6nm 2, 1 More preferably, the thickness is from 0.0 nm 2 to 2.0 nm 2 .
- the stress strain parameter S is smaller than the above range, the shrinkage stress due to the zinc oxide layer may not be sufficient to cancel the shrinkage stress due to the metal electrode layer 10.
- the stress strain parameter S is larger than the above range, the shrinkage stress due to the zinc oxide layer is large, so that the amount of warpage of the solar battery cell until the metal electrode layer 10 is formed tends to increase. Even in the cell after the metal electrode layer 10 is formed, the side on which the zinc oxide layer is formed may warp greatly in a concave shape.
- the warpage amount parameter W is 0.3 ⁇ 10 ⁇ . 5 nm to 2.9 ⁇ 10 ⁇ 5 nm is preferable, 0.5 ⁇ 10 ⁇ 5 nm to 2.6 ⁇ 10 ⁇ 5 nm is more preferable, and 1.0 ⁇ 10 ⁇ 5 nm to More preferably, it is 2.0 ⁇ 10 ⁇ 5 nm.
- the zinc oxide layer reflects the profile of the concavo-convex structure of the crystalline silicon substrate 1 and has a fine concavo-convex structure on the outermost surface thereof, that is, the surface on the collector electrode 5 side, having a smaller height difference than the concavo-convex structure of the silicon substrate 1. It is preferable to have. As will be described later, zinc oxide is a suitable material for forming such a fine concavo-convex structure.
- a zinc oxide layer having a controlled crystal structure is used from the viewpoint of suppressing cell warpage.
- the thickness of the zinc oxide layer it is necessary to increase the thickness of the zinc oxide layer to, for example, 300 nm or more.
- the optical thickness of the transparent conductive layer exceeds the range that can effectively function as an antireflection layer. There is a concern that the amount of light incident on the light source decreases.
- the formation of a fine concavo-convex structure on the surface of the light incident side transparent conductive layer 4 increases the scattering of incident light. That is, since external light (sunlight) is scattered at each of the air / light incident side transparent conductive layer 4 interface and the light incident side transparent conductive layer 4 / reverse conductivity type (p-type) silicon-based thin film layer 3 interface, The incident angle of light into the crystalline silicon substrate becomes larger than when a transparent conductive layer having no fine uneven structure is used, and the optical path length is increased. Furthermore, since multiple reflection occurs due to a fine uneven structure on the surface of the light incident side transparent conductive layer 4, an antireflection effect is obtained.
- the light absorption loss in the transparent conductive layer is considered to be large as compared with the case where an ITO layer having a thickness of about 100 nm is formed as the light incident side transparent conductive layer.
- a solar battery cell having high photoelectric conversion characteristics can be obtained.
- the surface area of the transparent conductive layer is increased by forming a fine concavo-convex structure, and the effect that the adhesion between the transparent conductive layer 4 and the collector electrode 5 is enhanced is also obtained.
- the concavo-convex structure on the surface of the zinc oxide layer that is, the size of the concavo-convex structure on the light incident side surface of the light incident side transparent conductive layer 4 can be characterized by the difference in height as in the concavo-convex structure of the crystalline silicon substrate.
- the height difference H2 can be determined by the distance between the straight line connecting the vertices T3 and T4 of the convex portions of the adjacent concavo-convex structure and the valley V2 between the vertices.
- the height difference H2 of the light incident side transparent conductive layer can be measured by the same method as described above as the method of measuring the height difference H1 of the uneven structure of the crystalline silicon substrate.
- the height difference H2 of the concavo-convex structure of the transparent conductive layer is preferably 20 nm to 250 nm, and more preferably 50 nm to 200 nm. If the thickness of the zinc oxide layer is within the above range, in addition to the increase in optical path length due to light scattering, interface reflection at the light incident side interface of the transparent conductive layer, that is, the interface between the zinc oxide layer and air is reduced. The above effect is efficiently obtained, and the photoelectric conversion characteristics are improved. If the height difference H2 is small, the light scattering effect in the wavelength region of 300 to 1200 nm that can be absorbed by single crystal silicon and the antireflection effect at the air interface tend not to be sufficiently obtained.
- the interval L2 of the concavo-convex structure on the light incident side surface of the light incident side transparent conductive layer 4 is preferably smaller than the interval L1 of the concavo-convex structure of the crystalline silicon substrate 1.
- the interval L2 of the concavo-convex structure in the transparent conductive layer can be obtained from the distance between the vertices T3 and T4. If there is a distribution in the uneven structure, measure the surface shape at any position on the surface of the transparent conductive layer in the same manner as the calculation of the difference in height of the uneven structure, and calculate the uneven structure by the above method.
- an average value of the interval of the concavo-convex structure is obtained, and this may be set as the interval L2 of the concavo-convex structure.
- the interval L2 of the concavo-convex structure is smaller than L1
- a minute concavo-convex structure is formed more densely on the surface of the light incident side transparent conductive layer 4. Therefore, the surface area of the transparent conductive layer 4 is increased, and the adhesion strength between the collector electrode and the transparent conductive layer is increased.
- the thickness d ZnO of the zinc oxide layer is preferably 300 nm to 2500 nm, more preferably 700 nm to 2100 nm, and further preferably 1000 nm to 1500 nm.
- the height difference H2 of the uneven structure tends to be small, and when the thickness of the zinc oxide layer is large, the height difference H2 tends to be large.
- the height difference H2 can be adjusted to a preferable range.
- the crystal structure is controlled and the fine uneven structure is formed on the surface is a characteristic unique to zinc oxide. That is, in general, tin oxide, ITO, indium-titanium oxide, and the like are used as the transparent conductive layer in addition to zinc oxide. When these metal oxide layers are formed, zinc oxide is used.
- a fine concavo-convex structure is not formed as in the case of using, but only a concavo-convex structure reflecting the profile of the concavo-convex structure of the underlayer is formed. When the thickness of these metal oxide layers is increased, the uneven profile of the underlayer tends to be relaxed.
- the solar cell of the present invention can realize photoelectric conversion characteristics equivalent to or higher than those of a conventional heterojunction solar cell in which a silicon substrate having a thickness of about 300 ⁇ m is used.
- the preferential orientation direction of the zinc oxide layer, the lattice constant of the a axis, and the shape of the concavo-convex structure can be controlled by the film forming conditions of the zinc oxide layer.
- the zinc oxide layer having the predetermined characteristics is preferably formed by a thermal CVD method. Formation of the zinc oxide layer by the thermal CVD method is performed by supplying organic zinc and an oxidizing agent as a main agent gas, a doping gas, and a diluting gas in a heated / depressurized atmosphere.
- organic zinc diethyl zinc (DEZ), dimethyl zinc or the like
- DEZ is preferable because of its good reactivity with an oxidizing agent and easy procurement of raw materials.
- a gas He, Ar, Xe, Kr, Rn
- nitrogen, hydrogen, or the like can be used, but it is preferable to use hydrogen that has high thermal conductivity and excellent thermal uniformity in the substrate.
- B 2 H 6), alkyl aluminum, And the like may be used Rukirugariumu, it is preferable to use a good diborane doping effect.
- the doping gas is preferably fed diluted with dilution gas.
- the material gas By reacting these material gases on the heated substrate surface, for example, under a reduced pressure of 5 to 100 Pa, preferably 5 to 40 Pa, and further adhering to the substrate surface, the material gas has a predetermined crystal structure and has a surface A zinc oxide layer having a fine concavo-convex structure is formed.
- the substrate refers to a silicon substrate on which a silicon-based thin film is formed.
