FIELD OF THE INVENTION

[0001] The subject matter disclosed herein relates generally to forming a conductive transparent oxide film layer. More particularly, the subject matter disclosed herein relates to methods of forming a conductive transparent oxide film layer for use in cadmium telluride thin film photovoltaic devices.

BACKGROUND OF THE INVENTION

[0002] Thin film photovoltaic (PV) modules (also referred to as "solar panels") based on cadmium telluride (CdTe) are gaining wide acceptance and interest in the industry. CdTe is a semiconductor material having characteristics particularly suited for conversion of solar energy to electricity. For example, CdTe has an energy bandgap of about 1.45 eV, which enables it to convert more energy from the solar spectrum as compared to lower bandgap semiconductor materials historically used in solar cell applications (e.g., about 1.1 eV for silicon). Also, CdTe converts radiation energy in lower or diffuse light conditions as compared to the lower bandgap materials and, thus, has a longer effective conversion time over the course of a day or in cloudy conditions as compared to other conventional materials. The junction of the n-type layer and the p-type layer is generally responsible for the generation of electric potential and electric current when the CdTe PV module is exposed to light energy, such as sunlight. Specifically, the cadmium telluride (CdTe) layer and a layer of cadmium sulfide (CdS) form a p-n heterojunction, where the CdTe layer acts as a p- type layer (i.e., an electron accepting layer) and the CdS layer acts as a n-type layer (i.e., an electron donating layer).

[0003] A transparent conductive oxide ("TCO") layer is commonly used between the window glass and the junction forming layers. For example, the TCO layer may be sputtered from a cadmium stannate (i.e., Cd ₂ Sn0 ₄ ) target by either of two processes: hot sputtering or cold sputtering. When hot sputtered, the TCO layer is typically deposited at sputtering temperatures above about 250° C in a one step sputtering process. When cold sputtered (e.g., at about room temperature), the TCO layer must be annealed following sputtering of the layer in a second step to convert the layer from an amorphous layer to a crystalline layer.

[0004] Though the hot sputtering process is more streamlined (i.e., only requiring a single step), the hot sputtered TCO layers can have a much higher resistivity than the cold sputtered TCO layers - even when sputtered from the same material (e.g., cadmium stannate) - making the hot sputtered TCO layer less attractive for the end use. Although not wishing to be bound by any particular theory, it is believed that this difference in resistivities between the hot sputtered layer and the cold sputtered layer likely stems from a difference in the as-deposited stoichiometry. For example, when sputtering from a cadmium stannate target, it is presently believed that cold sputtering produces a layer having the stoichiometry Cd ₂ Sn0 ₄ , which is the desired stoichiometry for cadmium stannate. However, other processing issues exist that hinders the viability of cold sputtering to form the TCO layer, especially from a cadmium stannate target. For example, the annealing process can sublimate cadmium atoms off of the TCO layer, altering the stoichiometry of the TCO layer, especially along its outer surface.

[0005] To counteract this loss of cadmium atoms from the surface of the TCO layer, the TCO layer is typically annealed in contact with an anneal plate containing cadmium. For instance, an anneal plate having cadmium sulfide on its surface contacting the TCO layer can be used to provide additional cadmium to the TCO layer during annealing to inhibit the loss of cadmium from the TCO layer.

[0006] However, a contact plate is awkward for manufacturing use in a large commercial-scale manufacturing setting, and becomes depleted of cadmium during repeated use, requiring plate change. As such, the use of such anneal plates adds manufacturing processes and materials, effectively increasing the manufacturing cost and complexity for formation of the PV modules. Thus, a need exists for methods of forming a TCO layer having the conductivity of cold sputtered layers with the processing ease found in those hot sputtered layers. BRIEF DESCRIPTION OF THE INVENTION

[0007] Aspects and advantages of the invention will be set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the invention.

[0008] Methods are generally provided for forming a conductive oxide layer on a substrate. In one embodiment, the method includes sputtering a target to deposit a transparent conductive oxide layer (e.g., comprising comprises cadmium, tin, and oxygen) on the substrate; positioning an anneal surface in close proximity to the transparent conductive oxide layer (e.g., about 3 cm or less); and, annealing the transparent conductive oxide layer while the anneal surface is in close proximity to the transparent conductive oxide layer (e.g., at an anneal temperature of about 500° C to about 700° C). The anneal surface can include a material reactive with oxygen at the anneal temperature (e.g., graphite, titanium, zirconium, aluminum, tin, cadmium, nickel, zinc, magnesium, chromium, tantalum, tungsten, or mixtures, or alloys thereof). In one particular embodiment, the transparent conductive oxide layer is annealed while the anneal surface is in close proximity to the transparent conductive oxide layer to create a localized cadmium vapor between the transparent conductive oxide layer and the anneal surface.

[0009] Apparatus is also generally provided for annealing a thin film layer on a substrate. In one embodiment, the apparatus includes a conveyor system configured to transport a substrate through the apparatus; an anneal surface (e.g., having a material reactive with oxygen at the anneal temperature) positioned so as to be in close proximity to the thin film layer as the substrate is transported through the apparatus on the conveyor system; and, a heating element configured to heat the thin film layer on the substrate as the substrate is transported through the apparatus on the conveyor system.

