Patent Application
20120031604
The invention relates generally to the manufacture of electronic devices. More particularly, the invention relates to a method and a system for forming photovoltaic light absorbing Chalcopyrite compound layers of copper indium gallium diselenide (CIGS) on substrates for fabrication of thin film solar cells and modules.
Thin film solar cells have attracted significant attention and investment in recent years due to the potential for lowering the manufacturing costs of photovoltaic solar panels. Most solar panels are fabricated from crystalline silicon and polycrystalline silicon. While silicon-based technology enables fabrication of high efficiency solar cells (up to 20% efficiency), material costs are high due the embodied energy to refine and grow the bulk silicon ingots of silicon from silicon dioxide. In addition, sawing these ingots into wafers results in approximately 50% of the material being wasted. These solar cells are the primary component of the majority of solar panels made and sold today. Presently, silicon solar cells are approximately 90 μm thick. In contrast, thin film solar cells include layers that are approximately 1 μm to 3 μm thick and are deposited directly onto low cost substrates. Among the most popular materials used are amorphous silicon, copper indium diselenide and its alloys with gallium or aluminum (CIS, CIGS, CIAS) and cadmium telluride (CdTe).
Typically, amorphous silicon has the lowest manufacturing costs in terms of cost per unit of power produced, but the efficiencies of the solar cells are generally less than 10% which is low relative to the efficiencies of other materials. CIGS and CdTe cells have higher efficiencies and in the lab have achieved efficiencies approaching and sometime exceeding the efficiencies of silicon-based cells. Small area laboratory-scale cells have demonstrated efficiencies in excess of 20% and 18% for CIGS and CdTe, respectively; however, the transition to volume manufacturing and larger substrates is difficult and substantially lower efficiencies are realized.
Recently, CIGS solar cells have been produced in the laboratory and in production using a three phase co-evaporation process. In this process effusion sources of copper (Cu), indium (In) and gallium (Ga) evaporate at the same time in the presence of a selenium source. In this manner, deposition and selenization occur in a single step as long as the substrate temperature is maintained between about 400° C. and 600° C. Typically, higher temperatures result in higher efficiencies; however, not all substrates are compatible with higher temperatures. Sodium is often added to the mixture of sources and has been shown to enhance minority carriers and to improve voltage. Sodium may also passivate surfaces and grain boundaries. The deposition is repeated three times. For each deposition, the relative concentrations of copper, indium and gallium are changed, thus producing a graded compositional structure that can be more effective at absorbing and converting incident light into electrical power.
Scaling the three phase co-evaporation process to production levels is complicated due to a number of fundamental difficulties. First, effusion sources require high power consumption at production scale because the sources need to be maintained at temperatures as high as 1,500° C. At these high temperatures many materials are extremely reactive. Longevity of system components is decreased and process control and maintenance are difficult. Thus costs associated with production systems are high and downtime can be significant.
The substrate temperature is high during the selenization process. Consequently, the selenium residence time on the substrate surface is small and the selenium utilization efficiency is low. Selenium utilization and unwanted accumulation in various regions of the process chamber make the co-evaporation process difficult to manage in a production environment.
A number of groups have fabricated solar cells using the co-evaporation process while other groups have adopted production-compatible alternatives. One common alternative approach is based on a two-step process that typically includes depositing the metals (copper, indium and gallium) on a substantially cold substrate, that is, a substrate near or at ambient temperature. The deposited metals are then selenized in a hydrogen selenide (H2Se) gas or in a selenium vapor from a solid source. An ambient temperature is maintained between about 250° C. and 600° C.
The metals are typically deposited by electroplating, sputter deposition or printing. The metal deposition step is often followed by a cold deposition of selenium prior to the substrate entering a selenization furnace. The selenium deposition thickness is in the range of approximately 1 μm to 2 μm. By creating a sacrificial selenium layer on top of the CIG layer, indium is prevented from diffusing out of the metal layer in the form of a volatile indium selenide during the ramping of the furnace temperature. The temperature ramp can be of long duration, especially for thick glass substrates; however, for thin flexible foils, rapid temperature ramps (e.g., 10° C./s) are possible and are significant in reducing the problem of indium depletion. This two-step process is more controllable and easier to implement in system equipment in comparison to the co-evaporation technique; however, the resulting efficiencies generally are lower than those obtained by co-evaporation by 2% to 4%. The lower efficiencies are due to non-ideal grain formation and to the segregation of gallium and indium during the selenization step. Typically, gallium diffuses toward the back electrode to form a CuGaSe compound, while indium diffuses toward the barrier layer to form an indium rich compound near the front surface of the cell. Sulfur is sometimes added to the selenium in the furnace to compensate for this diffusion problem by increasing the bandgap of the material at the surface; however, the resulting absorbing layer is not a true CuInGaSe2 compound and the known advantages of adding gallium to CIS are moderated.
