Abstract:
Efficient photovoltaic devices with quantum dots are provided. Quantum dots have numerous desirable properties that can be used in solar cells, including an easily selected bandgap and Fermi level. In particular, the size and composition of a quantum dot can determine its bandgap and Fermi level. By precise deposition of quantum dots in the active layer of a solar cell, bandgap gradients can be present for efficient sunlight absorption, exciton dissociation, and charge transport. Mismatching Fermi levels are also present between adjacent quantum dots, allowing for built-in electric fields to form and aid in charge transport and the prevention of exciton recombination.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority from U.S. Provisional Patent Application 61/070,690 filed Mar. 24, 2008, which is incorporated herein by reference. 
    
    
     FIELD OF THE INVENTION 
     The invention relates generally to photovoltaic cells. More particularly, the present invention relates to quantum dot solar cells (QDSCs). 
     BACKGROUND 
     Solar cells and photovoltaic devices convert light, particularly sunlight, into electrical power. More particularly, photovoltaic devices convert incoming photons into charge carriers, such as electrons and holes, which are directed to conductors to perform useful work. Solar cells are currently used for a variety of applications at the personal, industrial, and, more recently, utility levels. Widespread adoption of photovoltaic cells can make significant contributions to solving a variety of national and global issues, including energy use, global climate change, and security. 
     However, market penetration of solar cells has been limited at least partly due to technological obstacles. Despite active and intensive research on improving photovoltaic technology, current solar cell efficiencies have generally been limited to about 10-15%. Today, the most commonly manufactured photovoltaic devices are silicon solar cells. Efficient silicon solar cells rely on extremely precise and uniform crystal structures of high quality silicon. However, these materials can be costly and have limited availability. In addition, drastic technological improvements of silicon solar cell efficiency are unlikely achievable. 
     In addition to traditional crystalline silicon solar cells, active research has been directed to thin film solar cells and nanoparticle (or quantum dot) solar cells with the goal of improving efficiency and/or decreasing cost. Unfortunately, these research directions also face many technological obstacles. In particular, existing nanoparticle solar cells face difficulties with photon absorption and exciton recombination, where an exciton is a particle comprised of a bound electron-hole pair. Even when excitons are successfully disassociated and not recombined, existing nanoparticle solar cells have limited efficiencies due to difficulties with charge transport. Furthermore, nanoparticle solar cells are generally fabricated using drop-casting or spin-casting of colloidal particles, or Stransky-Krastinow growth techniques, which do not allow for precise control of nanoparticle properties and positioning in the solar cell. 
     The present invention addresses at least the difficult problem of efficient photovoltaic devices and advances the art with a novel quantum dot solar cell. 
     SUMMARY OF THE INVENTION 
     The present invention is directed to a photovoltaic device having quantum dots and a bandgap gradient. In a preferred embodiment, the photovoltaic device includes a first conductor layer, a second conductor layer, and an active layer situated between the first and second conductor layers, wherein the active layer includes a matrix material and a plurality of quantum dots deposited in the matrix material, wherein each of the quantum dots has a bandgap, wherein the position of each quantum dot is based on the size of its bandgap, wherein the quantum dots having larger bandgaps are positioned closer to the first conductor layer than the quantum dots with smaller bandgaps, thereby a bandgap gradient is present in the active layer. Preferably, a size gradient of the quantum dots is present in the active layer, wherein the bandgap gradient is created by the size gradient. Alternatively or additionally, at least some of the quantum dots have different compositions and the bandgap gradient is created by the different compositions of the quantum dots. 
     In certain embodiments of the present invention, each of the quantum dots has a Fermi level, wherein at least two adjacent quantum dots have different Fermi levels, and wherein the differences in Fermi levels of the adjacent quantum dots creates a built-in electric field. In a preferred embodiment, quantum dots with higher Fermi levels are positioned closer to the first conductor layer than the quantum dots with lower Fermi levels. 
     In an embodiment, the photovoltaic device also includes a tunnel junction layer situated between the first and the second conductor layers. In an embodiment, the device includes an n+ layer situated between the first conductor layer and the active layer and a p+ layer situated between the second conductor layer and the active layer, wherein the n+ and p+ layers create an electric field in the active layer. 
