The present disclosure relates generally to semiconductor devices, and more specifically to methods for fabricating solar cells.
Solar cells are devices that convert light energy into electrical energy by way of the photovoltaic effect. Solar cells operate through the photogeneration of charge carriers (electrons and holes) in absorbing material. The charge carriers so produced are then collected by conductive contacts to produce an electrical current.
In operation, photons 127 impinge upon the solar cell 101. Some of these photons are scattered by the ARC 113. Other photons of a suitable energy are absorbed by the p-type silicon 103, where they dislodge electrons from the atoms in the semiconductor lattice. The dislodged electrons flow through the p-type silicon 103 and into the N-type silicon 109, where they are gathered by the surface contacts 121 and produce an electrical current in circuit 117. Corresponding holes are also generated which are collected in P+ wells 115 created in the p-type silicon 103.
Silicon-based solar cells constitute a large portion of the global photovoltaic market, and may be made by known semiconductor fabrication techniques. In recent years, the high demand for silicon-based solar cells has created a shortage in the raw polysilicon feedstock used to manufacture these cells. This shortage has resulted in significant price increases in the final solar cell modules. Consequently, considerable effort has been expended in the art towards developing less expensive photovoltaic modules.
One approach to reducing the price of photovoltaic modules is to reduce the amount of silicon used in these modules. This approach is currently being pursued by several photovoltaic manufacturers who use alternative thin film technologies, such as those based on amorphous silicon, copper indium gallium selenide (CIGS), and cadmium telluride (CdTe). However, these approaches frequently yield lower efficiency solar cells, or suffer from volume manufacturing issues.
Another general approach of forming silicon-based thin film solar cells is through the use of layer transfer methods such as those typified by the SMART CUT® or ELTRAN® (Epitaxial Layer Transfer) processes. An example of the SMART CUT® process is illustrated in
With reference to
As shown in
Referring now to
After splitting, the SOI structure 215 exhibits micro-roughness along the surface of the thin layer of monocrystalline silicon 213. Wafer 203 has a similarly roughened surface 211. These surfaces are thus subjected to polishing as shown in
In the ELTRAN® process, a porous layer of silicon is created on a second substrate using HF-based etchants, and then an epitaxial Si film is grown on this porous layer. Wafer bonding is used to attach the top of the porous film to a first substrate. Splitting of the second substrate from the epitaxial film along the porous layer is accomplished via the use of a water jet.
While the foregoing processes have been moderately successful in creating lab-scale solar cells, none has reached commercial production levels. In the case of the ELTRAN® process, this failure is believed to arise, at least in part, from the presence of defects in the epitaxial layers. In the case of the SMART CUT® method, this failure is believed to be attributable to materials and temperature incompatibility issues that either lead to delamination of the transferred layers from the SOI structure 215 (see
While a thin film solar cell of the type achievable with the foregoing processes will theoretically have a higher conversion efficiency (for conversion of solar energy to electrical energy) compared to thick film or bulk devices as a result of reduced minority carrier recombination, the use of thin films also typically results in less absorption of optical photons. In general, the thickness of the device should exceed the absorption length for efficient light absorption. Therefore, it is frequently desirable to increase the optical path of photons in the thin film device through a suitable optical confinement technique.
One optical confinement technique known to the art involves texturing of the emitter regions and the application of an anti reflection coating (ARC) layer on top of those portions of the emitter regions which are not covered by contacts. These approaches are exemplified, for example, by the structures depicted in
Backside texturing, though less commonly used, is theoretically more effective in increasing the optical path of the photons. However, conventional backside texturing has its own challenges, since the front side has to be masked while the backside is etched for texturing. The backside must then be thoroughly cleaned so that the deposited metal forms a good ohmic contact after alloying or sintering. This process is complicated by the fact that the alloying or sintering steps create a deep graded layer at the metal-semiconductor interface that actually absorbs photons rather than reflecting them back into the semiconductor where they can be used for generating electron-hole pairs. There is thus a need in the art for a method for creating backside texturing to increase the optical absorption of any low energy photons that did not get used up to generate charge carriers before reaching the back surface.
One common rule of thumb utilized in designing solar cells is that the minority carrier diffusion length should be at least twice the thickness of the solar cell. In a monocrystalline or a large grain multicrystalline Si wafer, the diffusion length is around 100 μm or more. However, as the device gets thinner, surface (and not bulk) recombination becomes more important in such wafers. For electrons in p type silicon, the surface recombination velocity Sn at untreated surfaces, and at interfaces with metallic contacts, is in the range of 1,000-100,000 cm/s. When the surface is passivated with a layer of silicon dioxide, the oxide shields the minority carriers from defects at the surface and reduces Sn to less than 100 cm/s. In a conventional solar cell, the rear surface is doped more heavily to create a back surface field, which helps to reduce the loss of carriers through surface recombination. The extra p+-p junction also adds to the built-in bias of the cell and may enhance VOC.