A hybrid technique has been used to implement a co-sputtering/selenization; however, selenium poisoning of the sputtering targets can occur and the hot substrate results in poor selenium utilization. Thus this technique is generally more difficult to control than the co-evaporation process.
In one aspect, the invention features a vapor trap that includes an inner module, an outer module and a cooling system. The inner module has an outer surface, a pair of opposing ends, a transport channel extending between the opposing ends and a plurality of plenums. Each of the plenums extends from the transport channel to the outer surface. The transport channel has a cross section to pass a substrate and to limit conductance of a vapor. The inner module is configured for maintaining a temperature that is greater than a condensation temperature of the vapor. The outer module includes a plurality of collection surfaces. Each collection surface is disposed at an end of a respective one of the plenums opposite to the transport channel. The cooling system is in thermal communication with the outer module and is configured to maintain a temperature of each of the collection surfaces to be less that a condensation temperature of the vapor.
In another aspect, the invention features a selenium trap that includes an inner module, an outer module and a cooling system. The inner module has an outer surface, a pair of opposing ends, a transport channel extending between the opposing ends and a plurality of plenums each extending from the transport channel to the outer surface. The transport channel has a cross section to pass a substrate and to limit conductance of a selenium vapor. The inner module is configured for maintaining a temperature that is greater than a condensation temperature of the selenium vapor. The outer module includes a surface having a plurality of pockets. Each of the pockets is disposed at an end of a respective one of the plenums opposite to the transport channel. The cooling system is in thermal communication with the outer module and is configured to maintain a temperature of each of the pockets to be less than a condensation temperature of the selenium vapor.
The above and further advantages of this invention may be better understood by referring to the following description in conjunction with the accompanying drawings, in which like numerals indicate like structural elements and features in the various figures. For clarity, not every element may be labeled in every figure. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
The systems and methods of the present invention may include any of the described embodiments or combinations of the described embodiments in an operable manner. In brief overview, the systems and methods of the invention enable the deposition of a CIGS thin film by sputtering deposition on metal and plastic thin foils and discrete substrates. As used herein, a discrete substrate means an individual component such as a glass plate, a glass panel or a wafer. The flexibility and bandgap engineering advantages of co-evaporation techniques are realized without the production scaling problems of prior art co-evaporation systems. CIGS devices having high conversion efficiencies are manufactured using a multistep process that includes sputtering and selenization sequences. First, a substantially thin metal layer of CuInGa (e.g., approximately 0.15 μm thickness) is deposited onto a cold web substrate or a discrete substrate. For example, the substrate temperature in the sputtering region is preferably as low as practical (e.g., ambient temperature) but may be up to 300° C. due to operation of the sputtering equipment. Subsequently, selenization occurs in a selenization furnace which is in-line with the sputtering system. The process is repeated a number of times until a desired thickness of the absorber layer is attained (e.g., approximately 2.5 μm). The composition of each incremental thin metal layer can be varied throughout the full deposition process to achieve desired bandgap gradients and other film properties. Segregation of gallium and indium is substantially reduced or eliminated because each incremental layer is selenized before the next incremental layer is deposited. This epitaxial growth process (or layer-by-layer method) by a co-sputtering/selenization process eliminates the problems associated with the presence of selenium in the sputtering chamber. The process can be implemented in a roll-to-roll production system to deposit CIGS films on metal and plastic foils. Alternatively, the process can be implemented in a discrete substrate production system to deposit CIGS films on discrete substrates such as glass substrates and wafers.