     In an embodiment, at least one of the conductor layers is optically transparent and/or at least one of the conductor layers is optically reflective. In a preferred embodiment, the quantum dots are deposited by atomic layer deposition (ALD), layer-by-layer assembly, Langmuir-Blodgett deposition, or a combination thereof. Preferably, the distance between adjacent quantum dots in the active layer is sufficiently small to allow charge tunneling between adjacent quantum dots. In an embodiment, the distance between adjacent quantum dot ranges from about 0.5 nm to about 10 nm. 
     The quantum dots in embodiments of the present invention can be metallic quantum dots, semiconducting quantum dots, or any combination thereof. In an embodiment, each of the quantum dots range in size from about 0.5 nm to about 50 nm and have one or more shapes selected from the group consisting of rods, spheres, disks, pyramids, triangles, squares, and tetrapods. In an embodiment the matrix material includes an insulator, a semiconductor, or a combination thereof. In a preferred embodiment, the matrix material conducts a first type of charge carrier and the quantum dots conduct a second type of charge carrier. 
     Certain embodiments of the present invention are directed to a photovoltaic device including a first conductor layer, a second conductor layer, and a plurality of active layers situated between the first and the second conductor layers. Each of the active layers include a matrix material and a plurality of quantum dots deposited in the matrix material, wherein each of the quantum dots has a bandgap, wherein for each of the active layers, the position of the quantum dots is based on the size of its bandgap, and wherein a bandgap gradient is present in each of the active layers. In a preferred embodiment, the position of each active layer is based on the bandgap of its quantum dots, wherein active layers having quantum dots with larger bandgaps are closer to the first conductor layer than active layers having quantum dots with smaller bandgaps. In a preferred embodiment, the device includes one or more tunnel junction layers situated between two of the active layers. In an embodiment, the matrix materials of at least two of the active layers have different dielectric constants. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
       The present invention together with its objectives and advantages will be understood by reading the following description in conjunction with the drawings, in which: 
         FIG. 1  shows an example of a quantum dot solar cell comprising an active layer with a quantum dot size gradient according to the present invention. 
         FIGS. 2A-C  show plots of electron density, electric field, and voltage, respectively, versus position near two quantum dots of differing sizes an according to the present invention. 
         FIG. 3  shows a diagram of built-in voltage formation due to mismatching Fermi levels of nearby quantum dots according to the present invention. 
         FIG. 4  shows an example of a quantum dot solar cell having a bandgap gradient due to different quantum dot compositions according to the present invention. 
         FIG. 5  shows an example of a quantum dot solar cell comprising multiple active layers and a bandgap gradient formed a gradient in quantum dot size and composition according to the present invention. 
         FIG. 6A  shows an example of a quantum dot solar cell comprising electrodes on the sides of the active layer according to the present invention. 
         FIG. 6B  shows an example of a quantum dot solar cell having a hub-and-spoke configuration according to the present invention. 
         FIG. 7A  shows an example of a quantum dot solar cell according to the present invention. 
         FIG. 7B  shows a plot of current versus voltage for the quantum dot solar cell of  FIG. 7A . 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Developing efficient and cost-effective solar cells can be a daunting task, but one with considerable payoffs in terms of global climate change and energy security. Some existing photovoltaic technologies employ nanoparticles or quantum dots in the active photovoltaic material. However, many existing techniques face difficulties with exciton recombination, charge transport, and limited device efficiency. The present invention is directed to a quantum dot solar cell (QDSC) having bandgap gradients for greater efficiency. 
     In embodiments of the present invention, quantum dots are used in the active photovoltaic material for converting photons into charge carriers, primarily by disassociating excitons (particles comprised of pairs of negatively-charged electrons and positively-charged holes). Quantum dots have many desirable physical properties in photovoltaics, such as a tunable bandgap and Fermi level. A quantum dot&#39;s bandgap can be much different than the bulk material due to the small size of the quantum dot. Oftentimes, a material may not be semiconducting (i.e. it has zero bandgap) in the bulk, but when the material is sufficiently small, a finite bandgap forms. In general, the bandgap of a quantum dot is inversely related to the quantum dot size, thereby quantum dots of the present invention can be tuned to have the desired bandgaps. In an embodiment of the present invention, the quantum dots have bandgaps ranging from about 0 eV to about 3 eV, a range that is appropriate for sunlight. 
