Patent Description:
Thin film solar cells or photovoltaic (PV) devices typically include a plurality of semiconductor layers disposed on a transparent substrate, wherein one layer serves as a window layer and a second layer serves as an absorber layer. The window layer allows the penetration of solar radiation to the absorber layer, where the optical energy is converted to usable electrical energy. The window layer further functions to form a heterojunction (p-n junction) in combination with an absorber layer. Cadmium telluride/cadmium sulfide (CdTe/CdS) heterojunction-based photovoltaic cells are one such example of thin film solar cells, where CdS functions as the window layer.

However, thin film solar cells may have low conversion efficiencies. An example of a thin film solar cell is provided in <CIT>). Thus, one of the main focuses in the field of photovoltaic devices is the improvement of conversion efficiency. Absorption of light by the window layer may be one of the phenomena limiting the conversion efficiency of a PV device. Further, a lattice mismatch between the window layer and absorber layer (e.g., CdS/CdTe) layer may lead to high defect density at the interface, which may further lead to shorter interface carrier lifetime. Thus, it is desirable to keep the window layer as thin as possible to help reduce optical losses by absorption. However, for most of the thin-film PV devices, if the window layer is too thin, a loss in performance can be observed due to low open circuit voltage (VOC) and fill factor (FF).

Thus, there is a need for improved thin film photovoltaic devices configurations, and methods of manufacturing these.

The subject matter of the present invention is defined in claim <NUM>.

These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings, wherein:.

As discussed in detail below, some of the embodiments of the invention include photovoltaic devices including selenium.

Accordingly, a value modified by a term or terms, such as "about", and "substantially" is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.

In the following specification and the claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. As used herein, the term "or" is not meant to be exclusive and refers to at least one of the referenced components (for example, a layer) being present and includes instances in which a combination of the referenced components may be present, unless the context clearly dictates otherwise.

The terms "transparent region" and "transparent layer" as used herein, refer to a region or a layer that allows an average transmission of at least <NUM>% of incident electromagnetic radiation having a wavelength in a range from about <NUM> to about <NUM>.

As used herein, the term "layer" refers to a material disposed on at least a portion of an underlying surface in a continuous or discontinuous manner. Further, the term "layer" does not necessarily mean a uniform thickness of the disposed material, and the disposed material may have a uniform or a variable thickness. Furthermore, the term "a layer" as used herein refers to a single layer or a plurality of sub-layers, unless the context clearly dictates otherwise.

As used herein, the term "disposed on" refers to layers disposed directly in contact with each other or indirectly by having intervening layers therebetween, unless otherwise specifically indicated. The term "adjacent" as used herein means that the two layers are disposed contiguously and are in direct contact with each other.

In the present disclosure, when a layer is being described as "on" another layer or substrate, it is to be understood that the layers can either be directly contacting each other or have one (or more) layer or feature between the layers. Further, the term "on" describes the relative position of the layers to each other and does not necessarily mean "on top of" since the relative position above or below depends upon the orientation of the device to the viewer. Moreover, the use of "top," "bottom," "above," "below," and variations of these terms is made for convenience, and does not require any particular orientation of the components unless otherwise stated.

As discussed in detail below, some embodiments of the invention are directed to a photovoltaic device including selenium. A photovoltaic device <NUM>, according to some embodiments of the invention, is illustrated in <FIG>. As shown in <FIG>, the photovoltaic device <NUM> includes a layer stack <NUM> and an absorber layer <NUM> disposed on the layer stack <NUM>. The absorber layer <NUM> includes selenium, and an atomic concentration of selenium varies non-linearly across a thickness of the absorber layer <NUM>.

The term "atomic concentration" as used in this context herein refers to the average number of selenium atoms per unit volume of the absorber layer. The terms "atomic concentration" and "concentration" are used herein interchangeably throughout the text. The term "varies non-linearly across the thickness" as used herein means that the rate-of-change in concentration itself varies across the thickness of the absorber layer <NUM>.

As used herein the term "linear gradient" refers to the first derivative of a given property, which when measured respect to a dimensional parameter, such as the distance from the front contact is both continuous and constant. For example, a stepwise distribution with a fixed concentration of selenium (Se) at the front contact, which then abruptly transitions to a different concentration after some distance away from the front contact, is non-linear due to the fact that the first derivative is non-continuous at the point where the concentration of Se transitions from one value to another. An exponentially varying distribution is another example of a non-linear distribution since the value of the first derivative continuously changes as a function of distance. The linearity of a given distribution may be readily assessed by plotting the logarithm of the measured property versus the logarithm of the dimensional parameter. A linear gradient implies that the data when plotted this manner can be fit to a line with a unity slope. A super-linear distribution will have a slope greater than unity and a sub-linear distribution will have a slope less than <NUM>.

Measurement of a first derivative of a material property in a real material implies averaging of the material property over a defined dimension and length scale, since the atomic nature of real materials may lead to local discontinuities of the first derivative. The non-linear distributions of interest according to some embodiments of the invention are in the axis that goes from the front contact to the back contact, which will be referred to as the z-axis or z-dimension. Thus, to measure the non-linearity of the distribution of a property along the z-axis, it may be useful to average the measured properties over the orthogonal axes, x, y in order to minimize the effect of grain-boundaries and other local inhomogeneities on the measurement.

A lower limit for the averaging window is set by the polaron radius of the material which scales the typical "size" of a charge carrier within a real material: <MAT> where h is Planck's constant, m is the effective mass of the charge carrier, and ω is the highest angular frequency of a typical vibration of the lattice, which is typically an optical phonon. In cadmium telluride (CdTe), the effective mass of the electron is about <NUM>e, where me is the mass of an electron in free space and the phonon angular frequency is about <NUM>×<NUM><NUM>. Thus, the calculated polaron radius is about <NUM> and a calculated polaron diameter is about <NUM>. Since proto-typical Gaussian or exponential wave functions have significant amplitude about <NUM>-<NUM> times their nominal characteristic size, then an estimate of the 'size' of charge carrier in CdTe based material is about <NUM>. A typical charge carrier in a CdTe type material will sample a <NUM> diameter sphere at any given time, and its behavior will to a large extent be determined by the average physical properties within this sphere. Thus, to determine the degree of non-linearity relevant to the performance of the photovoltaic cells in accordance with some embodiments of the invention, it may not be necessary to resolve non-linearities in the distribution of a given property or composition below a length scale of about <NUM>. An upper limit on the averaging required is set by the need to sample a sufficient number of points, i.e. <NUM>, along the z axis so that the linearity of the distribution may be determined.