[0010] These and other features, aspects and advantages of the present invention will become better understood with reference to the following description and appended claims. The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] A full and enabling disclosure of the present invention, including the best mode thereof, directed to one of ordinary skill in the art, is set forth in the

specification, which makes reference to the appended figures, in which:

[0012] Fig. 1 shows a general schematic of a cross-sectional view of an exemplary cadmium telluride thin film photovoltaic device according to one embodiment of the present invention;

[0013] Fig. 2 shows a flow diagram of an exemplary method of manufacturing a photovoltaic module including a cadmium telluride thin film photovoltaic device;

[0014] Fig. 3 shows a general schematic of a cross-sectional view of an exemplary sputtering chamber according to one embodiment of the present invention;

[0015] Fig. 4 shows a general schematic of an exemplary anneal oven according to one embodiment of the present invention;

[0016] Fig. 5 shows a general schematic of an exemplary anneal oven according to another embodiment of the present invention; and,

[0017] Fig. 6 shows a general schematic of an exemplary anneal oven according to yet another embodiment of the present invention.

[0018] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements.

DETAILED DESCRIPTION OF THE INVENTION

[0019] Reference now will be made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention, not limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment can be used with another embodiment to yield a still further

embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.

[0020] In the present disclosure, when a layer is being described as "on" or "over" another layer or substrate, it is to be understood that the layers can either be directly contacting each other or have another layer or feature between the layers. Thus, these terms are simply describing the relative position of the layers to each other and do not necessarily mean "on top of since the relative position above or below depends upon the orientation of the device to the viewer. Additionally, although the invention is not limited to any particular film thickness, the term "thin" describing any film layers of the photovoltaic device generally refers to the film layer having a thickness less than about 10 micrometers ("microns" or "μιη").

[0021] It is to be understood that the ranges and limits mentioned herein include all ranges located within the prescribed limits (i.e., subranges). For instance, a range from about 100 to about 200 also includes ranges from 110 to 150, 170 to 190, 153 to 162, and 145.3 to 149.6. Further, a limit of up to about 7 also includes a limit of up to about 5, up to 3, and up to about 4.5, as well as ranges within the limit, such as from about 1 to about 5, and from about 3.2 to about 6.5.

[0022] Methods are generally disclosed for forming a transparent conductive oxide layer ("TCO layer") on a substrate (e.g., via sputtering) followed by annealing the TCO layer in contact with or in close proximity to an annealing surface. The TCO layer generally includes cadmium, such as a TCO layer including cadmium stannate (i.e., Cd ₂ Sn0 ₄ ) or stoichiometric variation of cadmium, tin, and oxygen. Other materials may also be present in the TCO layer, including other oxides (e.g., tin oxide, zinc oxide, or indium tin oxide, or mixtures thereof). Additionally, the TCO layer can include other conductive, transparent materials.

[0023] After forming the TCO layer onto the substrate, the TCO layer is annealed while in close proximity to (including in contact with) an annealing surface to re- crystallize the TCO layer into a more uniform thin film layer on the substrate.

Without wishing to be bound by any particular theory, it is believed that the proximity of the annealing surface with the TCO layer can inhibit sublimation of cadmium atoms from the surface of the substrate during the annealing process. For instance, during annealing, the close proximity of the anneal surface creates a local

environment saturated with cadmium vapor (as it initially sublimates from the TCO layer during anneal). This cadmium vapor in the local environment close to the TCO layer during annealing forms an equilibrium-type relationship between the surface of the TCO layer and the local environement to force more cadmium atoms to remain in the TCO layer during the annealing process. As such, the transparent conductive oxide layer can be annealed while in close proximity to the transparent conductive oxide layer to create a localized cadmium vapor between the transparent conductive oxide layer and the anneal surface.

[0024] Additionally, by including a material reactive with oxygen at the anneal temperature, the anneal surface can remove oxygen atoms from the TCO layer during annealing by acting as an oxygen getter. Specifically, oxygen can sublimate from the TCO layer and be adsorbed by or can react with the anneal surface during annealing such that the crystallized TCO layer (i.e., the post-anneal TCO layer) has less oxygen after annealing than the as-deposited TCO layer (i.e., prior to annealing). For example, if formed from graphite, oxygen can react with the graphite to form a carbon-oxide molecule (e.g., CO, C0 ₂ , etc.). Without wishing to be bound by any particular theory, it is believed that the removal of oxygen atoms from the TCO layer during annealing can promote oxygen vacancies in the resulting recrystalized TCO layer, which can lead to high carrier concentration. Thus, the crystallized TCO layer formed after annealing can have high conductivity (e.g., greater than about 5500 S/cm).

[0025] In one particular embodiment, the TCO layer can be formed by sputtering (e.g., DC sputtering or RF sputtering) on the substrate from a target (e.g., a target including cadmium stannate or a target including an alloy of cadmium and tin). For example, a cadmium stannate layer can be formed by sputtering a hot-pressed target containing cadmium stannate (Cd ₂ Sn0 ₄ ) and/or stoichiometric amounts of Sn0 ₂ and CdO onto the substrate in a stoichiometric ratio of about 1 to about 2. Alternatively, a cadmium stannate layer can be formed by sputtering a metal target of cadmium and tin in an oxidizing atmosphere (e.g., a sputtering atmosphere comprising oxygen at about 100% by volume).