     It is important to note that the size of a quantum dot typically also determines its Fermi level. Similar to the bandgap, the location of the Fermi level of a quantum dot is inversely related to the quantum dot size; quantum dots of smaller sizes generally have higher Fermi levels than larger quantum dots of the same composition. As will be described in greater detail below, by having neighboring and proximate quantum dots with different Fermi levels, a built-in voltage can form, thereby reducing likelihood of exciton recombination and contributing to charge transport. 
     The present invention is directed to QDSCs that take advantage of at least the above properties relating to bandgaps and Fermi levels of quantum dots.  FIG. 1  shows an example of a preferred embodiment of a QDSC  100 . The QDSC  100  includes a first conductor layer  110 , a second conductor layer  120 , and an active layer  130 . The first  110  and second  120  conductor layers can be any material suitable for conducting charges (e.g. electrons, holes, or any other charge carriers). In operation, a photon  160  is absorbed in the active layer  130  and dissociates at least one exciton, thereby creating pairs of charge carriers. The charge carriers are transported to the first  110  and second  120  conductor layers. In an embodiment, the first conductor layer  110  is optically transparent to allow the photon  160  to pass through it and be absorbed in the active layer  130 . Additionally, the second conductor layer  120  can be optically reflective to increase the probability that the photon  160  will interact with the active layer  130 . 
     The active layer  130  includes a plurality of quantum dots  150  and a matrix material  140  for hosting the quantum dots  150 . It is important to note that the quantum dots  150  are preferably positioned in the active layer  130  to form a bandgap gradient between the conductor layers  110 - 120 . In other words, quantum dots  150  having larger bandgaps are positioned closer to one of the conductor layers, e.g. the first conductor layer  110 , than quantum dots  150  having smaller bandgaps. In an embodiment, quantum dots  150  having larger bandgaps are positioned more closely to the region of the QDSC where the incoming photon  160  is absorbed, however, alternative directions of the bandgap gradient can also be used. 
     In the embodiment shown in  FIG. 1 , the bandgap gradient is created by a size gradient of the quantum dots  150 . In other words, smaller quantum dots  150  are positioned closer to the first conductor layer  110  than larger quantum dots  150 . The quantum dots  150  of the present invention preferably range in size between about 0.5 nm to about 50 nm. As discussed above, by tuning the size of a quantum dot, a desired bandgap can be achieved and placed accordingly in the matrix material  140  of the active layer  130 . 
       FIGS. 2-3  show plots and diagrams that display advantageous properties of having proximate quantum dots of different sizes and/or Fermi levels.  FIGS. 2A-C  show plots of the electron density difference, the electric field, and the voltage, respectively, versus position near a small quantum dot  210  and a neighboring large quantum dot  220 . As can be seen in these plots, an electron density difference between the two quantum dots  210 - 220  leads to a built-in field and voltage. In particular,  FIG. 2C  shows a built-in voltage formed in the region between the large quantum dot  220  and the small quantum dot  210 . In an embodiment, the voltage drops from the region near the large quantum dot  220  to the region closer to the small quantum dot  210 . 
       FIG. 3  shows a diagram of how a built-in voltage V bi  can form between proximate quantum dots having different sizes. The top diagram in  FIG. 3  shows a large quantum dot  320  and a smaller quantum dot  310  spaced apart such that they are essentially isolated. The top diagram also shows an example energy band diagram of the two quantum dots  310 - 320 , including the conduction band energy E c  and the valence band energy E v . The conduction band is also referred to as the lowest unoccupied molecular orbital (LUMO) and the valence band is also referred to as the highest occupied molecular orbital (HOMO). The difference in the conduction band and the valence band is the bandgap. It is noted that the smaller quantum dot  310  has a larger bandgap than the larger quantum dot  320 . The diagram shows that in isolation the Fermi level E f1  of the large quantum dot  320  is less than the Fermi level E f2  of the smaller quantum dot  310 . The bottom diagram of  FIG. 3  shows how placing the quantum dots  310 - 320  in close proximity causes the system to equilibrate, thereby creating a built-in voltage V bi . More particularly, the process of equilibration includes equalizing the Fermi levels E f1 , E f2  by altering the band structure, which causes the built-in voltage V bi  to form. 