In some embodiments, there is a step-change in the concentration of selenium across the thickness of the absorber layer. In such instances, the selenium concentration may remain substantially constant for some portion of the thickness. The term "substantially constant" as used in this context means that the change in concentration is less than <NUM> percent across that portion of the thickness.

In some embodiments, the concentration of selenium varies continuously across the thickness of the absorber layer <NUM>. Further, in such instances, the variation in the selenium concentration may be monotonic or non-monotonic. In certain embodiments, the concentration of selenium varies non-monotonically across a thickness of the absorber layer. In some instances, the rate-of-change in concentration may itself vary through the thickness, for example, increasing in some regions of the thickness, and decreasing in other regions of the thickness. A suitable selenium profile may include any higher order non-linear profile. Non-limiting examples of suitable selenium profiles include an exponential profile, a top-hat profile, a step-change profile, a square-wave profile, a power law profile (with exponent greater than <NUM> or less than <NUM>), or combinations thereof. <FIG> illustrates a few examples of representative non-linear selenium profiles in the absorber layer <NUM>. As will be appreciated by one of ordinary skill in the art, the profile of the selenium concentration may further vary after the processing steps, and the final device may include a diffused version of the profiles discussed here.

In some embodiments, the selenium concentration decreases across the thickness of the absorber layer <NUM>, in a direction away from the layer stack <NUM>. In some embodiments, the selenium concentration monotonically decreases across the thickness of the absorber layer <NUM>, in a direction away from the layer stack <NUM>. In some embodiments, the selenium concentration continuously decreases across a certain portion of the absorber layer <NUM> thickness, and is further substantially constant in some other portion of the absorber layer <NUM> thickness.

In certain embodiments, the absorber layer <NUM> includes a varying concentration of selenium such that there is higher concentration of selenium near the front interface (interface closer to the front contact) relative to the back interface (interface closer to the back contact).

In certain embodiments, the band gap in the absorber layer <NUM> may vary across a thickness of the absorber layer <NUM>. In some embodiments, the concentration of selenium may vary across the thickness of the absorber layer <NUM> such that the band gap near the front interface is lower than the band gap near the back interface.

Without being bound by any theory, it is believed that a higher concentration of selenium near the front interface relative to the back interface may further allow for a higher fraction of incident radiation to be absorbed in the absorber layer <NUM>. Moreover, selenium may improve the passivation of grain boundaries and interfaces, which can be seen through higher bulk lifetime and reduced surface recombination. Further, the lower band gap material near the front interface may enhance efficiency through photon confinement.

In some embodiments, the photovoltaic device <NUM> is substantially free of a cadmium sulfide layer. The term "substantially free of a cadmium sulfide layer" as used herein means that a percentage coverage of the cadmium sulfide layer (if present) on the underlying layer (for example, the interlayer or the buffer layer) is less than <NUM> percent. In some embodiments, the percentage coverage is in a range from about <NUM> percent to about <NUM> percent. In some embodiments, the percentage coverage is in a range from about <NUM> percent to about <NUM> percent. In certain embodiments, the photovoltaic device is completely free of the cadmium sulfide layer.

In certain embodiments, the absorber layer <NUM> may include a heterojunction. As used herein, a heterojunction is a semiconductor junction that is composed of layers/regions of dissimilar semiconductor material. These materials usually have non-equal band gaps. As an example, a heterojunction can be formed by contact between a layer or region having an excess electron concentration with a layer or region having an excess of hole concentration e.g., a "p-n" junction.

As will be appreciated by one of ordinary skill in the art, by varying the concentration of selenium in the absorber layer <NUM>, a particular region of the absorber layer <NUM> may be rendered n-type and another region of the absorber layer <NUM> may be rendered p-type. In certain embodiments, the absorber layer <NUM> includes a "p-n" junction. The "p-n" junction may be formed between a plurality of regions of the absorber layer <NUM> having different band gaps. Without being bound by any theory, it is believed that the variation in selenium concentration may allow for a p-n junction within the absorber layer <NUM> or formation of a junction between the absorber layer and the underlying TCO layer.

In some embodiments, the photovoltaic device may further include a window layer (including a material such as CdS). In some embodiments, the absorber layer <NUM> may form a p-n junction with the underlying buffer layer or the window layer. As described earlier, the thickness of the window layer (including a material such as CdS) is typically desired to be minimized in a photovoltaic device to achieve high efficiency. With the presence of the varying concentration of selenium in the absorber layer, the thickness of the window layer (e.g., CdS layer) may be reduced or the window layer may be eliminated, to improve the performance of the present device. Moreover, the present device may achieve a reduction in cost of production because of the use of lower amounts of CdS or elimination of CdS.

In some embodiments, as indicated in <FIG>, the absorber layer <NUM> includes a first region <NUM> and a second region <NUM>. As illustrated in <FIG>, the first region <NUM> is disposed proximate to the layer stack <NUM> relative to the second region <NUM>. In some embodiments, an average atomic concentration of selenium in the first region <NUM> is greater than an average atomic concentration of selenium in the second region <NUM>.

In some embodiments, the selenium concentration in the first region <NUM>, the second region <NUM>, or both the regions may further vary across the thickness of the respective regions. In some embodiments, the selenium concentration in the first region <NUM>, the second region <NUM>, or both the regions may continuously change across the thickness of the respective regions. As noted earlier, in some instances, the rate-of-rate-of-change in concentration may itself vary through the first region <NUM>, the second region <NUM>, or both the regions, for example, increasing in some portions, and decreasing in other portions.