[0026] The sputtering temperature of the substrate during deposition of the TCO layer containing cadmium stannate is, in one particular embodiment, relatively low and can be referred to as "cold sputtering." For example, the sputtering temperature can be about 10° C to about 100° C, such as about 20° C to about 50° C. In one particular embodiment, the sputtering temperature can be room temperature (e.g., about 20° C to about 25° C). [0027] Sputtering deposition generally involves ejecting material from a target, which is the material source, and depositing the ejected material onto the substrate to form the film. DC sputtering generally involves applying a direct current to a metal target (i.e., the cathode) positioned near the substrate (i.e., the anode) within a sputtering chamber to form a direct-current discharge. The sputtering chamber can have a reactive atmosphere (e.g., an oxygen atmosphere, nitrogen atmosphere, fluorine atmosphere) that forms a plasma field between the metal target and the substrate. Other inert gases (e.g., argon, etc.) may also be present. The pressure of the reactive atmosphere can be between about 1 mTorr and about 20 mTorr for magnetron sputtering. The pressure can be even higher for diode sputtering (e.g., from about 25 mTorr to about 100 mTorr). When metal atoms are released from the target upon application of the voltage, the metal atoms deposit onto the surface of the substrate. For example, when the atmosphere contains oxygen, the metal atoms released from the metal target can form a metallic oxide layer on the substrate. The current applied to the source material can vary depending on the size of the source material, size of the sputtering chamber, amount of surface area of substrate, and other variables. In some embodiments, the current applied can be from about 2 amps to about 20 amps.

[0028] Conversely, RF sputtering involves exciting a capacitive discharge by applying an alternating-current (AC) or radio-frequency (RF) signal between the target (e.g., a ceramic source material) and the substrate. The sputtering chamber can have an inert atmosphere (e.g., an argon atmosphere) which may or may not contain reactive species (e.g., oxygen, nitrogen, etc.) having a pressure between about 1 mTorr and about 20 mTorr for magnetron sputtering. Again, the pressure can be even higher for diode sputtering (e.g., from about 25 mTorr to about 100 mTorr).

[0029] Fig. 3 shows a general schematic as a cross-sectional view of an exemplary DC sputtering chamber 60 according to one embodiment of the present invention. A DC power source 62 is configured to control and supply DC power to the chamber 60. As shown, the DC power source applies a voltage to the cathode 64 to create a voltage potential between the cathode 64 and an anode formed by the chamber wall, such that the substrate is in between the cathode and anode. The substrate 12 is held between top support 66 and bottom support 67 via wires 68 and 69, respectively. Generally, the substrate 12 is positioned within the sputtering chamber 60 such that the TCO layer 14 is formed on the surface facing the cathode 64.

[0030] A plasma field 70 is created once the sputtering atmosphere is ignited, and is sustained in response to the voltage potential between the cathode 64 and the chamber wall acting as an anode. The voltage potential causes the plasma ions within the plasma field 70 to accelerate toward the cathode 64, causing atoms from the cathode 64 to be ejected toward the surface on the glass substrate 12. As such, the cathode 64 can be referred to as a "target" and acts as the source material for the formation of the TCO layer 14 on the surface facing the cathode 64. The cathode 64 can be a metal alloy target, such as elemental tin, elemental zinc, or mixtures thereof. Additionally, in some embodiments, a plurality of cathodes 64 can be utilized. A plurality of cathodes 64 can be particularly useful to form a layer including several types of materials (e.g., co-sputtering). If the sputtering atmosphere contains oxygen gas, oxygen particles of the plasma field 70 can react with the ejected target atoms to form an oxide layer on the TCO layer 14 on the glass substrate 12.

[0031] Although only a single DC power source 62 is shown, the voltage potential can be realized through the use of multiple power sources coupled together.

Additionally, the exemplary sputtering chamber 60 is shown having a vertical orientation, although any other configuration can be utilized.

[0032] For example, the TCO layer can be formed via sputtering at the specified sputtering temperature (i.e., cold sputtering) from a cadmium stannate target to form a cadmium stannate TCO layer on the substrate. After sputtering the TCO layer, the substrate with the TCO layer can then be transferred into an anneal oven.

[0033] After deposition of the TCO layer via sputtering, the resulting as-deposited TCO layer is annealed as discussed above. Each of Figs. 4 and 5 shows a side-view diagram of an exemplary annealing oven 100 suitable for annealing the TCO layer in close proximity to a annealing surface. A substrate 12, which has the as-deposited TCO layer 14 on its surface, can pass from the sputtering chamber and into the anneal chamber 100 though the slit 101, past the anneal system 124, and out of the anneal chamber 100 through the slit 103. The substrate 12 is shown traveling along rollers 105 through the anneal oven 100, although any carrier system can be utilized to transport the substrate 12 though the anneal oven 100 (e.g., a conveyor system, etc.). The sputtering chamber can be adjacent to the anneal chamber 100 or may be separated from the anneal chamber 100, as long as the sputtering atmosphere in the sputtering chamber is separated from the annealing atmosphere in the anneal chamber 100.

[0034] The anneal oven 100 can be connected to a vacuum pump 102 to control the annealing pressure of the annealing atmosphere within the anneal oven 100.