     The built-in voltage V bi  allows for many desirable properties for the operation of a QDSC. For example, the built-in voltage V bi  helps prevent exciton recombination, whereby the charge carriers generated from a dissociated exciton are not transported to the conductor layers, but instead recombine due to their mutual Coulombic attraction. Having a built-in voltage V bi  reduces the Coulombic attraction between the two charge carriers as the field generated from the built-in voltage V bi  directs a positively-charged carrier one direction and the negatively-charged carrier the opposite direction. In addition, built-in voltage V bi  also helps to dissociate the excitons into free electrons and free holes. 
     In addition to its contribution toward deterring exciton recombination, the built-in voltage also aids in charge transport. By arranging the quantum dots such that a gradient in Fermi levels is present, the built-in voltage of the quantum dots can help direct the charge carriers to the appropriate conductor layers. For example, in  FIG. 1 , the smaller quantum dots  150  have higher Fermi levels than the larger quantum dots  150 , therefore a built-in voltage will form in the active layer  130 , which drives electrons toward the first conductor layer  110  and the oppositely-charged holes toward the second conductor layer  120 . It is noted that the built-in voltage does not require additional energy costs as the field is generated by the system itself without external input. 
     Charge transport is an important consideration for efficiency of QDSCs. It is noted that in embodiments of the present invention, the charge carriers can be transported through a variety of physical mechanisms, including charge conduction and through quantum tunneling. In a preferred embodiment, the spacing between quantum dots in the active layer is sufficiently small to allow the charges to tunnel between adjacent quantum dots. In certain embodiments, the distance between adjacent quantum dots ranges from about 0.5 nm to about 10 nm. 
     QDSCs having quantum dots with small spacing and bandgap gradients formed by precise positioning of the quantum dots can be difficult to fabricate using conventional solar cell fabrication techniques. In a preferred embodiment, the quantum dots are positioned using atomic layer deposition (ALD), which enables extremely precise deposition of quantum dots in the host matrix material. When area-selective ALD is performed by selectively removing regions of a blocking layer, features may be placed with resolution only limited by the lithographic technique used to pattern the blocking layer. With conventional lithography, the resolution is on the ˜100 nm scale, with electron-beam lithography the resolution approaches 20 nm, and with lithography performed by the tip of an atomic force microscope, the resolution is in the single nm regime. In an alternative technique, which may be more cost effective in fabrication but yield less ordered films, ALD may be used to self-assemble quantum dots, where nucleation and growth of the quantum dots is a random process. It is noted that the present invention is not limited to QDSCs fabricated by ALD; other fabrication techniques can also be employed. In particular, other deposition techniques, such as layer-by-layer assembly and Langmuir-Blodgett deposition can also be used. In another embodiment, the QDSCs are fabricated by spin-coating or drop-casting. 
     Though  FIG. 1  shows a QDSC  100  having a size gradient of quantum dots  150  to form a bandgap gradient, the present invention is also directed to other physical properties, such as composition and shape, to establish a bandgap gradient.  FIG. 4  shows a QDSC  400  with a first conductor layer  410 , a second conductor layer  420 , an active layer  430 , a matrix material  440  in the active layer  430 , and multiple layers of quantum dots  450 - 480  of different composition deposited in the matrix material  440 . The various layers of quantum dots  450 - 480  are deposited such that a bandgap gradient exists between the first  410  and the second  420  conductor layers. For example, the quantum dots in layer  450  have a larger bandgap than the quantum dots in layer  460 , the quantum dots in layer  460  have a larger bandgap than the quantum dots in layer  470 , and so on. Thereby, a bandgap gradient is formed by compositional differences in the quantum dots of the QDSC  400 . 