In some embodiments, the selenium concentration in the first region <NUM>, the second region <NUM>, or both the regions may be substantially constant across the thickness of the respective regions. In some other embodiments, the selenium concentration may be substantially constant in at least a portion of the first region <NUM>, the second region <NUM>, or both the regions. The term "substantially constant" as used in this context means that the change in concentration is less than <NUM> percent across that portion or region.

The absorber layer <NUM> may be further characterized by the concentration of selenium present in the first region <NUM> relative to the second region <NUM>. In some embodiments, a ratio of the average atomic concentration of selenium in the first region <NUM> to the average atomic concentration of selenium in the second region <NUM> is greater than about <NUM>. In some embodiments, a ratio of the average atomic concentration of selenium in the first region <NUM> to the average atomic concentration of selenium in the second region <NUM> is greater than about <NUM>. In some embodiments, a ratio of the average atomic concentration of selenium in the first region <NUM> to the average atomic concentration of selenium in the second region <NUM> is greater than about <NUM>.

The first region <NUM> and the second region <NUM> may be further characterized by their thickness. In some embodiments, the first region <NUM> has a thickness in a range from about <NUM> nanometer to about <NUM> nanometers. In some embodiments, the first region <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers. In some embodiments, the first region <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers. In some embodiments, the second region <NUM> has a thickness in a range from about <NUM> nanometer to about <NUM> nanometers. In some embodiments, the second region <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers. In some embodiments, the second region <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers.

Referring again to <FIG>, in some embodiments, the first region <NUM> has a band gap that is lower than a band gap of the second region <NUM>. In such instances, the concentration of selenium in the first region <NUM> relative to the second region <NUM> may be in a range such that the band gap of the first region <NUM> is lower than the band gap of the second region <NUM>.

The absorber layer <NUM> also includes a plurality of grains separated by grain boundaries. In some embodiments, an atomic concentration of selenium in the grain boundaries is higher than the atomic concentration of selenium in the grains.

Selenium may be present in the absorber layer <NUM>, in its elemental form, as a dopant, as a compound, or combinations thereof. In certain embodiments, at least a portion of selenium is present in the absorber layer in the form of a compound. The term "compound", as used herein, refers to a macroscopically homogeneous material (substance) consisting of atoms or ions of two or more different elements in definite proportions, and at definite lattice positions. For example, cadmium, tellurium, and selenium have defined lattice positions in the crystal structure of a cadmium selenide telluride compound, in contrast, for example, to selenium-doped cadmium telluride, where selenium may be a dopant that is substitutionally inserted on cadmium sites, and not a part of the compound lattice.

In some embodiments, at least a portion of selenium is present in the absorber layer <NUM> in the form of a ternary compound, a quaternary compound, or combinations thereof. In some embodiments, the absorber layer <NUM> may further include cadmium and tellurium. In certain embodiments, at least a portion of selenium is present in the absorber layer in the form of a compound having a formula CdSexTe<NUM>-x, wherein x is a number greater than <NUM> and less than <NUM>. In some embodiments, x is in a range from about <NUM> to about <NUM>, and the value of "x' varies across the thickness of the absorber layer <NUM>.

In some embodiments, the absorber layer <NUM> may further include sulfur. In such instances, at least a portion of the selenium is present in the absorber layer <NUM> in the form of a quaternary compound including cadmium, tellurium, sulfur, and selenium. Further, as noted earlier, in such instances, the concentration of selenium may vary across a thickness of the absorber layer <NUM>.

The absorber layer <NUM> may be further characterized by the amount of selenium present. In some embodiments, an average atomic concentration of selenium in the absorber layer <NUM> is in a range from about <NUM> atomic percent to about <NUM> atomic percent of the absorber layer <NUM>. In some embodiments, an average atomic concentration of selenium in the absorber layer <NUM> is in a range from about <NUM> atomic percent to about <NUM> atomic percent of the absorber layer <NUM>. In some embodiments, an average atomic concentration of selenium in the absorber layer <NUM> is in a range from about <NUM> atomic percent to about <NUM> atomic percent of the absorber layer <NUM>.

As noted, the absorber layer <NUM> is a component of a photovoltaic device <NUM>. In some embodiments, the photovoltaic device <NUM> includes a "superstrate" configuration of layers. Referring now to <FIG>, in such embodiments, the layer stack <NUM> further includes a support <NUM>, and a transparent conductive oxide layer <NUM> (sometimes referred to in the art as a front contact layer) is disposed on the support <NUM>. As further illustrated in <FIG>, in such embodiments, the solar radiation <NUM> enters from the support <NUM>, and after passing through the transparent conductive oxide layer <NUM>, the buffer layer <NUM>, and optional intervening layers (for example, interlayer <NUM> and window layer <NUM>) enters the absorber layer <NUM>. The conversion of electromagnetic energy of incident light (for instance, sunlight) to electron-hole pairs (that is, to free electrical charge) occurs primarily in the absorber layer <NUM>.

In some embodiments, the support <NUM> is transparent over the range of wavelengths for which transmission through the support <NUM> is desired. In one embodiment, the support <NUM> may be transparent to visible light having a wavelength in a range from about <NUM> to about <NUM>. In some embodiments, the support <NUM> includes a material capable of withstanding heat treatment temperatures greater than about <NUM>, such as, for example, silica or borosilicate glass. In some other embodiments, the support <NUM> includes a material that has a softening temperature lower than <NUM>, such as, for example, soda-lime glass or a polyimide. In some embodiments certain other layers may be disposed between the transparent conductive oxide layer <NUM> and the support <NUM>, such as, for example, an anti-reflective layer or a barrier layer (not shown).

