JP7281444B2 - Solar cell manufacturing method - Google Patents

Description

The present invention relates to a method for manufacturing a solar cell.

Conventionally, a solar cell has generally been of a double-sided electrode type in which electrodes are arranged on both sides (light-receiving surface and back surface) of a semiconductor substrate. In recent years, a back-contact (back surface electrode) type solar cell in which an electrode is arranged only on the back surface, as disclosed in Patent Document 1, has been developed as a solar cell without shielding loss due to electrodes.

Japanese Patent Application Laid-Open No. 2009-200267

However, in a back-contact solar cell, a p-type semiconductor layer and an n-type semiconductor layer must be electrically separated and formed in a back surface area that is narrower than that of a double-sided electrode type solar cell. A laser beam is used to electrically separate the p-type semiconductor layer and the n-type semiconductor layer. For this reason, the back-contact solar cell has a problem that manufacturing is much more complicated than, for example, a double-sided electrode solar cell.

In addition, if the electrical separation between the p-type semiconductor layer and the n-type semiconductor layer is performed in a complicated manner using a laser beam, the insulation separation may be insufficient due to insufficient accuracy of the laser beam, insufficient output of the laser beam, or the like. Sometimes you can't. In such a case, there is also the problem that the performance of the back-contact solar cell is degraded. In particular, when the p-type semiconductor layer and the n-type semiconductor layer are formed on textured shapes, the risk of performance deterioration increases.

SUMMARY OF THE INVENTION The present invention has been made to solve the above conventional problems, and an object of the present invention is to easily manufacture a high-performance back-contact solar cell.

In order to achieve the above object, one aspect of the present invention provides a step of forming a first semiconductor layer of a first conductivity type on one of two main surfaces facing each other in a semiconductor substrate; forming a lift-off layer containing a silicon-based thin film material on one semiconductor layer; selectively removing the lift-off layer and the first semiconductor layer; and one main surface including the lift-off layer and the first semiconductor layer. forming a second semiconductor layer of the second conductivity type on top; and removing the second semiconductor layer overlying the lift-off layer by using an etching solution to remove the lift-off layer. In the step of selectively removing the lift-off layer and the first semiconductor layer, after the lift-off layer is removed, the first semiconductor layer is removed by plasma etching in which a gas containing hydrogen as a main component is introduced.

According to the present invention, a high-performance back-contact solar cell can be easily manufactured.

FIG. 1 is a schematic cross-sectional view partially showing a solar cell according to one embodiment. FIG. 2 is a plan view showing the back main surface of the crystal substrate that constitutes the solar cell according to one embodiment. FIG. 3 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 4 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 5 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 6 is a modification of the method for manufacturing a solar cell according to one embodiment, and is a partial schematic cross-sectional view showing a process that replaces FIG. FIG. 7 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 8 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 9 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment. FIG. 10 is a partial schematic cross-sectional view showing one step of a method for manufacturing a solar cell according to one embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail based on the drawings. The following description of preferred embodiments is merely exemplary in nature and is not intended to limit the invention, its applications or its uses. Also, the dimensional ratio of each component in the drawings is for convenience of illustration and does not necessarily represent the actual dimensional ratio.

(one embodiment)
An embodiment of the present invention will be described with reference to the drawings.

FIG. 1 shows a partial cross-sectional view of a solar cell (cell) according to this embodiment. As shown in FIG. 1, a solar cell 10 according to this embodiment uses a crystalline substrate 11 made of silicon (Si). The crystal substrate 11 has two main surfaces 11S (11SU, 11SB) facing each other. Here, the main surface on which light is incident is called front side main surface 11SU, and the main surface on the opposite side is called back side main surface 11SB. For the sake of convenience, the front main surface 11SU is defined as a light-receiving side on the side that more positively receives light than the back main surface 11SB, and a non-light-receiving side on the side that does not positively receive light.

The solar cell 10 according to the present embodiment is a so-called heterojunction crystalline silicon solar cell, and is a back-contact type (back electrode type) solar cell in which an electrode layer is arranged on the back main surface 11SB.

Solar cell 10 includes crystalline substrate 11, intrinsic semiconductor layer 12, conductive semiconductor layer 13 (p-type semiconductor layer 13p, n-type semiconductor layer 13n), low reflection layer 14, and electrode layer 15 (transparent electrode layer 17, metal electrode layer 18).

Hereinafter, for the sake of convenience, members individually corresponding to the p-type semiconductor layer 13p or the n-type semiconductor layer 13n may be added with "p" or "n" at the end of the reference numerals. Also, since the conductivity types are different, such as p-type and n-type, one conductivity type is sometimes referred to as the "first conductivity type" and the other conductivity type as the "second conductivity type".

The crystal substrate 11 may be a semiconductor substrate made of monocrystalline silicon or a semiconductor substrate made of polycrystalline silicon. A single crystal silicon substrate will be described below as an example.

Even if the conductivity type of the crystal substrate 11 is an n-type single crystal silicon substrate into which impurities (for example, phosphorus (P) atoms) that introduce electrons into silicon atoms are introduced, holes are introduced into silicon atoms. A p-type single crystal silicon substrate into which impurities (for example, boron (B) atoms) are introduced may be used. An n-type single crystal substrate, which is said to have a long carrier life, will be described below as an example.