Heating elements 104 are configured to heat the annealing atmosphere within the anneal oven 100 to the desired annealing temperature (e.g., about 500° C to about 700° C), which can in-turn heat the substrate 12 and the TCO layer 14 to the anneal temperature. Although shown inside the anneal oven 100, any heating element 104, positioned inside or outside of the anneal oven can be used to provide heat to the anneal oven 100. In one particular embodiment, the inner walls 106 of the anneal oven 100 can be hot oven walls (i.e., heated to about the annealing temperature) to provide heat to the annealing atmosphere inside the anneal oven 100. Additionally, any number of heating elements 104 can be utilized in conjunction with the anneal oven 100.

[0035] Source gas lines 107, 108 can supply various gases to the anneal oven 100, while valves 110, 111 can control the gas flow rate of a particular gas through the source gas lines 107, 108 from a gas source 113, 114, respectively, into the anneal oven 100. For example, a first source gas line 107 controlled by valve 110 can regulate the amount of inert gas in annealing atmosphere of the anneal oven 100 supplied from the cadmium source tank 1 13, while a second source gas line 108 controlled by valve 111 can regulate the amount of optional gas (e.g., a reducing gas, a cadmium-source gas, etc.) in the annealing atmosphere of the anneal oven 100 supplied from the inert gas source tank 114. Of course, any suitable design of an anneal oven can be utilized in accordance with the present disclosure, including any number of suitable source gas lines and gas sources.

[0036] Fig. 4 shows an anneal system 124 driven in an endless loop within the anneal oven 100 around sprockets 126, with the endless loop having a bottom leg 131 that moves in a conveyance direction of the substrates 12 through the anneal oven 100, and an upper leg 129 that moves in an opposite return direction. The anneal system 124 includes a plurality of interconnected slats 128, each defining flat outer surface. Thus, the interconnected slats 128 form a planar anneal surface 130 defined by adjacent slats 128 along the bottom leg 131 of the anneal system 124 such that the outer surfaces of the slats 128 lie in a common horizontal plane and define an uninterrupted annealing surface. As the substrates 12 pass into the anneal oven 100, the TCO layer 14 on the substrate 12 can be annealed within close proximity to or in contact with the planar anneal surface 130.

[0037] A tension control 127 can move one or both of the sprockets 126 horizontally to adjust the tension in the anneal system 124 (i.e., out to increase tension or in to decrease tension), in turn controlling the distance that the anneal surface 130 is from the outer surface of the TCO layer 14 on the substrate 12. For instance, in one embodiment, the planar anneal surface 130 can contact the TCO layer 14 during annealing or can be in close proximity to the TCO layer 14 during annealing, such as about 3 centimeters (cm) or closer. For example, the planar anneal surface 130 can be about 0.1 millimeter (mm) to about 1 cm from the surface of the TCO layer, such as about 1 mm to about 5 mm (e.g., about 2 mm to about 4 mm). In one particular embodiment, the planar anneal surface 130 can rest on top of the TCO layer 14 and move in unison with the substrate 12 as it travels along rollers 105 through the anneal oven 100.

[0038] The slats 128 can be configured to withstand the anneal temperatures and the deposition of the cap material. For example, the slats 128 can be constructed from graphite, a ceramic (e.g., alumina, etc.), quartz, high temperature metallic materials (e.g., molybdenum, titanium, or alloys thereof), and the like.

[0039] As discussed above, no matter the internal composition of the slats 128, the slats 128 have an outer surface defining the anneal surface 130 that is composed of a material reactive with oxygen at the anneal temperature. In one embodiment, the anneal surface 130 can include graphite (e.g., can consist essentially of graphite). Alternatively, the anneal surface 130 can include an oxygen reactive metal (e.g., titanium, zirconium, aluminum, tin, cadmium, nickel, zinc, magnesium, chromium, tantalum, tungsten, or alloys thereof), such as consisting essentially of an oxygen reactive metal. [0040] Fig. 5 shows another exemplary embodiment of an annealing oven 100 that is similar to that shown in Fig. 4, except for the anneal system 124. As shown in Fig. 5, the anneal system 124 includes a continuous belt 132 around rollers 136. The continuous belt 132 defines an upper leg 133 of the anneal system 124, and an anneal surface 134 on the bottom leg of the anneal system 124. As the substrates 12 pass into the anneal oven 100, the TCO layer 14 on the substrate 12 can be annealed within close proximity to or in contact with the cap material on the surface of the continuous belt 132.

[0041] A tension control system 138 can adjust the tension in the anneal system 124, in turn controlling the distance that the anneal surface 134 is from the outer surface of the TCO layer 14 on the substrate 12. As shown, a tension roll 140 can move vertically between two directional rollers 139. As the tension roll 140 moves, the tension of the continuous belt 132 can be adjusted (i.e., up to decrease tension and down to increase tension). In one embodiment, the anneal surface 134 can contact the TCO layer 14 during annealing or can be in close proximity to the TCO layer 14 during annealing, such as about 3 cm or closer. For example, the anneal surface 134 can be about 0.1 mm to about 1 cm from the surface of the TCO layer, such as about 1 mm to about 3.5 mm. In one particular embodiment, the anneal surface 134 can rest on top of the TCO layer 14 and move in unison with the substrate 12 as it travels along rollers 105 through the anneal oven 100.