The term "transparent conductive oxide layer" as used herein refers to a substantially transparent layer capable of functioning as a front current collector. In some embodiments, the transparent conductive oxide layer <NUM> includes a transparent conductive oxide (TCO). Non-limiting examples of transparent conductive oxides include cadmium tin oxide (Cd<NUM>SnO<NUM> or CTO); indium tin oxide (ITO); fluorine-doped tin oxide (SnO:F or FTO); indium-doped cadmium-oxide; doped zinc oxide (ZnO), such as aluminum-doped zinc-oxide (ZnO:Al or AZO), indium-zinc oxide (IZO), and zinc tin oxide (ZnSnOx); or combinations thereof. Depending on the specific TCO employed and on its sheet resistance, the thickness of the transparent conductive oxide layer <NUM> may be in a range of from about <NUM> to about <NUM>, in one embodiment.

The term "buffer layer" as used herein refers to a layer interposed between the transparent conductive oxide layer <NUM> and the absorber layer <NUM>, wherein the layer <NUM> has a higher sheet resistance than the sheet resistance of the transparent conductive oxide layer <NUM>. The buffer layer <NUM> is sometimes referred to in the art as a "high-resistivity transparent conductive oxide layer" or "HRT layer".

Non-limiting examples of suitable materials for the buffer layer <NUM> include tin dioxide (SnO<NUM>), zinc tin oxide (zinc-stannate (ZTO)), zinc-doped tin oxide (SnO<NUM>:Zn), zinc oxide (ZnO), indium oxide (In<NUM>O<NUM>), or combinations thereof. In some embodiments, the thickness of the buffer layer <NUM> is in a range from about <NUM> to about <NUM>.

In some embodiments, as indicated in <FIG>, the layer stack <NUM> may further include an interlayer <NUM> disposed between the buffer layer <NUM> and the absorber layer <NUM>. The interlayer may include a metal species. Non limiting examples of metal species include magnesium, gadolinium, aluminum, beryllium, calcium, barium, strontium, scandium, yttrium, hafnium, cerium, lutetium, lanthanum, or combinations thereof. The term "metal species" as used in this context refers to elemental metal, metal ions, or combinations thereof. In some embodiments, the interlayer <NUM> may include a plurality of the metal species. In some embodiments, at least a portion of the metal species is present in the interlayer <NUM> in the form of an elemental metal, a metal alloy, a metal compound, or combinations thereof. In certain embodiments, the interlayer <NUM> includes magnesium, gadolinium, or combinations thereof.

In some embodiments, the interlayer <NUM> includes (i) a compound including magnesium and a metal species, wherein the metal species includes tin, indium, titanium, or combinations thereof; or (ii) a metal alloy including magnesium; or (iii) magnesium fluoride; or combinations thereof. In certain embodiments, the interlayer includes a compound including magnesium, tin, and oxygen. In certain embodiments, the interlayer includes a compound including magnesium, zinc, tin, and oxygen.

As indicated in <FIG> and <FIG>, in certain embodiments, the absorber layer <NUM> is disposed directly in contact with the layer stack <NUM>. However, as further noted earlier, in some embodiments, the photovoltaic device <NUM> may include a discontinuous cadmium sulfide layer interposed between the layer stack <NUM> and the absorber layer <NUM> (embodiment not shown). In such instances, the coverage of the CdS layer on the underlying layer (for example, interlayer <NUM> and the buffer layer <NUM>) is less than about <NUM> percent. Further, at least a portion of the absorber layer <NUM> may contact the layer stack <NUM> through the discontinuous portions of the cadmium sulfide layer.

Referring now to <FIG> and <FIG>, in some embodiments, the layer stack <NUM> may further include a window layer <NUM> disposed between the interlayer <NUM> and the absorber layer <NUM>. The term "window layer" as used herein refers to a semiconducting layer that is substantially transparent and forms a heterojunction with an absorber layer <NUM>. Non-limiting exemplary materials for the window layer <NUM> include cadmium sulfide (CdS), indium III sulfide (In<NUM>S<NUM>), zinc sulfide (ZnS), zinc telluride (ZnTe), zinc selenide (ZnSe), cadmium selenide (CdSe), oxygenated cadmium sulfide (CdS:O), copper oxide (Cu<NUM>O), zinc oxihydrate (ZnO:H), or combinations thereof. In certain embodiments, the window layer <NUM> includes cadmium sulfide (CdS). In certain embodiments, the window layer <NUM> includes oxygenated cadmium sulfide (CdS:O).

In some embodiments, the absorber layer <NUM> may function as an absorber layer in the photovoltaic device <NUM>. The term "absorber layer" as used herein refers to a semiconducting layer wherein the solar radiation is absorbed, with a resultant generation of electron-hole pairs. In one embodiment, the absorber layer <NUM> includes a p-type semiconductor material.

In one embodiment, a photoactive material is used for forming the absorber layer <NUM>. Suitable photoactive materials include cadmium telluride (CdTe), cadmium zinc telluride (CdZnTe), cadmium magnesium telluride (CdMgTe), cadmium manganese telluride (CdMnTe), cadmium telluride sulfide (CdTeS), zinc telluride (ZnTe), lead telluride (PbTe), mercury cadmium telluride (HgCdTe), lead sulfide (PbS), or combinations thereof. The above-mentioned photoactive semiconductor materials may be used alone or in combination. Further, these materials may be present in more than one layer, each layer having different type of photoactive material, or having combinations of the materials in separate layers.

As will be appreciated by one of ordinary skill in the art, the absorber layer <NUM> as described herein further includes selenium. Accordingly, the absorber layer <NUM> may further include a combination of one or more of the aforementioned photoactive materials and selenium, such as, for example, cadmium selenide telluride, cadmium zinc selenide telluride, zinc selenide telluride, and the like. In certain embodiments, cadmium telluride is used for forming the absorber layer <NUM>. In certain embodiments, the absorber layer <NUM> includes cadmium, tellurium, and selenium.