In general, a silicon-metal interface is more defective than a silicon-silicon dioxide interface. Therefore, it is advantageous to form rear contacts as well as point contacts while the non-contacting regions are passivated with silicon dioxide similar to the front side. However, in order to do this, one has to create gaps in the oxide film to dope the base region heavily and to diffuse the metal locally in order to form the rear contact. There is thus a need in the art for a method for creating a defect free rear interface that reduces surface recombination at the metal-semiconductor interface without the need for additional complexity such as lithography and etch of the passivating oxide and localized diffusion of rear contacts.
The foregoing needs in the art may be met by the devices and methodologies disclosed herein and hereinafter described.
In one aspect, a method for forming a photovoltaic device is provided which comprises (a) providing a first substrate having a metal layer disposed thereon; (b) providing a second substrate which comprises a semiconductor material; (c) bringing the metal layer and the second substrate into contact with each other; and (d) interdiffusing the metal layer and the semiconductor material.
In another aspect, a method for forming a photovoltaic device is provided which comprises (a) providing a first substrate having a metal layer disposed thereon; (b) providing a plurality of structures, wherein each of said structures comprises a semiconductor layer; (c) bringing the metal layer and the plurality of semiconductor structures into contact with each other; and (d) interdiffusing the metal layer and the semiconductor layers of the plurality of structures.
In a further aspect, a photovoltaic device is provided which comprises (a) a substrate; (b) a semiconductor layer; and (c) a metal silicide layer disposed between said substrate and said semiconductor layer.
It has now been found that the aforementioned needs in the art may be met through the use of metal silicides or other metal-semiconductor intermetallic compounds to fabricate solar cells. Such materials may be utilized to simultaneously create a bonding agent, a back surface field (BSF), an optical reflecting layer, and/or a low resistivity rear ohmic contact in solar cell structures. The methodologies described herein may be utilized to fabricate low cost thin film solar cells having high efficiency, and may also be employed to create structures having multiple solar cells disposed on a common substrate, wherein the cells themselves may be fabricated using other techniques and structures as are known to the art.
By way of example, devices may be made in accordance with the teachings herein by a process which includes (a) splitting a semiconducting thin film from a semiconductor substrate; (b) depositing a metal film on a handle substrate such as stainless steel, metal foil, plastic or glass; and (c) bonding the metalized handle substrate to the semiconductor substrate with the use of an annealing treatment to form an intermetallic compound such as a metal silicide layer. The metal silicide and the processing conditions utilized may be chosen such that a textured layer is formed between the semiconducting layer and the metalized substrate. Such a textured layer increases the optical absorption path for photons. The silicide film may also be chosen such that a back surface field is created due to preferential accumulation of the dopants at the silicide-silicon interface, and so that it also forms a low resistivity rear ohmic contact to the base region. Finally, thermal sequences may be utilized which do not adversely affect conventional downstream silicon solar cell processing.
The second substrate 322 is preferably a semiconductor substrate, and is more preferably a silicon substrate. N-type monocrystalline silicon substrates may be utilized as the second substrate 322, although multicrystalline and p-type wafers may also be utilized. In some embodiments, other types of substrates, such as, for example, substrates comprising Ge or GaAs, may also be utilized. The second substrate 322 has a thickness which is preferably within the range of about 500 μm to about 700 μm, and more preferably within the range of about 550 μm to about 650 μm. Most preferably, the second substrate 322 has a thickness of about 600 μm in the case of N-type substrates.
Referring now to
Still referring to
Various doping levels may be employed in forming the p-type layer 324 with the first dopant, although a concentration within the range of about 1×1016 to about 1×1020 ions/cm3 is preferred. The average energy of the B3+ ions used in the implantation process is preferably chosen such that the p-type layer 324 has a depth within the range of about 0.01 μm to about 10 μm, and more preferably within the range of about 0.1 μm to about 1 μm. Most preferably, the p-type layer 324 has a depth of about 0.2 μm.
In some embodiments, it may be advantageous to utilize a second implantation step to implant a second dopant (at a higher dose than the first dopant) in the top surface of the second substrate 322 such that, in the resulting structure, a p+ type layer (not shown) is formed on top of the (lower doped) p-type layer 324. Such an approach may be utilized to form a p+-p junction for a rear BSF, and may facilitate at a subsequent stage the formation of the NiSi2 silicide phase (if Ni is used) at the metal-silicon interface. The second dopant may be any suitable dopant, and may be the same as, or different from, the first dopant. Preferably, however, in such embodiments, the first and second dopant are the same.