     It is noted that the quantum dots can have the same or different sizes and the bandgap gradient can be created by differences in quantum dot size, composition, shape, or any combination thereof. In a preferred embodiment, the quantum dot composition is selected from the group consisting of PbS, PbSe, PbTe, CdS, CdSe, CdTe, HgTe, HgS, HgSe, ZnS, ZnSe, InAs, InP, GaAs, GaP, AlP, AlAs, Si, and Ge. More generally, the quantum dots can comprise metallic quantum dots, semiconducting quantum dots, or any combination thereof. Quantum dots can conduct or allow tunneling for positive charges, negative charges, or both. In an embodiment, the quantum dot shape is selected from the group consisting of rods, spheres, disks, squares, triangles, pyramids, tetrapods, or any other shape. 
       FIG. 5  shows another embodiment of a QDSC  500  of the present invention. The QDSC  500  includes a first conductor layer  510 , a second conductor layer  520 , and multiple active layers  530  and  550 . Each of the active layers  530  and  550  comprises a matrix material  540  and  560 , respectively, and quantum dots  535  and  555 , respectively. Though the QDSC  500  shown in  FIG. 5  only has two active layers  530  and  550 , it is noted that embodiments of the present invention can have any number of active layers. 
     In a preferred embodiment, the position of the quantum dots in each of the active layers is based on the bandgaps of the quantum dots, wherein a bandgap gradient is present in each of the active layers. It is noted that the bandgap gradient can be formed due to a size gradient, compositional differences as in the active layer  430  of  FIG. 4 , or any other physical differences in the quantum dots. Preferably, the position of each of the active layers is based on the bandgaps of its quantum dots, wherein the active layers having quantum dots with larger bandgaps are closer to one of the conductor layers than the active layers having quantum dots with smaller bandgaps. For example, in  FIG. 5 , quantum dots  535  of active layer  530  have larger bandgaps than quantum dots  555  of active layer  550 , therefore active layer  530  is positioned closer to the first conductor layer  510  than active layer  550 . 
     In the embodiment shown in  FIG. 5 , both active layers  530  and  550  have quantum dot size gradients within the active layer. However the quantum dots in active layer  550  are of a different composition than the quantum dots in active layer  530 , and a monotonic bandgap gradient exists between the first conductor layer  510  and the second conductor layer  520  due to the quantum dot size gradient within each active layer  530  and  550  and the composition differences between the active layers  530  and  550 . As would be appreciated by one of ordinary skill in the art, other configurations using quantum dot size, composition, shape, or any combination thereof can be possible to establish a bandgap gradient between the conductor layers  510  and  520 . 
     In addition to having quantum dots of different compositions between the active layers  530  and  550 , it is noted that the matrix materials  540  and  560  can be different or the same. For example, matrix material  540  can have a different dielectric constant as matrix material  560 . In an embodiment, materials having certain dielectric constants are chosen based on charge-screening and charge transport properties. The matrix materials may also have different bandgaps. The bandgaps would be chosen based on tunneling or carrier transport considerations balanced by the desirability of absorbing light in the matrix materials as opposed to in the quantum dots. Generally, a higher bandgap gives larger tunneling resistance but also provides a more effective confinement potential for the quantum dots. 
     The matrix material in the active layer can be an insulating material, a semiconducting material, or any combination thereof. In an embodiment, the matrix material conducts one type of charge carrier while the quantum dots conduct a different type of charge carrier. For example, the matrix material conducts holes while the quantum dots deposited in it conduct electrons. In other embodiments, the matrix material conducts both charge carriers or does not significantly conduct any charge. 
     In an embodiment of the present invention, a QDSC also includes a tunnel junction layer located between the first and the second conductor layers. In an embodiment, the tunnel junction includes two adjacent semiconducting layers that have opposite doping (heavily n-doped versus heavily p-doped). Band bending in the regime of the tunnel junction is sufficiently steep to allow electrons in the conduction band of the n+ layer to tunnel through the bandgap and combine with a hole in the p+ layer. If a tunnel junction is included, current matching should be enforced on each light absorbing layer of the solar cell. Since a tunnel junction effectively places two solar cells in series, the current through each cell must be continuous. This would place constraints on the thicknesses and optical densities of each layer. The advantage of a tunnel junction is that by placing the solar cells in series, the voltage of each light active layer effectively adds. The top layer delivers the highest voltage, based on the bandgap of QDs in that layer, while lower layers add a voltage based on their bandgaps. Therefore, as in a triple junction solar cell, the Shockley-Queisser efficiency limit does not apply, and efficiencies substantially in excess of 40% may be reasonably achieved. For certain embodiments having multiple active layers, a tunnel junction layer is located between two adjacent active layers. For example,  FIG. 5  shows an exemplary embodiment of a QDSC  500  with two active layers  530  and  550 , and a tunnel junction layer  570  situated between active layers  530  and  550 . 
