Photovoltaic cells can be a viable energy source by utilizing their ability to convert sunlight to electrical energy. Silicon is a common example of a semiconductor material used in the manufacture of photovoltaic cells.
Photovoltaic cells have a measurable property defined as a breakdown voltage. Under certain operating conditions, a reverse bias occurs across a p-n junction of a photovoltaic device. If the reverse bias voltage is high enough, the p-n junction can break down, and current will flow in a reverse direction, causing failure of the photovoltaic device. The reverse bias voltage where breakdown occurs is defined as the breakdown voltage for a given cell.
What is needed is a simple manufacturing process to produce a photovoltaic device with characteristics that raise a breakdown voltage.
The present photovoltaic devices, and related methods provide means for raising breakdown voltage. Devices are described below that include a textured surface on the semiconductor substrate, formed by etching the surface using a first etchant chemistry to form an etched surface, and etching the etched surface using a second etchant chemistry to broaden sharp edges in the etched surface. Manufacturing equipment is also described below to fabricate photovoltaic devices with high breakdown voltages.
To better illustrate the photovoltaic devices, and related methods disclosed herein, a non-limiting list of examples is now provided:
In Example 1, a method of forming a photovoltaic cell includes texturing a surface of a first conductivity type doped semiconductor substrate, including etching the surface using a first etchant chemistry to form an textured surface, etching the textured surface using a second etchant chemistry to broaden sharp edges in the etched surface, forming a doped layer of a second conductivity type at the textured surface to form a p-n junction coupling a first electrical conductor to the doped layer of second conductivity type, and coupling a second electrical conductor to a back surface of the semiconductor substrate.
In Example 2, the method of Example 1 is optionally provided such that etching the surface using the first etchant chemistry includes etching the surface using an acid etchant chemistry.
In Example 3, the method of any one or any combination of Examples 1-2 is optionally provided such that etching the surface using a first etchant chemistry includes etching the surface using a first nitric acid and hydrofluoric acid chemistry, and etching the etched surface using a second etchant chemistry includes etching the etched surface using a second nitric acid and hydrofluoric acid chemistry with a higher nitric acid concentration and a lower hydrofluoric acid concentration than the first etchant chemistry.
In Example 4, the method of any one or any combination of Examples 1-3 is optionally provided such that etching the surface using a second etchant chemistry includes etching the surface using a first nitric acid and hydrofluoric acid chemistry in a molar ratio greater than or equal to approximately 2.5 to 1.
In Example 5, the method of any one or any combination of Examples 1-4 is optionally provided such that etching the surface using a second etchant chemistry includes etching the surface to etch an amount of silicon between approximately 0.5μ, and 2.0μ.
In Example 6, the method of any one or any combination of Examples 1-5 is optionally provided such that etching the surface using a second etchant chemistry includes etching the surface to etch an amount of silicon between approximately 1.0μ and 1.5μ.
In Example 7, the method of any one or any combination of Examples 1-6 is optionally provided such that texturing a surface of a first conductivity type doped semiconductor substrate includes texturing a surface of a p-doped semiconductor substrate.
In Example 8, a photovoltaic device, includes a semiconductor substrate doped with a first conductivity type dopant, a textured surface on the semiconductor substrate, formed by etching the surface using a first etchant chemistry to form an etched surface, and etching the etched surface using a second etchant chemistry to broaden sharp edges in the etched surface, a layer of second conductivity type dopant formed at the textured surface, forming a p-n junction with the semiconductor substrate, a dielectric layer over the textured surface, a first electrical conductor coupled to the textured surface, and a second electrical conductor coupled to a back surface of the semiconductor substrate.
In Example 9, the photovoltaic device of Example 8 is optionally provided to further include an anti-reflective coating over the dielectric layer.
In Example 10, the photovoltaic device of any one or any combination of Examples 8-9 is optionally configured such that the textured surface on the semiconductor substrate is formed by etching the surface using a first etchant chemistry of nitric acid to hydrofluoric acid in a molar ratio of approximately 1 to 1 to form an etched surface, and etching the etched surface using a second etchant chemistry of nitric acid to hydrofluoric acid in a molar ratio greater than or equal to approximately 2.5 to 1, to broaden sharp edges in the etched surface.