- the substrate temperature (film formation temperature) at the time of forming the zinc oxide layer may not be constant, and the film formation may be performed under the condition that the film formation temperature includes a range of 120 ° C. or higher and 240 ° C. or lower.
- the film When the film is formed at a temperature lower than the substrate temperature of 120 ° C., zinc oxide preferentially oriented in the (0002) plane direction tends to be formed, and the height difference H1 of the concavo-convex structure tends to be small. Therefore, if the substrate temperature is excessively low, the light scattering characteristics by the transparent conductive layer 4 and the adhesion between the transparent conductive layer and the collector electrode may be insufficient. Further, if the film forming temperature is excessively low, the film forming speed is remarkably reduced, which is uneconomical.
- the film forming temperature of a zinc oxide layer is 240 degrees C or less.
- the substrate temperature is set to 130 ° C. or higher and 180 ° C. or lower, a low-resistance zinc oxide layer having more excellent translucency and light scattering characteristics can be formed. More preferably, the range of 130 to 180 ° C. is included.
- the preferential orientation direction of the zinc oxide layer mainly changes depending on the substrate temperature during film formation.
- the substrate temperature is approximately 120 ° C. or higher and 210 ° C. or lower
- hexagonal zinc oxide preferentially oriented in the (10-10) plane direction is obtained at the initial stage of film formation, and the (11-20) plane as the film formation proceeds.
- hexagonal zinc oxide preferentially oriented in the direction is obtained. Therefore, when the film thickness of the zinc oxide layer is small in the above temperature range, the zinc oxide layer is preferentially oriented in the (10-10) plane direction, and as the film thickness of the zinc oxide layer increases (11 -20) There is a tendency to obtain a zinc oxide layer preferentially oriented in the plane direction.
- hexagonal zinc oxide preferentially oriented in the (10-11) plane direction is easily obtained.
- the lattice constant a ZnO of the zinc oxide layer a-axis can also be controlled by the substrate temperature during film formation.
- a ZnO tends to decrease
- a ZnO tends to increase. Therefore, in order to increase the stress strain parameter S, the substrate temperature may be increased, and in order to decrease the stress strain parameter S, the substrate temperature may be decreased.
- the zinc oxide layer a-axis lattice constant a ZnO can also be adjusted by forming a zinc oxide layer and then subjecting it to an annealing treatment by heating.
- the annealing temperature can be set as appropriate, it is easy to obtain the effect of annealing if annealing is preferably performed at a temperature 30 to 100 ° C. higher than the film forming temperature.
- a zinc oxide layer is formed at a substrate temperature of 120 ° C., it is preferable to perform annealing at a temperature of 150 ° C. or higher.
- the higher the annealing temperature the larger the a-axis lattice constant a ZnO and the smaller the stress strain parameter S.
- Annealing treatment is likely to cause a decrease in carrier density when carried out in the air, so it is preferably carried out under a reduced pressure of 100 Pa or less, and more preferably under a vacuum of 10 Pa or less.
- the annealing temperature is excessively high, it may cause a decrease in the carrier density of zinc oxide, and may also cause deterioration of the i-type silicon thin film layer and the conductive silicon thin film layer. Is preferably carried out at 240 ° C. or lower.
- the height difference H2 and the interval L2 of the concavo-convex structure on the surface of the zinc oxide layer can be controlled by the substrate temperature during film formation and the thickness of the zinc oxide layer.
- the substrate temperature is increased, both the height difference H2 of the unevenness and the interval L2 tend to decrease, and when the substrate temperature is decreased, both H2 and L2 tend to decrease.
- the thickness d ZnO of the zinc oxide layer is increased, the crystal growth of zinc oxide proceeds, and therefore H2 tends to increase.
- the amount of dopant gas (for example, B 2 H 6 gas) introduced during the formation of the zinc oxide layer depends on the film forming conditions. It is determined.
- the introduction amount of the dopant gas is preferably adjusted so that the carrier density is 3 ⁇ 10 19 cm ⁇ 3 to 2.5 ⁇ 10 20 cm ⁇ 3 .
- the carrier density is less than 3 ⁇ 10 19 cm ⁇ 3 , the resistance of the zinc oxide layer may be too high, and when it exceeds 2.5 ⁇ 10 20 cm ⁇ 3 , the transmittance of the infrared region is reduced, so that a short circuit of the solar cell is caused.
- the current density may decrease.
- the carrier density may be obtained by a Hall measurement method.
- a zinc oxide layer is formed by a thermal CVD method
- a dopant gas at the initial stage of the formation of the zinc oxide layer. It is preferable to reduce it. That is, it is desirable to form a film so that the doped impurity concentration on the side of the crystalline silicon substrate of the zinc oxide layer is lower than the doped impurity concentration on the side opposite to the crystalline silicon substrate.
- the silicon substrate side of the zinc oxide layer and the side opposite to the crystalline silicon substrate are respectively the most conductive silicon-based thin films when the cross section of the zinc oxide layer is divided into 1/3 each in the film thickness direction. The portion closest to the layer 3 side and the portion closest to the collector electrode 5 side are indicated.
- the doped impurity concentration on the conductive silicon-based thin film layer side of the zinc oxide layer and the doped impurity concentration on the side opposite to the silicon substrate may not be uniform in each part (region of 1/3 of the thickness).
- a profile may be provided in which the impurity concentration gradually changes by setting the amount of impurity addition at the interface with the silicon-based thin film layer to zero and increasing the amount of dopant gas introduced with the time of film formation. Further, a profile having a maximum point of impurity concentration can be provided inside the portion of the zinc oxide layer opposite to the crystalline silicon substrate.
- the light incident side transparent conductive layer 4 may be composed of a single layer of the zinc oxide layer as described above, or may be composed of a plurality of layers. When the light incident side transparent conductive layer 4 is composed of a plurality of layers, it is excellent in transparency and conductivity between the zinc oxide layer and the conductive silicon thin film layer 3 or on the light incident side surface of the zinc oxide layer.
- a metal oxide layer is preferably used. As such a metal oxide, for example, a metal oxide such as tin oxide, indium tin oxide (ITO), or indium-titanium oxide, or a dopant such as In or Si that tends to have a dense structure is included.
- a zinc oxide layer or the like is used.
- the light incident side transparent conductive layer 4 is preferably composed of a single layer of a zinc oxide layer.
- a zinc oxide layer having a concavo-convex structure on the surface can be used as in the light incident side transparent conductive layer 4, but a reflective layer or metal electrode is formed on the back side of the back side transparent conductive layer 8.
- the back surface side transparent conductive layer 8 does not need to have a fine surface uneven structure like the light incident side transparent conductive layer 4.
- a metal oxide such as tin oxide, zinc oxide, indium tin oxide (ITO), indium-titanium oxide is formed by a method such as CVD, sputtering, or vapor deposition. Used.
- the thickness of the back side transparent conductive layer 8 is preferably 60 to 120 nm, and more preferably 80 to 110 nm.
- the back side transparent conductive layer 8 may be a single layer or may be composed of a plurality of layers.
- the layers formed on the opposite side of the crystalline silicon substrate 1 and the transparent conductive layer 4 are electrically short-circuited, and the solar cell characteristics May decrease.
- the material of the transparent conductive layer adhering to the side surface of the silicon substrate may be removed by a chemical method such as etching, or may be removed by a physical method such as polishing.
- the collector electrode 5 is formed on the light incident side transparent conductive layer 4, and the metal electrode layer 10 is formed on the back side transparent conductive layer 8.
- the cell can also be annealed to solidify the conductive paste used for the collector electrode 5 and the metal electrode layer 10.