[0042] The continuous belt 132 can be configured to withstand the anneal temperatures and the deposition of the cap material. For example, the continuous belt 132 can be constructed from a high-temperature, non-reactive, flexible material, including but not limited to, austenitic nickel-chromium-based superalloys (e.g., materials available under the trade name Inconel® from Special Metals Corporation, Huntington, WV). No matter the construction of the continuous belt 132, the anneal surface 134 defined by the belt is composed of a material reactive with oxygen at the anneal temperature. In one embodiment, the anneal surface 134 can include graphite (e.g., can consist essentially of graphite).

[0043] In one embodiment, the belt 132 can be "etched" periodically (e.g., after each pass) through wet chemical etching or dry etching (e.g., ion milling, reactive ion etch, etc.) to restore its reactivity with oxygen after each pass. [0044] Fig. 6 shows yet another embodiment of an anneal oven 100. As shown, an anneal plate 150 is positioned within the anneal oven so as to define a planar anneal surface 130 can contact the TCO layer 14 during annealing or can be in close proximity to the TCO layer 14 during annealing, such as about 3 centimeters (cm) or closer. For example, the planar anneal surface 130 can be about 0.1 millimeter (mm) to about 1 cm from the surface of the TCO layer, such as about 1 mm to about 3.5 mm. In one particular embodiment, the planar anneal surface 130 can rest on top of the TCO layer 14 and move in unison with the substrate 12 as it travels along rollers 105 through the anneal oven 100.

[0045] While the anneal plate 150 remains stationary during the annealing process, individual substrates 12 are conveyed through the anneal oven 100 with the TCO layer 14 facing the anneal surface 152. The anneal plate 150 is sized to be greater than the substrate such that an entire area of the transparent conductive oxide layer 14 is in close proximity to the anneal plate 150. As such, the anneal surface 152 of the anneal plate 150 is positioned so as to be substantially parallel to the

transparent conductive oxide layer 14 while the substrate 10 is conveyed through the anneal oven 100.

[0046] In this embodiment, the anneal surface 152 does not contact the

transparent conductive oxide layer 14 while the substrate 10 is conveyed through the anneal oven 100. Rather, the anneal surface 152 is positioned to be about 3 centimeters (cm) or closer, without contacting, the TCO layer 14. For example, the planar anneal surface 130 can be about 0.1 millimeter (mm) to about 1 cm from the surface of the TCO layer, such as about 1 mm to about 3.5 mm.

[0047] No matter the configuration of the anneal oven 100, the annealing atmosphere generally includes, in most embodiments, an inert gases (e.g., argon, etc.). Other gases may also be present in the annealing atmosphere, such as a reducing gas, a cadmium source gas, etc. A reducing gas may help improve conductivity of the TCO layer by increasing the oxygen vacancies in a TCO layer of cadmium stannate. On particularly suitable reducing gas is hydrogen sulfide (H ₂ S), although any reducing gas may be used such as hydrogen gas (H ₂ ), etc. For example, a reducing gas may constitute about 1% to about 25% by volume of the annealing atmosphere, such as about 5% to about 15% by volume. A cadmium source (e.g., an organo- cadmium gas, including, but not limited to, dimethyl cadmium, diethylcadmium, diphenylcadmium, diisoamylcadmium, etc., and mixtures thereof) gas in the annealing atmosphere may help form an equilibrium-type relationship with the surface of the substrate (i.e., the TCO layer as it is being deposited) forcing more cadmium atoms to remain in the TCO layer during the annealing process, when present, cadmium can constitute any portion of the total annealing pressure suitable to inhibit cadmium from sublimating off of the surface of the substrate during annealing of the TCO layer. For example, cadmium can constitute about 1% to about 50% by volume of the annealing atmosphere, such as about 5% to about 25% by volume.

[0048] In one particular embodiment, the annealing atmosphere may be substantially free from other reactive gasses, such as oxygen, nitrogen, and/or halogen-containing gasses. As used herein, the term "substantially free" means no more than an insignificant trace amount present and encompasses completely free (e.g., 0 % up to about 0.0001%> by volume of the annealing atmosphere).

[0049] The overall pressure of the annealing atmosphere during annealing can be from about 50 mTorr to about 1000 Torr (e.g., from about 1 Torr to about 850 Torr, such as from about 10 Torr to about 800 Torr). In one particular embodiment, the overall pressure of the annealing atmosphere can be about room pressure (e.g., about 760 Torr).

[0050] The presently provided methods of depositing and annealing a TCO layer can be utilized in the formation of any film stack that utilizes a TCO layer, particularly those including a TCO layer of cadmium stannate. For example, the TCO layer can be used during the formation of any cadmium telluride device that utilizes a cadmium telluride layer, such as in the cadmium telluride thin film photovoltaic device disclosed in U.S. Publication No. 2009/0194165 of Murphy, et al. titled "Ultrahigh Current Density Cadmium Telluride Photovoltaic Modules."