In Example 11, the photovoltaic device of any one or any combination of Examples 8-10 is optionally configured such that the textured surface on the semiconductor substrate is formed by etching the surface using a first etchant chemistry of nitric acid to hydrofluoric acid in a ratio of 1 to 1 to form an etched surface, and polishing the etched surface using a second etchant chemistry of nitric acid, hydrofluoric acid, and sulfuric acid in a molar ratio of approximately 2.5 to 1 to 1.5, to broaden sharp edges in the etched surface.
In Example 12, the photovoltaic device of any one or any combination of Examples 8-11 is optionally configured such that the semiconductor substrate is doped with a p-type dopant, and the layer of second conductivity type dopant is n-type.
In Example 13, the photovoltaic device of any one or any combination of Examples 8-12 is optionally configured such that the device includes multiple cells electrically connected together to form a module.
In Example 14, the photovoltaic device of any one or any combination of Examples 8-13 is optionally configured such that the device includes 3 strings of 24 cells electrically connected together to form a module.
In Example 15, a photovoltaic manufacturing system includes a device to provide a first etchant including nitric acid and hydrofluoric acid, to create a surface texture on a substrate, and a device to provide a second etchant to broaden sharp edges of the surface texture, wherein the second etchant includes nitric acid and hydrofluoric acid wherein a ratio of nitric acid to hydrofluoric acid is increased from the first etchant.
In Example 16, the photovoltaic manufacturing system of Example 15 is optionally configured such that the device to provide a second etchant is configured to etch an amount of silicon between approximately 0.5μ and 2.0μ.
In Example 17, the photovoltaic manufacturing system of any one or any combination of Examples 15-16 is optionally configured such that the device to provide a second etchant is configured to etch an amount of silicon between approximately 1.0μ and 1.5μ.
In Example 18, the photovoltaic manufacturing system of any one or any combination of Examples 15-17 is optionally configured to further include a device to rinse the surface texture between etching operations.
In Example 19, the photovoltaic manufacturing system of any one or any combination of Examples 15-18 is optionally configured such that the device to provide the first etchant includes a device to provide nitric acid and hydrofluoric acid in a ratio of 1 to 1.
In Example 20, the photovoltaic manufacturing system of any one or any combination of Examples 15-19 is optionally configured such that the device to provide the second etchant includes a device to provide nitric acid and hydrofluoric acid in a molar ratio greater than or equal to approximately 2.5 to 1.
In Example 21, the photovoltaic manufacturing system of any one or any combination of Examples 15-20 is optionally configured such that the device to provide the second etchant includes a device to provide nitric acid, hydrofluoric acid, and sulfuric acid in a molar ratio approximately equal to approximately 2.5 to 1 to 1.5.
These and other examples and features of the photovoltaic devices, systems, and related methods will be set forth in part in the following detailed description. This overview is intended to provide non-limiting examples of the present subject matter—it is not intended to provide an exclusive or exhaustive explanation. The detailed description below is included to provide further information about the present devices, systems, and methods.
In the drawings, like numerals can be used to describe similar elements throughout the several views. Like numerals having different letter suffixes can be used to represent different views of similar elements. The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.
In the following detailed description, reference is made to the accompanying drawings. The drawings form a part of the description and are provided by way of illustration, but not of limitation. The drawing embodiments are described in sufficient detail to enable those skilled in the art to practice the present subject matter. Other embodiments may be utilized and mechanical, structural, or material changes may be made without departing from the scope of the present patent document.
Reference will now be made in detail to certain examples of the disclosed subject matter, some of which are illustrated in the accompanying drawings. While the disclosed subject matter will largely be described in conjunction with the accompanying drawings, it should be understood that such descriptions are not intended to limit the disclosed subject matter to those drawings. On the contrary, the disclosed subject matter is intended to cover all alternatives, modifications, and equivalents, which can be included within the scope of the presently disclosed subject matter, as defined by the claims.