- the annealing temperature is preferably around 150 ° C., for example. If the annealing temperature is too high, the diffusion of dopant from the conductive silicon thin film layer to the intrinsic silicon thin film layer, the formation of impurity levels due to the diffusion of different elements from the transparent conductive layer to the silicon thin film layer, or amorphous
- the solar cell characteristics may deteriorate due to the formation of defect levels in the silicon-based thin film layer.
- the cell annealing step may also serve as annealing of the zinc oxide layer of the light incident side transparent conductive layer 4. That is, the cell annealing and the zinc oxide layer annealing can be performed simultaneously by heating the cell at a temperature at which the zinc oxide layer can be annealed and at which the above-described problems are unlikely to occur.
- the crystalline silicon solar cell 11 (solar cell) formed in this way is sealed with two base materials 13 and 14 via a filler 12 to be modularized. It is preferable.
- a glass plate, a plastic film, or the like is used as the base materials 13 and 14.
- the EVA resin 12 is used as the filler, and the PET film 14 as the protective film base material is laminated on the glass plate 13, thereby sealing the solar battery cell.
- the solar battery cell 11 is connected to an external circuit (load) through the light incident side collector electrode 5 and the metal electrode layer 10.
- n-type crystalline silicon substrate As the crystalline silicon substrate 1.
- n is used instead of the p-type silicon thin film layer 3.
- a p-type silicon-based thin film layer is formed instead of the n-type silicon-based thin film layer 7, a solar cell can be formed in the same manner as when an n-type crystalline silicon substrate is used. .
- Example 1 As Example 1, a crystalline silicon solar cell shown in the schematic cross-sectional view of FIG. 1 according to the present invention was prepared.
- the crystalline silicon solar cell of this example is a heterojunction solar cell, and the n-type crystalline silicon substrate 1 has a concavo-convex structure on both sides.
- An i-type amorphous silicon layer 2 / p-type amorphous silicon layer 3 / zinc oxide layer 4 is formed on the light incident surface of the n-type crystalline silicon substrate 1.
- a collector electrode 5 is formed on the zinc oxide layer 4.
- an i-type amorphous silicon layer 6 / n-type amorphous silicon layer 7a / n-type microcrystalline silicon layer 7b / indium oxide (ITO) layer 8 is formed on the back side of the n-type crystalline silicon substrate 1. ing. An Ag metal electrode layer 10 is formed on the ITO layer 8.
- the crystalline silicon solar cell of Example 1 was manufactured as follows.
- n-type crystalline silicon substrate having an incident plane of (100) and a thickness of 100 ⁇ m is immersed in a 2% by weight HF aqueous solution for 3 minutes to remove the silicon oxide film on the surface and rinse with ultrapure water. I went twice.
- the silicon substrate was immersed in a 5/15 wt% KOH / isopropyl alcohol aqueous solution maintained at 70 ° C. for 15 minutes, and the surface of the n-type crystalline silicon substrate was etched to form an uneven structure. Thereafter, rinsing with ultrapure water was performed twice, followed by drying with warm air.
- FIG. 6A One of the atomic force microscope images of the silicon substrate surface is shown in FIG. 6A.
- a pyramidal concavo-convex structure was continuously formed on the surface of the silicon substrate.
- the apex T1, T2 and valley V1 are selected from FIG. 6A, and the height difference H1 of the concavo-convex structure of the crystalline silicon substrate is based on the cross-sectional view (FIG. 6B) along the straight line (white line in FIG. 6A) passing through T1, T2.
- the interval L1 between the concavo-convex structures of the crystalline silicon substrate was 12 ⁇ m.
- the etched n-type crystalline silicon substrate was introduced into a CVD apparatus, and an i-type amorphous silicon layer 2 having a thickness of 3 nm was formed on one main surface (light incident side) of the silicon substrate.
- the film thickness of the formed silicon thin film was calculated by forming a silicon thin film on a glass substrate under the same conditions, calculating the film forming speed from the film thickness measured by spectroscopic ellipsometry, It is calculated from the product of the speed and the film formation time on the assumption that the film is formed on the silicon substrate at the same film formation speed as that on the glass substrate.
- the film forming conditions for the i-type amorphous silicon layer were a substrate temperature of 170 ° C., a pressure of 120 Pa, a SiH 4 / H 2 flow rate ratio of 3/10, and an input power density of 0.011 W / cm ⁇ 2 .
- a p-type amorphous silicon layer 3 having a thickness of 4 nm was formed on the i-type amorphous silicon layer.
- the deposition conditions for the p-type amorphous silicon layer were a substrate temperature of 170 ° C., a pressure of 60 Pa, a SiH 4 / B 2 H 6 flow rate ratio of 1/3, and an input power density of 0.01 W / cm ⁇ 2 .
- the B 2 H 6 flow rate in the present example represents the flow rate of the gas diluted with H 2 to a B 2 H 6 concentration of 5000 ppm. The same applies to the B 2 H 6 flow rates in the following examples and comparative examples.
- an i-type amorphous silicon layer 6 having a film thickness of 6 nm was formed on the opposite main surface (back surface side) of the silicon substrate.
- the film forming conditions for the i-type amorphous silicon layer were a substrate temperature of 170 ° C., a pressure of 120 Pa, a SiH 4 / H 2 flow rate ratio of 3/10, and an input power density of 0.011 W / cm ⁇ 2 .
- An n-type amorphous silicon layer 7a was formed on the i-type amorphous silicon layer 6 to a thickness of 4 nm.
- the film forming conditions for the n-type amorphous silicon layer were a substrate temperature of 170 ° C., a pressure of 60 Pa, a SiH 4 / PH 3 flow rate ratio of 1/2, and an input power density of 0.01 W / cm ⁇ 2 .
- An n-type microcrystalline silicon layer 7b was formed with a film thickness of 6 nm on the n-type amorphous silicon layer 7a.
- the deposition conditions for the n-type microcrystalline silicon layer are as follows: the substrate temperature is 170 ° C., the pressure is 800 Pa, the SiH 4 / PH 3 / H 2 flow rate ratio is 1/5/180, and the input power density is 0.08 W / cm ⁇ 2 . there were.
- the PH 3 flow rate in this example represents the flow rate of the gas diluted with H 2 to a PH 3 concentration of 5000 ppm. The same applies to the PH 3 flow rates in the following examples and comparative examples.
- the crystalline silicon substrate on which these layers were formed was introduced into a thermal CVD apparatus, and a zinc oxide layer was formed as a transparent conductive layer 4 on the p-type amorphous silicon layer 3 by thermal CVD.
- a material gas was introduced to form a zinc oxide layer.
- the material gas diethyl zinc, water, H 2 , and B 2 H 6 gas were introduced so as to have a flow rate ratio of 1/2/20/10.
- the B 2 H 6 gas a gas diluted with H 2 to a B 2 H 6 concentration of 5000 ppm was used.
- the film forming pressure was adjusted to 10 Pa using a pressure regulating valve.
- the film formation time was 22 minutes.
- the film thickness of the zinc oxide layer obtained from the product of the film forming speed and the film forming time was 1300 nm.
- the film formation speed of the zinc oxide layer is prepared in advance by preparing a sample in which a zinc oxide layer is formed on a flat silicon substrate for a predetermined time, and measuring the film thickness by observing the cross-sectional shape of this sample with an SEM, Calculated by film thickness / film formation time.
- the surface shape of the transparent conductive layer 4 was observed with an atomic force microscope with a size of 5 ⁇ 5 ⁇ m 2 .
- One of the atomic force microscope images of the light incident side transparent conductive layer surface is shown in FIG. 7A.
- a fine concavo-convex structure was continuously formed on the surface of the transparent conductive layer.
- the calculated value was 180 nm.