[0051] Fig. 1 represents an exemplary cadmium telluride thin film photovoltaic device 10 that can be formed according to methods described herein. The exemplary device 10 of Fig. 1 includes a transparent substrate 12 (e.g., a glass substrate) employed as the "superstrate," as it is the substrate on which the subsequent layers are formed even though it faces upward to the radiation source (e.g., the sun) when the cadmium telluride thin film photovoltaic device 10 is in use. The top sheet of glass 12 can be a high-transmission glass (e.g., high transmission borosilicate glass), low- iron float glass, or other highly transparent glass material. The glass is generally thick enough to provide support for the subsequent film layers (e.g., from about 0.5 mm to about 10 mm thick), and is substantially flat to provide a good surface for forming the subsequent film layers. In one embodiment, the glass 12 can be a low iron float glass containing less than about 0.015% by weight iron (Fe), and may have a

transmissiveness of about 0.9 or greater in the spectrum of interest (e.g., wavelengths from about 300 nm to about 900 nm). In another embodiment, borosilicate glass may be utilized so as to better withstand high temperature processing.

[0052] The transparent conductive oxide (TCO) layer 14 is shown on the glass 12 of the exemplary device 10 of Fig. 1. The TCO layer 14 allows light to pass through with minimal absorption while also allowing electric current produced by the device 10 to travel sideways to opaque metal conductors (not shown). For instance, the TCO layer 14 can have a sheet resistance less than about 30 ohm per square, such as from about 4 ohm per square to about 20 ohm per square (e.g., from about 8 ohm per square to about 15 ohm per square). In certain embodiments, the TCO layer 14 can have a thickness between about 0.1 μιη and about 1 μιη, for example from about 0.1 μιη to about 0.5 μιη, such as from about 0.25 μιη to about 0.35 μιη.

[0053] A resistive transparent buffer layer 16 (RTB layer) is shown on the TCO layer 14 on the exemplary cadmium telluride thin film photovoltaic device 10. The RTB layer 16 is generally more resistive than the TCO layer 14 and can help protect the device 10 from chemical interactions between the TCO layer 14 and the subsequent layers during processing of the device 10. For example, in certain embodiments, the RTB layer 16 can have a sheet resistance that is greater than about 1000 ohms per square, such as from about 10 kOhms per square to about 1000 MOhms per square. The RTB layer 16 can also have a wide optical bandgap (e.g., greater than about 2.5 eV, such as from about 2.7 eV to about 3.0 eV).

[0054] Without wishing to be bound by a particular theory, it is believed that the presence of the RTB layer 16 between the TCO layer 14 and the cadmium sulfide layer 18 can allow for a relatively thin cadmium sulfide layer 18 to be included in the device 10 by reducing the possibility of interface defects (i.e., "pinholes" in the cadmium sulfide layer 18) creating shunts between the TCO layer 14 and the cadmium telluride layer 22. Thus, it is believed that the RTB layer 16 allows for improved adhesion and/or interaction between the TCO layer 14 and the cadmium telluride layer 22, thereby allowing a relatively thin cadmium sulfide layer 18 to be formed thereon without significant adverse effects that would otherwise result from such a relatively thin cadmium sulfide layer 18 formed directly on the TCO layer 14.

[0055] The RTB layer 16 can include, for instance, a combination of zinc oxide (ZnO) and tin oxide (Sn0 ₂ ), which can be referred to as a zinc tin oxide layer ("ZTO"). In one particular embodiment, the RTB layer 16 can include more tin oxide than zinc oxide. For example, the RTB layer 16 can have a composition with a stoichiometric ratio of ZnO/Sn0 ₂ between about 0.25 and about 3, such as in about an one to two (1 :2) stoichiometric ratio of tin oxide to zinc oxide. The RTB layer 16 can be formed by sputtering, chemical vapor deposition, spraying pryolysis, or any other suitable deposition method. In one particular embodiment, the RTB layer 16 can be formed by sputtering (e.g. DC sputtering or RF sputtering) on the TCO layer 14 (as discussed below in greater detail with respect to the deposition of the cadmium sulfide layer 18). For example, the RTB layer 16 can be deposited using a DC sputtering method by applying a DC current to a metallic source material (e.g., elemental zinc, elemental tin, or a mixture thereof) and sputtering the metallic source material onto the TCO layer 14 in the presence of an oxidizing atmosphere (e.g., 0 ₂ gas). When the oxidizing atmosphere includes oxygen gas (i.e., 0 ₂ ), the atmosphere can be greater than about 95% pure oxygen, such as greater than about 99%.

[0056] In certain embodiments, the RTB layer 16 can have a thickness between about 0.075 μιη and about 1 μιη, for example from about 0.1 μιη to about 0.5 μιη. In particular embodiments, the RTB layer 16 can have a thickness between about 0.08 μιη and about 0.2 μιη, for example from about 0.1 μιη to about 0.15 μιη.

[0057] A cadmium sulfide layer 18 is shown on RTB layer 16 of the exemplary device 10 of Fig. 1. The cadmium sulfide layer 18 is a n-type layer that generally includes cadmium sulfide (CdS) but may also include other materials, such as zinc sulfide, cadmium zinc sulfide, etc., and mixtures thereof as well as dopants and other impurities. In one particular embodiment, the cadmium sulfide layer may include oxygen up to about 25% by atomic percentage, for example from about 5% to about 20% by atomic percentage. The cadmium sulfide layer 18 can have a wide band gap (e.g., from about 2.25 eV to about 2.5 eV, such as about 2.4 eV) in order to allow most radiation energy (e.g., solar radiation) to pass. As such, the cadmium sulfide layer 18 is considered a transparent layer on the device 10.