In addition, from the viewpoint of confining received light, the crystal substrate 11 has a texture structure TX (first texture structure) composed of peaks (convex) and valleys (concave) on the two main surfaces 11S. may have The texture structure TX (uneven surface) is formed, for example, by anisotropic etching that applies the difference between the etching rate of the crystal substrate 11 having a (100) plane orientation and the etching rate having a (111) plane orientation. can be formed.

The size of the texture structure TX can be defined, for example, by the number of vertices (mountains). In the present invention, from the viewpoint of light capture and productivity, the range is preferably 50,000/mm ² or more and 100,000/mm ² or less, and particularly 70,000/mm ² or more and 85,000/mm ² or less. A range is preferred.

The thickness of the crystal substrate 11 may be 250 μm or less. The measurement direction when measuring the thickness is perpendicular to the average plane of the crystal substrate 11 (the average plane means the plane of the entire substrate independent of the texture structure TX). Therefore, hereinafter, this vertical direction, that is, the direction in which the thickness is measured will be referred to as the thickness direction.

If the thickness of the crystal substrate 11 is set to 250 μm or less, the amount of silicon used can be reduced, so it becomes easier to secure the silicon substrate and the cost can be reduced. In addition, the back contact structure in which the holes and electrons generated by photoexcitation in the silicon substrate are recovered only on the back side is preferable from the viewpoint of the free path of each exciton.

On the other hand, if the thickness of the crystal substrate 11 is too small, the mechanical strength will be lowered, and the outside light (sunlight) will not be sufficiently absorbed, resulting in a decrease in the short-circuit current density. Therefore, the thickness of the crystal substrate 11 is preferably 50 μm or more, more preferably 70 μm or more. When the textured structure TX is formed on the main surface of the crystal substrate 11, the thickness of the crystal substrate 11 is represented by the distance between straight lines connecting the apexes of the convexes in the concave-convex structures on the light receiving side and the back side. be done.

By the way, an intrinsic (i-type) semiconductor layer 12 can be arranged between the crystal substrate 11 and the conductive semiconductor layer 13 . By covering both main surfaces 11S (11SU, 11SB) of the crystal substrate 11 with the intrinsic semiconductor layers 12 (12U, 12p, 12n), diffusion of impurities into the crystal substrate 11 is suppressed and surface passivation is performed. It should be noted that the term “intrinsic (i-type)” is not limited to a completely intrinsic material containing no conductive impurities, but rather a “weakly conductive material” containing a small amount of n-type or p-type impurities to the extent that the silicon-based layer can function as an intrinsic layer. It also includes layers that are substantially intrinsic of "n-type" or "weakly p-type."

It should be noted that the intrinsic semiconductor layers 12 (12U, 12p, 12n) are not essential, and may be appropriately formed as needed.

Although the material of the intrinsic semiconductor layer 12 is not particularly limited, it may be an amorphous silicon-based material, and the thin film may be a hydrogenated amorphous silicon-based thin film (a-Si:H thin film) containing silicon and hydrogen. There may be. The term "amorphous" as used herein means a structure having no long-period order, that is, not only complete disorder but also short-period order is included.

The thickness of the intrinsic semiconductor layer 12 is not particularly limited, but may be 2 nm or more and 20 nm or less. This is because when the thickness is 2 nm or more, the effect as a passivation layer for the crystal substrate 11 is enhanced, and when the thickness is 20 nm or less, deterioration of conversion characteristics caused by high resistance can be suppressed.

A method for forming the intrinsic semiconductor layer 12 is not particularly limited, but a plasma enhanced chemical vapor deposition (CVD) method is used. According to this method, it is possible to effectively passivate the substrate surface while suppressing the diffusion of impurities into single crystal silicon. Further, with the plasma CVD method, by changing the hydrogen concentration in the intrinsic semiconductor layer 12 in the thickness direction, it is possible to form an energy gap profile effective for recovering carriers.

The conditions for forming a thin film by the plasma CVD method include, for example, a substrate temperature of 100° C. or higher and 300° C. or lower, a pressure of 20 Pa or higher and 2600 Pa or lower, and a high frequency power density of 0.003 W/cm ² or higher and 0.5 W/cm2. cm ² or less.

In the case of the intrinsic semiconductor layer 12, the raw material gas used for forming the thin film includes silicon-containing gases such as monosilane (SiH ₄ ) and disilane (Si ₂ H ₆ ), or these gases and hydrogen (H ₂ ). and may be a mixed gas.

Incidentally, a gas containing a different element such as methane (CH ₄ ), ammonia (NH ₃ ) or monogermane (GeH ₄ ) is added to the above gas to form silicon carbide (SiC) or silicon nitride (SiN _{x )} . ) or a silicon compound such as silicon germanium (SIGe) to change the energy gap of the thin film accordingly.

Conductive semiconductor layer 13 includes p-type semiconductor layer 13p and n-type semiconductor layer 13n. As shown in FIG. 1, p-type semiconductor layer 13p is formed on part of back surface 11SB of crystal substrate 11 with intrinsic semiconductor layer 12p interposed therebetween. N-type semiconductor layer 13n is formed on another portion of the back main surface of crystal substrate 11 with intrinsic semiconductor layer 12n interposed therebetween. In other words, between the p-type semiconductor layer 13p and the crystal substrate 11 and between the n-type semiconductor layer 13n and the crystal substrate 11, the intrinsic semiconductor layer 12 is interposed as an intermediate layer serving as passivation.