- the interval L2 of the concavo-convex structure of the transparent conductive layer 4 was 0.6 ⁇ m, which was smaller than the interval L1 of the concavo-convex structure of the crystalline silicon substrate.
- FIG. 8 shows the result of observing the cross section of the silicon substrate on which the transparent conductive layer was formed, with a scanning electron microscope.
- the film thickness of the transparent conductive layer 4 was measured from the cross-sectional view, it was 1300 nm, which was consistent with the film thickness calculated from the product of the film forming speed and time.
- the crystalline silicon substrate on which the zinc oxide layer 4 was formed was introduced into a sputtering apparatus, and an ITO film having a thickness of 250 nm was formed on the n-type microcrystalline silicon layer 7b on the back surface as the back-side transparent conductive layer 8.
- a sintered body of indium oxide and tin oxide (content of tin oxide 5 wt%) was used as the ITO sputtering target.
- the surface shape of the ITO layer reflects the surface shape of the silicon substrate, and a fine uneven structure as in the case of the zinc oxide layer was not formed.
- the sign of the amount of warpage is positive when the cell is placed with the light incident surface side up, and when the air gap is formed in the outer periphery (when the back surface is warped convexly), the reverse side is up.
- the case where a void was formed when the light incident surface side warped convexly was negative.
- a silver paste (Fujikura Kasei FA-333) was formed on the transparent conductive layer 4 by screen printing to form a comb-shaped pattern collector electrode.
- drying was performed using a warm air oven, and the temperature and time were 120 ° C. and 10 minutes, respectively.
- the thickness of the silver paste after drying was 30 ⁇ m.
- the back surface metal electrode layer 10 having a thickness of 15 ⁇ m was formed by applying a silver paste to the entire surface of the ITO layer 8 without patterning and drying in the same manner.
- the solar cell 11 thus produced was sealed by laminating a glass substrate 13 and a PET film base material 14 as a protective film via an EVA resin as a filler 12.
- the solar cell module thus obtained was converted into a photoelectric conversion characteristic using a solar simulator having a spectral distribution of AM1.5 and simulated solar light at an energy density of 100 mW / cm 2 at 25 ° C.
- the output characteristics were measured by irradiating with an open circuit voltage, and the open circuit voltage (Voc), the short circuit current density (Jsc), the fill factor (FF), and the conversion efficiency (Eff) were obtained.
- the above silver paste was screen-printed on the light incident side transparent conductive layer 4 over a 30 mm square.
- a layer having a thickness of 30 ⁇ m was formed, and a sample for adhesion strength test was obtained.
- the adhesion strength of the collector electrode was evaluated by a tape peeling test. In the tape peeling test, the silver paste layer was cut into a 2 mm wide grid with a cutter knife, a test tape (550P, Sumitomo 3M) was attached, and peeled off at a stretch in the vertical direction.
- Adhesion strength was evaluated based on the following five levels by measuring the adhesion rate of the collector electrode to the peeled tape adhesive surface.
- the p-type amorphous silicon layer 3 and the transparent conductive layer are formed on the i-type amorphous silicon layer 2 on the uneven silicon substrate under the same conditions as described above.
- Layer 4 was formed, and the X-ray diffraction pattern of the transparent conductive layer was measured in 2 ⁇ / ⁇ mode using an X-ray diffractometer. During measurement, the tilt angle was set to 35 ° in order to suppress the appearance of diffraction peaks due to Si.
- FIG. 3 shows the measurement results.
- the transparent conductive layer 4 was hexagonal zinc oxide preferentially oriented in the (11-20) plane direction. Further, the carrier density of the transparent conductive layer was evaluated by hole measurement and found to be 8 ⁇ 10 19 cm ⁇ 3 .
- Example 2 the solar cell was produced and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the film formation time of the light incident side transparent conductive layer was 27 minutes.
- Example 3 the solar cell was produced and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the film formation time of the light incident side transparent conductive layer was 18 minutes.
- Example 4 the solar cell was manufactured and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the film formation time of the light incident side transparent conductive layer was 11 minutes.
- Example 5 the solar cell was manufactured and evaluated in the same manner as in Example 1. However, only after the formation of the zinc oxide layer, vacuum annealing treatment was performed at 180 ° C. for 20 minutes. It was different. The vacuum annealing treatment was performed by an infrared image furnace connected to a vacuum pump. The degree of vacuum during the annealing process was set to the 10 ⁇ 2 Pa level.
- Example 6 the solar cell was produced and evaluated in the same manner as in Example 5, but only in that the vacuum annealing treatment temperature and time after the formation of the zinc oxide layer were 200 ° C. and 10 minutes, respectively. It was different from Example 5.
- Example 7 the solar cell was produced and evaluated in the same manner as in Example 5, but only in that the vacuum annealing treatment temperature and time after the formation of the zinc oxide layer were 240 ° C. and 4 minutes, respectively. It was different from Example 5.
- Example 8 the solar cell was produced and evaluated in the same manner as in Example 5. However, only in that the vacuum annealing treatment temperature and time after the formation of the zinc oxide layer were 280 ° C. and 4 minutes, respectively. It was different from Example 5.
- Example 9 the solar cell was fabricated and evaluated in the same manner as in Example 5. However, the solar cell was different from Example 5 only in that the annealing treatment was performed in the atmosphere at 240 ° C. for 4 minutes. Atmospheric annealing was performed by introducing air into an infrared image furnace.
- Example 10 the solar cell was produced and evaluated in the same manner as in Example 1, but only in that the film formation temperature of the zinc oxide layer was 170 ° C. and the film formation time was 15 minutes. Was different.
- the thickness of the zinc oxide layer was 1300 nm
- the height difference of the concavo-convex structure was 130 nm
- the interval between the concavo-convex structures was 0.4 ⁇ m.
- the crystal structure of zinc oxide was hexagonal and preferentially oriented in the (11-20) plane direction.
- Example 11 In Example 11, the solar cell was produced and evaluated in the same manner as in Example 1, but only in that the film formation temperature of the zinc oxide layer was 210 ° C. and the film formation time was 8 minutes. It was different from 1.
- the thickness of the zinc oxide layer was 1300 nm
- the height difference of the concavo-convex structure was 100 nm
- the interval between the concavo-convex structures was 0.3 ⁇ m.
- the crystal structure of zinc oxide was hexagonal and preferentially oriented in the (10-11) plane direction.
- Example 12 In Example 12, the solar cell was produced and evaluated in the same manner as in Example 1, but only in that the film formation temperature of the zinc oxide layer was 260 ° C. and the film formation time was 25 minutes. Was different.
- the thickness of the zinc oxide layer was 1300 nm
- the height difference of the concavo-convex structure was 50 nm
- the interval between the concavo-convex structures was 0.3 ⁇ m.
- the crystal structure of zinc oxide was hexagonal and preferentially oriented in the (10-11) plane direction.
- Example 13 the solar cell was fabricated and evaluated in the same manner as in Example 1, but differed from Example 1 only in that the thickness of the crystalline silicon substrate was 150 ⁇ m.
- Example 14 the solar cell was fabricated and evaluated in the same manner as in Example 1. However, it was different from Example 1 only in that the thickness of the crystalline silicon substrate was 75 ⁇ m.
- Example 15 In Example 15, the solar cell was manufactured and evaluated in the same manner as in Example 1. However, it was different from Example 1 only in that the thickness of the crystalline silicon substrate was 50 ⁇ m.
- Example 16 solar cells were produced and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the thickness of the crystalline silicon substrate was 200 ⁇ m.