       FIG. 5  also shows two optional layers to embodiments of the present invention, an n+ layer  580  and a p+ layer  590 . The n+  580  and p+  590  layers provide an electric field across the active layer or layers in the QDSC for preventing exciton recombination and helping charge transport to the conductor layers  510  and  520 . The n+  580  and p+  590  layers are positioned adjacent to the first  510  and second  520  conductor layers, respectively. In addition to providing an electric field across the active layer or layers, the n+  580  and p+  590  layers also act as barrier layers against certain types of charge carriers. For example, if the intended purpose of the first conductor layer  510  is to collect electrons, the n+  580  layer provides a barrier to prevent holes from being transported into the first conductor layer  510 . Either or both of the n+  580  and p+  590  layers can act as barriers for electrons or holes. 
     In an embodiment, the n+  580  and p+  590  layers include a doped semiconductor material. Preferably, the n+ layer has a high Fermi level and the p+ layer has a low Fermi level. In an exemplary embodiment, the p+ layer is comprised of B-doped Si and the n+ layer is comprised of P (phosphorus)-doped Si. 
       FIGS. 6A-B  show further embodiments of the present invention having different geometric configurations than the QDSCs of  FIGS. 1 ,  4 , and  5 . The QDSC  600  shown in  FIG. 6A  includes a first conductor layer  610 , a second conductor layer  620 , an active layer  630  with a matrix material  640  and a plurality of quantum dots  635 , and a metal reflector  650 . Similar to QDSC  100  shown in  FIG. 1 , QDSC  600  has a bandgap gradient between the first conductor layer  610  and the second conductor layer  620 . However, the bandgap gradient of QDSC  600  is oriented in a different direction than the bandgap gradient of QDSC  100  with respect to the direction of incoming photons  605 . 
       FIG. 6B  shows an alternative embodiment of a QDSC  660  with a hub-and-spoke configuration. QDSC  660  includes a first conductor  670 , a second conductor  680 , and an active layer comprising a plurality of quantum dots  685  and a matrix material  690 . The second conductor  680  can be circularly shaped and a radial bandgap gradient is present. It is noted that the present invention is not limited to the configurations described in the figures and one of ordinary skill in the art would appreciate other geometric configurations that do not depart from the principles of the present invention. 
       FIG. 7A  shows an example QDSC  700  that has been fabricated for experimental purposes. QDSC  700  includes a Pt conductor layer  710 , a ZrO 2  matrix material  720 , a first layer of PbS quantum dots  770 , another ZrO 2  matrix material  730 , a second layer of PbS quantum dots  780 , a SiO 2  layer  740 , a p+ Si layer  750 , and a Cu conductor layer. Current versus voltage measurements were performed for the QDSC  700  with different sizes of quantum dots in layers  770  and  780 .  FIG. 7B  shows a plot of current density versus voltage for three different devices. Plot  791  shows current versus voltage measurements when quantum dots in both layers  770  and  780  are 2 nm in diameter. Plot  792  shows current versus voltage measurements when quantum dots in both layers  770  and  780  are 5 nm in diameter. As shown by these plots  791 - 792 , neither of these devices demonstrates high performance. Plot  793  shows current versus voltage measurements when quantum dots in layer  770  are 5 nm in diameter and quantum dots in layer  780  are 2 nm in diameter. In other words, the measurements shown in plot  793  are of a device having a bandgap gradient resulting from the size gradient with improved performance over devices without any bandgap gradients. 
     As one of ordinary skill in the art will appreciate, various changes, substitutions, and alterations could be made or otherwise implemented without departing from the principles of the present invention, e.g. other materials not listed herein can be used for the various layers and quantum dots. Accordingly, the scope of the invention should be determined by the following claims and their legal equivalents.