Each thickness of the p-type semiconductor layer 13p and the n-type semiconductor layer 13n is not particularly limited, but may be 2 nm or more and 20 nm or less. This is because when the thickness is 2 nm or more, the effect as a passivation layer for the crystal substrate 11 is enhanced, and when the thickness is 20 nm or less, deterioration of conversion characteristics caused by high resistance can be suppressed.

P-type semiconductor layer 13p and n-type semiconductor layer 13n are arranged on the back side of crystal substrate 11 so that p-type semiconductor layer 13p and n-type semiconductor layer 13n are electrically separated. The width of the conductive semiconductor layer 13 may be 50 μm or more and 3000 μm or less, and more preferably 80 μm or more and 500 μm or less. In addition, the gap between the p-type semiconductor layer 13p and the n-type semiconductor layer 13n may be 3000 μm or less, and more preferably 1000 μm or less (the width of the semiconductor layer and the width of the electrode layer described later are , unless otherwise specified, is the length of a portion of each patterned layer, which is intended to be the length in a direction orthogonal to the extending direction of the portion that has been made linear by patterning, for example).

When photoexcitons (carriers) generated in the crystal substrate 11 are taken out through the conductive semiconductor layer 13, holes have a larger effective mass than electrons. Therefore, from the viewpoint of reducing transport loss, the width of p-type semiconductor layer 13p may be narrower than that of n-type semiconductor layer 13n. For example, the width of the p-type semiconductor layer 13p may be 0.5 to 0.9 times the width of the n-type semiconductor layer 13n, or 0.6 to 0.8 times the width of the n-type semiconductor layer 13n. more preferred.

The low-reflection layer 14 is a layer that suppresses reflection of light received by the solar cell 10 . The material of the low-reflection layer 14 is not particularly limited as long as _it is a light-transmitting material that transmits _light . Titanium (TiO _x ) may be mentioned. As a method for forming the low-reflection layer 14, for example, a resin material in which nanoparticles of an oxide such as zinc oxide or titanium oxide are dispersed may be applied.

Electrode layer 15 is formed to cover p-type semiconductor layer 13p or n-type semiconductor layer 13n, respectively, and is electrically connected to each conductive semiconductor layer 13 . Thereby, the electrode layer 15 functions as a transport layer that guides carriers generated in the p-type semiconductor layer 13p or the n-type semiconductor layer 13n.

The electrode layers 15p and 15n corresponding to the semiconductor layers 13p and 13n are spaced apart to prevent a short circuit between the p-type semiconductor layer 13p and the n-type semiconductor layer 13n.

Moreover, the electrode layer 15 may be formed only of a highly conductive metal. In addition, from the viewpoint of electrical connection with each of the p-type semiconductor layer 13p and the n-type semiconductor layer 13n, or from the viewpoint of suppressing the diffusion of atoms into both the metal semiconductor layers 13p and 13n, which are electrode materials, the transparent An electrode layer 15 made of a conductive oxide may be provided between the metal electrode layer and the p-type semiconductor layer 13p and between the metal electrode layer and the n-type semiconductor layer 13n.

In this embodiment, the electrode layer 15 made of a transparent conductive oxide is referred to as a transparent electrode layer 17 and the metal electrode layer 15 is referred to as a metal electrode layer 18 . Further, as shown in the plan view of the back main surface 11SB of the crystal substrate 11 shown in FIG. 2, in the p-type semiconductor layer 13p and the n-type semiconductor layer 13n each having a comb-teeth shape, an electrode layer is formed on the back of the comb. are called busbar portions, and the electrode layers formed on the comb tooth portions are sometimes called finger portions.

_The material of _the transparent electrode layer 17 is not particularly limited. SnO _x ), tungsten oxide (WO _x ), molybdenum oxide (MoO _x ), or the like is added at a concentration of 1% by weight or more and 10% by weight or less.

The thickness of the transparent electrode layer 17 may be 20 nm or more and 200 nm or less. Methods for forming a transparent electrode layer suitable for this thickness include, for example, a physical vapor deposition (PVD) method such as a sputtering method, or a metal organic layer using a reaction between an organometallic compound and oxygen or water. Chemical vapor deposition method (MOCVD:Metal-Organic Chemical Vapor Deposition) method etc. are mentioned.

Although the material of the metal electrode layer 18 is not particularly limited, examples thereof include silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), and the like.

The thickness of the metal electrode layer 18 may be 1 μm or more and 80 μm or less. A method of forming the metal electrode layer 18 suitable for this thickness includes a printing method in which a material paste is printed by inkjet printing or screen printing, or a plating method. However, the method is not limited to this, and vapor deposition or sputtering may be employed when a vacuum process is employed.

Moreover, the width of the comb tooth portions in the p-type semiconductor layer 13p and the n-type semiconductor layer 13n may be approximately the same as the width of the metal electrode layer 18 formed on the comb tooth portions. However, the width of the metal electrode layer 18 may be narrower than the width of the comb tooth portion. Moreover, the width of the metal electrode layer 18 may be wider than the width of the comb tooth portion as long as it is configured to prevent leakage current between the metal electrode layers 18 .

In this embodiment, the intrinsic semiconductor layer 12, the conductive semiconductor layer 13, the low-reflection layer 14, and the electrode layer 15 are laminated on the back side main surface 11SB of the crystal substrate 11, and passivation and conduction of each joint surface are performed. A predetermined annealing treatment is performed for the purpose of suppressing generation of defect levels in the semiconductor layer 13 and its interface and crystallizing the transparent conductive oxide in the transparent electrode layer 17 .