Referring now to
Subsequent to the ion implantation, the second substrate 322 may be subjected to a suitable anneal to join the microcavities formed by the ion implantation step and thereby complete the defect surface 326. This anneal may be conducted, for example, at a temperature of about 500° C. for a duration of about 30 minutes. Of course, it will be appreciated that, at this stage of the process, the portion of the second substrate above the defect surface 326 remains attached to the remainder of the second substrate 322.
Referring now to
When the second substrate 322 comprises silicon, a preferred metal of choice for the metal film 314 is Ni, since Ni readily forms nickel silicide under rapid thermal annealing at temperatures within the range of about 350° C. to about 1200° C., and preferably within a range of from about 400° C. to about 700° C. The preferred phase is NiSi2, which is stable at temperatures up to about 800° C. Advantageously, in the presence of either tensile lattice strain or a heavy doping of boron atoms (p+) in the first substrate 322, the silicon lattice of the second substrate 322 shrinks by an appropriate amount such that the formation of the NiSi2 phase is favored over the usual NiSi phase.
The morphology of the face centered cubic (FCC) NiSi2 phase is such that it forms with facets along {111} planes of the diamond cubic silicon lattice due to near perfect lattice matching between NiSi2 and Si under these conditions. This leads to a lowering of the interfacial energy of formation of the new phase so that the resultant phase formation with {111} facets forms a textured layer which is excellent for causing multiple reflections of incident photons in the thin film solar cell. Hence, this phase formation increases the optical path of the photons for increased absorption within the thin film solar cell thus formed.
The use of a p-type layer 324 facilitates the formation of the NiSi2 phase. It should be noted, however, that if the temperature requirements for downstream processing exceed about 850° C., then other metals may be used whose silicides can withstand higher temperatures. Examples of such metals include, but are not limited to, Ti, Co, W and Mo. The respective silicides of these metals (TiSi2, CoSi2, WSi, and MoSi) are stable up to 1000° C. or more for several seconds. Furthermore, dopant segregation occurs readily at the silicide-silicon interface during silicidation, thereby leading to lower barrier heights and contact resistivities. This phenomenon may be utilized to lower the series resistance of the solar cell device and, therefore, to increase its efficiency.
In some embodiments, formation of a uniform silicide may significantly reduce defects at the metal-silicide boundary, since dangling bonds are passivated at the metal-silicon interface by the formation of intermetallic silicide compounds. This effect is similar to that observed with oxide films which passivate the front or rear surface of otherwise free silicon, thereby reducing the effective surface recombination velocity and increasing the chances that photo-generated carriers are collected for producing electrical current. This is especially true in the case of NiSi2 formation, since NiSi2 forms with near perfect lattice matching to the contacting silicon substrate and, therefore, may give rise to fewer defects or dangling bonds at the interface. Metal silicides are generally also good conductors of electricity, and form good ohmic contacts to silicon.
The metal silicide formed during the rapid thermal anneal serves multiple purposes. These include the formation of an ohmic contact, the formation of an optical backside reflector, the formation of a backside surface field that repels minority carriers, and the formation of an intimate bond between the first 312 and second 322 substrates.
It should also be noted that, in some embodiments of the methodology described herein, after the second substrate 322 has been implanted with H, He, or Ar ions for splitting, a second metal film may be deposited on the top surface of this wafer in addition to the metal film 314 formed on the first substrate 312. These two substrates may then be bonded via diffusion bonding to create an intimate bond. In this case, the diffusion bonding conditions (e.g., temperature, pressure, and atmosphere) that are selected may be different from the downstream annealing/RTA conditions that form the silicide upon further annealing. However, through appropriate selection of the diffusion bonding conditions, a silicide film having the desired properties mentioned above can still be obtained.
As shown in
In some embodiments, the anneal used to complete the definition of the defect surface 326 may be used to split the wafer, in which case the first 312 and second 322 substrates may be brought together as shown in
As seen in
With reference to
As shown in
A blanket etch of the insulating film 356 is then utilized to remove the insulating film 356 from the top of the metal layer 354 and the semiconductor surfaces while providing isolation to the sides of the cells as shown in
As shown in
A final step of depositing an SiO2 film followed by an ARC film (which preferably comprises SiN) (shown collectively as element 360) completes the integration of the solar cell module as shown in
The second substrate 422 is preferably a semiconductor substrate, and is more preferably a silicon substrate. The use of p-type monocrystalline silicon substrates as the second substrate 422 in this particular embodiment is preferred. The second substrate 422 preferably has a dopant concentration within the range of about 1×1016 to about 1×1020 cm−3. In some embodiments, substrates containing materials other than silicon, such as, for example, substrates comprising Ge or GaAs, may also be utilized. The second substrate 422 has a thickness which is preferably within the range of about 500 μm to about 700 μm, and more preferably within the range of about 550 μm to about 650 μm. Most preferably, the second substrate 422 has a thickness of about 600 μm.