- Example 17 In Example 17, the solar cell was produced and evaluated in the same manner as in Example 1, but the flow rate ratio of diethyl zinc / water / H 2 / B 2 H 6 gas in the formation of the zinc oxide layer was It differs from Example 1 only in the point set to 1/2/25/5. At this time, the carrier density of the zinc oxide layer was 6 ⁇ 10 19 cm ⁇ 3 .
- Example 18 In Example 18, the solar cell was produced and evaluated in the same manner as in Example 1, but the flow rate ratio of diethyl zinc / water / H 2 / B 2 H 6 gas in the formation of the zinc oxide layer was It differs from Example 1 only in the point set to 1/2/26/4. At this time, the carrier density of the zinc oxide layer was 5 ⁇ 10 19 cm ⁇ 3 .
- Example 19 In Example 19, the solar cell was produced and evaluated in the same manner as in Example 1.
- the flow rate ratio of diethyl zinc / water / H 2 / B 2 H 6 gas in the formation of the zinc oxide layer was It differs from Example 1 only in the point set to 1/2/0/30. At this time, the carrier density of the zinc oxide layer was 2 ⁇ 10 20 cm ⁇ 3 .
- Example 20 In Example 20, the solar cell was produced and evaluated in the same manner as in Example 1.
- the flow rate ratio of diethyl zinc / water / H 2 / B 2 H 6 gas in the formation of the zinc oxide layer was Example 1 was different from Example 1 only in that the flow ratio of diethyl zinc, water, H 2 , and B 2 H 6 gas was 1/2/0/45.
- the carrier density of the zinc oxide layer was 3 ⁇ 10 20 cm ⁇ 3 .
- Example 21 In Example 21, the solar cell was produced and evaluated in the same manner as in Example 1.
- the flow rate ratio of diethyl zinc / water / H 2 / B 2 H 6 gas in the formation of the zinc oxide layer was It differs from Example 1 only in the point set to 1/2/30/0. At this time, the carrier density of the zinc oxide layer was 4 ⁇ 10 20 cm ⁇ 3 .
- Example 22 solar cells were produced and evaluated in the same manner as in Example 1.
- the flow rate ratio of zinc / water / H 2 / B 2 H 6 gas is set to 1/2/30/0 and B 2 H 6 gas is not supplied, and in the remaining 12 minutes (corresponding to a film forming thickness of about 600 nm)
- the flow rate ratio is 1/2/20/10, which is different from Example 1 only in that the dopant concentration on the crystalline silicon substrate side of the zinc oxide layer is lower than the dopant concentration on the opposite side of the crystalline silicon substrate. It was.
- the carrier density (average in the film thickness direction) of the zinc oxide layer was 6 ⁇ 10 20 cm ⁇ 3 .
- Comparative Example 1 In Comparative Example 1, a solar cell was manufactured and evaluated in the same manner as in Example 1. However, as the transparent conductive layer 4, an ITO layer having a thickness of 100 nm was formed by sputtering instead of forming a zinc oxide layer. . The height difference of the uneven structure on the surface of the ITO layer was substantially flat at 5 nm, and the fine unevenness as in Example 1 was not formed.
- Comparative Example 2 In Comparative Example 2, the solar cell was produced and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the film formation time of the light incident side transparent conductive layer was 2 minutes.
- the zinc oxide layer had a thickness of 100 nm, the surface shape was substantially flat, and a fine uneven structure was not formed.
- Comparative Example 3 a solar cell was produced and evaluated in the same manner as in Example 1. However, the solar cell was different from Example 1 only in that the film formation time of the light incident side transparent conductive layer was set to 35 minutes.
- Example 4 In Comparative Example 4, the solar cell was produced and evaluated in the same manner as in Example 1.
- Example 1 was only performed in that the film formation temperature of the zinc oxide layer was 110 ° C. and the film formation time was 40 minutes. Was different.
- the thickness of the zinc oxide layer was 1300 nm
- the height difference of the concavo-convex structure was 15 nm
- the interval between the concavo-convex structures was 0.1 ⁇ m.
- the crystal structure of zinc oxide was evaluated by the X-ray diffraction method, only the diffraction peak due to the (0002) plane was observed, and the a-axis lattice constant could not be evaluated.
- Comparative Example 5 a solar cell was fabricated and evaluated in the same manner as in Example 1. However, instead of forming a zinc oxide layer by a CVD method as the transparent conductive layer 4, a zinc oxide layer having a thickness of 1000 nm by a sputtering method was used. Formed. The surface shape of the zinc oxide layer was substantially flat, and a fine uneven structure was not formed. An uneven structure was formed on the surface of the zinc oxide layer by etching. The height difference of the uneven structure of the zinc oxide layer was 120 nm, and the interval between the uneven structures was 0.5 ⁇ m. Further, when the crystal structure of zinc oxide was evaluated by the X-ray diffraction method, only the diffraction peak due to the (0002) plane was observed, and the a-axis lattice constant could not be evaluated.
- Comparative Example 6 the solar cell was produced and evaluated in the same manner as in Example 5, but only in that the vacuum annealing treatment temperature and time after forming the zinc oxide layer were 320 ° C. and 4 minutes, respectively. It was different from Example 5.
- Example 7 In Comparative Example 7, a solar cell was produced and evaluated in the same manner as in Example 1.
- Example 1 was only performed in that the film formation temperature of the zinc oxide layer was 300 ° C. and the film formation time was 29 minutes. Was different.
- the thickness of the zinc oxide layer was 1300 nm, the height difference of the concavo-convex structure was 50 nm, and the interval between the concavo-convex structures was 0.3 ⁇ m.
- the crystal structure of zinc oxide was hexagonal and preferentially oriented in the (10-11) plane direction.
- Comparative Example 8 In Comparative Example 8, a solar cell was produced and evaluated in the same manner as in Example 1, but differed from Example 1 only in that the thickness of the crystalline silicon substrate was 40 ⁇ m. At this time, the silicon substrate was very easily damaged, and a measurable solar cell could not be formed.
- Table 1 shows the configurations of solar cells in Examples and Comparative Examples and the amount of warpage of the substrate before electrodes are formed. Further, Table 2 shows the photoelectric conversion characteristics, warpage amount, and adhesion strength of the collecting electrode of the solar battery cell after electrode formation.
- Comparative Example 3 in which the thickness of the zinc oxide layer is as large as 2700 nm, and in Comparative Example 2 in which the lattice constant of the a-axis of zinc oxide is small because the thermal CVD temperature during formation of the zinc oxide layer is as high as 300 ° C., formation of the metal electrode layer Although the subsequent warpage was small, the warpage after forming the zinc oxide layer was large. In mass production of such solar cells, it is considered that defects due to the warpage of the substrate are likely to occur in the process from the formation of the zinc oxide layer to the formation of the metal electrode layer.
- FIG. 9 shows the amount of warpage of the subsequent substrate plotted on the vertical axis.
- the warpage amount of the substrate after the formation of the transparent conductive layer and the stress strain parameter S of the zinc oxide layer have a linear relationship, and as the stress strain parameter increases, The amount of warpage increases monotonously.
- the stress strain parameter of the zinc oxide layer By adjusting the stress strain parameter of the zinc oxide layer, the amount of warpage of the substrate after the formation of the transparent conductive layer is adjusted, and by balancing with the stress due to the metal electrode layer, the warpage of the solar cell is reduced. I know you get.
- the warpage amount parameter W increases as the thickness of the silicon substrate decreases. And the tendency for the curvature amount after transparent conductive layer formation to become large is seen.
- the stress strain parameter S is within the above range, the stress on the front and back of the silicon substrate can be reduced. It turns out that the curvature of a final photovoltaic cell can be suppressed by making it balance.