An annealing treatment according to the present embodiment includes, for example, an annealing treatment in which the crystal substrate 11 having the above layers formed thereon is placed in an oven heated to 150° C. or higher and 200° C. or lower. In this case, the atmosphere in the oven may be the air, and if hydrogen or nitrogen is used as the atmosphere, more effective annealing can be performed. Further, this annealing treatment may be an RTA (Rapid Thermal Annealing) treatment in which the crystal substrate 11 on which each layer is formed is irradiated with infrared rays from an infrared heater.

[Method for manufacturing solar cell]
A method for manufacturing the solar cell 10 according to this embodiment will be described below with reference to FIGS. 3 to 10. FIG.

First, as shown in FIG. 3, the crystal substrate 11 having the texture structure TX on each of the front main surface 11SU and the back main surface 11SB is prepared.

Next, as shown in FIG. 4, on the front main surface 11SU of the crystal substrate 11, for example, an intrinsic semiconductor layer 12U is formed. Subsequently, the antireflection layer 14 is formed on the formed intrinsic semiconductor layer 12U. Silicon nitride (SiN _x ) or silicon oxide (SiO _x ) having a suitable light absorption coefficient and refractive index is used for the antireflection layer 14 from the viewpoint of the light confinement effect of confining incident light.

Next, as shown in FIG. 5, a p-type semiconductor layer 13p is formed on the back main surface 11SB of the crystal substrate 11. Next, as shown in FIG. In FIG. 5, as described above, the intrinsic semiconductor layer 12p using, for example, i-type amorphous silicon is formed between the crystal substrate 11 and the p-type semiconductor layer 13p. Therefore, in the present embodiment, the step of forming the p-type semiconductor layer (first semiconductor layer) 13p is performed before forming the p-type semiconductor layer 13p on one main surface of the crystal substrate (semiconductor substrate) 11. A step of forming an intrinsic semiconductor layer (first intrinsic semiconductor layer) 12p on the (back side main surface) 11S is included.

The p-type semiconductor layer 13p is a silicon layer to which a p-type dopant (such as boron (B)) is added, and is preferably formed of amorphous silicon from the viewpoint of suppressing impurity diffusion or suppressing series resistance. On the other hand, when the n-type semiconductor layer 13n is used instead of the p-type semiconductor layer 13p, a silicon layer to which an n-type dopant (phosphorus (P) or the like) is added is a non-silicon layer similar to the p-type semiconductor layer 13p. It is preferably made of crystalline silicon. Silicon-containing gas such as monosilane (SiH ₄ ) or disilane (Si ₂ H ₆ ), or a mixed gas of silicon-based gas and hydrogen (H ₂ ) may be used as the material gas for the conductive semiconductor layer 13 . As the dopant gas, diborane (B ₂ H ₆ ) or the like can be used for forming the p-type semiconductor layer 13p, and phosphine (PH ₃ ) or the like can be used for forming the n-type semiconductor layer. Further, since the amount of impurities such as boron (B) or phosphorus (P) to be added may be very small, a mixed gas obtained by diluting a dopant gas with a raw material gas may be used.

Further, in order to adjust the energy gap of the p-type semiconductor layer 13p or the n-type semiconductor layer 13n, a different kind of gas such as methane (CH ₄ ), carbon dioxide (CO ₂ ), ammonia (NH ₃ ) or monogermane (GeH ₄ ) is used. The p-type semiconductor layer 13p or the n-type semiconductor layer 13n may be compounded by adding a gas containing the element.

Subsequently, as shown in FIG. 5, lift-off layers LF (LF1, LF2) are formed on the formed p-type semiconductor layer 13p. The lift-off layer LF is removed by patterning in the process shown in FIG. 7 which will be described later, and is removed simultaneously with the n-type semiconductor layer 13n in the process shown in FIG. In this embodiment, the lift-off layer LF is formed on the back main surface 11SB of the crystal substrate 11 in order of the first lift-off layer LF1 and the second lift-off layer LF2. The first lift-off layer LF1 may be mainly composed of silicon oxide (SiO _x ) or silicon nitride (SiN _x ).

When the first lift-off layer LF1 is mainly composed of silicon oxide, its refractive index may be 1.45 or more and 1.90 or less. Furthermore, if the refractive index of the first lift-off layer LF1 in this case is 1.50 or more and 1.80 or less, particularly 1.55 or more and 1.72 or less, the undercut in the process shown in FIG. , is preferable from the viewpoint of balance with lift-off in the process shown in FIG. This is because the difference in refractive index depends on the silicon content in the layer and is a factor affecting the etching rate of the lift-off layer LF.

Similarly, when the first lift-off layer LF1 is mainly composed of silicon nitride, its refractive index may be 1.60 or more and 2.10 or less. Furthermore, the refractive index of the first lift-off layer LF1 in this case is preferably 1.70 or more and 2.00 or less, particularly 1.80 or more and 1.95 or less. The above refractive index is preferably obtained by fitting from the dielectric function in spectroscopic ellipsometry measurement and extracting the numerical value for light with a wavelength of 632 nm.

Although the structure of the first lift-off layer LF1 is not particularly limited, for example, a structure including physical or chemical voids (defects) inside the layer can be mentioned. For example, if the first lift-off layer LF1 is formed by a CVD (Chemical Vapor Deposition) method, growing particles grow so as to pile up almost perpendicularly to the film formation surface. In this case, a large number of granules formed of grown grains are produced, and gaps may be formed between these granules. In the case of the lift-off layer LF1 including such voids, the etching solution can easily penetrate into the inside of the layer, so that the etching rate may be increased. Therefore, it is possible to shorten the time of the lift-off process, which will be described later.