Still referring to
A buried n-type layer 424 is then formed in the second substrate 422. Preferably, the n-type layer 424 is formed by implanting a first dopant (which is preferably an ionic species such as phosphorus) into the top surface of the second substrate 422. The thickness d of this buried n-type layer 424 is typically within the range of about 0.05 microns to about 5 microns, and more preferably is within the range of about 0.1 microns to about 1 micron. The depth x of the n-type layer 424 below the top surface is typically within the range of about 0.1 microns to about 50 microns, and is preferably within the range of about 0.2 microns to about 5 microns. Multiple implants may be required in some implementations in order to achieve uniformly distributed dopant concentrations within this thickness.
If necessary, the dopant may then be activated after implantation through a suitable rapid thermal anneal process. The rapid thermal anneal process may involve, for example, exposing the second substrate 422 to 1000° C. in an N2 atmosphere. A diffusion anneal may be employed to achieve a uniform distribution of dopant within the n-type layer, as well as to activate the dopant.
Referring now to
Subsequent to the ion implantation, the second substrate 422 may be subjected to a suitable anneal to join the microcavities formed by the ion implantation step and thereby complete the defect surface 426. This anneal may be conducted, for example, at a temperature of about 500° C. for a duration of about 30 minutes. Of course, it will be appreciated that, at this stage of the process, the portion of the second substrate above the defect surface 426 remains attached to the remainder of the second substrate 422.
Referring now to
As shown in
The second substrate 522 is preferably a semiconductor substrate, and is more preferably a silicon substrate. The use of p-type monocrystalline silicon substrates as the second substrate 522 in this particular embodiment is preferred. The second substrate 522 preferably has a dopant concentration within the range of about 1×1016 to about 1×1020 cm−3. In some embodiments, the top surface of this substrate 522 may be doped with higher concentration than the bulk to provide a p+ doped layer. This may be accomplished through ion implantation or through gaseous or solid state diffusion methods. In some embodiments, substrates containing materials other than silicon, such as, for example, substrates comprising Ge or GaAs, may also be utilized. The second substrate 522 has a thickness which is preferably within the range of about 500 μm to about 700 μm, and more preferably within the range of about 550 μm to about 650 μm. Most preferably, the second substrate 522 has a thickness of about 600 μm.
A metal film 514 is then deposited on the first substrate 512. The metal film 514 may comprise any of the various metals as described in the previous embodiments, and may be formed by any of the methods described with respect to those embodiments.
Still referring now to
Subsequent to the ion implantation, the second substrate 522 may be subjected to a suitable anneal to join the microcavities formed by the ion implantation step and thereby complete the defect surface 526. This anneal may be conducted, for example, at a temperature of about 500° C. for a duration of about 30 minutes. Of course, it will be appreciated that, at this stage of the process, the portion of the second substrate above the defect surface 526 remains attached to the remainder of the second substrate 522.
Referring now to
As shown in
As shown in
With reference to
Referring now to
Various modifications and substitutions may be made to the foregoing embodiments. For example, while frequent reference has been made herein to first substrates and second substrates, it will be appreciated that the methodologies described herein may be applied to various types of substrates, whether or not they constitute wafers. Such substrates include, for example, semiconductor chips, and various types of sheets and surfaces.
Moreover, while the metal silicide layer is preferably patterned by controlling the conditions under which it is formed (e.g., by utilizing conditions which favor the formation of NiSi2 with facets along the {111} planes), other methods of patterning the metal silicide layer may be used in the devices and methodologies described herein, either in place of, or in combination with, this preferred methodology. For example, the metal silicide layer may be patterned by patterning the metal layer or the surface upon which the metal silicide layer is disposed (see, e.g., the method of
Moreover, while it is preferred that the metal silicide layer is used as a bonding layer to join two substrates together, it will be appreciated that structures and methodologies in accordance with the teachings herein are possible where this is not the case. For example, in some embodiments, the textured metal silicide layer may be formed in a first structure or substrate, after which the first structure or substrate may be joined to a second structure or substrate. As a specific example of this approach, the first and second structures or substrates may be equipped with first and second oxide layers, respectively, and the first and second structures or substrates may be joined together by joining the first and second oxide layers after the textured metal silicide layer is formed.
The above description of the present invention is illustrative, and is not intended to be limiting. It will thus be appreciated that various additions, substitutions and modifications may be made to the above described embodiments without departing from the scope of the present invention. Accordingly, the scope of the present invention should be construed in reference to the appended claims.