[0058] The cadmium sulfide layer 18 can be formed by sputtering, chemical vapor deposition, chemical bath deposition, and other suitable deposition methods. In one particular embodiment, the cadmium sulfide layer 18 can be formed by sputtering (e.g., direct current (DC) sputtering or radio frequency (RF) sputtering) on the resistive transparent layer 16. Sputtering deposition generally involves ejecting material from a target, which is the material source, and depositing the ejected material onto the substrate to form the film. DC sputtering generally involves applying a voltage to a metal target (i.e., the cathode) positioned near the substrate (i.e., the anode) within a sputtering chamber to form a direct-current discharge. The sputtering chamber can have a reactive atmosphere (e.g., an oxygen atmosphere, nitrogen atmosphere, fluorine atmosphere) that forms a plasma field between the metal target and the substrate. The pressure of the reactive atmosphere can be between about 1 mTorr and about 20 mTorr for magnetron sputtering. When metal atoms are released from the target upon application of the voltage, the metal atoms can react with the plasma and deposit onto the surface of the substrate. For example, when the atmosphere contains oxygen, the metal atoms released from the metal target can form a metallic oxide layer on the substrate. Conversely, RF sputtering generally involves exciting a capacitive discharge by applying an alternating-current (AC) or radio-frequency (RF) signal between the target (e.g., a ceramic source material) and the substrate. The sputtering chamber can have an inert atmosphere (e.g., an argon atmosphere) having a pressure between about 1 mTorr and about 20 mTorr.

[0059] Due to the presence of the resistive transparent layer 16, the cadmium sulfide layer 18 can have a thickness that is less than about 0.1 μιη, such as between about 10 nm and about 100 nm, such as from about 50 nm to about 80 nm, with a minimal presence of pinholes between the resistive transparent layer 16 and the cadmium sulfide layer 18. Additionally, a cadmium sulfide layer 18 having a thickness less than about 0.1 μιη reduces any absorption of radiation energy by the cadmium sulfide layer 18, effectively increasing the amount of radiation energy reaching the underlying cadmium telluride layer 22. [0060] A cadmium telluride layer 20 is shown on the cadmium sulfide layer 18 in the exemplary cadmium telluride thin film photovoltaic device 10 of Fig. 1. The cadmium telluride layer 20 is a p-type layer that generally includes cadmium telluride (CdTe) but may also include other materials. As the p-type layer of device 10, the cadmium telluride layer 20 is the photovoltaic layer that interacts with the cadmium sulfide layer 18 (i.e., the n-type layer) to produce current from the absorption of radiation energy by absorbing the majority of the radiation energy passing into the device 10 due to its high absorption coefficient and creating electron-hole pairs. For example, the cadmium telluride layer 20 can generally be formed from cadmium telluride and can have a bandgap tailored to absorb radiation energy (e.g., from about 1.4 eV to about 1.5 eV, such as about 1.45 eV) to create the maximum number of electron-hole pairs with the highest electrical potential (voltage) upon absorption of the radiation energy. Electrons may travel from the p-type side (i.e., the cadmium telluride layer 20) across the junction to the n-type side (i.e., the cadmium sulfide layer 18) and, conversely, holes may pass from the n-type side to the p-type side. Thus, the p-n junction formed between the cadmium sulfide layer 18 and the cadmium telluride layer 20 forms a diode in which the charge imbalance leads to the creation of an electric field spanning the p-n junction. Conventional current is allowed to flow in only one direction and separates the light induced electron-hole pairs.

[0061] The cadmium telluride layer 20 can be formed by any known process, such as vapor transport deposition, chemical vapor deposition (CVD), spray pyrolysis, electro-deposition, sputtering, close-space sublimation (CSS), etc. In one particular embodiment, the cadmium sulfide layer 18 is deposited by a sputtering and the cadmium telluride layer 20 is deposited by close-space sublimation. In particular embodiments, the cadmium telluride layer 20 can have a thickness between about 0.1 μιη and about 10 μιη, such as from about 1 μιη and about 5 μιη. In one particular embodiment, the cadmium telluride layer 20 can have a thickness between about 2 μιη and about 4 μιη, such as about 3 μιη.

[0062] A series of post-forming treatments can be applied to the exposed surface of the cadmium telluride layer 20. These treatments can tailor the functionality of the cadmium telluride layer 20 and prepare its surface for subsequent adhesion to the back contact layer(s) 22. For example, the cadmium telluride layer 20 can be annealed at elevated temperatures (e.g., from about 350° C to about 500° C, such as from about 375° C to about 424° C) for a sufficient time (e.g., from about 1 to about 10 minutes) to create a quality p-type layer of cadmium telluride. Without wishing to be bound by theory, it is believed that annealing the cadmium telluride layer 20 (and the device 10) converts the normally lightly p-type doped, or even n-type doped cadmium telluride layer 20 to a more strongly p-type cadmium telluride layer 20 having a relatively low resistivity. Additionally, the cadmium telluride layer 20 can recrystallize and undergo grain growth during annealing.

[0063] Annealing the cadmium telluride layer 20 can be carried out in the presence of cadmium chloride in order to dope the cadmium telluride layer 20 with chloride ions. For example, the cadmium telluride layer 20 can be washed with an aqueous solution containing cadmium chloride and then annealed at the elevated temperature.