In some embodiments, the absorber layer <NUM> may further include sulfur, oxygen, copper, chlorine, lead, zinc, mercury, or combinations thereof. In certain embodiments, the absorber layer <NUM> may include one or more of the aforementioned materials, such that the amount of the material varies across a thickness of the absorber layer <NUM>. In some embodiments, one or more of the aforementioned materials may be present in the absorber layer as a dopant. In certain embodiments, the absorber layer <NUM> further includes a copper dopant.

In some embodiments, the absorber layer <NUM>, the window layer <NUM>, or both the layers may contain oxygen. Without being bound by any theory, it is believed that the introduction of oxygen to the window layer <NUM> (e.g., the CdS layer) may result in improved device performance. In some embodiments, the amount of oxygen is less than about <NUM> atomic percent. In some instances, the amount of oxygen is between about <NUM> atomic percent to about <NUM> atomic percent. In some instances, for example in the absorber layer <NUM>, the amount of oxygen is less than about <NUM> atomic percent. Moreover, the oxygen concentration within the absorber layer <NUM> may be substantially constant or compositionally graded across the thickness of the respective layer.

In some embodiments, the photovoltaic device <NUM> may further include a p+-type semiconductor layer <NUM> disposed on the absorber layer <NUM>, as indicated in <FIG>. The term "p+-type semiconductor layer" as used herein refers to a semiconductor layer having an excess mobile p-type carrier or hole density compared to the p-type charge carrier or hole density in the absorber layer <NUM>. In some embodiments, the p+-type semiconductor layer has a p-type carrier density in a range greater than about <NUM> × <NUM><NUM> per cubic centimeter. The p+-type semiconductor layer <NUM> may be used as an interface between the absorber layer <NUM> and the back contact layer <NUM>, in some embodiments.

In one embodiment, the p+-type semiconductor layer <NUM> includes a heavily doped p-type material including amorphous Si:H, amorphous SiC:H, crystalline Si, microcrystalline Si:H, microcrystalline SiGe:H, amorphous SiGe:H, amorphous Ge, microcrystalline Ge, GaAs, BaCuSF, BaCuSeF, BaCuTeF, LaCuOS, LaCuOSe, LaCuOTe, LaSrCuOS, LaCuOSe<NUM>Te<NUM>, BiCuOSe, BiCaCuOSe, PrCuOSe, NdCuOS, Sr<NUM>Cu<NUM>ZnO<NUM>S<NUM>, Sr<NUM>CuGaO<NUM>S, (Zn,Co,Ni)Ox, or combinations thereof. In another embodiment, the p+-type semiconductor layer <NUM> includes a p+-doped material including zinc telluride, magnesium telluride, manganese telluride, beryllium telluride, mercury telluride, arsenic telluride, antimony telluride, copper telluride, elemental tellurium or combinations thereof. In some embodiments, the p+-doped material further includes a dopant including copper, gold, nitrogen, phosphorus, antimony, arsenic, silver, bismuth, sulfur, sodium, or combinations thereof.

In some embodiments, the photovoltaic device <NUM> further includes a back contact layer <NUM>, as indicated in <FIG>. In some embodiments, the back contact layer <NUM> is disposed directly on the absorber layer <NUM> (embodiment not shown). In some other embodiments, the back contact layer <NUM> is disposed on the p+-type semiconductor layer <NUM> disposed on the absorber layer <NUM>, as indicated in <FIG>.

In some embodiments, the back contact layer <NUM> includes gold, platinum, molybdenum, tungsten, tantalum, titanium, palladium, aluminum, chromium, nickel, silver, graphite, or combinations thereof. The back contact layer <NUM> may include a plurality of layers that function together as the back contact.

In some embodiments, another metal layer (not shown), for example, aluminum, may be disposed on the back contact layer <NUM> to provide lateral conduction to the outside circuit. In certain embodiments, a plurality of metal layers (not shown), for example, aluminum and chromium, may be disposed on the back contact layer <NUM> to provide lateral conduction to the outside circuit. In certain embodiments, the back contact layer <NUM> may include a layer of carbon, such as, graphite deposited on the absorber layer <NUM>, followed by one or more layers of metal, such as the metals described above.

Referring again to <FIG>, as indicated, the absorber layer <NUM> further includes a first region <NUM> and a second region <NUM>. As further illustrated in <FIG>, the first region <NUM> is disposed proximate to the layer stack <NUM> relative to the second region <NUM>. In some embodiments, the first region <NUM> is disposed directly in contact with the window layer <NUM>. In some embodiments, the first region <NUM> is disposed directly in contact with the buffer layer <NUM> (embodiment not shown). Further, as discussed earlier, an average atomic concentration of selenium in the first region <NUM> is greater than an average atomic concentration of selenium in the second region <NUM>. In other embodiments, an average atomic concentration of selenium in the first region <NUM> is lower than an average atomic concentration of selenium in the second region <NUM>.

In alternative embodiments, as illustrated in <FIG>, a photovoltaic device <NUM> including a "substrate" configuration is presented. The photovoltaic device <NUM> includes a layer stack <NUM> and an absorber layer <NUM> disposed on the layer stack. The layer stack <NUM> includes a transparent conductive oxide layer <NUM> disposed on the absorber layer, as indicated in <FIG>. The absorber layer <NUM> is further disposed on a back contact layer <NUM>, which is disposed on a substrate <NUM>. As illustrated in <FIG>, in such embodiments, the solar radiation <NUM> enters from the transparent conductive oxide layer <NUM> and enters the absorber layer <NUM>, where the conversion of electromagnetic energy of incident light (for instance, sunlight) to electron-hole pairs (that is, to free electrical charge) occurs.

In some embodiments, the composition of the layers illustrated in <FIG>, such as, the substrate <NUM>, the transparent conductive oxide layer <NUM>, the absorber layer <NUM>, and the back contact layer <NUM> may have the same composition as described above in <FIG> for the superstrate configuration.