On the other hand, the second lift-off layer LF2 may be hydrogenated amorphous silicon. In the patterning of the lift-off layer LF described in the process shown in FIG. 7, the second lift-off layer LF2 serves as a resist, which is preferable because it eliminates the need for a photoresist composed of an organic substance. The thickness of the lift-off layer LF may be 20 nm or more and 600 nm or less as a whole in the region not shielded by the mask 20 described later. In particular, the thickness of the lift-off layer LF is preferably 50 nm or more and 450 nm or less. Of these, the second lift-off layer LF2 preferably has a thickness of about 10 nm to 20 nm in the region not shielded by the mask 20, and a thickness of 5 nm or less, particularly preferably 3 nm or less in the region shielded by the mask 20. When the lift-off layer LF has a laminated structure of three or more layers, hydrogenated amorphous silicon is preferably used for the upper lift-off layer.

Further, in the present embodiment, as a modified example thereof, in the process shown in FIG. A mask 20 for selectively forming a film on the etching region may be arranged on the upper side of the main surface 11SB. That is, as shown in FIG. 6, the region to be removed by patterning may be a structure shielded by the mask 20 . In CVD film formation, even in the region shielded by the mask 20, the reaction gas during the film formation is leaked. is smaller compared to the unoccluded area. As a result, in the step of selectively removing the p-type semiconductor layer (first semiconductor layer) 13p (hereinafter referred to as a patterning step) shown in FIG. Removal of layer LF is facilitated. It is preferable that the mask 20 is spaced from the back main surface 11SB of the crystal substrate 11 and is held so as not to come into contact with the back main surface 11SB. The distance between the back surface of the mask 20 and the back main surface 11SB of the crystal substrate 11 is not particularly limited, but can be set to approximately 0.5 mm or more and 1.2 mm or less as an example.

Next, in the patterning step shown in FIG. 7, at least the p-type semiconductor layer 13p and the lift-off layer LF formed in the step shown in FIG. 5 are removed by patterning. A known method can be used for this step, and patterning using an etchant is preferable. In the present embodiment, the back surface 11SB of the crystal substrate 11 also has the texture structure TX from the viewpoint of prioritizing the light intake efficiency. In this case, the patterning process using laser light becomes somewhat difficult from the viewpoint of productivity. The first lift-off layer LF1 and the second lift-off layer LF2 formed in the process shown in FIG. 5 are each etched with hydrofluoric acid and a basic aqueous solution that generates hydroxide ions. In the region shielded by the mask 20 in the process shown in FIG. 6, the film thickness of the second lift-off layer LF2 made of hydrogenated amorphous silicon positioned above is extremely small. Therefore, since many pinholes exist in this shielding region, patterning of the first lift-off layer LF1 and the second lift-off layer LF2 can be performed only with hydrofluoric acid.

Furthermore, in this patterning step, plasma etching (hydrogen plasma etching) introducing a gas containing hydrogen as a main component may be used to etch the intrinsic semiconductor layer 12p and the p-type semiconductor layer 13p. For example, a gas containing hydrogen (H ₂ ) as a main component is introduced into the crystal substrate 11 placed in a vacuum chamber, plasma is generated using a high-frequency power supply, and etching is performed by the generated plasma. The main component here means that hydrogen accounts for 90% by volume or more of the total amount of gas introduced into the vacuum chamber. More preferably, the volume ratio of this hydrogen is 95% or more. Examples of introduced gas species other than hydrogen include SiH ₄ and CH ₄ .

Further, in this patterning process, etching is performed up to the intrinsic semiconductor layer 12p, and the crystal substrate 11 can be exposed in the patterning region. By doing so, it is possible to further suppress the decrease in the lifetime of carriers generated by photoelectric conversion.

Next, in the process shown in FIG. 8, the n-type semiconductor layer 13n is formed. The n-type semiconductor layer 13n can be formed over the entire back surface 11SB of the crystal substrate 11 . That is, the n-type semiconductor layer 13n is also formed on the lift-off layer LF. In addition, the intrinsic semiconductor layer 12n is formed between the crystal substrate 11 and the n-type semiconductor layer 13n in the same manner as in the process shown in FIG. In this case, the n-type semiconductor layer 13n covers not only the upper surface of the lift-off layer LF but also the side surfaces (end faces) of the lift-off layer LF, the p-type semiconductor layer 13p and the intrinsic semiconductor layer 12p via the intrinsic semiconductor layer 12n. It is formed. Therefore, in the present embodiment, the step of forming the n-type semiconductor layer (second semiconductor layer) 13n includes the lift-off layer LF of the crystal substrate (semiconductor substrate) 11 and the A step of forming an intrinsic semiconductor layer (second intrinsic semiconductor layer) 12n on one main surface (back side main surface) 11S including the p-type semiconductor layer is included.

Further, when the crystal substrate 11 is exposed as described above, a step of cleaning the surface of the crystal substrate 11 exposed in the patterning step of FIG. 7 may be provided before forming the intrinsic semiconductor layer 12n. do not have. The cleaning process is intended to remove defects and impurities generated on the surface of the crystal substrate 11 in the patterning process, and may be processed with hydrofluoric acid, for example.