References in the specification to “one embodiment”, “an embodiment”, “an example embodiment”, etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
In this document, the terms “a” or “an” are used to include one or more than one and the term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation.
In fabrication of photovoltaic devices, to increase the amount of solar energy captured, a surface of the substrate may be textured to provide greater surface area incident to incoming light, and to reduce reflection of incoming light away from the surface.
Textured surface 110 may be formed by etching top side 102 with an etchant. In one example, the etchant used to form etched surface 110 is an acid etch. Examples of acid etchants include, but are not limited to, acid chemistries formed from nitric acid (HNO3) and hydrofluoric acid (HF). In one example, the first etchant used to form the textured surface 110 includes an acid chemistry with a molar ratio of nitric acid to hydrofluoric acid of less than or equal to approximately 2 to 1. In one example, the first etchant used to form the textured surface 110 includes an acid chemistry with a molar ratio of nitric acid to hydrofluoric acid of between approximately 2 to 1 and 2/3 to 1. In one example, the first etchant used to form the textured surface 110 includes an acid chemistry with a molar ratio of nitric acid to hydrofluoric acid of approximately 1 to 1.
In one example, the etch variables of the first etching operation (etchant chemistry, time, temperature, etc.) are selected to provide a material removal in a range of approximately 3.0μ to 8.0μ. In one example, the etch variables of the first etching operation (etchant chemistry, time, temperature, etc.) are selected to provide a material removal in a range of approximately 4.0μ to 4.5μ. This amount of material removal is effective to form the textured surface 110.
In
In one example, the etch variables of the second etching operation (etchant chemistry, time, temperature, etc.) are selected to provide a material removal in a range of approximately 0.5μ to 2.0μ. In one example, the etch variables of the second etching operation (etchant chemistry, time, temperature, etc.) are selected to provide a material removal in a range of approximately 1.0μ to 1.5μ. This amount of material removal is effective to broaden edges 114, 116 of the textured surface 110, while substantially maintaining the surface roughness range 118.
The surface roughness range 118 provides the desirable high surface area for incident light, and the low reflection of incoming light away from the surface 130, while the broadening of rough edges 114, 116 provides a higher breakdown voltage for subsequently formed photovoltaic devices.
One example of a second etchant chemistry includes an acid etchant with components of nitric acid and hydrofluoric acid at a predetermined concentration ratio. An example concentration ratio of HNO3 to HF includes a molar ratio greater than or equal to 2.5 to 1 (2.5M HNO3 to 1M HF). In one example, a concentration ratio of HNO3 to HF includes a molar ratio between approximately 2.5 to 1 and 10 to 1. In one example, a concentration ratio of HNO3 to HF is approximately 4 to 1.
In one example, the second etchant chemistry includes sulfuric acid (H2SO4) in addition to the 2.5 to 1 molar concentration of HNO3 to HF. One example of a molar ratio of HNO3 to HF to H2SO4 includes 2.5 to 1 to 1.5. One example of a second etchant chemistry including an alkaline etchant includes a potassium hydroxide (KOH) etchant in a concentration range of approximately 10 to 20% heated to a temperature in a range of approximately 50° C. to 90° C.
In selected examples, other substantially etching-neutral components are included in the second etchant chemistry in addition to acids, such as nitric acid, hydrofluoric acid, or sulfuric acid, or alkaline etchants, such as KOH, without affecting the broadening of edges 114, 116. Examples of substantially etching-neutral additions include, but are not limited to, surfactants, salts for chemical activity enhancement, and acids for viscosity or surface tension adjustments.
A layer 204 of opposite conductivity type to the substrate 202 is formed to provide a p-n junction 206. In one example, the substrate 202 is doped p-type and the layer 204 is doped n-type. In one example, the substrate 202 is doped n-type and the layer 204 is doped p-type. The layer 204 can be formed by a number of processes. In one example the layer 204 is formed by diffusion of an n-type dopant, such as phosphorous. In one example, the broader, more rounded texture of the surface 220 provides a more consistent diffusion profile when forming the layer 204.