A method of making a photovoltaic device is also presented. The method generally includes providing an absorber layer on a layer stack, wherein the absorber layer includes selenium, and wherein an atomic concentration of selenium varies non-linearly across a thickness of the absorber layer. With continued reference to <FIG>, in some embodiments the method includes providing an absorber layer <NUM> on a layer stack <NUM>.

In some embodiments, as indicated in <FIG>, the step of providing an absorber layer <NUM> includes forming a first region <NUM> and a second region <NUM> in the absorber layer <NUM>, the first region <NUM> disposed proximate to the layer stack <NUM> relative to the second region <NUM>. As noted earlier, in some embodiments, an average atomic concentration of selenium in the first region <NUM> is greater than an average atomic concentration of selenium in the second region <NUM>.

The absorber layer <NUM> may be provided on the layer stack <NUM> using any suitable technique. In some embodiments, the step of providing an absorber layer <NUM> includes contacting a semiconductor material with a selenium source. The terms "contacting" or "contacted" as used herein means that at least a portion of the semiconductor material is exposed to, such as, in direct physical contact with a suitable selenium source in a gas, liquid, or solid phase. In some embodiments, a surface of the absorber layer may be contacted with the suitable selenium source, for example using a surface treatment technique. In some other embodiments, the semiconductor material may be contacting with a suitable selenium source, for example, using an immersion treatment.

In some embodiments, the semiconductor material includes cadmium. Non-limiting examples of a suitable semiconductor material include cadmium telluride (CdTe), cadmium zinc telluride (CdZnTe), cadmium magnesium telluride (CdMgTe), cadmium manganese telluride (CdMnTe), cadmium sulfur telluride (CdSTe), zinc telluride (ZnTe), lead telluride (PbTe), lead sulfide (PbS), mercury cadmium telluride (HgCdTe), or combinations thereof. In certain embodiments, the semiconductor material includes cadmium and tellurium.

The term "selenium source" as used herein refers to any material including selenium. Non-limiting examples of a suitable selenium source include elemental selenium, cadmium selenide, oxides of cadmium selenide, such as, for example, cadmium selenite (CdSeO<NUM>), hydrogen selenide, organo-metallic selenium, or combinations thereof.

The portion of the semiconductor material contacted with the selenium source may depend, in part, on the physical form of the selenium source during the contacting step. In some embodiments, the selenium source is in the form of a solid (for example, a layer), a solution, a suspension, a paste, vapor, or combinations thereof.

The selenium source may be in the form a vapor, and the method may include depositing the selenium source using a suitable vapor deposition technique. For example, the absorber layer <NUM> may be heat treated in the presence of a selenium source (for example, selenium vapor) to introduce selenium into at least a portion of the absorber layer <NUM>.

For example, the selenium source may be in the form of a layer, and the method may include depositing a selenium source layer on the semiconductor material, or, alternatively, depositing the semiconductor material on a layer of the selenium source. The method may further include subjecting the semiconductor material to one or more post-processing steps to introduce the selenium into the semiconductor material.

Referring now to <FIG>, in some embodiments, the step of providing an absorber layer includes (a) disposing a selenium source layer <NUM> on the layer stack <NUM>; (b) disposing an absorber layer <NUM> on the selenium source layer <NUM>; and (c) introducing selenium into at least a portion of the absorber layer <NUM>. It should be noted, that the steps (b) and (c) may be performed sequentially or simultaneously.

The selenium source layer <NUM> may be disposed on the layer stack <NUM> using any suitable deposition technique, such as, for example, sputtering, sublimation, evaporation, or combinations thereof. The deposition technique may depend, in part, on one or more of the selenium source material, the selenium source layer <NUM> thickness, and the layer stack <NUM> composition. In certain embodiments, the selenium source layer <NUM> may include elemental selenium and the selenium source layer <NUM> may be formed by evaporation. In certain embodiments, the selenium source layer <NUM> may include cadmium selenide, and the selenium source layer <NUM> may be formed by sputtering, evaporation, or sublimation.

The selenium source layer may include a single selenium source layer or a plurality of selenium source layers. The selenium source may be the same or different in the plurality of source layers. The selenium source layer includes a plurality of selenium source layers, such as, for example, a stack of elemental selenium layer and a cadmium selenide layer, or vice versa.

The selenium source layer <NUM> may have a thickness in a range from about <NUM> nanometer to about <NUM> nanometers. The selenium source layer <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers. In some embodiments, the selenium source layer <NUM> has a thickness in a range from about <NUM> nanometers to about <NUM> nanometers.

As noted, the method further includes disposing an absorber layer <NUM> on the selenium source layer <NUM>. The absorber layer <NUM> may be deposited using a suitable method, such as, close-space sublimation (CSS), vapor transport deposition (VTD), ion-assisted physical vapor deposition (IAPVD), radio frequency or pulsed magnetron sputtering (RFS or PMS), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), or electrochemical deposition (ECD).

The method further includes introducing selenium into at least a portion of the absorber layer <NUM>. The method includes introducing selenium into at least a portion of the absorber layer <NUM> such that a concentration of selenium varies non-linearly across the thickness of the absorber layer <NUM>.

At least a portion of selenium is introduced in the absorber layer <NUM> simultaneously with the step of disposing the absorber layer <NUM>. In some embodiments, at least a portion of selenium may be introduced after the step of disposing the absorber layer <NUM>, for example, during the cadmium chloride treatment step, during the p+-type layer formation step, during the back contact formation step, or combinations thereof.

In some embodiments, the step of providing an absorber layer <NUM> includes co-depositing a selenium source material and a semiconductor material. Suitable non-limiting examples of co-deposition include co-sputtering, co-sublimation, or combinations thereof. Non-limiting examples of a suitable selenium source material in such instance includes elemental selenium, cadmium selenide, hydrogen selenide, cadmium telluride selenide, or combinations thereof. Thus, by way of example, in some embodiments, an absorber layer <NUM> may be provided by depositing the semiconductor material in the presence of selenium source (for example, selenium containing vapor or hydrogen selenide vapor).