Next, in the step of removing the n-type semiconductor layer (second semiconductor layer) 13n covering the lift-off layer LF (hereinafter referred to as a lift-off step) shown in FIG. The intrinsic semiconductor layer 12n and the n-type semiconductor layer 13n are removed at the same time. While the patterning process shown in FIG. 7 uses the photolithography method, this process does not require a resist coating process such as photolithography and a development process. Therefore, pattern formation on the n-type semiconductor layer 13n can be easily performed. Further, when a film containing silicon oxide or silicon nitride as a main component is applied to the lift-off layer LF, hydrofluoric acid is used as the etchant in this step.

Next, as shown in FIG. 10, on the back main surface 11SB of the crystal substrate 11, that is, on each of the p-type semiconductor layer 13p and the n-type semiconductor layer 13n, for example, by sputtering using a mask, A transparent electrode layer 17 (17p, 17n) is formed so as to create a separation groove 25. Then, as shown in FIG. The transparent electrode layers 17 (17p, 17n) may be formed in the following manner instead of the sputtering method. For example, a transparent conductive oxide film is formed on the entire back surface 11SB without using a mask, and then a transparent conductive film is formed on the p-type semiconductor layer 13p and the n-type semiconductor layer 13n by photolithography. It may be formed by performing etching to leave a protective oxide film. Here, by forming the isolation groove 25 for isolating and insulating the p-type semiconductor layer 13p and the n-type semiconductor layer 13n from each other, the leakage current is less likely to occur.

After that, a linear metal electrode layer 18 (18p, 18n) is formed on the transparent electrode layer 17 using, for example, a mesh screen (not shown) having openings.

Through the steps described above, the back contact solar cell 10 is formed.

The present invention is not limited to the above embodiments, and various modifications are possible within the scope of the claims. That is, the technical scope of the present invention also includes embodiments obtained by combining technical means appropriately modified within the scope of the claims.

For example, in the method for manufacturing a solar cell described above, the lift-off layer LF is of a multi-layer type, but it is not limited to this. For example, only a single-layer lift-off layer LF may be used. Note that such a single layer is preferably formed of the first lift-off layer LF1.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. Examples and comparative examples were produced as follows (see [Table 1]).

[Crystal substrate]
First, a single crystal silicon substrate having a thickness of 200 μm was adopted as a crystal substrate. Anisotropic etching was performed on both main surfaces of the single crystal silicon substrate. As a result, a pyramidal textured structure was formed on the crystal substrate.

[Intrinsic semiconductor layer]
Next, the crystal substrate was introduced into a CVD apparatus, and intrinsic semiconductor layers (thickness: 8 nm) made of silicon were formed on both main surfaces of the introduced crystal substrate. The deposition conditions were a substrate temperature of 150° C., a pressure of 120 Pa, a flow ratio of SiH ₄ /H ₂ of 3/10, and a power density of 0.011 W/cm ² .

[p-type semiconductor layer (first conductivity type semiconductor layer)]
Next, a crystalline substrate having intrinsic semiconductor layers formed on both main surfaces thereof was introduced into a CVD apparatus, and a p-type hydrogenated amorphous silicon thin film (thickness 10 nm) was deposited on the intrinsic semiconductor layer on the back main surface of the crystalline substrate. ) was formed.

The deposition conditions were a substrate temperature of 150° C., a pressure of 60 Pa, a flow ratio of SiH ₄ /B ₂ H ₆ of 1/3, and a power density of 0.01 W/cm ² . The flow rate of the B ₂ H ₆ gas in this example is the flow rate of the diluent gas obtained by diluting the B ₂ H ₆ with H ₂ to 5000 ppm.

[Lift-off layer]
Next, two lift-off layers were formed on the p-type semiconductor layer. The lift-off layer was formed with the following two compositions.

(Silicon oxide-based lift-off layer)
As the first lift-off layer used in Examples 1 and 2 and Comparative Examples 1 and 3, silicon oxide (SiO _x ) was formed with a film thickness of 200 nm (mask unshielded region) using a plasma CVD apparatus. The substrate temperature was 150° C., the pressure was 0.9 kPa, the flow ratio of SiH ₄ /CO ₂ /H ₂ was 1/10/750, and the power density was 0.15 W/cm ² . Subsequently, as a second lift-off layer, hydrogenated amorphous silicon was formed on the first lift-off layer with a film thickness of 15 nm (mask-unshielded region) using a plasma CVD apparatus. The substrate temperature was 150° C., the pressure was 120 Pa, the SiH ₄ /H ₂ flow ratio was 3/10, and the power density was 0.011 W/cm ² .

(Silicon nitride-based lift-off layer)
As the first lift-off layer used in Examples 3 and 4, silicon nitride (SiN _x ) was formed with a film thickness of 200 nm (mask unshielded region) using a plasma CVD apparatus. The substrate temperature was 150° C., the pressure was 0.2 kPa, the flow ratio of SiH ₄ /HN ₃ /H ₂ was 1/4/50, and the power density was 0.15 W/cm ² . Subsequently, hydrogenated amorphous silicon was formed with a film thickness of 15 nm (mask unshielded region) on the first lift-off layer as a second lift-off layer using a plasma CVD apparatus. The substrate temperature was 150° C., the pressure was 120 Pa, the SiH ₄ /H ₂ flow ratio was 3/10, and the power density was 0.011 W/cm ² .

[Patterning of lift-off layer]
Next, the crystal substrate on which the p-type semiconductor layer was formed was immersed in hydrofluoric acid having a concentration of 1% by weight, and after the lift-off layer in the exposed region was removed, it was rinsed with pure water.