Referring to
The payout zone 14 includes a payout roll 30 of web material 34, such as a thin plastic or metal foil, that is dispensed and transported through the other zones. The payout zone 14 also includes an idler roll 38A, a load cell 42 to maintain web tension and a cooling roll 46A that has a substantially larger diameter than the other rolls. The take-up zone 26 includes a take-up roll 50 to receive the web 34 after passage through the other zones. The take-up zone also includes rolls 38B, 42B and 46B that function as counterparts to rolls in the payout zone 14. At least one of the payout roll 30 and the take-up roll 50 is coupled to a web transport mechanism as is known in the art that enables the web 34 to pass through the intervening zones. The operation of the payout roll 30 and the take-up roll 50 can be reversed, that is, the payout roll 30 can also perform as a take-up roll and the take-up roll 50 can perform as a payout roll when the web is transported in a reverse direction (right to left) as described below with respect to
The first sputtering zone 18A is a chamber having a plurality of sputtering magnetrons 54. The magnetrons 54 can be planar magnetrons or rotating cylindrical magnetrons as are known in the art. Target material composition for each magnetron 54 can vary relative to the materials of the targets for the other magnetrons 54 to achieve a graded composition structure in the resulting film.
The selenization zone 22 includes two cooling rolls 58 that surround two differentially pumped selenium traps 62 and a selenization furnace 66 having a selenium source 70. A multiple zone resistive heater comprising heating components 74 enables the furnace temperature along the web path through the selenization furnace 66 to vary.
After the first incremental layer is deposited, the web 34 enters the selenization zone 22. The web 34 first passes over a cooling roll 58A to cool (step 106) the web 34 before it enters a multistage differentially pumped selenium trap 62A. The trap 62A prevents selenium that may escape from the selenization furnace 66 from entering the sputtering zone 18A. The web 34 is pre-coated (step 108) with a thin layer (e.g., approximately 0.5 μm) of selenium in the trap 62A before entering the furnace 66. The relatively cold web temperature (e.g., less than 150° C.) allows selenium to condense on the web 34 as it moves through the trap 62. The web 34 then moves through the furnace 66 where selenization occurs (step 110) at a pressure that is substantially higher than the sputter pressure and at a temperature between 250° C. and 600° C. For example, the selenization can occur at a pressure in a range between 0.0001 Torr and 10 Torr. The pre-coating of selenium is advantageous in preventing indium depletion when the web temperature increases rapidly inside the furnace 66.
After exiting the furnace 66, the web 34 is cooled (step 112) to a lower temperature (e.g., less than 100° C.) by a second cooling roll 58B. The web 34 then passes through the second sputtering zone 18A where a second incremental layer of copper indium gallium of varying composition is deposited (step 114).
Once most of the web material from the payout roll 30 has been processed by transport in the forward direction, that is, dispensed from the payout roll 30 through the intervening zones and accumulated onto the payout roll 50, the deposition method 100 continues by transporting the web 34 in the reverse direction (step 116). While the web 34 moves back through the intervening zones, the original payout zone 14 functions as a take-up zone and the original take-up zone 26 functions as a payout zone. The web 34 passes through the sputtering and selenization zones 18 and 22 in reverse order to execute a sequence of steps (steps 118 to 128) that is reversed to the sequence of steps used during the forward transport. Thus a third incremental layer of copper indium gallium is deposited (step 118) on top of the second incremental layer in the second sputtering zone 18B before the second selenium pre-deposition occurs (step 122). Selenization is performed (step 124) during passage through the furnace 66 before a fourth incremental layer of copper indium gallium (step 128) is deposited onto the web 34.
Except for the first pass of the web 34 through the first sputtering zone 18A, it can be seen that selenization is performed after two consecutive passes of the web 34 through the same sputtering zone 18A or 18B. Thus two incremental layers are formed on the web 34 before selenization is performed. Advantageously, in some embodiments the power densities for the sputtering magnetrons can be reduced relative to the power densities for a single pass deposition of an incremental layer prior to selenization. In addition, because the power densities can be changed between passes, the composition of each layer can be changed without the need to change targets.
Forward and reverse transport processing are repeated a number of times until a CuInGaSe2 film of a desired total thickness is deposited onto the web 34 (as determined at step 130). It should be noted that at the end of the process, the magnetrons in the sputtering zone 18A or 18B used after the last passage through the selenization furnace 66 are disabled (step 132) and the web 34 is cooled before a final rewind (step 134).