In some embodiments, the absorber layer <NUM> may be provided by sputtering from a single target (for example, cadmium selenide telluride target) or a plurality of targets (for example, cadmium telluride and cadmium selenide targets). As will be appreciated by one of ordinary skill in the art, the concentration of selenium in the absorber layer <NUM> may be varied by controlling one or both of target(s) composition and sputtering conditions.

As noted earlier, the photovoltaic device <NUM> and the layer stack <NUM> may further include one or more additional layers, for example, a support <NUM>, a transparent conductive oxide layer <NUM>, a buffer layer <NUM>, an interlayer <NUM>, a p+-type semiconductor layer <NUM>, and a back contact layer <NUM>, as depicted in <FIG>.

As understood by a person skilled in the art, the sequence of disposing the three layers or the whole device may depend on a desirable configuration, for example, "substrate" or "superstrate" configuration of the device.

A method for making a photovoltaic <NUM> in superstrate configuration is described. Referring now to <FIG>, the method further includes disposing the transparent conductive oxide layer <NUM> on a support <NUM>. The transparent conductive oxide layer <NUM> is disposed on the support <NUM> by any suitable technique, such as sputtering, chemical vapor deposition, spin coating, spray coating, or dip coating. Referring again to <FIG>,a buffer layer <NUM> may be deposited on the transparent conductive oxide layer <NUM> using sputtering. The method may further include disposing an interlayer <NUM> on the buffer layer <NUM> to form a layer stack <NUM>, as indicated in <FIG>.

The method may further include disposing a window layer <NUM> on the interlayer <NUM> to form a layer stack <NUM>, as indicated in <FIG> and <FIG>. Non-limiting examples of the deposition methods for the window layer <NUM> include one or more of close-space sublimation (CSS), vapor transport deposition (VTD), sputtering (for example, direct current pulse sputtering (DCP), electro-chemical deposition (ECD), and chemical bath deposition (CBD).

The method further includes providing an absorber layer <NUM> on the layer stack <NUM>, as described in detail earlier. In some embodiments, a series of post-forming treatments may be further applied to the exposed surface of the absorber layer <NUM>. These treatments may tailor the functionality of the absorber layer <NUM> and prepare its surface for subsequent adhesion to the back contact layer(s) <NUM>. For example, the absorber layer <NUM> may be annealed at elevated temperatures for a sufficient time to create a quality p-type layer. Further, the absorber layer <NUM> may be treated with a passivating agent (e.g., cadmium chloride) and a tellurium-enriching agent (for example, iodine or an iodide) to form a tellurium-rich region in the absorber layer <NUM>. Additionally, copper may be added to absorber layer <NUM> in order to obtain a low-resistance electrical contact between the absorber layer <NUM> and a back contact layer(s) <NUM>.

Referring again to <FIG>, a p+-type semiconducting layer <NUM> may be further disposed on the absorber layer <NUM> by depositing a p+-type material using any suitable technique, for example PECVD or sputtering. In an alternate embodiment, as mentioned earlier, a p+-type semiconductor region may be formed in the absorber layer <NUM> by chemically treating the absorber layer <NUM> to increase the carrier density on the back-side (side in contact with the metal layer and opposite to the window layer) of the absorber layer <NUM> (for example, using iodine and copper). In some embodiments, a back contact layer <NUM>, for example, a graphite layer may be deposited on the p+-type semiconductor layer <NUM>, or directly on the absorber layer <NUM> (embodiment not shown). A plurality of metal layers may be further deposited on the back contact layer <NUM>.

One or more of the absorber layer <NUM>, the back contact layer <NUM>, or the p+-type layer <NUM> (optional) may be further heated or subsequently treated (for example, annealed) after deposition to manufacture the photovoltaic device <NUM>.

In some embodiments, other components (not shown) may be included in the exemplary photovoltaic device <NUM>, such as, buss bars, external wiring, laser etches, etc. For example, when the device <NUM> forms a photovoltaic cell of a photovoltaic module, a plurality of photovoltaic cells may be connected in series in order to achieve a desired voltage, such as through an electrical wiring connection. Each end of the series connected cells may be attached to a suitable conductor such as a wire or bus bar, to direct the generated current to convenient locations for connection to a device or other system using the generated current. In some embodiments, a laser may be used to scribe the deposited layers of the photovoltaic device <NUM> to divide the device into a plurality of series connected cells.

A cadmium telluride photovoltaic device was made by depositing several layers on a cadmium tin oxide (CTO) transparent conductive oxide (TCO)-coated substrate. The substrate was a <NUM> millimeters thick PVN++ glass, which was coated with a CTO transparent conductive oxide layer and a thin high resistance transparent zinc tin oxide (ZTO) buffer layer. A magnesium-containing capping layer was then deposited on the ZTO buffer layer to form an interlayer. The window layer (approximately <NUM> nanometers thick) containing cadmium sulfide (CdS:O, with approximately <NUM> molar % oxygen in the CdS layer) was then deposited on the interlayer by DC sputtering and then annealed at an elevated temperature. An approximately <NUM> thick Cd(Te,Se) film was then deposited by close space sublimation from a source material with a Se/(Se+Te) ratio of approximately <NUM>%. The pressure was fixed at approximately <NUM> Torr with a small amount of oxygen in the He background gas. After deposition, the stack was treated with CdCl<NUM> and then baked at temperature greater than <NUM>. Following the bake excess CdCl<NUM> was removed. Approximately <NUM> microns CdTe film was then deposited by close space sublimation in the presence of about <NUM> Torr of O<NUM>. After the second deposition, a second CdCl<NUM> treatment and subsequent bake followed by removal of excess CdCl<NUM> was performed before forming a back contact.

The Se deposition profile in the device was measured using dynamic secondary ion mass spectroscopy (DSIMS) performed. Prior to the measurement, the samples were polished to reduce the effects of surface roughness. The results for Se ion concentration (in atoms/cm<NUM>) are shown in <FIG>. The peak of the Se concentration is near the location window and buffer layers. The depth axis is the distance in microns from the polished edge of the sample. Since the polishing procedure removes some amount of CdTe, the total thickness of the alloy layer is less than the thickness of the Cd(Se)Te alloy layer of the original solar cell.