[Patterning of intrinsic semiconductor layer and p-type semiconductor layer]
Subsequently, after patterning the lift-off layer, the intrinsic semiconductor layer and the p-type semiconductor layer were patterned using hydrogen plasma etching. Hereinafter, this step is abbreviated as a p-type semiconductor layer patterning step.

As described below, the case of using only hydrogen (H ₂ ) as a reaction gas and the case of adding silane (SiH ₄ ) to hydrogen (H ₂ ) were compared.

(Hydrogen plasma etching: P-1)
For Examples 1 and 3 and Comparative Example 2, the crystal substrate was placed in a vacuum chamber, the substrate temperature was set to 150° C., hydrogen (H ₂ ) was introduced so that the pressure was 0.4 kPa, and the power density was set to 0. 011 W/cm ² .

(Silane-added hydrogen plasma etching: P-2)
For Examples 2 and 4, the crystal substrate was placed in a vacuum chamber, the substrate temperature was 150° C., the pressure was 0.4 kPa, the SiH ₄ /H ₂ flow ratio was 1/330, and the power density was 0.011 W/. ^cm2 . [n-type semiconductor layer (second conductivity type semiconductor layer)]
Subsequently, after the p-type semiconductor layer patterning step, the crystal substrate, the exposed portion of the back side of which has been washed with hydrofluoric acid having a concentration of 2% by weight, is introduced into a CVD apparatus. A hydrogenated amorphous silicon-based thin film (thickness: 10 nm) was formed.

The deposition conditions were a substrate temperature of 150° C., a pressure of 60 Pa, a flow rate ratio of SiH ₄ /PH ₃ of 1/2, and a power density of 0.01 W/cm ² . The flow rate of the _PH3 gas in this example is the flow rate of the diluent gas obtained by diluting _PH3 with _H2 to 5000 ppm.

[Removal of lift-off layer and n-type semiconductor layer (lift-off)]
Next, the crystal substrate on which the n-type semiconductor layer was formed was immersed in hydrofluoric acid having a concentration of 5% by weight. This simultaneously removed the lift-off layer, the n-type semiconductor layer covering the lift-off layer, and the intrinsic semiconductor layer between the lift-off layer and the n-type semiconductor layer.

[Electrode layer]
Next, using a magnetron sputtering apparatus, an oxide film (thickness: 100 nm) serving as the base of the transparent electrode layer was formed on the conductive semiconductor layer of the crystal substrate. As a transparent conductive oxide, indium oxide (ITO) containing tin oxide at a concentration of 10% by weight was used as a target. A mixed gas of argon (Ar) and oxygen (O ₂ ) was introduced into the chamber of the sputtering apparatus, and the pressure inside the chamber was set to 0.6 Pa. The mixing ratio of argon and oxygen was set to the lowest resistivity (so-called bottom) condition. In addition, film formation was performed using a DC power supply at a power density of 0.4 W/cm ² .

Next, etching was performed by photolithography so as to leave only the transparent conductive oxide film on the p-type semiconductor layer and the n-type semiconductor layer to form a transparent electrode layer. The transparent electrode layer formed by this etching prevented conduction between the transparent conductive oxide film on the p-type semiconductor layer and the transparent conductive oxide film formed on the n-type semiconductor layer.

Further, an undiluted silver paste (Dotite FA-333 manufactured by Fujikura Kasei Co., Ltd.) was screen-printed on the transparent electrode layer and heat-treated in an oven at a temperature of 150° C. for 60 minutes. Thus, a metal electrode layer was formed.

Next, an evaluation method for back-contact solar cells will be described. Refer to [Table 1] for the evaluation results.

[Evaluation of film thickness and etchability]
The film thickness and etching state of the lift-off layer were observed and measured at a magnification of 100,000 times using an SEM (Field Emission Scanning Electron Microscope S4800: manufactured by Hitachi High-Technologies Corporation). After the p-type semiconductor layer patterning process, when etching was completed according to the designed patterning removal area, it was evaluated as "O", and when the lift-off layer was excessively etched, it was evaluated as "X".

In the lift-off process, when the lift-off layer was removed, it was evaluated as "◯", and when the lift-off layer remained, it was evaluated as "x".

In Examples 1 to 4 and Comparative Examples 1 and 3, in the process of forming the intrinsic semiconductor layer, the p-type semiconductor layer and the lift-off layer, a mask is arranged to cover the regions where these layers are removed.

Further, in Examples 1 to 4 and Comparative Example 2, hydrogen plasma etching is used for etching the p-type semiconductor layer and the intrinsic semiconductor layer. However, in Comparative Example 2, although the mask is arranged, the thickness of each layer within the shielding region is increased. Comparative Examples 1 and 3 were not subjected to hydrogen plasma etching.

In Comparative Example 1, since hydrogen plasma etching was not performed, the p-type semiconductor layer was not sufficiently patterned in the p-type semiconductor layer patterning process, and therefore, "x" was given. In Comparative Example 2, the lift-off layer was removed in the p-type semiconductor layer patterning process, and evaluation in the subsequent lift-off process was impossible.

[Evaluation of refractive index]
The refractive index of the thin film formed on the glass substrate under the same conditions was obtained by measuring the refractive index using a spectroscopic ellipsometry (trade name: M2000, manufactured by JA Woollam Co.). From the fitting results, the refractive index for light with a wavelength of 632 nm was extracted.