The iterative selenization implemented throughout the process reduces or eliminates the gallium and indium segregation problem that is common to two-step CIG processes because the first incremental layer and the pairs of consecutive incremental layers from round-trip passage through a sputtering zone 18 are selenized before the next pair of incremental layers is deposited. Moreover, because the layers to be selenized are thin, the time required for the web 34 to pass through the selenization furnace 66 can be short. Consequently, the web transport speed can be high. The multiple pass forward and reverse process and high web transport speed permit efficient construction of a multilayer structure having a varying composition and bandgap.
Although the apparatus 10 and method 100 described above relate primarily to a configuration having a single selenization furnace 66 and a pair of sputtering zones 18, it should be recognized that other configurations are contemplated according to principles of the invention. For example, multiple selenization furnaces and additional sputtering zones can be employed to enable multiple layers to be deposited and subsequently selenized while the web is transported in a single direction.
In some embodiments the selenization furnace 66 has multiple heating zones.
Various types of selenium traps can be used. For example, different schemes based on differential pumping to gradually transition from a higher pressure region to a lower pressure region as are known in the art can be used.
The traps 304 enable various other system modules to operate under high vacuum conditions while maintaining a high selenium partial pressure in the oven 300. For example, the selenium partial pressure can be between 0.050 Ton and 10 Torr. In alternative applications, one or more selenium traps 304 can be used in systems in which various system modules operate near or at atmospheric pressure.
Each selenium trap 304 includes an inner module 308 and an outer module 312 that together function to recapture selenium that escapes through the oven apertures 316A and 316B. In a preferred embodiment, the inner module 308 is fabricated from graphite. Graphite is a suitable choice of material due to its relatively light weight and corrosive resistance. The inner module 308 includes a transport channel 320 to pass a web substrate 34 or discrete substrate. The transport channel 320 extends between a first trap aperture 328A at one end of the module 308 and a second trap aperture 328B at the opposite end of the module 308. Preferably the trap apertures 328 are shaped as slits. The trap apertures 328 and cross-section of the transport channel 320 are sized to pass the web substrate 34 (or discrete substrates) with sufficient clearance while limiting selenium vapor conductance from the selenization oven 300. By way of a numerical example, the slits can have a height of 5 mm and a width that is several millimeters greater than the width of the web substrate 34. A thin rectangular shape is also preferred for a discrete substrate system where the trap apertures 328 have a vertical dimension that is not substantially greater than the thickness of the discrete substrates.
Reference is also made to
The outer module 312 includes a number of collection surfaces, preferably in the form of recessed regions or “pockets” 340 (
In some embodiments, the inner module 308 includes one or more heaters, such as an electrical cartridge heater, to ensure that the inner module 308 remains above the condensation temperature of the selenium vapor (approximately 200° C.). In other embodiments, heat conducted due to a direct coupling of the inner module 308 to the selenization oven 300 (e.g., by attachment) is sufficient to maintain the inner module temperature above the selenium condensation temperature. The outer module 312 is maintained at a temperature substantially below the selenization condensation temperature by a cooling system. In the illustrated embodiment, the cooling system includes coolant channels 344 that are arranged vertically and horizontally and that receive a coolant, such as water, from a coolant pump or other coolant source.
The inner and outer modules 308, 312 can be fabricated as compact units that enable the selenium traps 304 to be easily mounted along the transport path of the substrate at both sides of the selenization oven 300. By way of a numerical example, the length of the traps 304 can be between 10 cm and 30 cm and the width of the traps 304 is determined primarily according to the width of the substrate.
During operation of the illustrated embodiment as shown in
The cold pocket surfaces allow efficient operation of the selenium pump 304. The arrangement of plenums 332 and pockets 340 act as a multi-stage differential pumping apparatus. For example, the selenium pressure is reduced by approximately a factor of ten for each stage progressing away from the selenization oven 300.
The trap 304 is configured to allow selenium that accumulates during system operation to be reclaimed. As described above, the density of the vapor in the plenums 332 decreases as the distance to the selenization oven 300 decreases, therefore the depth of a pocket 340 is preferably selected to accommodate the corresponding selenium accumulation rate for that pocket 340. Maintenance personnel can open the outer module 312, for example, by unbolting the body sections 312A, 312B and 312C to obtain access to the pockets 340 and to permit reclamation of the selenium deposits. After removal of the selenium, the body components of the outer module 312 are secured together about the inner module 308 so that the trap 304 can be reused. The reclaimed selenium can be reused in subsequent system operations.