- the thickness of the silicon substrate is excessively small, the silicon substrate itself is easily cracked, and the warpage amount parameter W becomes excessively large, which may cause a problem that a solar cell cannot be formed as in Comparative Example 8 .
- the short-circuit current density is higher than that of Comparative Example 1 in which ITO having a thickness of 100 ⁇ m is formed as the light incident side transparent conductive layer. From this, in the present invention, although the absorption loss may occur due to the large thickness of the transparent conductive layer on the light incident side, there is a light scattering effect due to the formation of a fine uneven structure on the surface of the zinc oxide layer. It is presumed that the short circuit current density has risen above the disadvantages due to absorption loss. In addition, it should be noted that in Examples 14 and 15 in which a silicon substrate having a thickness smaller than that of Comparative Example 1 is used, a short-circuit current density higher than that of Comparative Example 1 is obtained.
- Comparative Example 5 in which the zinc oxide layer was formed by sputtering and the concavo-convex structure was formed by etching, the concavo-convex structure was formed on the surface of the transparent conductive layer.
- the open circuit voltage was equivalent to that of Comparative Example 1.
- Example 1 When Example 1 is compared with Examples 5 to 10 and Comparative Example 6, by performing vacuum annealing after forming the zinc oxide layer, photoelectric conversion characteristics are improved, but when the annealing temperature is too high, It can be seen that the photoelectric conversion characteristics tend to decrease. Moreover, in Example 9, since annealing was performed in air
- Examples 1, 10 to 12 and Comparative Examples 4 and 7 having different deposition temperatures of the zinc oxide layer by thermal CVD are compared, in Examples 1, 10, and 11, zinc oxide is in the (11-20) plane direction.
- Examples 12 and 13 and Comparative Example 3 which are preferentially oriented and have a higher film forming temperature, it can be seen that zinc oxide tends to preferentially orient in the (10-11) plane direction.
- the elevation difference H2 of the unevenness tends to increase as the film forming temperature rises.
- Comparative Example 4 where the film forming temperature is less than 120 ° C. it can be seen that zinc oxide is preferentially oriented in the (0002) plane direction, and there are no irregularities that cause effective light scattering.
- the fill factor decreases when the carrier density of the zinc oxide layer is low, and the short-circuit current density when the carrier density is high.
- the carrier density is preferably in the range of 3 ⁇ 10 19 to 2.5 ⁇ 10 20 cm ⁇ 3 .
- Example 1 and Example 21 are contrasted, by making the dopant density
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Abstract
Description
本発明の製造方法は、少なくとも一方主面に凹凸構造が形成された厚みが50μm~200μmの一導電型シリコン結晶基板1を準備するシリコン基板準備工程;シリコン結晶基板1の凹凸構造が形成された面上に、光入射側i型シリコン系薄膜層2、および逆導電型シリコン系薄膜層3をこの順に形成する光入射側シリコン系薄膜形成工程;シリコン結晶基板1の他方主面に、裏面側i型シリコン系薄膜層6、および一導電型シリコン系薄膜層7をこの順に形成する裏面側シリコン系薄膜形成工程;逆導電型シリコン系薄膜層3側の面に光入射側透明導電層4を形成する光入射側透明導電層形成工程;一導電型シリコン系薄膜層7側の面に裏面側透明導電層8を形成する裏面側透明導電層形成工程;光入射側透明導電層4側の面に集電極5を形成する集電極形成工程;および、裏面側透明導電層8側の面に金属電極層10を形成する金属電極層形成工程、を有する。
aZnO=λ/sin(θa) ・・・ (式1)
式1において、λはX線の波長であり、例えば、X線源にCu Kα線が使用される場合は、λ=0.154nmである。
実施例1として、本発明に従う、図1の模式的断面図に表される結晶シリコン系太陽電池を作成した。本実施例の結晶シリコン系太陽電池はヘテロ接合太陽電池であり、n型結晶シリコン基板1は両面にそれぞれ凹凸構造を備えている。n型結晶シリコン基板1の光入射面にはi型非晶質シリコン層2/p型非晶質シリコン層3/酸化亜鉛層4が製膜されている。酸化亜鉛層4の上には集電極5が形成されている。一方、n型結晶シリコン基板1の裏面側にはi型非晶質シリコン層6/n型非晶質シリコン層7a/n型微結晶シリコン層7b/酸化インジウム(ITO)層8が製膜されている。ITO層8の上にはAg金属電極層10が形成されている。実施例1の結晶シリコン系太陽電池は以下のようにして製造した。
1: 付着率80%以上
2: 付着率60%以上80%未満
3: 付着率40%以上60%未満
4: 付着率20%以上40%未満
5: 付着率20%未満
図3に測定結果を示す。透明導電層4は(11-20)面方向に優先配向した六方晶の酸化亜鉛であった。また、ホール測定によりこの透明導電層のキャリア密度を評価したところ、8×1019cm-3であった。
実施例2において、実施例1と同様に太陽電池の作製および評価が行われたが、光入射側透明導電層の製膜時間を27分間とした点においてのみ、実施例1と異なっていた。
実施例3において、実施例1と同様に太陽電池の作製および評価が行われたが、光入射側透明導電層の製膜時間を18分間とした点においてのみ、実施例1と異なっていた。
実施例4において、実施例1と同様に太陽電池の作製および評価が行われたが、光入射側透明導電層の製膜時間を11分間とした点においてのみ、実施例1と異なっていた。
実施例5において、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜後、180℃、20分間の真空アニール処理を施した点においてのみ実施例1と異なっていた。真空アニール処理は、真空ポンプと接続した赤外線イメージ炉により行った。アニール工程中の真空度は10―2Pa台とした。
実施例6において、実施例5と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜後の真空アニール処理温度および時間をそれぞれ200℃、10分間とした点においてのみ、実施例5と異なっていた。
実施例7において、実施例5と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜後の真空アニール処理温度および時間をそれぞれ240℃、4分間とした点においてのみ、実施例5と異なっていた。