To assess the non-linear nature of the distribution of the Se within the absorber layer the data was filtered to remove points after the peak of the Se distribution in the in data. The data was then plotted on a log-log plot. The data is shown in <FIG>. Two functions were fitted on the log-log plot: one a linear fit which a slope of <NUM>, which is indicative of super-linear distribution. Since the overall fit quality was poor, the log-log data was also fit to an exponentially rising function, which gave a significantly better fit indicating that the measured Se distribution is highly non-linear.

To illustrate some of the non-linear profiles, simulations were carried out using the one-dimensional solar cell simulation program SCAPS v. <NUM> (<NPL>) The program numerically solves the Poisson and continuity equations for electrons and holes in a single dimension to determine the band-diagram of the device and its response to illumination, voltage bias, and temperature. Performance calculations were made using simulated IV sweeps in the simulation under illumination by the AM1. <NUM> spectrum at 100mW/cm<NUM> of intensity and <NUM>, also known as Standard Test Conditions (STC). The model parameters for CdTe and device design were set according to the parameters given by Gloeckler et. for CdTe solar cells. (<NPL>)), except that the CdTe absorber layer thickness was increased to <NUM> microns and the nature of the deep trap in the CdTe absorber layers was changed from 'donor' to neutral. The CdSe parameters were set to have the same values as the CdTe parameters, except that the deep trap density in the CdSe is a factor of ten lower and the band gap is <NUM> eV. A model for the variation in the properties of the alloy material CdTe<NUM>-xSex as a function of x, the faction Se substitution, was constructed. The model assumes that the Eg of the CdTe is equal to <NUM> eV, the gap of the CdSe is equal to <NUM> and a bowing parameter, b = <NUM>. The band gap of the alloy is given by: <MAT>.

The other material properties, such as carrier mobilities and dielectric constant values were assumed to be independent of alloy composition and the deep donor concentration varied linearly between the CdTe and CdSe values as function of x.

In Example <NUM>, simulation was conducted using the measured DSIMS Se profile as input. The measured DSIMS profile was fit to a bi-exponential decay profile and the parameters from the fit used to calculate a Se concentration profile throughout the <NUM> micron thickness of the absorber layer.

In Example <NUM>, an exponential Se concentration profile was assumed, rising from about x = <NUM> in the back to <NUM> in the front. The total amount of Se in the device was about <NUM> times that of the device described in Example <NUM>.

In Example <NUM>, a top-hat Se concentration profile was assumed. In the particular top-hat profile, x = <NUM> from the back of the device until about <NUM> microns from the front interface, whereupon it rises. From this point, x = <NUM> until the front of the absorber layer is reached. The total amount of Se in the device was about <NUM> times that of the device described in Example <NUM>.

For this simulation, the device had no Se and used the inputs as specified by Gloeckler except for the modifications noted previously. The calculated performance metrics of this model cell (efficiency, Voc, Jsc, and fill factor (FF)) were used as the reference levels for the other examples and their respective performance metrics were normalized to this baseline case.

For this simulation, a linear Se concentration profile was used assuming the same total amount of Se as determined via the DSIMS profile. In this calculation, a linear gradient in Se concentration was input into the device model. The value of x was set to <NUM> at the back contact and to about <NUM> in front.

For this simulation, a constant Se concentration profile with x= <NUM> was assumed throughout the absorbing layer of the device. The total amount of Se in the device was about <NUM> times that of the device described in Example <NUM>.

For this simulation, the Se concentration profile was assumed to be a linear ramp starting from x=<NUM> at the back contact and rising to x= <NUM> at the front of the device. The total amount of Se in the device is about <NUM> times that of the device described in Example <NUM>.

The performance metrics of Examples <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> relative to the baseline cell of Comparative Example <NUM> are reported in Table <NUM>. <FIG> shows the Se concentration profile as a function of CdTe thickness for Comparative Examples <NUM>-<NUM> and Examples <NUM>-<NUM>.

As illustrated in Table <NUM>, the device performance parameters showed improvement for the devices with a non-linear graded CdTeSe layer (Examples <NUM>-<NUM>) when compared to the device without a CdTeSe layer (Comparative Example <NUM>). For the same amount of Se, the device performance parameters further showed improvement for the devices with a non-linear graded CdTeSe layer (Example <NUM>) when compared to the device with a linear gradient of Se in CdTeSe layer (Comparative Example <NUM>). Both the 'exponential' and 'top-hat' non-linear Se concentration profiles (Examples <NUM>-<NUM>) demonstrated superior efficiency to cells that had either constant or linearly graded Se concentration profiles (Comparative Examples <NUM> and <NUM>), despite have a much lower total amount of Se present in the layer.

It should be noted that while the profiles in the example set are primarily confined the front, some degree of shifting of the Se profile may lead to improvement in overall device performance, particularly if the doping profiles or the energy levels of the front and back contacts are adjusted. In such cases it is possible that optimal position of the peak of the Se is not at the front interface next to the buffer layer.

Claim 1:
A photovoltaic device (<NUM>, <NUM>), comprising:
a layer stack (<NUM>, <NUM>);
a back contact layer (<NUM>, <NUM>); and
an absorber layer (<NUM>, <NUM>) disposed on the layer stack (<NUM>, <NUM>), the absorber layer (<NUM>, <NUM>) comprising a front interface and a back interface; wherein:
the absorber layer (<NUM>, <NUM>) is an alloy comprising cadmium, tellurium, and selenium;
an atomic concentration of selenium varies non-linearly across a thickness of the absorber layer (<NUM>, <NUM>); and
the absorber layer (<NUM>, <NUM>) includes a varying concentration of selenium such that there is a higher concentration of selenium near the front interface relative to the back interface.