It will be appreciated that the selenium trap can be adapted for a variety of other systems and applications, and that various changes to the structural features are contemplated. For example, in other embodiments the trap is a vapor trap used to restrict the location of other types of vapors for a variety of purposes, such as preventing contamination of surfaces or system components located away from a region of high vapor concentration and reclamation of other types of deposits from vapor condensation in the trap. Various features of the vapor trap, such as the number of plenums and the shapes and cross-sectional areas of the plenums and transport channel, can vary according to a particular application without departing from the principles of the invention. Moreover, the temperatures of the inner and outer modules for trapping various types of vapors are generally determined according to the condensation temperatures of the vapors.
The metal deposition zone 152 can be a sputtering zone as is known in the art. The selenization zone 154 receives the discrete substrates after they pass through the metal deposition zone 152. Except for the final pass through the system 150, the return cooling chamber 156 receives the discrete substrates after they exit the selenization zone 154. The return cooling chamber 156 cools the discrete substrates before the substrates arrive at the metal deposition zone 152 for deposition of the next incremental layer.
The deposition system 160 also includes two load locks 168 and 174, and buffer stations 170A and 170B. In the illustrated embodiment, a load mechanism 176 (e.g., a robotic load station) retrieves discrete substrates from a supply of discrete substrates and places them onto a substrate transport system. Once the final pass through the sputtering chamber 162 and selenization furnace 164 is completed, an unload mechanism 178 (e.g., a robotic unload station) removes the discrete substrates from the substrate transport system 180 after the discrete substrates emerge from the exit load lock 174.
The sputtering chamber 162 includes a plurality of sputtering magnetrons 54, such as planar magnetrons or rotating cylindrical magnetrons. In some embodiments in which a copper indium gallium diselenide film is deposited, the targets are composed of copper, indium, or alloys of each with gallium or aluminum. In various embodiments, the target material composition for each magnetron 54 varies with respect to the target material composition for the other magnetrons 54 so that a graded composition structure is achieved in the deposited film.
In various embodiments, the selenization furnace 164 operates in a temperature range of about 250° C. to 600° C. Optionally, the selenization furnace 164 can include a multiple zone resistive heater so that the temperature along the closed path 158 within the furnace varies. The two selenium traps 172 on each side of the selenization furnace 164 preferably are differentially pumped multistage traps. The selenium traps 172 prevent selenium that may escape the furnace 164 from entering the sputtering chamber 162 or adversely affecting other system components.
The sputtering chamber 162 and selenization furnace 164 are coupled to separate pump systems (not shown) to permit the vacuum levels for each of these zones to be independently controlled. Low conductance apertures, or substrate passages, at locations between system components and selenium traps 172 results in a high degree of vacuum isolation and enables more efficient vacuum control.
The cooling chamber 166 operates at atmospheric pressure is configured to reduce the temperature of the discrete substrates prior to a subsequent pass through the sputtering chamber 162 and selenization furnace 164. Various forms of coolers may be employed. In one embodiment, a cold plate extending at least along a portion of the length of the cooling chamber 166 is mounted above the substrate path such that discrete substrates passing underneath are cooled by atmospheric conduction.
Although the embodiments of a system for discrete substrates described above relate to transporting the discrete substrates along a closed path, in alternative embodiments the system transports discrete substrates along an open path, that is, a path that includes two ends: a load end and an unload end.
While the invention has been shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as recited in the accompanying claims.
This application is a continuation-in-part of U.S. patent application Ser. No. 13/101,538, titled “System and Method for Fabricating Thin-Film Photovoltaic Devices” and filed May 5, 2011, which is a continuation-in-part application of U.S. patent application Ser. No. 12/850,939, titled “System and Method for Fabricating Thin-Film Photovoltaic Devices” and filed Aug. 5, 2010.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13101538 | May 2011 | US |
| Child | 13173100 | US | |
| Parent | 12850939 | Aug 2010 | US |
| Child | 13101538 | US |