実施例8において、実施例5と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜後の真空アニール処理温度および時間をそれぞれ280℃、4分間とした点においてのみ、実施例5と異なっていた。
実施例9において、実施例5と同様に太陽電池の作製および評価が行われたが、アニール処理が大気中240℃で4分間行われた点においてのみ、実施例5と異なっていた。大気アニール処理は、赤外線イメージ炉内に大気を導入することによりおこなった。
実施例10において、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜温度が170℃であり、製膜時間を15分間とした点においてのみ実施例1と異なっていた。酸化亜鉛層の膜厚は1300nm、凹凸構造の高低差は130nm、凹凸構造の間隔は0.4μmであった。また、酸化亜鉛の結晶構造は六方晶で(11-20)面方向に優先配向していた。
実施例11においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜温度が210℃であり、製膜時間を8分とした点においてのみ実施例1と異なっていた。酸化亜鉛層の膜厚は1300nm、凹凸構造の高低差は100nm、凹凸構造の間隔は0.3μmであった。また、酸化亜鉛の結晶構造は六方晶で(10-11)面方向に優先配向していた。
実施例12において、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜温度が260℃であり、製膜時間を25分とした点においてのみ実施例1と異なっていた。酸化亜鉛層の膜厚は1300nm、凹凸構造の高低差は50nm、凹凸構造の間隔は0.3μmであった。また、酸化亜鉛の結晶構造は六方晶で(10-11)面方向に優先配向していた。
実施例13においては、実施例1と同様に太陽電池の作製および評価が行われたが、結晶シリコン基板の厚みを150μmとした点においてのみ実施例1と異なっていた。
実施例14においては、実施例1と同様に太陽電池の作製および評価が行われたが、結晶シリコン基板の厚みを75μmとした点においてのみ実施例1と異なっていた。
実施例15においては、実施例1と同様に太陽電池の作製および評価が行われたが、結晶シリコン基板の厚みを50μmとした点においてのみ実施例1と異なっていた。
実施例16においては、実施例1と同様に太陽電池の作製および評価が行われたが、結晶シリコン基板の厚みを200μmとした点においてのみ実施例1と異なっていた。
実施例17においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜における、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、1/2/25/5とした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度は6×1019cm-3であった。
実施例18においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜における、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、1/2/26/4とした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度は5×1019cm-3であった。
実施例19においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜における、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、1/2/0/30とした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度は2×1020cm-3であった。
実施例20においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜における、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、ジエチル亜鉛、水、H2、B2H6ガスの流量比を1/2/0/45とした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度は3×1020cm-3であった。
実施例21においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜における、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、1/2/30/0とした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度は4×1020cm-3であった。
実施例22においては、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜において、製膜開始から10分(製膜厚み約600nmに相当)は、ジエチル亜鉛/水/H2/B2H6ガスの流量比を、1/2/30/0としてB2H6ガスの供給を行わず、残りの12分(製膜厚み約600nmに相当)において、流量比を1/2/20/10とすることで、酸化亜鉛層の結晶シリコン基板側のドーパント濃度を、結晶シリコン基板と反対側のドーパント濃度よりも低くした点においてのみ実施例1と異なっていた。このときの酸化亜鉛層のキャリア密度(膜厚方向の平均)は6×1020cm-3であった。
比較例1において、実施例1と同様に太陽電池の作製および評価が行われたが、透明導電層4として、酸化亜鉛層を形成する代わりに、スパッタ法により厚み100nmのITO層が形成された。ITO層表面の凹凸構造の高低差は5nmと実質的に平坦であり、実施例1のような微細な凹凸は形成されていなかった。
比較例2において、実施例1と同様に太陽電池の作製および評価が行われたが、光入射側透明導電層の製膜時間を2分間とした点においてのみ、実施例1と異なっていた。酸化亜鉛層の厚みは100nmで、表面形状は実質的に平坦であり、微細な凹凸構造は形成されていなかった。
比較例3において、実施例1と同様に太陽電池の作製および評価が行われたが、光入射側透明導電層の製膜時間を35分間とした点においてのみ、実施例1と異なっていた。
比較例4において、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜温度が110℃であり、製膜時間を40分間とした点においてのみ実施例1と異なっていた。酸化亜鉛層の膜厚は1300nm、凹凸構造の高低差は15nm、凹凸構造の間隔は0.1μmであった。また、酸化亜鉛の結晶構造をX線回折法で評価したところ、(0002)面による回折ピークのみが観測され、a軸の格子定数は評価することは出来なかった。
比較例5において、実施例1と同様に太陽電池の作製および評価が行われたが、透明導電層4として、酸化亜鉛層をCVD法で形成する代わりに、スパッタ法により厚み1000nmの酸化亜鉛層が形成された。この酸化亜鉛層の表面形状は実質的に平坦であり、微細な凹凸構造は形成されていなかった。この酸化亜鉛層の表面をエッチングにより凹凸構造を形成した。酸化亜鉛層の凹凸構造の高低差は120nm、凹凸構造の間隔は0.5μmであった。また、酸化亜鉛の結晶構造をX線回折法で評価したところ、(0002)面による回折ピークのみが観測され、a軸の格子定数は評価することは出来なかった。
比較例6において、実施例5と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜後の真空アニール処理温度および時間をそれぞれ320℃、4分間とした点においてのみ、実施例5と異なっていた。
比較例7において、実施例1と同様に太陽電池の作製および評価が行われたが、酸化亜鉛層の製膜温度が300℃であり、製膜時間を29分とした点においてのみ実施例1と異なっていた。酸化亜鉛層の膜厚は1300nm、凹凸構造の高低差は50nm、凹凸構造の間隔は0.3μmであった。また、酸化亜鉛の結晶構造は六方晶で(10-11)面方向に優先配向していた。
比較例8において、実施例1と同様に太陽電池の作製および評価が行われたが、結晶シリコン基板の厚みを40μmとした点においてのみ実施例1と異なっていた。このとき、シリコン基板は極めて破損しやすく、測定可能な太陽電池を形成することは出来なかった。
光入射側透明導電層として厚み100μmのITOが形成された比較例1およびスパッタにより酸化亜鉛層が形成された比較例5においては、透明導電層形成後には、基板の反りが発生していないが、金属電極層形成後に絶対値が1mmを超える反りが発生していた。また、酸化亜鉛層の厚みが100nmと小さい比較例2、および高温で酸化亜鉛層のアニールが行われた比較例6においても、同様の傾向がみられた。
実施例1~19においては、光入射側透明導電層として厚み100μmのITOが形成された比較例1に比して、短絡電流密度が上昇している。このことから、本発明においては、光入射側の透明導電層の厚みが大きいために吸収ロスが生じ得るものの、酸化亜鉛層の表面に微細な凹凸構造が形成されていることによる光散乱効果が吸収ロスによるデメリットを上回り、短絡電流密度が上昇しているものと推定される。また、比較例1よりも厚みの小さいシリコン基板が用いられている実施例14および15においても、比較例1よりも高い短絡電流密度が得られていることは注目すべきである。
2 i型シリコン系薄膜層
3 導電型シリコン系薄膜層
4 透明導電層
5 集電極
6 i型シリコン系薄膜層
7 導電型シリコン系薄膜層
8 透明導電層
10 金属電極層
11 結晶シリコン系太陽電池
12 充填剤
13 基材
14 基材
Claims (12)
- 一導電型結晶シリコン基板の光入射側主面に、光入射側i型シリコン系薄膜層、逆導電型シリコン系薄膜層、光入射側透明導電層、および集電極が、結晶シリコン基板側からこの順に形成され、前記結晶シリコン基板の他方主面に、裏面側i型シリコン系薄膜層、一導電型シリコン系薄膜層、裏面側透明導電層、および金属電極層が、結晶シリコン基板側からこの順に形成された結晶シリコン系太陽電池であって、
前記結晶シリコン基板は、厚みが50μm~200μmであり、結晶シリコン基板は少なくとも光入射側主面に凹凸構造を有し、
前記光入射側透明導電層の光入射側表面は凹凸構造を有し、光入射側透明導電層の凹凸構造の高低差は、前記結晶シリコン基板の光入射面側の凹凸構造の高低差より小さく、かつ、光入射側透明導電層の凹凸構造の間隔は、前記結晶シリコン基板の光入射面側の凹凸構造の間隔より小さく、