[0064] In one particular embodiment, after annealing the cadmium telluride layer 20 in the presence of cadmium chloride, the surface can be washed to remove any cadmium oxide formed on the surface. This surface preparation can leave a Te-rich surface on the cadmium telluride layer 20 by removing oxides from the surface, such as CdO, CdTeCh, CdTe ₂ 0 ₅ , etc. For instance, the surface can be washed with a suitable solvent (e.g., ethylenediamine also known as 1,2 diaminoethane or "DAE") to remove any cadmium oxide from the surface.

[0065] Additionally, copper can be added to the cadmium telluride layer 20. Along with a suitable etch, the addition of copper to the cadmium telluride layer 20 can form a surface of copper-telluride on the cadmium telluride layer 20 in order to obtain a low-resistance electrical contact between the cadmium telluride layer 20 (i.e., the p-type layer) and the back contact layer(s). Specifically, the addition of copper can create a surface layer of cuprous telluride (Cu ₂ Te) between the cadmium telluride layer 20 and the back contact layer 22. Thus, the Te-rich surface of the cadmium telluride layer 20 can enhance the collection of current created by the device through lower resistivity between the cadmium telluride layer 20 and the back contact layer 22.

[0066] Copper can be applied to the exposed surface of the cadmium telluride layer 20 by any process. For example, copper can be sprayed or washed on the surface of the cadmium telluride layer 20 in a solution with a suitable solvent (e.g., methanol, water, or the like, or combinations thereof) followed by annealing. In particular embodiments, the copper may be supplied in the solution in the form of copper chloride, copper iodide, or copper acetate. The annealing temperature is sufficient to allow diffusion of the copper ions into the cadmium telluride layer 20, such as from about 125° C to about 300° C (e.g. from about 150° C to about 200° C) for about 5 minutes to about 30 minutes, such as from about 10 to about 25 minutes.

[0067] A back contact layer 22 is shown on the cadmium telluride layer 20. The back contact layer 22 generally serves as the back electrical contact, in relation to the opposite, TCO layer 14 serving as the front electrical contact. The back contact layer 22 can be formed on, and in one embodiment is in direct contact with, the cadmium telluride layer 20. The back contact layer 22 is suitably made from one or more highly conductive materials, such as elemental nickel, chromium, copper, tin, aluminum, gold, silver, technetium or alloys or mixtures thereof. Additionally, the back contact layer 22 can be a single layer or can be a plurality of layers. In one particular embodiment, the back contact layer 22 can include graphite, such as a layer of carbon deposited on the p-layer followed by one or more layers of metal, such as the metals described above. The back contact layer 22, if made of or comprising one or more metals, is suitably applied by a technique such as sputtering or metal evaporation. If it is made from a graphite and polymer blend, or from a carbon paste, the blend or paste is applied to the semiconductor device by any suitable method for spreading the blend or paste, such as screen printing, spraying or by a "doctor" blade. After the application of the graphite blend or carbon paste, the device can be heated to convert the blend or paste into the conductive back contact layer. A carbon layer, if used, can be from about 0.1 μιη to about 10 μιη in thickness, for example from about 1 μιη to about 5 μιη. A metal layer of the back contact, if used for or as part of the back contact layer 22, can be from about 0.1 μιη to about 1.5 μιη in thickness.

[0068] The encapsulating glass 24 is also shown in the exemplary cadmium telluride thin film photovoltaic device 10 of Fig. 1.

[0069] Other components (not shown) can be included in the exemplary device 10, such as bus bars, external wiring, laser etches, etc. For example, when the device 10 forms a photovoltaic cell of a photovoltaic module, a plurality of photovoltaic cells can 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 can be attached to a suitable conductor such as a wire or bus bar, to direct the photovoltaically generated current to convenient locations for connection to a device or other system using the generated electric. A convenient means for achieving such series connections is to laser scribe the device to divide the device into a series of cells connected by interconnects. In one particular embodiment, for instance, a laser can be used to scribe the deposited layers of the semiconductor device to divide the device into a plurality of series connected cells.

[0070] Fig. 2 shows a flow diagram of an exemplary method 30 of manufacturing a photovoltaic device according to one embodiment of the present invention.

According to the exemplary method 30, a TCO layer is formed on a glass substrate at 32 (e.g., via sputtering). At 34, an anneal surface is positioned in close proximity to the TCO layer, and the TCO layer is annealed in close proximity to the anneal surface at 36 (e.g., as shown in Figs. 4-6). At 38, a resistive transparent layer is formed on the TCO layer. An n-type window layer (e.g., a cadmium sulfide layer) is formed on the resistive transparent layer at 40, and an absorber layer (e.g., a cadmium telluride layer) is formed on the n-type window layer at 42. At 44, back contact layer(s) can be applied over the absorber layer, and an encapsulating glass can be applied over the back contact layer at 46.

[0071] One of ordinary skill in the art should recognize that other processing and/or treatments can be included in the method 30. For instance, the method may also include laser scribing to form electrically isolated photovoltaic cells in the device. These electrically isolated photovoltaic cells can then be connected in series to form a photovoltaic module. Also, electrical wires can be connected to positive and negative terminals of the photovoltaic module to provide lead wires to harness electrical current produced by the photovoltaic module.

[0072] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.