In one example, the device 200 of
The example of
Using methods for texturization described in examples above, a breakdown voltage of each individual cell 602 is increased above 14.2 volts, and the device 600 is able to use 24 cells in each string without risk of an individual cell 602 failing due to an extreme reverse bias condition as described above. One of ordinary skill in the art, having the benefit of the present disclosure will recognize that other numbers of cells and strings are within the scope of the invention, and that an acceptable breakdown voltage may change depending on other variables such as the operating current, etc.
In one example, device 704 includes etch variables (etchant chemistry, time, temperature, etc.) to provide a material removal in a range of approximately 0.5μ to 2.0μ. In one example, device 704 includes etch variables (etchant chemistry, time, temperature, etc.) to provide a material removal in a range of approximately 1.0μ to 1.5μ.
In one example, the second etchant chemistry includes a concentration ratio of HNO3 to HF includes a molar ratio greater than, or equal to 2.5 to 1 (2.5M HNO3 to 1M HF). In one example, the second etchant chemistry includes sulfuric acid (H2SO4) in addition to the 2.5 to 1 molar concentration of HNO3 to HF. One example of a molar ratio of HNO3 to HF to H2SO4 includes 2.5 to 1 to 1.5. In one example, device 704 is operable to form a polished surface, similar to the polished surface 130 described in
In one example, the system 700 of
In one example other devices are included subsequent in processing order to the first device 702 and the second device 704. In one example, a device 706 is included in the system 700 to provide dilute potassium hydroxide (KOH). In one example, a device 708 is included in the system 700 to provide a hydrofluoric acid/hydrochloric acid solution for removal of trace metals from a surface of the substrate. Although two additional devices 706 and 708 are shown in the system 700 other example devices 700 may include more than two additional devices, or no additional devices apart from device 702 and device 704. In one example, the photovoltaic manufacturing system 700 of
A second operation 804 includes etching the textured surface using a second etchant chemistry to broaden sharp edges in the etched surface. Examples of etching the textured surface using a second etchant chemistry include an alkaline etchant or an acid etchant. In one example, the second chemical etchant includes nitric acid and hydrofluoric acid with a higher nitric acid to hydrofluoric acid concentration ratio than the first etchant from operation 802, such as by having a higher nitric acid concentration and a lower hydrofluoric acid concentration than the first etchant from operation 802.
In one example, etch variables of the second operation 804 (etchant chemistry, time, temperature, etc.) provide a material removal in a range of approximately 0.5μ to 2.0μ. In one example, device 704 includes etch variables (etchant chemistry, time, temperature, etc.) to provide a material removal in a range of approximately 1.0μ to 1.5μ.
In one example, the second etchant in operation 804 includes a concentration ratio of HNO3 to HF includes a molar ratio greater than, or equal to 2.5 to 1 (2.5M HNO3 to 1M HF). In one example, the second etchant chemistry includes sulfuric acid (H2SO4) in addition to the 2.5 to 1 molar concentration of HNO3 to HF. One example of a molar ratio of HNO3 to HF to H2SO4 includes 2.5 to 1 to 1.5.
A third operation 806 includes forming a doped layer of a second conductivity type at the textured surface to form a p-n junction. A fourth operation 808 includes coupling a first electrical conductor to the doped layer of second conductivity type. A fifth operation 810 includes coupling a second electrical conductor to a back surface of the semiconductor substrate.
While a number of embodiments of the present subject matter have been described, the above embodiments are not intended to be exhaustive. It will be appreciated by those of ordinary skill in the art that any arrangement configured to achieve silicon purification using directional solidification techniques, while maintaining consistent progression of a solid-liquid interface throughout a mold can be substituted for the specific embodiment shown. Combinations of the above embodiments, and other embodiments, will be apparent to those of skill in the art upon studying the above description. This application is intended to cover any adaptations or variations of the present subject matter. It is to be understood that the above description is intended to be illustrative and not restrictive.