前記光入射側透明導電層は、厚み300nm~2500nmの酸化亜鉛層を有し、
前記酸化亜鉛層が、(10-10)面、(11-20)面、または(10-11)面方向に優先配向した六方晶の酸化亜鉛を含み、前記六方晶の酸化亜鉛のa軸の格子定数が0.3225nm~0.3246nmの範囲である、結晶シリコン系太陽電池。 - 前記光入射側透明導電層の凹凸構造の高低差が20nm~250nmである、請求項1に記載の結晶シリコン系太陽電池。
- 前記結晶シリコン基板の光入射面側の凹凸構造の高低差が0.5μm~40μmである、請求項1または2に記載の結晶シリコン系太陽電池。
- 前記酸化亜鉛層の応力歪みパラメータS=(aZnO-0.3249)×dZnOが、0.3nm2~2.9nm2である、請求項1から3のいずれか1項に記載の結晶シリコン系太陽電池(ただし、aZnOは酸化亜鉛のa軸の格子定数、dZnOは酸化亜鉛層の厚みであり、単位はいずれもnmである)。
- 前記酸化亜鉛層の反り量パラメータW=(aZnO-0.3249)×dZnO/dSiが、0.3×10-5nm~2.9×10-5nmである、請求項1から4のいずれか1項に記載の結晶シリコン系太陽電池(ただし、aZnOは酸化亜鉛のa軸の格子定数、dZnOは酸化亜鉛層の厚み、dSiは結晶シリコン基板の厚みであり、単位はいずれもnmである)。
- 前記酸化亜鉛層の結晶シリコン基板側の不純物濃度が、前記酸化亜鉛層の結晶シリコン基板と反対側の不純物濃度よりも低い、請求項1から5のいずれか1項に記載の結晶シリコン系太陽電池。
- 前記酸化亜鉛層のキャリア密度が、3×101cm-3~2.5×1020cm-3である、請求項1から6のいずれか1項に記載の結晶シリコン系太陽電池。
- 結晶シリコン系太陽電池を製造する方法であって、
少なくとも一方主面に凹凸構造が形成された厚みが50μm~200μmの一導電型シリコン結晶基板を準備するシリコン基板準備工程;
前記シリコン結晶基板の凹凸構造が形成された面上に、光入射側i型シリコン系薄膜層、および逆導電型シリコン系薄膜層をこの順に形成する光入射側シリコン系薄膜形成工程;
前記シリコン結晶基板の他方主面に、裏面側i型シリコン系薄膜層、および一導電型シリコン系薄膜層をこの順に形成する裏面側シリコン系薄膜形成工程;
前記逆導電型シリコン系薄膜層側の面に光入射側透明導電層を形成する光入射側透明導電層形成工程;
前記一導電型シリコン系薄膜層側の面に裏面側透明導電層を形成する裏面側透明導電層形成工程;
光入射側透明導電層側の面に集電極を形成する集電極形成工程;および、
裏面側透明導電層8側の面に金属電極層10を形成する金属電極層形成工程、を有し、
前記光入射側透明導電層形成工程において、少なくとも光入射側透明導電層の集電極側表面に、熱CVD法により厚み300nm~2500nmの酸化亜鉛層が形成される、結晶シリコン系太陽電池の製造方法。 - 請求項1~7のいずれか1項に記載の結晶シリコン系太陽電池を製造する方法であって、
前記酸化亜鉛層が熱CVD法により製膜されることを特徴とする、結晶シリコン系太陽電池の製造方法。 - 前記酸化亜鉛層の製膜温度が120℃~240℃の範囲を含む、請求項8または9に記載の結晶シリコン系太陽電池の製造方法。
- 前記酸化亜鉛層が熱CVD法により製膜された後、さらに、酸化亜鉛層が形成された基板を150℃~240℃に加熱する酸化亜鉛層のアニール処理工程を含む、請求項8~10のいずれか1項に記載の結晶シリコン系太陽電池の製造方法。
- 前記アニール処理工程が減圧下で行われる、請求項11に記載の結晶シリコン系太陽電池の製造方法。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04280975A (ja) * | 1991-03-11 | 1992-10-06 | Makoto Konagai | ZnO透明導電膜の製造方法 |
JPH08508368A (ja) * | 1993-10-11 | 1996-09-03 | ユニヴェルシテ ドゥ ヌーシャテル アンスティチュ ドゥ ミクロテクニク | 光電池および光電池を製造するための方法 |
JPH10135497A (ja) * | 1996-10-31 | 1998-05-22 | Sanyo Electric Co Ltd | 太陽電池素子及び太陽電池モジュール |
JP2000252501A (ja) * | 1999-02-26 | 2000-09-14 | Kanegafuchi Chem Ind Co Ltd | シリコン系薄膜光電変換装置の製造方法 |
JP2001085722A (ja) * | 1999-09-17 | 2001-03-30 | Mitsubishi Heavy Ind Ltd | 透明電極膜の製造方法及び太陽電池 |
JP2004311704A (ja) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | 薄膜光電変換装置用基板及びそれを用いた薄膜光電変換装置 |
WO2006070799A1 (ja) * | 2004-12-28 | 2006-07-06 | Showa Shell Sekiyu K.K. | MOCVD(有機金属化学蒸着)法によるZnO系透明導電膜の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10163114A (ja) * | 1996-11-29 | 1998-06-19 | Matsushita Electron Corp | 半導体装置およびその製造方法 |
EP1443527A4 (en) * | 2001-10-19 | 2007-09-12 | Asahi Glass Co Ltd | SUBSTRATE WITH TRANSPARENT CONDUCTIVE OXIDE FILM AND METHOD OF MANUFACTURING THEREOF AND PHOTOELECTRIC IMPLEMENTATION ELEMENT |
JP4152197B2 (ja) | 2003-01-16 | 2008-09-17 | 三洋電機株式会社 | 光起電力装置 |
US20050056836A1 (en) * | 2003-09-12 | 2005-03-17 | Sanyo Electric Co., Ltd. | Photovoltaic apparatus |
JP2005260150A (ja) | 2004-03-15 | 2005-09-22 | Sanyo Electric Co Ltd | 光起電力装置及びその製造方法 |
JP4568254B2 (ja) * | 2006-07-20 | 2010-10-27 | 三洋電機株式会社 | 太陽電池モジュール |
JP2008297168A (ja) * | 2007-05-31 | 2008-12-11 | National Institute Of Advanced Industrial & Technology | ZnOウィスカー膜及びその作製方法 |
-
2010
- 2010-07-02 EP EP10794254.2A patent/EP2450961B1/en not_active Not-in-force
- 2010-07-02 JP JP2011520997A patent/JP5514207B2/ja active Active
- 2010-07-02 WO PCT/JP2010/061343 patent/WO2011002086A1/ja active Application Filing
- 2010-07-02 CN CN201080030021.8A patent/CN102473750B/zh active Active
- 2010-07-02 US US13/381,610 patent/US8546685B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04280975A (ja) * | 1991-03-11 | 1992-10-06 | Makoto Konagai | ZnO透明導電膜の製造方法 |
JPH08508368A (ja) * | 1993-10-11 | 1996-09-03 | ユニヴェルシテ ドゥ ヌーシャテル アンスティチュ ドゥ ミクロテクニク | 光電池および光電池を製造するための方法 |
JPH10135497A (ja) * | 1996-10-31 | 1998-05-22 | Sanyo Electric Co Ltd | 太陽電池素子及び太陽電池モジュール |
JP2000252501A (ja) * | 1999-02-26 | 2000-09-14 | Kanegafuchi Chem Ind Co Ltd | シリコン系薄膜光電変換装置の製造方法 |
JP2001085722A (ja) * | 1999-09-17 | 2001-03-30 | Mitsubishi Heavy Ind Ltd | 透明電極膜の製造方法及び太陽電池 |
JP2004311704A (ja) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | 薄膜光電変換装置用基板及びそれを用いた薄膜光電変換装置 |
WO2006070799A1 (ja) * | 2004-12-28 | 2006-07-06 | Showa Shell Sekiyu K.K. | MOCVD(有機金属化学蒸着)法によるZnO系透明導電膜の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2450961A4 * |
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CN102655125A (zh) * | 2012-01-16 | 2012-09-05 | 中国科学院上海微系统与信息技术研究所 | 一种双面溅射金属层减小硅圆片翘曲的结构 |
JP2013204074A (ja) * | 2012-03-28 | 2013-10-07 | Mitsubishi Materials Corp | 透明導電膜及びその製造方法 |
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KR101983361B1 (ko) * | 2013-03-05 | 2019-05-28 | 엘지전자 주식회사 | 양면 수광형 태양전지 |
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