[Evaluation of conversion efficiency]
A solar simulator was used to irradiate standard sunlight of AM (air mass) 1.5 at a light amount of 100 mW/cm ² to measure the conversion efficiency (Eff (%)) of the solar cell. Taking the conversion efficiency (solar cell characteristics) of Example 1 as 1.00, the relative values are shown in [Table 1].

In Examples 1 and 2, silicon oxide was used for the first lift-off layer. In Examples 3 and 4, silicon nitride was used for the first lift-off layer.

In the plasma etching process in the p-type semiconductor layer patterning process, in Examples 1 and 3 and Comparative Example 2, a process using only hydrogen (H ₂ ) gas was performed, and in Examples 2 and 4, silane (SiH ₄ ) gas was used. A plasma etching treatment was performed using the added hydrogen (H ₂ ) gas.

In Comparative Example 3, in the patterning removal of the intrinsic semiconductor layer and the p-conductivity semiconductor layer in the p-type semiconductor layer patterning step, ozone/hydrofluoric acid, which is a mixture of 5.5% by weight hydrofluoric acid and 20 ppm ozone, was used. It was immersed in liquid. That is, wet etching was performed.

Comparing the example and the comparative example, in this example, the intrinsic semiconductor layer, the p-type semiconductor layer, and the lift-off layer are shielded (masked) over the regions to be patterned and removed during deposition. When the film is formed using a mask, the film thickness on these regions becomes small. From this, it was found that good patterning can be easily performed by performing the subsequent plasma etching process.

In Comparative Example 3, although the film thickness of the patterning removed portion was reduced by film formation using a mask, the intrinsic semiconductor layer and the p-type semiconductor layer were removed with ozone/hydrofluoric acid, and the lift-off layer was also removed at the same time. It was non-conforming.

10 solar cell 11 crystal substrate (semiconductor substrate)
12 intrinsic semiconductor layer 13 conductivity type semiconductor layer 13p p-type semiconductor layer [first conductivity type first semiconductor layer/second conductivity type second semiconductor layer]
13n n-type semiconductor layer [second conductivity type second semiconductor layer/first conductivity type first semiconductor layer]
15 electrode layer 17 transparent electrode layer 18 metal electrode layer 20 mask LF lift-off layer

Claims (6)

forming a first semiconductor layer of a first conductivity type on one of two main surfaces facing each other in a semiconductor substrate;
forming a lift-off layer containing a silicon-based thin film material on the first semiconductor layer;
selectively removing the lift-off layer and the first semiconductor layer;
forming a second semiconductor layer of a second conductivity type on the one main surface including the lift-off layer and the first semiconductor layer;
removing the second semiconductor layer overlying the lift-off layer by removing the lift-off layer using an etching solution;
In the step of selectively removing the lift-off layer and the first semiconductor layer, after removing the lift-off layer with an etchant containing hydrofluoric acid, plasma etching is performed by introducing a gas containing hydrogen as a main component. A method of manufacturing a solar cell, comprising removing the first semiconductor layer. forming a first semiconductor layer of a first conductivity type on one of two main surfaces facing each other in a semiconductor substrate;
forming a lift-off layer containing a silicon-based thin film material on the first semiconductor layer;
selectively removing the lift-off layer and the first semiconductor layer;
forming a second semiconductor layer of a second conductivity type on the one main surface including the lift-off layer and the first semiconductor layer;
removing the second semiconductor layer overlying the lift-off layer by removing the lift-off layer using an etching solution;
In the step of selectively removing the lift-off layer and the first semiconductor layer, after removing the lift-off layer, the step of removing the first semiconductor layer by plasma etching in which a gas containing hydrogen as a main component is introduced. ,
The method for manufacturing a solar cell, wherein the lift-off layer includes a layer containing silicon oxide as a main component and has a refractive index of 1.55 or more and 1.72 or less for light with a wavelength of 632 nm. In the method for manufacturing a solar cell according to claim 1 ,
The method for manufacturing a solar cell, wherein the lift-off layer includes a layer containing silicon nitride as a main component, and has a refractive index of 1.60 or more and 2.10 or less for light with a wavelength of 632 nm. In the method for manufacturing a solar cell according to any one of claims 1 to 3,
In the step of forming the first semiconductor layer and the step of forming the lift-off layer,
forming the first semiconductor layer and the lift-off layer by a chemical vapor deposition method, and
A method for manufacturing a solar cell, wherein a mask for shielding the region is arranged at a distance from the region where the second semiconductor layer is to be formed. In the method for manufacturing a solar cell according to any one of claims 1 to 4,
A method of manufacturing a solar cell, wherein at least a surface of the semiconductor substrate on which the first semiconductor layer and the second semiconductor layer are formed has a textured structure. In the method for manufacturing a solar cell according to any one of claims 1 to 5,
forming the first semiconductor layer includes forming a first intrinsic semiconductor layer on the one main surface of the semiconductor substrate before forming the first semiconductor layer;
selectively removing the first semiconductor layer comprises selectively removing the first intrinsic semiconductor layer subsequent to the first semiconductor layer;
The step of forming the second semiconductor layer includes forming a second intrinsic semiconductor on the one main surface including the lift-off layer and the first semiconductor layer of the semiconductor substrate before forming the second semiconductor layer. forming a layer;
The method of manufacturing a solar cell, wherein the step of removing the second semiconductor layer includes the step of selectively removing the second intrinsic semiconductor layer following the step of removing the second semiconductor layer.

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